Aryl-Decorated Ru(II) Polypyridyl-type Photosensitizer Approaching NIR Emission with Microsecond Excited State Lifetimes.

Bis-tridentate Ru(II) complexes based on the dqp scaffold (dqp is 2,6-di(quinolin-8-yl)pyridine) with multiple aryl substituents were explored to tailor the absorption and emission properties. A synthetic methodology was developed for the facile synthesis and purification of homo- and heteroleptic bis-tridentate Ru complexes. The effect of the aryl substituents in the para positions of the pyridine and quinoline subunits was detailed by X-ray crystallography, steady state and time-resolved spectroscopy, electrochemistry, and computational methods.

Synthesis and characterization of metallo-supramolecular polymers.

The incorporation of metal centers into the backbone of polymers has led to the development of a broad range of organometallic and coordination compounds featuring properties that are relevant for potential applications in diverse areas of research, ranging from energy storage/conversion to bioactive or self-healing materials. In this review, the basic concepts and synthetic strategies leading to these types of materials as well as the scope of available characterization techniques will be summarized and discussed.

Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes.

We report a series of cyanide-bridged, heterodinuclear iridium(III)-ruthenium(II) complexes with the generalized formula [Ir((R2)2-ppy)2(CN)(μ-CN)Ru(bpy)(tpy-R1)]PF6 (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine, and tpy = 2,2':6',2″-terpyridine). The structural, spectroscopic, and electrochemical properties were analyzed in the context of variation of the electron-withdrawing (e.g.

Glutamic Acid Residues in HIV-1 p6 Regulate Virus Budding and Membrane Association of Gag.

The HIV-1 Gag p6 protein regulates the final abscission step of nascent virions from the cell membrane by the action of its two late (L-) domains, which recruit Tsg101 and ALIX, components of the ESCRT system. Even though p6 consists of only 52 amino acids, it is encoded by one of the most polymorphic regions of the HIV-1 gag gene and undergoes various posttranslational modifications including sumoylation, ubiquitination, and phosphorylation. In addition, it mediates the incorporation of the HIV-1 accessory protein Vpr into budding virions.

Specific Surface versus Electrochemically Active Area of the Carbon/Polypyrrole Capacitor: Correlation of Ion Dynamics Studied by an Electrochemical Quartz Crystal Microbalance with BET Surface.

Carbon/polypyrrole (PPy) composites are promising electrode materials for energy storage applications such as lightweight capacitors. Although these materials are composed of relatively inexpensive components, there is a gap of knowledge regarding the correlation between surface, porosity, ion exchange dynamics, and the interplay of the double layer capacitance and pseudocapacitance. In this work we evaluate the specific surface area analyzed by the BET method and the area accessible for ions using electrochemical quartz-crystal microbalance (EQCM) for SWCNT/PPy and carbon black Vulcan XC72-R/PPy composites.

Multigrid MALDI mass spectrometry imaging (mMALDI MSI).

Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) is an important technique for the spatially resolved molecular analysis of tissue sections. The selection of matrices influences the resulting mass spectra to a high degree. For extensive and simultaneous analysis, the application of different matrices to one tissue sample is desirable.

Antibacterial effect of silver (I) carbohydrate complexes on oral pathogenic key species in vitro.

Background: It was the aim of this study to evaluate the antibacterial impact of two silver(I) carbohydrate complexes with tripodal thioglycosides, namely tris[2-(β-D-thio-glucopyranosyl)ethyl]-amine-silver(I)-nitrate (3) and tris[2-(α-D-thio-manno-pyranosyl)ethyl]-amine-silver(I)-nitrate (4), on five oral pathogenic bacterial strains. Furthermore, cytocompatibility was tested using human gingival fibroblasts (HGF).

Methods: Minimum inhibitory concentrations (MIC) were determined on five oral pathogenic bacterial strains by using the broth microdilution method: Fusobacterium nucleatum (ATCC 10953), Aggregatibacter actinomycetemcomitans (ATCC 33384), Porphyromonas gingivalis (ATCC 33277), Streptococcus mutans (ATCC 25175) and Enterococcus faecalis (DSMZ 20376).

Glycopolymer-Functionalized Cryogels as Catch and Release Devices for the Pre-Enrichment of Pathogens.

A highly porous cryogel is prepared and subsequently functionalized with an atom transfer radical polymerization (ATRP) initiator at the surface. Two new glycomonomers are introduced, which possess deprotected mannose as well as glucose moieties. These are copolymerized with -propylacrylamide (iPAm) from the cryogel surface, providing a highly hydrophilic porous material, which is characterized by SEM, FT-IR spectroscopy, and NMR spectroscopy.

Antigen delivery via hydrophilic PEG-b-PAGE-b-PLGA nanoparticles boosts vaccination induced T cell immunity.

Here, we evaluate the use of hydrophilic PEG-b-PAGE-b-PLGA (PPP) for the preparation of antigen loaded nanoparticles (NPs) as a platform for prophylactic vaccination. To investigate the suitability of PPP-NPs for antigen delivery, we used the double emulsion evaporation technique to prepare NPs of different sizes, antigen-loading efficiencies and -release kinetics for the model antigen Ovalbumin (OVA). Prior to applying the PPP-NPs in biological in vitro or in vivo models, all materials were tested for absence of cytotoxicity and endotoxins.

Assorted Phenoxyl-Radical Polymers and Their Application in Lithium-Organic Batteries.

The synthesis and electrochemical characterization of novel polymers bearing phenoxyl-radicals as redox-active side chains is described. The monomers are synthesized from the corresponding phenols and quinones, respectively. These compounds are subsequently poly-merized via ring-opening metathesis polymerization.

Cellular uptake of PLA nanoparticles studied by light and electron microscopy: synthesis, characterization and biocompatibility studies using an iridium(III) complex as correlative label.

We present the synthesis of polylactide by ring-opening polymerization using a luminescent iridium(III) complex acting as initiator. The polymer was formulated into nanoparticles, which were taken up by HEK-293 cells. We could show that the particles provided an appropriate contrast in both superresolution fluorescence and electron microscopy, and, moreover, are non-toxic, in contrast to the free iridium complex.

4,5-Diarylisoxazol-3-carboxylic acids: A new class of leukotriene biosynthesis inhibitors potentially targeting 5-lipoxygenase-activating protein (FLAP).

In this article, we report novel leukotriene (LT) biosynthesis inhibitors that may target 5-lipoxygenase-activating protein (FLAP) based on the previously identified isoxazole derivative (8). The design and synthesis was directed towards a subset of 4,5-diaryl-isoxazole-3-carboxylic acid derivatives as LT biosynthesis inhibitors. Biological evaluation disclosed a new skeleton of potential anti-inflammatory agents, exemplified by 39 and 40, which potently inhibit cellular 5-LO product synthesis (IC50 = 0.

Stimulated Emission Depletion Lithography with Mercapto-Functional Polymers.

Surface reactive nanostructures were fabricated using stimulated emission depletion (STED) lithography. The functionalization of the nanostructures was realized by copolymerization of a bifunctional metal oxo cluster in the presence of a triacrylate monomer. Ligands of the cluster surface cross-link to the monomer during the lithographic process, whereas unreacted mercapto functionalized ligands are transferred to the polymer and remain reactive after polymer formation of the surface of the nanostructure.

Poly(TEMPO)/Zinc Hybrid-Flow Battery: A Novel, "Green," High Voltage, and Safe Energy Storage System.

The combination of a polymer-based 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO) catholyte and a zinc anode, together with a cost-efficient size-exclusion membrane, builds a new type of semi-organic, "green," hybrid-flow battery, which features a high potential range of up to 2 V, high efficiencies, and a long life time.

Impact of PEG and PEG-b-PAGE modified PLGA on nanoparticle formation, protein loading and release.

The effect of modifying the well-established pharmaceutical polymer PLGA by different PEG-containing block-copolymers on the preparation of ovalbumin (OVA) loaded PLGA nanoparticles (NPs) was studied. The used polymers contained poly(d,l-lactic-co-glycolic acid) (PLGA), polyethylene glycol (PEG) and poly(allyl glycidyl ether) (PAGE) as building blocks. The double emulsion technique yielded spherical NPs in the size range from 170 to 220 nm (PDI<0.

Abundance correction for mass discrimination effects in polymer mass spectra.

Rationale: Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) is frequently used to analyze homo- and copolymers, i.e. for computing copolymer fingerprints.

Selective Uptake of a Fructose Glycopolymer Prepared by RAFT Polymerization into Human Breast Cancer Cells.

A new methacrylic fructose glycomonomer is synthesized and copolymerized with N-isopropyl acrylamide by reversible addition fragmentation chain transfer (RAFT) poly-merization. By additional copolymerization of the analog mannose, glucose, and galactose glycomonomers, a set of glycopolymers is obtained which vary in the type of sugar attached to the polyacrylamide backbone. The glycopolymers are subsequently deprotected and characterized by size exclusion chromatography, FT-IR and NMR spectroscopy, elemental analysis, as well as turbidimetry, revealing the thermoresponsive character of all synthesized glycopolymers.

Fluorinated Boronic Acid-Appended Bipyridinium Salts for Diol Recognition and Discrimination via (19)F NMR Barcodes.

Fluorinated boronic acid-appended benzyl bipyridinium salts, derived from 4,4'-, 3,4'-, and 3,3'-bipyridines, were synthesized and used to detect and differentiate diol-containing analytes at physiological conditions via (19)F NMR spectroscopy. An array of three water-soluble boronic acid receptors in combination with (19)F NMR spectroscopy discriminates nine diol-containing bioanalytes--catechol, dopamine, fructose, glucose, glucose-1-phosphate, glucose-6-phosphate, galactose, lactose, and sucrose--at low mM concentrations. Characteristic (19)F NMR fingerprints are interpreted as two-dimensional barcodes without the need of multivariate analysis techniques.

Preorganization in a Cleft-Type Anion Receptor Featuring Iodo-1,2,3-Triazoles As Halogen Bond Donors.

Preorganization via intramolecular hydrogen bonds was applied in a cleft-type receptor by exploiting the excellent halogen bond donor ability as well as hydrogen bond acceptor function of iodo-1,2,3-triazoles. As investigated by isothermal calorimetric titrations, the restriction of conformational freedom causes an enhanced entropic contribution resulting in a strongly increased binding affinity. This efficient way to improve the binding strength of 5-halo-1,2,3-triazoles paves the way for applications of new charge-neutral halogen bond donors in solution.

A new fluorescent dye for cell tracing and mitochondrial imaging in vitro and in vivo.

Mitochondria contribute to redox and calcium balance, and apoptosis thus regulating cellular fate. In the present study, mitochondrial staining applying a novel dye, V07-07059, was performed in human embryonic kidney cells, a human vascular endothelial cell line and primary human mononuclear cells. The new fluorescent mega Stokes dye (peak excitation: 488 nm, peak emission: 554 nm) showed superior fluorescent properties and stability.

Carbohydrate-Based Initiators for the Cationic Ring-Opening Polymerization of 2-Ethyl-2-Oxazoline.

The advancement in the field of living and controlled polymerization techniques provides the opportunity for careful bottom-up design of polymers for biomedical applications according to their specific needs. This contribution describes the detailed methodology to functionalize poly(2-ethyl-2-oxazoline), a polymer with properties very similar to polyethylene glycol, in a stereo-selective manner with a range of carbohydrates that can serve as biological targeting units. The obtained building blocks can subsequently be applied for the synthesis of more complex polymeric architectures.

Microwave-assisted cationic ring-opening polymerization of 2-oxazolines.

Unlike any other polymer class, the (co-)poly(2-oxazoline)s have tremendously benefited from the introduction of microwave reactors into chemical laboratories. This review focuses on the research activities in the area of (co-)poly(2-oxazoline)s prepared by microwave-assisted syntheses and, correspondingly, summarizes the current-state-of the-art of the microwave-assisted synthesis of 2-oxazoline monomers and the microwave-assisted ring-opening (co-)polymerization of 2-oxazolines as well as prominent examples of post-polymerization modification of (co-)poly(2-oxazoline)s. Special attention is attributed to the kinetic analysis of the microwave-assisted polymerization of 2-oxazolines and the discussion of non-thermal microwave effects.

An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials.

For renewable energy sources such as solar, wind, and hydroelectric to be effectively used in the grid of the future, flexible and scalable energy-storage solutions are necessary to mitigate output fluctuations. Redox-flow batteries (RFBs) were first built in the 1940s and are considered a promising large-scale energy-storage technology. A limited number of redox-active materials--mainly metal salts, corrosive halogens, and low-molar-mass organic compounds--have been investigated as active materials, and only a few membrane materials, such as Nafion, have been considered for RFBs.

A heterobimetallic copper-titanium oxo cluster with a new structural motif.

Abstract: Mixed-metal oxo clusters CuTiO(OOCR) (OOCR = methacrylate, propionate) were obtained by reaction of titanium alkoxides and copper carboxylates with propionic or methacrylic acid.

Micropatterns of [Fe-Fe]-Hydrogenase Active-Site Model Complexes Fabricated by Electro-Oxidative Lithography.

[Fe-Fe]-hydrogenase active site model complexes ([Fe(CO)3]2[(μ-SCH2)2C(CH2OH)2]) were immobilized on micropatterned n-octadecyltrichlorosilane (OTS) monolayers deposited on a Si substrate to form a microscale catalytic system. The micropatterns were generated by electro-oxidative lithography performed with a conductive TEM grid. The [Fe-Fe]-hydrogenase active-site complex molecules were selectively anchored in lithographic line areas with good coverage.