Lanthanide dota-like complexes containing a picolinate pendant: structural entry for the design of Ln(III)-based luminescent probes

In this contribution we present two ligands based on a do3a platform containing a picolinate group attached to the fourth nitrogen atom of the cyclen unit, which are designed for stable lanthanide complexation in aqueous solutions. Potentiometric measurements reveal that the thermodynamic stability of the complexes is very high (log K = 21.2-23.5), being comparable to that of the dota analogues. Luminescence lifetime measurements performed on solutions of the Eu(III) and Tb(III) complexes indicate that the complexes are nine coordinate with no inner-sphere water molecules. A combination of density functional theory (DFT) calculations and NMR measurements shows that for the complexes of the heaviest lanthanides there is a major isomer in solution consisting of the enantiomeric pair Λ(δδδδ) and Δ(λλλλ), which provides square antiprismatic coordination (SAP) around the metal ion. Analysis of the Yb(III)-induced paramagnetic shifts unambiguously confirms that these complexes have SAP coordination in aqueous solution. For the light lanthanide ions however both the SAP and twisted-square antiprismatic (TSAP) isomers are present in solution. Inversion of the cyclen ring appears to be the rate-determining step for the Λ(δδδδ) ? Δ(λλλλ) enantiomerization process observed in the Lu(III) complexes. The energy barriers obtained from NMR measurements for this dynamic process are in excellent agreement with those predicted by DFT calculations. The energy barriers calculated for the arm-rotation process are considerably lower than those obtained for the ring-inversion path. Kinetic studies show that replacement of an acetate arm of dota by a picolinate pendant results in a 3-fold increase in the formation rate of the corresponding Eu(III) complexes and a significant increase of the rates of acid-catalyzed dissociation of the complexes. However, these rates are 1-2 orders of magnitude lower than those of do3a analogues, which shows that the complexes reported herein are remarkably inert with respect to metal ion dissociation.     

A low-voltage electrokinetic nanochannel drug delivery system

Recent work has elucidated the potential of important new therapeutic paradigms, including metronomic delivery and chronotherapy, in which the precise timing and location of therapeutic administration has a significant impact on efficacy and toxicity. New drug delivery architectures are needed to not only release drug continuously at precise rates, but also synchronize their release with circadian cycles. We present an actively controlled nanofluidic membrane that exploits electrophoresis to control the magnitude, duration, and timing of drug release. The membrane, produced using high precision silicon fabrication techniques, has platinum electrodes integrated at the inlet and outlet that allow both amplification and reversal of analyte delivery with low applied voltage (at or below 2 VDC). Device operation was demonstrated with solutions of both fluorescein isothiocyanate conjugated bovine serum albumin and lysozyme using fluorescence spectroscopy, fluorescence microscopy, and a lysozyme specific bio-assay and has been characterized for long-term molecular release and release reversibility. Through a combination of theoretical and experimental analysis, the relative contributions of electrophoresis and electroosmosis have been investigated. The membrane's clinically relevant electrophoretic release rate at 2 VDC exceeds the passive release by nearly one order of magnitude, demonstrating the potential to realize the therapeutic paradigm goal.     

H,C, Pt NMR study on platinum(II) interaction with sulphur containing Amadori compounds

The NMR study on the interaction of Pt(II) with Amadori compounds is performed. The Amadori compounds are derived from the reaction of β-d-glucose with l-cystine leading to N,N′-di-(1-deoxy-β-fructos-1-yl)-l-cystine [FruCyscys], and with l-methionine leading to N-(1-deoxy-β-fructos-1-yl)-l-methionine [FruMet].     

Surface-templated formation of protein microfibril arrays.

Ordered arrays of collagen microfibrils form rapidly and spontaneously from a solution of monomers deposited onto a mica substrate. These arrays are well-ordered and apparently continuous over the entire substrate. Correlated atomic force microscope images and Laué diffraction patterns indicate that the protein alignment and microfibril formation is controlled by the crystal orientation of the mica substrate rather than fluid flow or drying effects. This surface-induced mechanism allows for immediate, robust, and reproducible pattern formation.     

Zur Analyse von Haut- und Haarwaschmitteln auf Basis synthetischer Tenside

Zusammenfassung Dusch- und Schaumbadepr?parate sowie Haarwaschmittel enthalten als Hauptbestandteile im allgemeinen anionische und nichtionische, gelegentlich auch noch amphotere Tenside. In der vorliegenden Arbeit wird ein Analysengang beschrieben, der nicht nur die Auftrennung der Tensidgemische und die Identifizierung und Bestimmung der eingesetzten Tenside behandelt, sondern auch Methoden für den Nachweis und die Bestimmung von Hilfs- und Zusatzstoffen angibt. Daneben wird versucht, die Analysenm?glichkeiten von Verbindungen aufzuzeigen, die den Pr?paraten besondere zus?tzliche Eigenschaften neben der prim?r gewünschten Reinigungswirkung verleihen. Zur Isolierung dieser Substanzen (wie z.B. der Sterine und Konditioniermittel) sind von uns Methoden erarbeitet worden, die in dieser Arbeit erstmalig mitgeteilt werden.

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On the analysis of body and hair shampoos based on synthetic tensides

Summary In general, body and hair shampoos contain as main components anionic and non-ionic, sometimes also amphoteric, detergents. A scheme of analysis is given here which not only deals with the separation of the detergent mixtures and the identification and determination of the surfactants employed but also with methods for the detection and determination of additive and auxiliary compounds. Moreover, the attempt is made to point out analytical methods for the determination of those compounds which impart special qualities to the bath preparations and shampoos besides the primary wanted cleaning effect. Methods for the isolation of these substances (as e.g. sterols and conditioning agents) have been elaborated and are described in this paper for the first time.

     

Magnetically responsive carboxylated magnetite-polydipyrrole/polydicarbazole nanocomposites of core-shell morphology. Preparation, characterization, and use in DNA hybridization

Novel bis-heterocyclic mono- and dicarboxylated dipyrrole and dicarbazole monomers have been synthesized in a modular manner. Their oxidative polymerization around magnetite nanosized particles has been investigated and optimized toward new magnetic magnetite-polydipyrrole/polydicarbazole nanocomposites (NCs) of a core-shell morphology. These NCs were thoroughly characterized by FT-IR, TGA (Thermal Gravimetric Analysis), low- and high-resolution TEM/HR-TEM microscopies, and M?ssbauer spectroscopy along with magnetization studies. Exploiting the versatile COOH chemistry (activation by water-soluble diimides) introduced by the polymeric shell, DNA hybridization experiments have been conducted onto NC surfaces using an efficient blue-colored HRP-based enzymatic screening biological system. Highly parallel NC-supported DNA hybridization experimentations revealed that these NCs presented an interesting potential for DNA-based diagnostic applications.     

Enhanced relaxation of nanoparticle-bound supercoiled DNA in X-ray radiation

A therapeutic methodology was developed based on the large X-ray absorption cross-section of gold nanoparticles at high photon energies (>81 keV). Experimental results showed that the amounts of the relaxed circular supercoiled DNA (scDNA) for gold nanoparticle-bound scDNA were more than doubled compared to that for free scDNA under otherwise identical radiation conditions.     

Design, self-assembly, and photophysical properties of pentameric metallomacrocycles: [M5(N-hexyl[1,2-bis(2,2':6',2''-terpyridin-4-yl)]carbazole)5][M = Fe(II), Ru(II), and Zn(II)

A novel family of metallopentacycles was constructed by the facile self-assembly of a bis(terpyridine)-carbazole monomer utilizing terpyridine-metal(II)-terpyridine connectivity; its photophysical properties were investigated.