Encapsulation of functional moieties within branched star polymers: effect of chain length and solvent on site isolation

Porphyrin and pyrene photoactive cores have been encapsulated within an isolating polymeric shell using an efficient and general strategy based on the use of dendritic initiators for the ring-opening polymerization of epsilon-caprolactone to yield functional core star polymers. The isolation of the core functionalities has been studied using fluorescence quenching and fluorescence resonance energy transfer (FRET) techniques as well as solvatochromic probes. With increasing chain length as well as solvent polarity, enhanced site isolation of the core has been observed. These findings have been correlated to actual molecular dimensions independently measured by pulsed field gradient spin-echo (PGSE) NMR. The developed synthetic methodology offers a rapid route to efficient encapsulation of functional moieties and therefore has potential for the design of new materials.     

The adsorption of endothelin 1 to phospholipids is governed by electrostatic interactions: A monolayer and fluorescence study

In order to elucidate the influence on the lipidic environment on the recognition process of its membrane associated receptor, the interactions of the vasoconstrictor peptide endothelin 1 with various phospholipids have been investigated using different lipidic model membranes: monolayers at constant surface pressure, vesicles and micelles. A monolayer study of ET1 adsorbed onto the water surface has shown that the C-terminus of the peptide points towards the aqueous phase. Penetration measurements into lipidic monolayers indicate that ET1 adsorbs to phospholipids with an orientation similar to that of the air–water interface and fluorescence measurements are in agreement with such an orientation of the peptide. This adsorption is selective for neutral phospholipids and indicates that the nature of the phospholipid headgroups is of major importance for the approach of the membrane associated receptor.     

Synthesis of enantiomerically enriched allenes by (-)-sparteine-mediated lithiation of alkynyl carbamates

[reaction: see text]. The alpha-deprotonation of alkynyl carbamates 3 with the chiral base (-)-sparteine (4)/n-butyllithium, transmetalation with ClTi(O(i)()Pr)3, and subsequent substitution with an aldehyde results in the formation of enantioenriched 4-hydroxyallenyl carbamates 11. Stereoselection is determined by dynamic resolution of the lithium/(-)-sparteine complexes by selective crystallization.     

Über die Polymerisation des Phosphornitrilchlorids II

Zusammenfassung Die Polymerisation des Phosphornitrilchlorids in Substanz erweist sich als thermisch gestartete Radikalpolymerisation, die mit gleicher Geschwindigkeit und gleicher Temperaturabhängigkeit wie die durch Sauerstoff aktivierte Polymerisation in Lösung verläuft. Schon geringer Lösungsmittelzusatz bringt die thermische Polymerisation zum Erliegen. Ein Reaktionsschema mit Start-Kette-Abbruch wird diskutiert, das sowohl die Substanz- wie die Lösungspolymerisation wiedergibt. Der seinerzeit beschriebene Einfluß von Sauerstoff auf den Ablauf der Polymerisation erfährt dadurch eine wesentliche Korrektur.Die Depolymerisation von polymerem Phosphornitrilchlorid wird von 350 bis 600° C verfolgt und als gegenläufige Reaktionsfolge zur Polymerisation gefunden. Für das aus Polymerisation und Depolymerisation resultierende Gleichgewicht werden Druck- und Temperaturabhängigkeit festgestellt.Mit 8 Abbildungen.Herrn Prof. Dr.A. Klemenc zu seinem 70. Geburtstage gewidmet.Als I soll die ArbeitPatat-Kollinsky ¹ Über die Polymerisation des Phosphornitrilchlorids¹ gelten, die im folgenden Text auch mit (I) bezeichnet wird.— Eine Literaturzusammenstellung Phosphornitrilchlorid findet sich in der Monographie vonL. F. Audrieth, R. Steinmann undA. O. F. Toy, Chem. Rev.32, 109 (1943).     

五氯化磷辅助下氨基酸的自组装成肽反应研究

L-α-氨基酸和D-α-氨基酸可与五氯化磷直接发生磷酰化反应，随后自组装成多肽，但β-氨基酸不能成肽，DL-α-氨基酸成肽困难；在SOCl2存在下，α-氨基酸也不能成肽，用电喷雾质谱研究了氨基酸的自组装反应，反应过程中有五元环状的氨基酸五配位磷中间体生成，使用硅烷基保护的氨基酸，在^31PNMR中可观察到五配位磷中间体。     

Full verification of the liquid exclusion-adsorption chromatography theory using monolithic capillary columns

Capillary electrochromatography (CEC) was used to separate alkyl phenol ethoxylates (APEs) as model diblock copolymers, with monolithic polymers as stationary phases. The order of elution indicate that the two polymer blocks follow distinct chromatographic modes: size-exclusion for the poly(oxyethylene) group and adsorption interaction for the alkyl part. Therefore, our experimental results were compared to the theory describing liquid exclusion-adsorption chromatography (LEAC). They were found in perfect agreement with the theory, which turned to be verified for the first time over the full range of polymer lengths.     

Oral <Emphasis Type="Italic">L</Emphasis>-Carnitine Supplementation and Exercise Metabolism

Summary. Oral L-carnitine supplementation is frequently reported to have beneficial effects on exercise capacity in clinical populations and has been considered as a potential ergogenic aid for endurance athletes. However, this latter view is largely unsubstantiated possibly due to many experimental studies being poorly controlled or difficult to compare. The potential for oral L-carnitine supplementation to influence skeletal muscle carnitine content has been questioned and there are several key factors identified that may explain variations between study outcomes. Recent more well controlled research suggests some potential for L-carnitine to act as a key regulator of cellular stress, possibly through an impact on the integration of carbohydrate and lipid metabolism, and this work should be followed up in future by well controlled studies in both athlete and clinical subject groups.     

Organoaluminium and -gallium compounds with N,N-diisopropylaminomethyl groups

The N,N-diisopropylaminomethyl aluminium compound [tBu2AlCH2NiPr2 x LiCl]2(1) and the gallium compounds Li[tBu2Ga(CH2NiPr2)2](2) and [tBu2GaCH2N(H)iPr2]Cl x tBu3Ga (3) were prepared by transmetallation of N,N-diisopropylaminomethyllithium LiCH2NiPr2 with di-tert-butylaluminium or -gallium chloride, and characterised by elemental analyses, multinuclear NMR spectroscopy (1H, 13C, 27Al, 7Li) and IR spectroscopy. The crystal structures have been determined by single crystal X-ray diffraction. Compound aggregates as a centrosymmetric dimer, with two Al-C-N units connected by a frame of two LiCl molecules [Al-Cl 2.367(1), Cl-Li 2.339(4) and 2.374(4), Li-N 1.977(4)A]. Compound 2 is a lithium organogallate with two weak LiN bonds [1.965(7) and 1.937(7)A]. Compound 3 contains two different moieties: tBu3Ga and a [tBu2GaCH2N(H)iPr2]+ cation, which are bridged by a Cl- anion [Ga-Cl 2.445(1) and 2.579(1), HCl 2.362(3)A].     

Gravity-induced convective flow in microfluidic systems: electrochemical characterization and application to enzyme-linked immunosorbent assay tests

A way of using gravity flow to induce a linear convection within a microfluidic system is presented. It is shown and mathematically supported that tilting a 1 cm long covered microchannel is enough to generate flow rates up to 1000 nL.min(-1), which represents a linear velocity of 2.4 mm.s(-1). This paper also presents a method to monitor the microfluidic events occurring in a covered microchannel when a difference of pressure is applied to force a solution to flow in said covered microchannel, thanks to electrodes inserted in the microfluidic device. Gravity-induced flow monitored electrochemically is applied to the performance of a parallel-microchannel enzyme-linked immunosorbent assay (ELISA) of the thyroid-stimulating hormone (TSH) with electrochemical detection. A simple method for generating and monitoring fluid flows is described, which can, for instance, be used for controlling parallel assays in microsystems.