E-H-Zyklotronechos in Plasmen

A new echo type with free electrons in a slight inhomogeneous magnetic field excited by one electric and one magnetic pulse is calculated. Thus features of cyclotron echos and spin echoes are combined. The first electric pulse accelerates all (cold) particles to the same velocity as in the case of usual cyclotron echoes. The second magnetic pulse (at t = τ) rotates the plane of precession in phase space, quite in analogy to the motion of magnetic moments in the case of spin echoes. The echo arises at t = 2τ. The E-H echoes make relaxation and diffusion measurements in plasmas possible, using the methods proved useful in spin echo technique. There are no complications as in the case of E-E cyclotron echoes which are based on the fact that a velocity-dependent collision frequency is necessary for the nonlinearity of that echo mechanism.     

Vibrational and optical properties of the mixed crystal NaCℓ1−xBrx

A one-dimensional model is developed for the [111] transverse modes of the mixed crystal NaC?_1?xBr_x. The frequencies and eigenvectors of the normal modes of vibration are calculated for ten random configurations at each of a number of compositions. The imaginary part of the dielectric function is calculated for the average configuration at each composition. The behavior of the system cannot be classified in terms of the usual one-mode or two-mode categories. Representative eigenvectors are displayed, and the random element isodisplacement model is discussed in the light of our results.     

<Emphasis Type="Italic">N</Emphasis>-arachidonoyl glycine,an abundant endogenous lipid,potently drives directed cellular migration through GPR18, the putative abnormal cannabidiol receptor

Background  

Microglia provide continuous immune surveillance of the CNS and upon activation rapidly change phenotype to express receptors that respond to chemoattractants during CNS damage or infection. These activated microglia undergo directed migration towards affected tissue. Importantly, the molecular species of chemoattractant encountered determines if microglia respond with pro- or anti-inflammatory behaviour, yet the signaling molecules that trigger migration remain poorly understood. The endogenous cannabinoid system regulates microglial migration via CB₂ receptors and an as yet unidentified GPCR termed the 'abnormal cannabidiol' (Abn-CBD) receptor. Abn-CBD is a synthetic isomer of the phytocannabinoid cannabidiol (CBD) and is inactive at CB₁ or CB₂ receptors, but functions as a selective agonist at this G_i/o-coupled GPCR. N-arachidonoyl glycine (NAGly) is an endogenous metabolite of the endocannabinoid anandamide and acts as an efficacious agonist at GPR18. Here, we investigate the relationship between NAGly, Abn-CBD, the unidentified 'Abn-CBD' receptor, GPR18, and BV-2 microglial migration.     

Site-directed conjugation of "clicked" glycopolymers to form glycoprotein mimics: binding to mammalian lectin and induction of immunological function

Synthesis of well-defined neoglycopolymer-protein biohybrid materials and a preliminary study focused on their ability of binding mammalian lectins and inducing immunological function is reported. Crucial intermediates for their preparation are well-defined maleimide-terminated neoglycopolymers (M(n) = 8-30 kDa; M(w)/M(n) = 1.20-1.28) presenting multiple copies of mannose epitope units, obtained by combination of transition-metal-mediated living radical polymerization (TMM LRP) and Huisgen [2+3] cycloaddition. Bovine serum albumin (BSA) was employed as single thiol-containing model protein, and the resulting bioconjugates were purified following two independent protocols and characterized by circular dichroism (CD) spectroscopy, SDS PAGE, and SEC HPLC. The versatility of the synthetic strategy presented in this work was demonstrated by preparing a small library of conjugating glycopolymers that only differ from each other for their relative epitope density were prepared by coclicking of appropriate mixtures of mannopyranoside and galactopyranoside azides to the same polyalkyne scaffold intermediate. Surface plasmon resonance binding studies carried out using recombinant rat mannose-binding lectin (MBL) showed clear and dose-dependent MBL binding to glycopolymer-conjugated BSA. In addition, enzyme-linked immunosorbent assay (ELISA) revealed that the neoglycopolymer-protein materials described in this work possess significantly enhanced capacity to activate complement via the lectin pathway when compared with native unmodified BSA.     

Neue Verbindungen im System CaO/SiO2/CaCl2/H2O

New Compounds in the System CaO/SiO₂/CaCl₂/H₂O The hydrothermal formation of novel calcium silicate hydrates of compositions 5 CaO · 2 SiO₂ · CaCl₂ · 4 H₂O, 5 CaO · 2 SiO₂ · CaCl₂ · 2 H₂O and 4 CaO · 2 SiO₂ · CaCl₂ · H₂O from Ca₃SiO₅ and mixtures of CaO and SiO₂, respectively, in presence of calciumchloride at 200°–350 °C is described. From molybdate-reaction, ²⁹Si MAS NMR, DTA and TG measurements it is concluded that these compounds are based on disilicate anions and are to be interpreted as calcium hydroxide disilicate chlorides.     

Novel zirconocene anticancer drugs?

From the reaction of Super Hydride (LiBEt₃H) with 6-(4-methoxyphenyl) fulvene (1a), 6-(2-fluoro-4-methoxyphenyl) fulvene (1b), and 6-(4-N,N-dimethylaminophenyl) fulvene (1c) lithiated cyclopentadienide intermediates (2a-c) were synthesised. These intermediates were then transmetallated to zirconium with ZrCl₄ to give benzyl-substituted zirconocenes bis-[(4-methoxybenzyl)cyclopentadienyl] zirconium(IV) dichloride (3a), bis-[(2-fluoro-4-methoxybenzyl)cyclopentadienyl] zirconium(IV) dichloride (3b) and bis-[(4-N,N-dimethylaminobenzyl)cyclopentadienyl] zirconium(IV) dichloride (3c). All three zirconocenes were characterised by single crystal X-ray diffraction and preliminary in vitro cell tests were performed with the zirconocene derivatives on the LLC-PK cell line in order to determine their cytotoxicity. Zirconocenes 3b and 3c did not show cytotoxicity up to a concentration of 170 μM, while 3a exhibited an IC50 value of 57 μM against LLC-PK.     

Weak attractive interactions between methylthio groups and electron-deficient alkenes in peri-naphthalenes: a competition with conjugative effects

The solid-state conformations of five peri-disubstituted naphthalenes bearing a methylthio group and an electron-deficient alkene indicate a weak attractive interaction between the functional groups in four cases in which out-of-plane displacements lead to a common orientation of the MeSsp(2)-C vector to the alkene bond. In some cases the interaction is not strong enough to outweigh the tendency of the alkene to conjugate with the aromatic ring, and in one case this optimisation of conjugation alone controls the molecular conformation. The methylthio group lies close to the aromatic plane in all but one example for which the plane of the sulfide group is presented to the alkene.     

Models for incomplete nucleophilic attack on a protonated carbonyl group and electron-deficient alkenes: salts and zwitterions from 1-dimethylamino-naphthalene-8-carbaldehyde

The X-ray crystal structures of salts and zwitterionic Knoevenagel products from 1-dimethylamino-naphthalene-8-carbaldehyde show long N-C bonds between peri-groups which provide models for incomplete nucleophilic attack on a protonated carbonyl group and electron-deficient alkenes respectively. For the salts the N-C bonds lie in the range 1.625-1.638 ? with C-OH bonds intermediate in length between single and double bonds, while for the zwitterions the N-C bonds lie in the range 1.612-1.660 ?. The structural assignment of the former is supported by solid state (13)C and (15)N NMR studies on doubly isotopically-labelled material. Several zwitterions were converted to naphtha[1,8-bc]azepines by a mechanism involving the tertiary amino effect.