Discarding metal incorporation in pyrazole macrocycles and the role of the substrate on single-layer assemblies.

Pyrazole derivatives are key in crystal engineering and liquid crystal fields and thrive in agriculture, pharmaceutical, or biomedicine industries. Such versatility relies in their supramolecular bond adaptability when forming hydrogen bonds or metal-pyrazole complexes. Interestingly, the precise structure of pyrazole-based macrocycles forming widespread porous structures is still unsolved.

Rapid plugged flow synthesis of nucleoside analogues via Suzuki-Miyaura coupling and heck Alkenylation of 5-Iodo-2'-deoxyuridine (or cytidine).

Unlabelled: Nucleosides modification via conventional cross-coupling has been performed using different catalytic systems and found to take place via long reaction times. However, since the pandemic, nucleoside-based antivirals and vaccines have received widespread attention and the requirement for rapid modification and synthesis of these moieties has become a major objective for researchers. To address this challenge, we describe the development of a rapid flow-based cross-coupling synthesis protocol for a variety of C5-pyrimidine substituted nucleosides.

Heparin-Coated Dendronized Hyperbranched Polymers for Antimalarial Targeted Delivery.

The rampant evolution of resistance in to all existing antimalarial drugs calls for the development of improved therapeutic compounds and of adequate targeted delivery strategies for them. Loading antimalarials in nanocarriers specifically targeted to the parasite will contribute to the administration of lower overall doses, with reduced side effects for the patient, and of higher local amounts to parasitized cells for an increased lethality toward the pathogen. Here, we report the development of dendronized hyperbranched polymers (DHPs), with capacity for antimalarial loading, that are coated with heparin for their specific targeting to red blood cells parasitized by .

Gold Nanoparticles Modification with Liquid Crystalline Polybenzylic Dendrons via 1,3-Dipolar Cycloaddition.

A series of six polybenzylic dendrons with an alkynyl focal point were synthesized for their incorporation to gold nanoparticles. Five of these compounds showed columnar mesomorphism in a wide range of temperatures. These dendrons were reacted with gold nanoparticles stabilized with a combination of a dodecanethiol and 11-azidoundecane-1-thiol.

Water-Soluble Pd-Imidate Complexes as Versatile Catalysts for the Modification of Unprotected Halonucleosides.

Modification of unprotected nucleosides has been attracting continuous interest, since these building blocks themselves and their phosphate-upgraded corresponding nucleotides have shown a plethora of uses in fields like biochemistry or pharmacy. Pd-catalyzed cross-coupling reactions, conducted in water or its mixtures with polar organic solvents, have frequently been the researchers' choice for the functionalization of the purine/pyrimidine base of the unprotected nucleosides. In this scenario, the availability of hydrophilic ligands and its water-soluble palladium complexes has markedly set the pace of the advances.

Dendron-functionalised hyperbranched bis-MPA polyesters as efficient non-viral vectors for gene therapy in different cell lines.

Gene therapy has become a relevant tool in the biomedical field to treat or even prevent some diseases. The effective delivery of genetic material into the cell remains a crucial step to succeed in this purpose. In the search for efficient non-viral vectors, a series of amino-terminated dendronized hyperbranched polymers (DHPs) of different generations based either on bis-MPA or bis-GMPA have been designed.

Quadrol-Pd(II) complexes: phosphine-free precatalysts for the room-temperature Suzuki-Miyaura synthesis of nucleoside analogues in aqueous media.

Commercially available Quadrol, ,,','-tetrakis(2-hydroxypropyl)ethylenediamine (THPEN), has been used for the first time as a N^N-donor neutral hydrophilic ligand in the synthesis and characterization of new water soluble palladium(II) complexes containing chloride, phthalimidate or saccharinate as co-ligands. [PdCl(THPEN)] (1) [Pd(phthal)(THPEN)] (2), [Pd(sacc)(THPEN)] (3) and the analogous complex with the closely related ,,','-tetrakis(2-hydroxyethyl)ethylenediamine (THEEN) [Pd(sacc)(THEEN)] (4) were efficiently prepared in a one-pot reaction from [PdCl(CHCN)] or Pd(OAc). Structural characterization of 1 and 3 by single crystal X-ray diffraction produced the first structures reported to date of palladium complexes with Quadrol.

A Highly Versatile Polymer Network Based on Liquid Crystalline Dendrimers.

Highly functional macromolecules with a well-defined architecture are the key to designing efficient and smart materials, and these polymeric systems can be tailored for specific applications in a diverse range of fields. Herein, the formation of a new liquid crystalline polymeric network based on the crosslinking of dendrimeric entities by the Cu-catalyzed variant of the Huisgen 1,3-dipolar cycloaddition of azides and alkynes to afford 1,2,3-triazoles is reported. The polymeric material obtained in this way is easy to process and exhibits a variety of properties, which include mesomorphism, viscoelastic behavior, and thermal contraction.

Interplay between non-covalent interactions in 1D supramolecular polymers based on 1,4-bis(iodoethynyl)benzene.

A study of the solution-phase, solid-state structures of halogen-bonded co-crystals of 1,4-bis(iodoethynyl)benzene (p-BIB) with three salts, namely, decyltrimethylammonium bromide (DTMABr), tetrapropylammonium bromide (TPABr), and tetrabutylammonium bromide (TBABr), has been carried out, along with theoretical calculations. Isothermal titration calorimetry (ITC) showed that the binding constant of bromide with p-BIB in THF is not strongly dependent on the cation, and that the entropic term clearly dominates the enthalpic one in the free energy of binding. In the three crystal structures, the bromide anion acts as a doubly connected node for halogen bonding interactions, which results in linear or angular open chains.

Controlled Growth of Dendrimer-Coated Gold Nanoparticles: A Solvent-Free Process in Mild Conditions.

Monodisperse dendrimer-coated gold nanoparticles with a spherical shape have been obtained by direct reduction of HAuCl with sodium borohydride in the presence of dodecanethiol as a stabilizer and subsequent functionalization by ligand exchange reaction with polybenzylic thiolated dendrons. The substitution pattern of the dendrimeric units plays a fundamental role in the rate of the functionalization exchange process and consequently conditions the size and the polydispersity of the NPs obtained. An ulterior growth process occurs by thermal stimuli (150 °C) in a solvent-free environment.

Micellar Nanocarriers from Dendritic Macromolecules Containing Fluorescent Coumarin Moieties.

The design of efficient drug-delivery vehicles remains a big challenge in materials science. Herein, we describe a novel class of amphiphilic hybrid dendrimers that consist of a poly(amidoamine) (PAMAM) dendritic core functionalized with MPA dendrons bearing cholesterol and coumarin moieties. Their self-assembly behavior both in bulk and in water was investigated.

Janus Dendrimers to Assess the Anti-HCV Activity of Molecules in Cell-Assays.

The use of nanocarriers has been revealed as a valid strategy to facilitate drug bioavailability, and this allows for expanding the drug libraries for the treatment of certain diseases such as viral diseases. In the case of Hepatitis C, the compounds iopanoic acid and 3,3',5-triiodothyroacetic acid (or tiratricol) were identified in a primary screening as bioactive allosteric inhibitors of viral NS3 protease, but they did not exhibit accurate activity inhibiting viral replication in cell-based assays. In this work, dendritic nanocarriers are proposed due to their unique properties as drug delivery systems to rescue the bioactivity of these two drugs.

Promising nanomaterials in the fight against malaria.

For more than one hundred years, several treatments against malaria have been proposed but they have systematically failed, mainly due to the occurrence of drug resistance in part resulting from the exposure of the parasite to low drug doses. Several factors are behind this problem, including (i) the formidable barrier imposed by the Plasmodium life cycle with intracellular localization of parasites in hepatocytes and red blood cells, (ii) the adverse fluidic conditions encountered in the blood circulation that affect the interaction of molecular components with target cells, and (iii) the unfavorable physicochemical characteristics of most antimalarial drugs, which have an amphiphilic character and can be widely distributed into body tissues after administration and rapidly metabolized in the liver. To surpass these drawbacks, rather than focusing all efforts on discovering new drugs whose efficacy is quickly decreased by the parasite's evolution of resistance, the development of effective drug delivery carriers is a promising strategy.

Coumarin-Containing Pillar[5]arenes as Multifunctional Liquid Crystal Macrocycles.

Liquid crystal macrocycles (LCMs) combine the unique properties of liquid crystals with those associated with macrocyclic compounds-shape persistence and the capability of hosting small molecules. Herein, we investigate the grafting of coumarin-containing promesogenic moieties to pillar[5]arene as a strategy to obtain multifunctional LCMs. Pillar[5]arenes containing 10 and 30 coumarin units are glassy materials with nematic mesomorphism.

Cyclotriphosphazenes as Scaffolds for the Synthesis of Metallomesogens.

(Amino)cyclotriphosphazenes have been used as new scaffolds for the synthesis of silver(I) metallomesogens. Two cyclotriphosphazenes, [NP(NHCy)] () and [NP(NHCy)(NMe)] (), were reacted with the silver complex having a pro-mesogenic ligand, [Ag(OTf)L] (L = CNCH{OC(O)CH(3,4,5-(OCH))}-4; OTf = OSOCF), in different molar ratios, 1:1, 1:2, or 1:3, to give two series of cationic metallophosphazenes, [NP(NHCy){AgL}](TfO) () and [NP(NHCy)(NMe){AgL}](TfO) () with = 1, 2, or 3. The chemical structure of these compounds, deduced from spectroscopic techniques, was in accordance with coordination of the silver fragments "AgL" to nitrogen atoms of the phosphazene ring, whereby their number depends on the molar ratio used.

Wild Red Foxes () as Sentinels of Rodent-Borne Hantavirus and Lymphocytic Choriomeningitis Virus in the Province of Soria, Northern Spain.

Three hundred and fourteen red foxes () in the province of Soria, Spain, were examined for hantavirus and lymphocytic choriomeningitis virus (LCMV) infection (and were likely to have been infected by feeding on infected rodents). Immunofluorescence and western blot assays confirmed 3.5% (11/314) to have antibodies to hantaviruses, and the immune fluorescence assay showed 2.

Electrically transmissive alkyne-anchored monolayers on gold.

Well-ordered, tightly-packed (surface coverage 0.97 × 10-9 mol cm-2) monolayer films of 1,4-bis((4-ethynylphenyl)ethynyl)benzene (1) on gold are prepared via a simple self-assembly process, taking advantage of the ready formation of alkynyl C-Au σ-bonds. Electrochemical measurements using [Ru(NH3)6]3+, [Fe(CN)6]3-, and ferrocenylmethanol [Fe(η5-C5H4CH2OH)(η5-C5H5)] redox probes indicate that the alkynyl C-Au contacted monolayer of 1 presents a relatively low barrier for electron transfer.

Micelle carriers based on dendritic macromolecules containing bis-MPA and glycine for antimalarial drug delivery.

Biomaterials for antimalarial drug transport still need to be investigated in order to attain nanocarriers that can tackle essential issues related to malaria treatment, e.g. complying with size requirements and targeting specificity for their entry into Plasmodium-infected red blood cells (pRBCs), and limiting premature drug elimination or drug resistance evolution.

Self-Assembling Hybrid Linear-Dendritic Block Copolymers: The Design of Nano-Carriers for Lipophilic Antitumoral Drugs.

Two series of amphiphilic block copolymers with a hybrid linear-dendritic structure are presented. The compounds consisted of a hydrophilic poly (ethylene glycol) (PEG) block and a 2,2'-bis(hydroxymethyl)propionic acid (bis-MPA) dendron functionalized with stearic acid chains that impart a hydrophobic nature to the block. Different self-assembled nanostructures with a hydrophobic interior and a hydrophilic external part were obtained depending on the length of the PEG chain ( = 2000 and = 5000) and the generation of the bis-MPA dendron.

Proton conductive ionic liquid crystalline poly(ethyleneimine) polymers functionalized with oxadiazole.

Two novel series of ionic liquid crystal polymers that display proton conductive properties are presented here. These materials are based on linear (-PEI) or branched (-PEI) poly(ethyleneimine) functionalized with unsymmetrical oxadiazole carboxylic acids derived from 1,3,4-oxadiazole (1,3,4-OXA ) or 1,2,4-oxadiazole (1,2,4-OXA ). The subscript "" indicates the length of the spacer between the rigid moiety and the carboxyl group, namely = 4 and 10.

Decisive Influence of the Metal in Multifunctional Gold, Silver, and Copper Metallacycles: High Quantum Yield Phosphorescence, Color Switching, and Liquid Crystalline Behavior.

Three cyclic trinuclear pyrazolate complexes with Au(I), Ag(I), or Cu(I) have been studied. These complexes have interesting and distinct optical and thermal properties depending on the metal, namely, liquid crystalline behavior, red or deep-red phosphorescence at room temperature, thermoluminochromism, and response to silver ions. The selected ligand, 4-hexyl-3,5-dimethylpyrazolate, maximizes the effect that the nature of the metals has on the properties of the complexes, thus allowing the intermolecular metallophilic interactions to be responsible for the optical properties.

Inspecting the Electronic Architecture and Semiconducting Properties of a Rosette-Like Supramolecular Columnar Liquid Crystal.

Computational and experimental studies unravel the structural and electronic properties of a novel supramolecular liquid crystal built through a hierarchical assembly process resulting in an H-bonded melamine rosette decorated with peripheral triphenylenes. The six-fold symmetry of the mesogen facilitates the formation of a highly organized hexagonal columnar mesophase stable at room temperature. X-ray diffraction and electron density maps confirm additional intra- and intercolumn segregation of functional subunits, and this paves the way for 1D charge transport.

Making Coaxial Wires Out of Janus Dendrimers for Efficient Charge Transport.

Highly conductive coaxial supramolecular wires are prepared by using a new family of dendrimers that combines two rigid aromatic parts and two flexible aliphatic parts. The two external regions consist of a promesogenic block based on a third generation Percec-type dendron with four terminal dodecyloxy alkyl chains, whereas the two internal regions are formed by one, two, or three carbazole units bearing flexible spacers. These functional dendrimers self-organize in columnar liquid crystal phases with a strong coaxial segregation within each column.

High surface coverage of a self-assembled monolayer by in situ synthesis of palladium nanodeposits.

Nascent metal|monolayer|metal devices have been fabricated by depositing palladium, produced through a CO-confined growth method, onto a self-assembled monolayer of an amine-terminated oligo(phenylene ethynylene) derivative on a gold bottom electrode. The high surface area coverage (85%) of the organic monolayer by densely packed palladium particles was confirmed by X-ray photoemission spectroscopy (XPS) and atomic force microscopy (AFM). The electrical properties of these nascent Au|monolayer|Pd assemblies were determined from the I-V curves recorded with a conductive-AFM using the Peak Force Tunneling AFM (PF-TUNA™) mode.

Additives Type Schiff's Base as Modifiers of the Optical Response in Holographic Polymer-Dispersed Liquid Crystals.

Schiff's bases with specific π-electron system have been synthesized and used as additives in holographic polymer-dispersed liquid crystals. It was observed that these substances modify different parameters such as current intensity, voltage, and diffracted light intensity. In addition, the maximum diffraction efficiency obtained in the reconstruction of the holograms is related to the additive molecule.