Reaction of Lactone-Containing Poly(benzofuran--arylacetic acid) with Diamines to Cross-Linked Products of Improved Thermal Conductivity.

The recently developed phenoplast-related polymer, poly(benzofuran--arylacetic acid), presents a versatile molecular structure containing lactone and carboxylic acid functionalities that offer significant flexibility in creating cured materials with tailored properties for diverse applications, wherein also the thermal conductivity is an important factor. This study analyses the possibility of forming amide moieties of poly(benzofuran--arylacetic acid) with diamines resulting in cross-linked products in order to control its thermal properties. The cross-linking process is achieved by utilizing three distinct diamines, 1,6-diaminohexane, -xylylenediamine, and 4,7,10-trioxa-1,13-tridecanediamine, each possessing different degrees of polarity, flexibility, and reactivity.

Formation and Reactions of Brønsted and Lewis Acid Adducts with Electron-Rich Heteroaromatic Compounds.

Electron-rich heteroaromatics, such as furan, thiophene and pyrrole, as well as their benzo-condensed derivatives, are of great interest as components of natural products and as starting substances for various products including high-tech materials. Although their reactions with Brønsted and Lewis acids play important roles, in particular as the primary step of various transformations, they are often disregarded and mechanistically not understood. The present publication gives a first overview about this chemistry focusing on the parent compounds.

Oxidative Polymerization of 3,4-Dihydroxybenzylamine─The Lower Homolog of Dopamine.

Polydopamine (PDA) formed by oxidative polymerization of dopamine has attracted wide interest because of its unique properties, in particular its strong adhesion to almost all types of surfaces. 3,4-Dihydroxybenzylamine (DHBA) as the lower homolog of PDA also contains a catechol unit and an amino group and thus can be expected to exhibit a similar adhesion and reaction behavior. In fact, autoxidation of DHBA with air in 2-amino-2-hydroxymethyl-propane-1,3-diol (Tris) buffer gives rise to deeply colored oligomer/polymer products (poly(3,4-dihydroxybenzylamine) (PDHBA)) that strongly adhere to several surfaces.

Translation of Collagen Ultrastructure to Biomaterial Fabrication for Material-Independent but Highly Efficient Topographic Immunomodulation.

Supplement-free induction of cellular differentiation and polarization solely through the topography of materials is an auspicious strategy but has so far significantly lagged behind the efficiency and intensity of media-supplementation-based protocols. Consistent with the idea that 3D structural motifs in the extracellular matrix possess immunomodulatory capacity as part of the natural healing process, it is found in this study that human-monocyte-derived macrophages show a strong M2a-like prohealing polarization when cultured on type I rat-tail collagen fibers but not on collagen I films. Therefore, it is hypothesized that highly aligned nanofibrils also of synthetic polymers, if packed into larger bundles in 3D topographical biomimetic similarity to native collagen I, would induce a localized macrophage polarization.

Intraindividual Embryo Morphokinetics Are Not Affected by a Switch of the Ovarian Stimulation Protocol Between GnRH Agonist vs. Antagonist Regimens in Consecutive Cycles.

The impact of controlled ovarian stimulation (COS) during medically assisted reproduction (MAR) on human embryogenesis is still unclear. Therefore, we investigated if early embryonic development is affected by the type of gonadotropin-releasing hormone (GnRH) analog used to prevent a premature LH surge. We compared embryo morphology and morphokinetics between GnRH agonist and antagonist cycles, both involving human chorionic gonadotropin (hCG)-trigger.

Refinement of Magnetite Nanoparticles by Coating with Organic Stabilizers.

Magnetite nanoparticles are of great importance in nanotechnology and nanomedicine and have found manifold applications. Here, the effect of coating of magnetite nanoparticles with organic stabilizers, such as -phosphoryl ethanolamine, glycerol phosphate, phospho-l-ascorbic acid, phospho-d,l-serine, glycolic acid, lactic acid, d,l-malic acid, and d,l-mandelic acid was studied. Remarkably, this procedure led to an improvement of saturation magnetization in three cases rather than to an unfavorable decrease as usually observed.

Micro- and nano-tubules built from loosely and tightly rolled up thin sheets.

Tubular structures built from amphiphilic molecules are of interest for nano-sensing, drug delivery, and structuring of oils. In this study, we characterized the tubules built in aqueous suspensions of a cholesteryl nucleoside conjugate, cholesterylaminouridine (CholAU) and phosphatidylcholines (PCs). In mixtures with unsaturated PCs having chain lengths comparable to the length of CholAU, two different types of tubular structures were observed; nano- and micro-tubules had average diameters in the ranges 50-300 nm and 2-3 μm, respectively.

Polydopamine--an organocatalyst rather than an innocent polymer.

Polydopamine (PDA) is easily available by oxidation of dopamine and is widely used for persistent coatings of various materials. It is hitherto considered to be inert in many interesting biomedical and other applications. Results presented here, reveal an unexpected behavior of polydopamine as an organocatalyst in direct aldol reactions under mild conditions.

Structure of polydopamine: a never-ending story?

Polydopamine (PDA) formed by the oxidation of dopamine is an important polymer, in particular, for coating various surfaces. It is composed of dihydroxyindole, indoledione, and dopamine units, which are assumed to be covalently linked. Although PDA has been applied in a manifold way, its structure is still under discussion.

Development and evaluation of a de-identification procedure for a case register sourced from mental health electronic records.

Background: Electronic health records (EHRs) provide enormous potential for health research but also present data governance challenges. Ensuring de-identification is a pre-requisite for use of EHR data without prior consent. The South London and Maudsley NHS Trust (SLaM), one of the largest secondary mental healthcare providers in Europe, has developed, from its EHRs, a de-identified psychiatric case register, the Clinical Record Interactive Search (CRIS), for secondary research.

Remote control of lipophilic nucleic acids domain partitioning by DNA hybridization and enzymatic cleavage.

Lateral partitioning of lipid-modified molecules between liquid-disordered (ld) and liquid-ordered (lo) domains depends on the type of lipid modification, presence of a spacer, membrane composition, and temperature. Here, we show that the lo domain partitioning of the palmitoylated peptide nucleic acid (PNA) can be influenced by formation of a four-component complex with the ld domain partitioning tocopherol-modified DNA: the PNA-DNA complex partitioned into the ld domains. Enzymatic cleavage of the DNA linker led to the disruption of the complex and restored the initial distribution of the lipophilic nucleic acids into the respective domains.

Spatial and temporal trends of global pollination benefit.

Pollination is a well-studied and at the same time a threatened ecosystem service. A significant part of global crop production depends on or profits from pollination by animals. Using detailed information on global crop yields of 60 pollination dependent or profiting crops, we provide a map of global pollination benefits on a 5' by 5' latitude-longitude grid.

Reduction-sensitive liposomes from a multifunctional lipid conjugate and natural phospholipids: reduction and release kinetics and cellular uptake.

The development of targeted and triggerable delivery systems is of high relevance for anticancer therapies. We report here on reduction-sensitive liposomes composed of a novel multifunctional lipidlike conjugate, containing a disulfide bond and a biotin moiety, and natural phospholipids. The incorporation of the disulfide conjugate into vesicles and the kinetics of their reduction were studied using dansyl-labeled conjugate 1 in using the dansyl fluorescence environmental sensitivity and the Förster resonance energy transfer from dansyl to rhodamine-labeled phospholipids.

Comparative study of liponucleosides in Langmuir monolayers as cell membrane models.

Liponucleosides may assist the anchoring of nucleic acid nitrogen bases into biological membranes for tailored nanobiotechnological applications. To this end precise knowledge about the biophysical and chemical details at the membrane surface is required. In this paper, we used Langmuir monolayers as simplified cell membrane models and studied the insertion of five lipidated nucleosides.

Lipid domain specific recruitment of lipophilic nucleic acids: a key for switchable functionalization of membranes.

Lipid domains in mammalian plasma membranes serve as platforms for specific recruitment or separation of proteins involved in various functions. Here, we have applied this natural strategy of lateral separation to functionalize lipid membranes at micrometer scale in a switchable and reversible manner. Membrane-anchored peptide nucleic acid and DNA, differing in their lipophilic moieties, partition into different lipid domains in model and biological membranes.

Microtubes self-assembled from a cholesterol-modified nucleoside.

We describe the formation of lipid microtubes from a novel cholesterol-modified nucleoside in binary mixture with phospholipids. Stable cylindrical structures with an outer diameter of 2-3 microm and a length of 20-40 microm were formed. By varying the preparation conditions, thinner tubules with nanometre-scale diameters could also be obtained.

Properties of lipophilic nucleoside monolayers at the air-water interface.

The capability of self-assembly and molecular recognition of biomolecules is essential for many nanotechnological applications, as in the use of alkyl-modified nucleosides and oligonucleotides to increase the cellular uptake of DNA and RNA. In this study, we show that a lipophilic nucleoside, which is an isomer mixture of 2'-palmitoyluridin und 3'-palmitoyluridin, forms Langmuir monolayers and Langmuir-Blodgett films as a typical amphiphile, though with a smaller elasticity. The nucleoside may be incorporated into dipalmitoyl phosphatidyl choline (DPPC) monolayers that serve as a simplified cell membrane model.

Lipid membranes carrying lipophilic cholesterol-based oligonucleotides--characterization and application on layer-by-layer coated particles.

Cholesterol-based lipophilic oligonucleotides incorporated into lipid membranes were studied using solid-state NMR, differential scanning calorimetry, and fluorescence methods. Lipophilic oligonucleotides can be used to build nanotechnological structures on membrane surfaces, taking advantage of the specific Watson-Crick base pairing. We used a cholesteryl-TEG anchor first described by Pfeiffer and Hook (J.

The novel calcineurin inhibitor CN585 has potent immunosuppressive properties in stimulated human T cells.

The Ca2+/calmodulin-dependent protein phosphatase calcineurin is a key mediator in antigen-specific T cell activation. Thus, inhibitors of calcineurin, such as cyclosporin A or FK506, can block T cell activation and are used as immunosuppressive drugs to prevent graft-versus-host reactions and autoimmune diseases. In this study we describe the identification of 2,6- diaryl-substituted pyrimidine derivatives as a new class of calcineurin inhibitors, obtained by screening of a substance library.

Secreted cyclophilin A, a peptidylprolyl cis-trans isomerase, mediates matrix assembly of hensin, a protein implicated in epithelial differentiation.

Hensin is a rabbit ortholog of DMBT1, a multifunctional, multidomain protein implicated in the regulation of epithelial differentiation, innate immunity, and tumorigenesis. Hensin in the extracellular matrix (ECM) induced morphological changes characteristic of terminal differentiation in a clonal cell line (clone C) of rabbit kidney intercalated cells. Although hensin is secreted in monomeric and various oligomeric forms, only the polymerized ECM form is able to induce these phenotypic changes.

2-Amino-7-nitro-fluorenes in neat and mixed solvents-optical band shapes and solvatochromism.

Femtosecond transient absorption spectroscopy of amino-nitro-fluorenes in the UV-visible range shows that the dynamic Stokes shift of the emission band is sensitive to infrared-active modes of the solvent. Bandshapes for stationary absorption and emission are needed to quantify the observed spectral evolution. They are reported for 2-amino-7-nitro-fluorene (ANF), 2-dimethylamino-7-nitro-fluorene (dM-ANF), and 2-di(n-butyl)amino-7-nitro-9-di(n-propyl)-fluorene (dBdP-ANF) in a variety of solvents.

Inhibition of calcineurin-NFAT signaling by the pyrazolopyrimidine compound NCI3.

Dephosphorylation of NFAT by the Ca(2+)-calmodulin-dependent Ser/Thr protein phosphatase calcineurin is a bottleneck of T cell receptor-dependent activation of T cells. In dimeric complexes with immunophilins, the immunosuppressants cyclosporine A (CsA) and tacrolimus (FK506) block this process by inhibition of the enzymatic activity of calcineurin. We have identified the pyrazolopyrimidine compound NCI3 as a novel inhibitor of calcineurin-NFAT signaling.

Lipophilic oligonucleotides spontaneously insert into lipid membranes, bind complementary DNA strands, and sequester into lipid-disordered domains.

For the development of surface functionalized bilayers, we have synthesized lipophilic oligonucleotides to combine the molecular recognition mechanism of nucleic acids and the self-assembly characteristics of lipids in planar membranes. A lipophilic oligonucleotide consisting of 21 thymidine units and two lipophilic nucleotides with an alpha-tocopherol moiety as a lipophilic anchor was synthesized using solid-phase methods with a phosphoramadite strategy. The interaction of the water soluble lipophilic oligonucleotide with vesicular lipid membranes and its capability to bind complementary DNA strands was studied using complementary methods such as NMR, EPR, DSC, fluorescence spectroscopy, and fluorescence microscopy.