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Monodisperse dendrimer-coated gold nanoparticles with a spherical shape have been obtained by direct reduction of HAuCl4 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. This method, carried out in mild conditions, allows the formation of highly monodisperse gold NPs with different sizes for different time reactions, and we discuss the mechanisms involved in this process. Finally, we demonstrate the chemical composition and stability of our compounds by structural, thermal, and chemical characterization of the samples before and after thermal treatment., This work was supported by the MINECO-FEDER funds (project PGC2018-097583-B-I00) and Gobierno de Aragón-FSE (Research Group E47_20R). The authors acknowledge the use of SAI (UZ), CEQMA (UZ-CSIC), and LMA (UZ-CSIC) services. J. A. Ulloa thanks the Becas-Chile program of the National Commission for Scientific and Technological Research (CONICYT, Chile) for his PhD grant.

Purpose: The current study aimed to identify metabolites associated with age-related macular degeneration (AMD) by performing the largest metabolome association analysis in AMD to date, as well as aiming to determine the effect of AMD-associated genetic variants on metabolite levels and investigate associations between the identified metabolites and activity of the complement system, one of the main AMD-associated disease pathways. Design: Case-control association analysis of metabolomics data. Participants: Five European cohorts consisting of 2267 AMD patients and 4266 control participants. Methods: Metabolomics was performed using a high-throughput proton nuclear magnetic resonance metabolomics platform, which allows quantification of 146 metabolite measurements and 79 derivative values. Metabolome–AMD associations were studied using univariate logistic regression analyses. The effect of 52 AMD-associated genetic variants on the identified metabolites was investigated using linear regression. In addition, associations between the identified metabolites and activity of the complement pathway (defined by the C3d-to-C3 ratio) were investigated using linear regression. Main Outcome Measures: Metabolites associated with AMD. Results: We identified 60 metabolites that were associated significantly with AMD, including increased levels of large and extra-large high-density lipoprotein (HDL) subclasses and decreased levels of very low-density lipoprotein (VLDL), amino acids, and citrate. Of 52 AMD-associated genetic variants, 7 variants were associated significantly with 34 of the identified metabolites. The strongest associations were identified for genetic variants located in or near genes involved in lipid metabolism (ABCA1, CETP, APOE, and LIPC) with metabolites belonging to the large and extra-large HDL subclasses. Also, 57 of 60 metabolites were associated significantly with complement activation levels, independent of AMD status. Increased large and extra-large HDL levels and decreased VLDL and amino acid levels were associated with increased complement activation. Conclusions: Lipoprotein levels were associated with AMD-associated genetic variants, whereas decreased essential amino acids may point to nutritional deficiencies in AMD. We observed strong associations between the vast majority of the AMD-associated metabolites and systemic complement activation levels, independent of AMD status. This may indicate biological interactions between the main AMD disease pathways and suggests that multiple pathways may need to be targeted simultaneously for successful treatment of AMD.

The synthesis and characterization of new water-soluble dinuclear palladacycles of the general formula [{Pd(R-C^N-SO3Na)(μ-AcO)}2] (R = H (1), OMe (2), Cl (3)) incorporating an ortho-metalated sodi...

4-Iodo-N-(4-pyridyl)benzamide (INPBA) and four derived coordination complexes were synthesized in order to explore the combination of halogen and hydrogen bonding interactions in coordination chemistry. An electron-withdrawing carbonyl group attached to the aromatic ring bearing an iodine atom has been introduced to increase its halogen bonding ability. Single crystal X-ray diffraction analyses of INPBA, [Ag(INPBA)2]NO3 (1), [ZnBr2(INPBA)2] (2), [Zn(OCOPh)2(INPBA)2] (3) and [HgI2(INPBA)]n (4) show the versatility of the INPBA building block yielding a variety of different interesting structures. Iodine atom arrangement plays a key role by reinforcing and extending crystalline structures into diverse 3D supramolecular networks via I⋯O, I⋯N, and I⋯I halogen bonding interactions. Besides this, the overall supramolecular architecture of the coordination complexes is modulated by the N–H⋯O, N–H⋯Br, and C–H⋯O hydrogen bonds formed by the carboxamide group. The combination of both, halogen and hydrogen bonds, allows very different coordination networks to be designed., The authors give thanks to the Crystallography Service of the University of Zaragoza-CSIC (Spain), the University of Pais Vasco (Spain), the National University of Singapore and the Servicio General de Apoyo a la Investigación SAI, Universidad de Zaragoza. This work was supported by the Ministerio de Economía, Industria y Competitividad under the projects PGC2018-093761-B-C31, PGC2018-097583-B-100 and MAT2017-84838-P. The authors acknowledge support from the Gobierno de Aragón-FEDER for funding the Crystal and Polymers Group (E47_20R, FEDER 2014-2020 Construyendo Europa desde Aragón).

This article belongs to the Special Issue Nanostructures Applied to Drug Delivery and Diagnosis., Clinical outcomes of conventional drug combinations are not ideal due to high toxicity to healthy tissues. Cisplatin (CDDP) is the standard component for many cancer treatments, yet its principal dose-limiting side effect is nephrotoxicity. Thus, CDDP is commonly used in combination with other drugs, such as the autophagy inhibitor chloroquine (CQ), to enhance tumor cell killing efficacy and prevent the development of chemoresistance. In addition, nanocarrier-based drug delivery systems can overcome chemotherapy limitations, decreasing side effects and increasing tumor accumulation. The aim of this study was to evaluate the toxicity of CQ and CDDP against tumor and non-tumor cells when used in a combined treatment. For this purpose, two types of micelles based on Pluronic® F127 hybrid dendritic–linear–dendritic block copolymers (HDLDBCs) modified with polyester or poly(esteramide) dendrons derived from 2,2′-bis(hydroxymethyl)propionic acid (HDLDBC-bMPA) or 2,2′-bis(glycyloxymethyl)propionic acid (HDLDBC-bGMPA) were explored as delivery nanocarriers. Our results indicated that the combined treatment with HDLDBC-bMPA(CQ) or HDLDBC-bGMPA(CQ) and CDDP increased cytotoxicity in tumor cells compared to the single treatment with CDDP. Encapsulations demonstrated less short-term cytotoxicity individually or when used in combination compared to the free drugs. However, and more importantly, a low degree of cytotoxicity against non-tumor cells was maintained, even when drugs were given simultaneously., This research was supported by Instituto de Salud Carlos III (ISCIII) (PI19/01007) and by Fondo Europeo de Desarrollo Regional (Feder) “Una manera de hacer Europa”. We also thank CIBER-BBN, an initiative funded by the VI National R&D&i Plan 2008–2011 financed by the Instituto de Salud Carlos III (ISCIII) with the assistance of the European Regional Development Fund. This research was funded by the Ministerio de Ciencia e Innovación, Spain, which included FEDER funds (PGC2018-097583-B-I00, PGC2018-093761-B-C31, A.L. grant FPU12/05210 and M.S.-A. grant BES-2016-078774. This study was also partially funded by the Aragon Government (T57_17R p and E47_20R, and Ph.D. grant number B054/12 to R.G.-P. and Predoctoral Research Contract to V.M-V) cofounded by Feder 2014–2020 “Building Europe from Aragon”.

We report a new family of liquid crystalline porphyrin-core dendrimers with coumarin units at the periphery of the dendrimer. These compounds have been prepared by copper-catalyzed azide–alkyne “click” cycloaddition (CuAAC). The mesomorphic properties have been investigated via polarized optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The peripheral coumarin units play a key role in the liquid crystal behavior, contributing to the appearance of discotic nematic mesophases with hole mobility values among the highest values reported for discotic liquid crystals (of the order of 1 cm2 V−1 s−1). It has also been demonstrated that excitation of the coumarin moieties leads to energy transfer (antenna effect) to the luminescent porphyrin core. Therefore, this strategy, which involves ‘click’ chemistry, has been proven to be a powerful and elegant synthetic tool for the preparation of optoelectronic materials based on complex dendritic architectures., This work was supported by the MINECO-FEDER funds (project CTQ2015-70174-P) and the Gobierno de Aragón-FSE (Research Group E47_17R). The authors would like to acknowledge the use of the SAI (UZ) and CEQMA (UZ-CSIC) Services. A. Golemme is grateful for the support from the ELIOTROPO project (PON03PE_00092_2). R. Termine was supported by the MERAVIGLIE project (CUP J28C17000080006).

This article belongs to the Special Issue Nanostructured Materials Based on Liquid Crystals., 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 CuI-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. The porous microstructure of the polymer network determines its capability to absorb solvent molecules and to encapsulate small molecules, like organic dyes, which can be released easily afterwards. Moreover, all these properties may be easily tuned by modifying the chemical structure of the constituent dendrimers, which makes this system a very interesting one for a number of applications., This work was supported by the MINECO-FEDER funds (project PGC2018-097583-B-I00) and Gobierno de Aragón-FSE (Research Group E47_20R).

In this contribution, pyrazole is identified as an excellent anchoring group capable of forming well-ordered Langmuir–Blodgett (LB) monolayers onto gold substrates. In contrast, the formation of self-assembled (SA) monolayers is prevented due to the extraction of gold atoms from the surface upon the incubation process required for the formation of these films. The electronic coupling strength of pyrazole–gold junctions is explored through evaluation of the electrical properties of LB films incorporating a double pyrazole terminated molecular wire, namely 1,4-bis(1H-pyrazol-4-ylethynyl)benzene, 1; these electrical properties are compared with those of molecules having a similar chemical structure, geometry and length. The conductance value for LB films of 1 is high when the monolayer is transferred from a Langmuir film prepared onto a basic subphase, 1.19 × 10−4G0, as it is more than four times larger than the conductance of the same compound incorporated on a LB film prepared from a water subphase, 0.27 × 10−4G0. These results are interpreted in terms of the deprotonation of the pyrazole group in a basic media that leads to the formation of the pyrazolate (deprotonated pyrazole) moiety. This results in a more efficient electronic coupling with the gold tip of the scanning tunnelling microscope used for film characterization., This project was supported by the Spanish Ministry of Science through the grant numbers MAT2016-78257-R and PID2019-105881RB-I00, including FEDER funding, by Gobierno de Aragón through the grant numbers LMP33-18, and E31_20R with European Social Fund (Construyendo Europa desde Aragón). A. V. acknowledges funding from the Royal Society (URF\R1\191241).

The Cre-Lox system is a highly versatile and powerful DNA recombinase mechanism, mainly used in genetic engineering to insert or remove desired DNA sequences. It is widely utilized across multiple fields of biology, with applications ranging from plants, to mammals, to microbes. A key feature of this system is its ability to allow recombination between mutant lox sites. Two of the most commonly used mutant sites are named lox66 and lox71, which recombine to create a functionally inactive double mutant lox72 site. However, a large portion of the published literature has incorrectly annotated these mutant lox sites, which in turn can lead to difficulties in replication of methods, design of proper vectors and confusion over the proper nomenclature. Here, we demonstrate common errors in annotations, the impacts they can have on experimental viability, and a standardized naming convention. We also show an example of how this incorrect annotation can induce toxic effects in bacteria that lack optimal DNA repair systems, exemplified by Mycoplasma pneumoniae. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement 634942 (MycoSynVac) and was also financed by the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme, under grant agreement 670216 (MYCOCHASSIS). We also acknowledge support of the Spanish Ministry of Economy, Industry and Competitiveness (MEIC) to the EMBL partnership, the Centro de Excelencia Severo Ochoa and the CERCA Programme/Generalitat de Catalunya

The monolithic materials of reduced graphene oxide (rGO) can be used successfully in CO2 adsorption. Here, the incorporation of CeO2 particles with and without polymer brushes grafted from the particles showed that the structural properties could be changed, affecting the adsorption of CO2. Polymer brushes of (1) poly(acrylic acid) (PAA), (2) poly(vinyl caprolactam) (PVCL) and (3) poly[(2-(methacryloyloxy)ethyl) trimethylammonium chloride] (PMETAC) were grafted from CeO2 via reversible addition−fragmentation chain transfer (RAFT) polymerization. The preparation of monoliths of rGO with different modified CeO2 particles led to different thermal properties (TGA), structural changes (BET isotherms) and CO2 adsorption. The responsive character of the CeO2@polymer was proven by the DLS and UV results. The responsive character of the particles incorporated into the rGO monolith affected not only the adsorption capacity but also the microstructure and values of the surface volume of the pores of the monolith. Monoliths with porosity values for better adsorption were affected by the responsive character of the polymer. This research was funded by the Basque government, grant number GV IT999-16.

12 pags, 11 figs, 4 tabs. -- Supplementary Information can be found at the Publisher's web, 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. The intrachain angles (IBr-I) of the 1D supramolecular polymers based on p-BIB depend on the geometry and size of the cation and vary from 180° for DMTABr to 75° for TBABr. Non-covalent interaction (NCI) analysis of selected motifs and optimized crystals demonstrates that the balance between halogen bonds, hydrogen bonds, and van der Waals interactions, especially type-I halogenhalogen contacts, determines the crystal structures., This work was supported by the Ministerio de Economía, Industria y Competitividad, under the projects PGC2018-093761-B-C31, PGC2018-097583-B-I00, and MAT2017-84838-P. The authors acknowledge support from Gobierno de Aragón-FEDER for funding the Crystal and Polymers Group (E47_20R, FEDER 2014–2020 Construyendo Europa desde Aragón).

It is well known that in cancer gene families some members are more frequently mutated in tumor samples than their family counterparts. A paradigmatic case of this phenomenon is KRAS from the RAS family. Different explanations have been proposed ranging from differential interaction with other proteins to preferential expression or localization. Interestingly, it has been described that despite the high amino acid identity between RAS family members, KRAS employs an intriguing differential codon usage. Here, we found that this phenomenon is not exclusive to the RAS family. Indeed, in the RAS family and other oncogene families with two or three members, the most prevalently mutated gene in tumor samples employs a differential codon usage that is characteristic of genes involved in proliferation. Prompted by these observations, we chose the RAS family to experimentally demonstrate that the translation efficiency of oncogenes that are preferentially mutated in tumor samples is increased in proliferative cells compared to quiescent cells. These results were further validated by assessing the translation efficiency of KRAS in cell lines that differ in their tRNA expression profile. These differences are related to the cell division rate of the studied cells and thus suggest an important role in context-specific oncogene expression regulation. Altogether, our study demonstrates that dynamic translation programs contribute to shaping the expression profiles of oncogenes. Therefore, we propose this codon bias as a regulatory layer to control cell context-specific expression and explain the differential prevalence of mutations in certain members of oncogene families. The work of X.H.-A. has been supported by a PhD fellowship from the Fundación Ramón Areces. We acknowledge the support of the Spanish Ministry of Science and Innovation to the European Molecular Biology Laboratory partnership, the Centro de Excelencia Severo Ochoa and the Centres de Recerca de Catalunya Programme/Generalitat de Catalunya

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 bisMPA dendrons bearing cholesterol and coumarin moieties. Their self-assembly behavior both in bulk and in water was investigated. All dendrimers exhibited smectic A or hexagonal columnar liquid crystal organizations, depending on the generation of the dendrimer. In water, these dendrimers self-assembled to form stable spherical micelles that could encapsulate Nile Red, a hydrophobic model compound. The cell viability in vitro of the micelles was studied in HeLa cell line, and proved to be non-toxic up to 72 h of incubation. Therefore, these spherical micelles allow the encapsulation of hydrophobic molecules, and at the same time provided fluorescent traceability due to the presence of coumarin units in their chemical structure, demonstrating the potential of these dendrimers as nanocarriers for drug-delivery applications., This work was supported by the MINECO-FEDER funds (PGC2018-097583-B-I00) and Gobierno de Aragón-FEDER (Research Group E47_17R).

In the present work, an abundant and unused residue (wheat straw) has been employed to synthesize a polyol as a substituent of castor oil in polyurethane foams. The liquefied product showed excellent properties for the proposed application. Castor oil was substituted with up to 50% wheat straw polyol in the formulation of polyurethane foams, which were prepared using two different isocyanates (methylene diphenyl diisocyanate (MDI) and toluene-2,4-diisocyanate (TDI)). The evaluation of physical, mechanical, and thermal properties of the foams revealed that these materials can successfully be formed with up to 40% wheat straw polyols since all the results were improved. Moreover, at this polyol concentration, the morphology of the foams was presented as a compact and ordered structure. Following this trend, the foams showed excellent biodegradability at 30 days (5.60 and 7.31% for TDI and MDI foams, respectively) and 60 days (8.49 and 9.88% for TDI and MDI foams, respectively) in the soil media tests carried out. Thus, the materials prepared in this work can be proposed for agricultural applications such as use in plant nurseries.

24 pags., 8 figs., 3 tabs. -- This article belongs to the Special Issue Dendrimers and Dendritic Materials against Infectious Diseases, 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. Specifically, four different amphiphilic Janus dendrimers synthesized by combining 2,2′-bis(hydroxymethyl)propionic acid (bis-MPA) and 2,2′-bis(glyciloxy)propionic acid (bis-GMPA) functionalized with either hydrophilic or lipophilic moieties at their periphery were used to entrap iopanoic acid and tiratricol. Interestingly, differences were found in the loading efficiencies depending on the dendrimer design, which also led to morphological changes of the resulting dendrimer aggregates. The most remarkable results consist of the increased water solubility of the bioactive compounds within the dendrimers and the improved antiviral activity of some of the dendrimer/drug aggregates, considerably improving antiviral activity in comparison to the free drugs. Moreover, imaging studies have been developed in order to elucidate the mechanism of cellular internalization., This research was funded by the Ministerio de Ciencia e Innovación, Spain, which included FEDER funds (PGC2018-097583-B-I00, PGC2018-093761-B-C31, MSA grant BES-2016-078774, AL grant FPU12/05210 and R.C.-G. grant FPU13/3870) Gobierno de Aragón-FSE (E47_20R); Miguel Servet Program from Instituto deSalud Carlos III (CPII13/00017 to OA); Fondo de Investigaciones Sanitarias from Instituto de Salud Carlos III and European Union (ERDF/ESF, “Investing in your future”) (PI15/00663 and PI18/00349 to O.A.); Diputación General de Aragón (Digestive Pathology Group B25_17R to O.A.); and Centro de Investigación Biomédica en Red en Enfermedades Hepáticas y Digestivas (CIBERehd).

In the present work, the extraction and characterization of polysaccharides derived from bay tree pruning waste and their upgrading into methyl levulinate (MLA) are reported. The extraction was car...

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. Moreover, the coumarin moieties afford the pillar[5]arene derivatives with enhanced film-forming and photoresponsive properties. Photodimerization of the coumarin moieties results in cross-linked polymer networks, which can be used as alignment layers. Therefore, liquid-crystal coumarin-containing pillar[5]arenes represent a significant addition to the family of LCMs and may become useful for the development of engineered, hierarchical structures and materials., J.D.B. acknowledges MINECO, FSE, and FEDER for funding through projects RYC-2015-18471 (Ramón y Cajal program) and CTQ2017-84087-R. T.O. acknowledges funding from JST CREST. C.S.-S. acknowledges MINECO for funding through project BIO2017-84246-C2-1-R, Gobierno de Aragón for project LMP150_18, and FEDER (EU). J.L.S acknowledges MINECO for funding through project PGC2018-097583-B-I00, FEDER, and Gobierno de Aragón (Research Group E47_17R). The authors thank access to the services of CEQMA (nuclear magnetic resonance, mass spectra, and thermal analysis) of the Universidad de Zaragoza-CSIC. A.C. thanks MINECO for a PhD fellowship.

Aggregates of Pseudomonas aeruginosa form a protective barrier against antibiotics and the immune system. These barriers, known as biofilms, are associated with several infectious diseases. One of the main components of these biofilms is alginate, a homo- and hetero-polysaccharide that consists of β-D-mannuronate (M) and α-L-guluronate (G) units. Alginate lyases degrade this sugar and have been proposed as biotherapeutic agents to dissolve P. aeruginosa biofilms. However, there are contradictory reports in the literature regarding the efficacy of alginate lyases against biofilms and their synergistic effect with antibiotics. We found that most positive reports used a commercial crude extract from Flavobacterium multivorum as the alginate lyase source. By using anion exchange chromatography coupled to nano LC MS/MS, we identified two distinct enzymes in this extract, one has both polyM and polyG (polyM/G) degradation activities and it is similar in sequence to a broad-spectrum alginate lyase from Flavobacterium sp. S20 (Alg2A). The other enzyme has only polyG activity and it is similar in sequence to AlyA1 from Zobellia galactanivorans. By characterizing both of these enzymes together with three recombinant alginate lyases (a polyM, a polyG and a polyM/G), we showed that only enzymes with polyM/G activity such as Alg2A and A1-II' (alginate lyase from Sphingomonas sp.) are effective in dissolving biofilms. Furthermore, both activities are required to have a synergistic effect with antibiotics. We acknowledge support of the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program under agreement No 670216 (MYCOCHASSIS), the Spanish Ministry of Economy and Competitiveness and Fondo Europeo de Desarrollo Regional (MINECO-FEDER) (BIO2015-63557-R), ‘Centro de Excelencia Severo Ochoa 2013-2017’, FEDER project from Instituto Carlos III (ISCIII, Acción Estratégica en Salud 2016) (reference CP16/00094) and “Secretaria d’Universitats i Recerca del Departament d’Economia i Coneixement de la Generalitat de Catalunya / CERCA programme” (2014SGR678 and 2017SGR1079). The CRG/UPF Proteomics Unit is part of the “Plataforma de Recursos Biomoleculares y Bioinformáticos (ProteoRed)” supported by grant PT13/0001 of Instituto de Salud Carlos III from the Spanish Government.

(Amino)cyclotriphosphazenes have been used as new scaffolds for the synthesis of silver(I) metallomesogens. Two cyclotriphosphazenes, [N3P3(NHCy)6] (phos-1) and nongem-trans-[N3P3(NHCy)3(NMe2)3] (phos-2), were reacted with the silver complex having a pro-mesogenic ligand, [Ag(OTf)L] (L = CNC6H4{OC(O)C6H2(3,4,5-(OC10H21)3)}-4; OTf = OSO2CF3), in different molar ratios, 1:1, 1:2, or 1:3, to give two series of cationic metallophosphazenes, [N3P3(NHCy)6{AgL}n](TfO)n (phos-1.n) and nongem-trans-[N3P3(NHCy)3(NMe2)3{AgL}n](TfO)n (phos-2.n) with n = 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 n depends on the molar ratio used. Despite the presence of the bulky substituents on the core N atoms, cyclotriphosphazenes coordinated to three “AgL” units exhibited mesomorphism at room temperature. The mesophase was characterized as columnar hexagonal according to the optical microscopy and X-ray diffraction studies. A model based on an intermolecular association in pairs of the metallocyclotriphosphazenes having three AgL units has been proposed in order to explain the mesomorphic columnar arrangement in these materials. Starting silver complex, [Ag(OTf)L], also exhibited a columnar hexagonal mesophase at room temperature., This work was funded by the Ministerio de Economia y Competitividad (MINECO)-FEDER, under the project grant number MAT2017-84838P, and Gobierno de Aragon-FEDER (Liquid Crystals and Polymers Group E47_17R, FEDER 2014-2020 “Construyendo Europa desde Aragón”).

A new rod-shaped benzothiadiazole fluorophore, namely, 4,7-di-(4-nonylphenyl)benzo[c][1,2,5]thiadiazole, which strongly emits fluorescence both in solution and in solid state has been synthesized, and its photophysical properties were rationalized with the help of density functional theory calculations. This molecule crystallizes in two distinct light-emitting crystalline phases, which can be interconverted in response to pressure, temperature, and solvent vapors. Powder X-ray diffraction indicates that in both polymorph, molecules adopt a lamellar packing, the different interlayer spacing being the main difference between the two structures. Single-crystal analysis of one of the polymorphs allows us to identify weak interaction planes, which presumably facilitates the polymorphic transformation through mechanically or thermally induced sliding processes. The polymorphic transformation and the origin of the switchable fluorescence have been rationalized through a spectroscopic and theoretical study. This study suggests that the different colors observed are due to different intermolecular aromatic interactions owing to the displacement of the molecules with respect to the layer normal. Interestingly, blending this molecule with a biodegradable polymer such as poly(vinyl alcohol) gives rise to a thermally activated reversible switchable fluorescent system, which entitles this material as an attractive candidate for technological applications, such as thermal sensors, security inks, or rewritable paper.

The self-assembly of liquid crystals (LCs) is an important method to control the organization of single molecules into periodically nanostructured phases that have found applications in organic electronics. Herein, we report a new family of LC porphyrin-core dendrimers bearing carbazole moieties at the periphery of the dendrimer. These compounds are synthetic light-harvesting antennas, which exhibit intramolecular energy transfer from the carbazole moieties to the central porphyrin core. We also demonstrate that it is possible to deposit spherical polymeric nanoparticles on ITO electrodes via electrochemical crosslinking of peripheral carbazole units. Moreover, the porphyrin-core dendrimers exhibit discotic nematic phases with excellent film-forming properties and a strong tendency towards defect-free homeotropic alignment. Charge mobility studies reveal promising semiconductor properties with high hole mobility values. Therefore, such carbazole-containing LC dendrimers exhibit a unique combination of interesting properties, opening the way for the preparation of new optoelectronic materials., This work was supported by the MINECO-FEDER funds (PGC2018-097583-B-I00) and Gobierno de Aragón-FEDER (Research Group E47_17R). R. T. was supported by the MERAVIGLIE project (CUP J28C17000080006).

Microwave-assisted cellulose grafting of eugenol was performed in order to incorporate bioactive capabilities to paper for food active packaging. The reaction was optimized using a Doehlert experimental design with three variables: power (200–300 W), time (120–240 s), and eugenol content (2–8 wt%) at constant molar ratio of BTCA:eugenol and SPHI:eugenol (2:1 and 1:1, respectively). The best bioactive paper properties (72.1% DPPH inhibition) were obtained at 230 W, 240 s, and 2 wt% eugenol. However, a high color difference was determined (ΔE* = 12.76) and poor mechanical properties are expected due to the high degradation obtained. A techno-economic study was performed between microwave curing and other as convection and infrared technologies. Despite paper final properties are slightly better in infrared technology; microwave-assisted allows reducing costs compared to convective or infrared technology (12.521 g of reagent/m2 and 0.015 kWh/m2 of paper respectively, i.e. 6.101 USD of total cost per m2 of paper produced).

We report here on a series of redox active benzothiadiazole-based luminophores ffinctionalized on one edge with a phenyl-nonyl substituent, which confers these molecules a rodlike shape and a tendency to self-assemble into layered superstructures. On the other edge, the molecules are endowed with different p-substituted phenyl rings, which allows the modulation of their redox and optical properties on the basis of the electronic nature of the terminal substituents. We have found that just one lateral alkyl chain is sufficient to induce mesomorphism in these molecules, which present nematic or smectic mesophases upon therinal treatment. Single-crystal analysis allows us to get an insight into the nature of the forces responsible for different supramolecular assemblies in these derivatives, and point to a strong contribution of the terminal groups in the different arrangements observed. The interesting redox and optical properties together with their self-assembling tendencies render these new materials interesting candidates for optoelectromcs.

Significance Protein–RNA interactions, key in biological processes, remained refractory to prediction algorithms. Here we present a new extension of the ModelX tool suite designed for this purpose. RNA–protein complexes in the Protein Data Bank were decomposed into small peptide–oligonucleotide interacting fragment pairs and used as building blocks to assemble big scaffolds representing complex RNA–protein interactions. This method has already been successful for designing DNA–protein and protein–protein interfaces. Areas under the curve up to 0.86 were achieved on binding site prediction showing the accuracy and coverage of our approach over established and in-house benchmarking sets. Together with FoldX protein design tool suite we were able to engineer backbone- and side chain-compatible interfaces using naked protein structures as input., RNA–protein interactions are crucial for such key biological processes as regulation of transcription, splicing, translation, and gene silencing, among many others. Knowing where an RNA molecule interacts with a target protein and/or engineering an RNA molecule to specifically bind to a protein could allow for rational interference with these cellular processes and the design of novel therapies. Here we present a robust RNA–protein fragment pair-based method, termed RnaX, to predict RNA-binding sites. This methodology, which is integrated into the ModelX tool suite (http://modelx.crg.es), takes advantage of the structural information present in all released RNA–protein complexes. This information is used to create an exhaustive database for docking and a statistical forcefield for fast discrimination of true backbone-compatible interactions. RnaX, together with the protein design forcefield FoldX, enables us to predict RNA–protein interfaces and, when sufficient crystallographic information is available, to reengineer the interface at the sequence-specificity level by mimicking those conformational changes that occur on protein and RNA mutagenesis. These results, obtained at just a fraction of the computational cost of methods that simulate conformational dynamics, open up perspectives for the engineering of RNA–protein interfaces.

The quantification of lignin functional groups constitutes an essential step for effective assessment of lignin transformation. A new, fast, economical, and simple method without the use of harmful solvents is presented for lignin phenolic hydroxyl group quantification. The new method is based on simultaneous conductometric and acid–base titration based on pH in aqueous medium, and it provides, in a single measurement, phenolic hydroxyl and carboxyl group quantification. The new method provokes an inherent error due to the phenolic structure of lignin. This error should be 10% maximum for the low amount of condensed structures in the analyzed technical lignin samples. Four industrial lignin samples (PB-Protobind lignin, ORG-Organolsolv lignin, KF-Kraft lignin, IND-Indulin lignin) have been analyzed using the new method, and the results were compared with six classical methods (UV, 31P NMR, 1H NMR, 13C NMR, Folin Ciocalteu, and aminolysis). The results showed good statistical correlation of the new method ...

We have prepared nanoporous polymers from columnar hexagonal hydrogen-bonded complexes, whose order is fixed by coumarin photoinduced [2 + 2] cycloaddition (photodimerization). Two different hydrogen-bonded complexes were used and consisted of a melamine (M) or tris(triazolyl)triazine (T) derivative acting as central templates and three peripheral carboxylic acids containing coumarin units. These coumarin units were employed for the cross-linking process by photodimerization in order to fix the LC arrangement. Template removal leads to the formation of self-standing nanoporous polymers keeping the columnar hexagonal order. Two nanoporous polymers with different pore diameters were obtained depending on size of the utilized template. These polymers with carboxylic acids at the pore surface demonstrate the ability to selectively adsorb certain molecules depending on their size. Moreover, after base treatment of the nanoporous polymers, they are able to adsorb cationic dyes over anionic and larger cations, demonstrating size- and charge-selective adsorption., This work was supported by the MINECO-FEDER funds (project CTQ2015-70174), Gobierno de Aragon-FSE (Research Group E04). The authors acknowledge the use of the SAI (UZ) and CEQMA (UZ-CSIC) Services. A. Concellon thanks MINECO (Spain) for his PhD grant.

Novel cationic poly(ester amide) dendrimers have been synthesized by copper(i) azide-alkyne cycloaddition (CuAAC) of a tripropargylamine core and azide-terminated dendrons, in turn prepared by iterative amide coupling of the new monomer 2,2′-bis(glycyloxymethyl)propionic acid (bis-GMPA). The alternation of ester and amide groups provided a dendritic scaffold that was totally biocompatible and degradable in aqueous media at physiological and acidic pH. The tripodal dendrimers naturally formed rounded aggregates with a drug that exhibited low water solubility, camptothecin, thus improving its cell viability and anti-Hepatitis C virus (anti-HCV) activity. The presence of numerous peripheral cationic groups enabled these dendrimers to form dendriplexes with both pDNA and siRNA and they showed effective in vitro siRNA transfection in tumoral and non-tumoral cell lines., This work was financially supported by the MINECO-FEDER funds (under the projects CTQ2015-70174-P and MAT2015-66208-C3-1-P), the Miguel Servet Program from the Instituto de la Salud Carlos III (CPII13/00017 to O.A.), Instituto de Salud Carlos III and European Union (ERDF/ESF, ‘‘Investing in your future’’) (PI15/00663) and the Gobierno de Aragón-FSE (E04 and B01 research groups). Centro de Investigacion Biomédica en Red en Enfermedades Hepaticas y Digestivas (CIBERehd); and Asociación Española de Gastroenterologia (AEG). A. L. and R. C.-G. thank the MECD for their FPU grants (FPU12/05210 and FPU13/3870). R. G.-P. and R. C.-G. thank the DGA for their EPIF grants.

Two novel series of ionic liquid crystal polymers that display proton conductive properties are presented here. These materials are based on linear (l-PEI) or branched (b-PEI) poly(ethyleneimine) functionalized with unsymmetrical oxadiazole carboxylic acids derived from 1,3,4-oxadiazole (1,3,4-OXAm) or 1,2,4-oxadiazole (1,2,4-OXAm). The subscript “m” indicates the length of the spacer between the rigid moiety and the carboxyl group, namely m = 4 and 10. The occurrence of proton transfer from the carboxylic acid to the amine groups was confirmed by FTIR and NMR measurements. The liquid crystalline properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction (XRD). All ionic complexes displayed enantiotropic smectic A mesophases and in the case of the l-PEI derivatives a nematic phase was also observed at high temperatures. All investigated derivatives presented good proton conductivity values as determined by electrochemical impedance spectroscopy (EIS). Therefore, these ionic LC hyperbranched polymers represent an effective approach for the preparation of proton-transporting polymeric materials with potential applications in electrochemical devices., This work was supported by the MINECO-FEDER funds (project CTQ2015-70174), Gobierno de Aragon-FSE (Research Group E47_17R). The authors acknowledge the use of the SAI (UZ) and CEQMA (UZ-CSIC) Services.

177Lu-Tyr3-octreotide and 177Lu-PSMA(inhibitor) radiopeptides were obtained with radiochemical purities of 98.7–100%, from lyophilized formulations after reconstitution with sterile solutions of 177LuCl3 (40 GBq/mL) without the need for further purification or sterilization processes. More than 50 radiochemical syntheses were performed with a failure rate of 0% and radiochemical yields of 94–97%. From one lyophilized kit of DOTA-Tyr3-octreotide or DOTA-iPSMA, it was possible to obtain from 5 (7.4 GBq) to 10 (3.7 GBq) doses suitable for patients. Also, by using a sterile solution of 177LuCl3 approved as a radiopharmaceutical precursor for human use, it is possible to obtain GMP-compliant 177Lu-peptides from sterile freeze-dried formulations without the need of using commercially-available radiochemical synthesizers.

Introduction: Asciminib is a new BCR-ABL1 inhibitor that differs from previous tyrosine kinase inhibitors (TKIs) in that it does not bind to the ATP-binding site of the kinase. Data from different clinical trials has shown an adequate safety and efficacy profile in chronic myeloid leukemia (CML) patients failing previous TKIs. However, no findings have been communicated in real life experience. The aim of our study is to present first results of asciminib in CML patients failing previous TKIs under the current compassionate use program. Methods: We retrospectively collected data from 31 patients treated with asciminib in 25 centers under compassionate use program. Data collecting was performed between October 2018 and June 2020. Patients baseline characteristics are shown in table 1. Most patients were heavily pretreated with 28 patients receiving 3 or more TKIs previous to asciminib. Eleven patients (35.5%) had been treated with ponatinib at some point throughout the disease. Twelve patients showed BCR-ABL1 mutations (only 1 case with T315I mutation). Switch to asciminib was due to intolerance in 22 patients and due to resistance in the remaining 9. Median dose of asciminib was 80mg per day (40mg every 12 hours). Treatment responses were evaluated according to European Leukemia Net recommendations. Data compilation and analysis were performed with REDCap Software and IBM SPSS (Version 25.0). Results: Median time on asciminib for the entire cohort was 35 weeks. Regarding toxicities, 13 patients (42%) experienced mild extra-hematological side effects (grade 1-2) being the most frequent fatigue (19%), joint pain (16%) and nausea (9%). Four patients (12,9%) showed severe (grade 3-4) extra-hematological events: fatigue, hepatotoxicity, hypertension and pericardial effusion (1 patient each). Three patients (9,7%) suffered from grade 4 thrombocytopenia, 2 of them associating grade 4 neutropenia. All toxicities according to previous TKIs adverse effects as well as cross-intolerance data is shown in table 2. Dose reduction had to be carried out in 9 patients (29%), 7 of those with temporary treatment interruptions; most owing to hematological adverse effects. In terms of efficacy (Graph 1), probability of reaching or at least maintaining previous response was 100%, 61.3% and 35.5% for complete hematological response (CHR), complete cytogenetic response (CCyR) and major molecular response (MMR), respectively. Regarding probabilities to improve previous responses, rates of CCyR and MMR were, respectively, 22,2% (2/9) and 22,2% (2/9) for resistant patients and 44% (4/9) and 62,5%. (10/16) for intolerant group. Amid the 11 patients previously treated with ponatinib, 3 patients (27,3%) showed improvement of response achieving at least MMR, 2 of them from the TKI-intolerant group and 1 from the TKI-resistant group. The median follow-up time was 40 weeks, after which 27 patients (87.1%) continued with asciminib. Treatment cessation happened in 2 patients due to progression to blastic phase and in 2 patients due to lack of efficacy. No patients discontinued due to side effects. Conclusion: The data presented, similar to that known from clinical trials, supports the use of asciminib in routine clinical practice in CML patients failing to previous TKIs. Disclosures Garcia-Gutiérrez: Novartis: Consultancy, Other: Travel, Accommodation, Expenses, Research Funding; Bristol-Myers Squibb: Consultancy, Other: Travel, Accommodation, Expenses, Research Funding; Pfizer: Consultancy, Other: Travel, Accommodation, Expenses, Research Funding; Incyte: Consultancy, Other: Travel, Accommodation, Expenses, Research Funding.

Praseodymium doped zirconium silicate pigments (PrxZr1-xSiO4) were synthesized by a solid-state reaction, and the influence of praseodymium fraction (x ​= ​0.03, 0.05 or 0.07), temperature (900, 1000, 1100 or at 1200 ​°C) and calcination time (6, 12, 24 or 48 ​h) was simultaneously tested to determine their effect on colorimetric properties. The chromatic properties are associated with the volume of the unit cell; thus, with the amount of Pr4+ that is integrated into the crystal structure, the ascending concentration of the Pr4+ into zircon structure increases the color intensity only in the range where the unit cell volume is close to 261 ​A3, lower or higher values result in pigments with lower yellow intensities. An intense reddish-yellow tone can be reached delimited by praseodymium fraction of 0.03 and 0.05, temperature between 900 and 1100 ​°C, and 6 ​h of calcination time.

The development of the site-selective Suzuki–Miyaura cross-coupling of dibromoanthracene as an efficient strategy toward organic light emitting diodes (OLEDs) is disclosed in this article. An unprecedented step-economic palladacycle-promoted triple Suzuki coupling protocol allowed the synthesis of three new OLED emitters and could prove to be a useful general strategy for researchers working in this field. Characterization of the synthesized molecules by UV–vis spectroscopy and thermogravimetric analysis–differential scanning calorimetry followed by density functional theory studies of the different properties strongly confirms the derivatives possess more significant hole mobility character than electron transfer capability.

The self-assembly in water of amphiphilic Janus dendrimers leads to micelles suitable to encapsulate camptothecin and act as therapy against the hepatitis C virus, HCV. Dendrimers consist of bis-MPA dendrons linked by their focal point through a CuAAC reaction. The hydrophilic dendron wears ammonium groups in its periphery whereas the lipophilic dendrons contain stearic acid chains. The morphology of the aggregates is controlled through the chemical structure of the dendrimers, particularly their molecular weight and the adequate combination of the lipophilic and hydrophilic blocks. Camptothecin-loaded dendrimer aggregates constitute effective systems to inhibit HCV replication and show low toxicity working at low drug concentrations., This work was financially supported by the MINECO-FEDER funds (under the projects CTQ2015-70174-P, MAT2015-66208-C3-1-P and BFU2013-47064-P), Miguel Servet Program from the Instituto de la Salud Carlos III (CP07/00289, CPII13/00017), Fondo de Investigaciones Sanitarias (PI15/00663) and the Gobierno de Aragón-FSE (E04, B89 and B01 research groups). A.L. and R.C-G thank the MECD for their FPU grants (FPU12/05210 and FPU13/3870). R.C-G thanks the DGA for the EPIF grant B136/13. The authors would like to acknowledge the use of Servicios Cientifico-Técnicos of CEQMA (Universidad de Zaragoza-CSIC), Servicio General de Apoyo a la Investigación-SAI (Universidad de Zaragoza), CIBA (IACS-Universidad de Zaragoza) and the LMA (INA-Universidad de Zaragoza).

We report a new family of multifunctional liquid-crystalline porphyrin-core dendrimers that have coumarin functional groups around the porphyrin core. Porphyrin metalation strongly affects the photophysical properties, and therefore Zn and Cu derivatives have also been prepared. All the synthesized dendrimers form a nematic discotic mesophase. Their high tendency for homeotropic alignment makes these dendrimers excellent candidates for device applications, owing to their easy processability, spontaneous alignment between electrodes, and self-healing of defects because of their dynamic nature. The charge mobility values of these materials are the highest ever reported for a nematic discotic phase. Moreover, these values are similar to the highest values reported for ordered columnar mesophases, and this shows that a supramolecular organization in columns is not necessary to achieve high charge mobility., This work was supported by the MINECO, Spain, under the project CTQ2012-35692 and CTQ2015-70174, FEDER funding, and Aragón Government (Research Group E04). A.C. thanks MINECO for his PhD grant. A. G. is grateful for support from the ELIOTROPO project (PON03PE_00092_2). R. T. was supported by MIUR underthe PRIN 2012 JHFYMC project.

Lignin, one of the main components of lignocellulosic biomass, is the largest renewable source of aromatics on the planet and presents an extraordinary opportunity for being used in the production of bio-based products. It can be transformed for the substitution of aromatic chemical-derived petrol as BTXs. The wide range of applications that it can be obtained from BTXs building blocks makes the selective depolymerization of lignin a great scientific challenge. This review emphasizes the different strategies for the fragmentation of lignin to monomers or aromatics hydrocarbons. Thus, a by-product traditionally discarded or used for energy generation, it could be valorized into high added-value products.

The C‐terminal sequence of a protein is involved in processes such as efficiency of translation termination and protein degradation. However, the general relationship between features of this C‐terminal sequence and levels of protein expression remains unknown. Here, we identified C‐terminal amino acid biases that are ubiquitous across the bacterial taxonomy (1,582 genomes). We showed that the frequency is higher for positively charged amino acids (lysine, arginine), while hydrophobic amino acids and threonine are lower. We then studied the impact of C‐terminal composition on protein levels in a library of Mycoplasma pneumoniae mutants, covering all possible combinations of the two last codons. We found that charged and polar residues, in particular lysine, led to higher expression, while hydrophobic and aromatic residues led to lower expression, with a difference in protein levels up to fourfold. We further showed that modulation of protein degradation rate could be one of the main mechanisms driving these differences. Our results demonstrate that the identity of the last amino acids has a strong influence on protein expression levels., Large‐scale genomics analyses combined with high‐throughput experimental assays reveal that the C‐terminal amino acid composition has a strong influence on protein expression levels in bacteria.

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. Two types of dendritic macromolecule that can form vehicles suitable for antimalarial drug transport are herein explored. A new hybrid dendritic-linear-dendritic block copolymer based on Pluronic® F127 and amino terminated 2,2′-bis(glycyloxymethyl)propionic acid dendrons with a poly(ester amide) skeleton (HDLDBC-bGMPA) and an amino terminated dendronized hyperbranched polymer with a polyester skeleton derived from 2,2′-bis(hydroxymethyl)propionic acid (DHP-bMPA) have provided self-assembled and unimolecular micelles. Both types of micelle carrier are biocompatible and exhibit appropriate sizes to enter into pRBCs. Targeting studies have revealed different behaviors for each nanocarrier that may open new perspectives for antimalarial therapeutic approaches. Whereas DHP-bMPA exhibits a clear targeting specificity for pRBCs, HDLDBC-bGMPA is incorporated by all erythrocytes. It has also been observed that DHP-bMPA and HDLDBC-bGMPA incorporate into human umbilical vein endothelial cells with different subcellular localization, i.e. cytosolic and nuclear, respectively. Drug loading capacity and encapsulation efficiencies for the antimalarial compounds chloroquine, primaquine and quinacrine ranging from 30% to 60% have been determined for both carriers. The resulting drug-loaded nanocarriers have been tested for their capacity to inhibit Plasmodium growth in in vitro and in vivo assays., This research was supported by grants BIO2014-52872-R, CTQ2015-70174-P, MAT2015-66208-C3-1-P (Ministerio de Ciencia, Innovación y Universidades, Spain, including FEDER funds), 2014-SGR-938 (Generalitat de Catalunya, Spain), and (Gobierno de Aragón-FSE). ISGlobal and IBEC are members of the CERCA Programme, Generalitat de Catalunya. A. L. thanks the Ministerio de Ciencia, Innovación y Universidades for his grant (FPU12/05210). L. N. B.-C. is supported by the European Commission under Horizon 2020's Marie Skłodowska-Curie Actions COFUND scheme (Grant Agreement no. 712754) and by the MINECO's Severo Ochoa programme (Grant SEV-2014-0425 (2015–2019))., The authors acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI).

Novel liquid crystalline Janus dendrimers that combine a mesogenic block and an electroactive block have been synthesised. The mesogenic block is based on two third-generation Percec-type dendrons bearing six or eight terminal dodecyloxy alkyl chains, whereas the electroactive blocks are formed by one or two carbazole units. The liquid crystal behaviour was investigated by polarised-light optical microscopy, differential scanning microscopy and X-ray diffraction. The Janus dendrimers with one electroactive unit exhibited cubic or columnar liquid crystal phases, whereas the Janus dendrimers with two electroactive units did not show liquid crystalline behaviour. The UV-vis absorption and emission properties of the Janus dendrimers were investigated. The spectra suggested the existence of π-π stacking and the formation of aggregates in the solid state. Electrodeposition of the carbazole-containing dendrimers afforded semi-globular particles in which the number of electropolymerizable units and the flexible or rigid character of the linker have a decisive influence in the particle size., This work was supported by the MINECO-FEDER funds (project CTQ2015-70174), Gobierno de Aragón-FSE (Research Group E47_17R).

Films containing bay leaves essential oils (BEOs) were prepared and evaluated for edible packaging applications. The BEOs were extracted by the Soxhlet method, using ethanol or methanol as organic solvent. Then, films were prepared by &ldquo, solvent casting&rdquo, technique using carboxymethyl cellulose (CMC), with different concentrations for the as-obtained BEOs (from 1% to 30% wt.). The resulting films were characterized to evaluate their physical (thickness, moisture content, water solubility and water vapor permeability), optical (transparency and UV-light barrier), mechanical (tensile strength and elongation at break), antioxidant and antimicrobiological properties Attractive films were obtained for food active packaging applications, as they presented a high antioxidant activity (up to 99%) and total phenolic content, and good barrier properties against water vapor (50% improved of CMC) in the case of CMC-film containing 15% wt. ethanolic extract. Related to optical properties, UV-light barrier effect was increased (almost 100% of protection) avoiding typical lipids oxidation in food systems. High water solubility (93%) was also found, ensuring also their biodegradability. Moreover, it was demonstrated that developed films inhibit microorganisms&rsquo, growth (Escherichia coli and Candida glabrata), this avoiding an early food oxidation.

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 (Mn = 2000 and Mn = 5000) and the generation of the bis-MPA dendron. The materials were characterized by transmission electron microscopy (TEM). The shapes of the aggregates ranged from spherical or cylindrical micelles to flexible bilayers. The hydrophobic core enabled these nanostructures to encapsulate the water-insoluble drug plitidepsin. The efficacy of these new plitidepsin-containing carriers was evaluated in four cancer cell-lines and they showed similar anticancer activity to the current standard drug formulation., This research was funded by the FP7 PEOPLE PROGRAMME, The Marie Curie Actions; ITN, no. 215884-2, the MINECO, Spain, (under projects: CTQ2015-70174-P and MAT2015-66208-C3-1-P), which included FEDER funding, and the Aragón Government-FSE (Project E47_17R). E.F. and A.L. acknowledge financial support from the EU as ESR fellowships in PharmaMar and A.L. thanks the MECD for a FPU grant, no. 12/05210., We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI).

Polysaccharides extracted from natural sources can be used as starting material for the preparation of nanoparticle supported composites. A novel family of bio-nanocomposites was mechanochemically synthesized by using niobium oxide and enzymatically produced polysaccharides. The structural, textural and surface properties of nanomaterials, were determined by X-Ray diffraction (XRD), nitrogen adsorption-desorption (N₂ porosimetry), pulse chromatography, infrared spectroscopy (ATR-IR) and dynamic light scattering (DLS). Selective oxidation of isoeugenol to vanillin was carried out to demonstrate the catalytic activity of the Nb-polysaccharides nanocomposites. Interestingly, most of our material showed high conversion of isoeugenol (60&ndash, 70%) with selectivity to vanillin over 40%. The optimum conversion and selectivity were achieved with a reaction time between 8 and 24 h.

New dinuclear cyclometallated palladium complexes of general formula [{Pd(μ-NCO)(CˆN)} 2 ] (CˆN = 2-benzoylpyridine (bzpy) I ; NCO = saccharinate (sacc) a , Phthalimidate (phthal) b or 4,5-dichlorophthalimidate (DiClphthal) c have been synthesized by a simple acid-base reaction involving the di-μ-hydroxo-precursor [{Pd(μ-OH)(bzpy)} 2 ] recently reported. Analogous to Ic , complex IIc with CˆN = 2-phenylpyridine (phpy) II has also been prepared, meaning the first examples reported to date of complexes including 4,5-dichlorophthalimidate as ligand coordinating a metal centre. The reaction of bridged imidato precursors against triphenylphosphine to form the mononuclear N-bonded imidato derivatives of general formula [Pd(CˆN)(N-imidate)(PPh 3 )] IaP , IbP , IcP and IIcP has been achieved under mild conditions. The new complexes were characterized by partial elemental analyses and spectroscopic methods. Structural characterization by X-ray diffraction of Ib and IIcP , the first crystal structure of a complex containing 4,5-diClphthal that has been deposited to date on the Cambridge Structural Database, have confirmed the proposed formulae.

New poly(propylene imine) (PPI) dendrimers modified at the periphery with mesomorphic 4-cyanobiphenyl units and cinnamate- or coumarin-based photoactive moieties were synthesised and structurally characterised. The photoactive moieties were structurally designed to be liquid crystalline compatible and to reduce the tendency towards crystallisation of the final material. Thermal and liquid crystal properties were studied by POM, DSC, TGA and XRD. The results show that all dendrimers displayed a smectic A mesophase. Dendrimers with high transparency in the visible region but with different absorption spectra were obtained, rendering materials that are easy to monitor in light-irradiation experiments., The authors thank the Spanish Ministerio de Economia y Competitividad (MINECO) and Fondo Europeo para el Desarrollo Regional (FEDER) (project numbers CTQ2012- 35692, MAT2012-38538-CO3-01 and MAT2014-55205-P), and the Gobierno de Aragón and Fondo Social Europeo (FSE) (research group E04).

A straightforward synthesis of mesogenic pyrazoles starting from benzaldehydes by a combination of efficient Henry and Michael reactions led to novel supramolecular liquid crystals. The mesogens are fluorescent 3,5-dimethyl-4-(di or trialkoxyphenyl)pyrazoles and, in spite of the tapered shape of these molecules and their structural simplicity (only one phenyl ring), columnar liquid-crystal phases were formed that are stable at room temperature. The self-assembled structure was studied by XRD and the columnar cross section contains two molecules on average with an antiparallel arrangement of pyrazoles interacting through hydrogen bonds. In contrast, the single-crystal structure of a trimethoxy analog did not show hydrogen-bonded pyrazoles but chains of head-to-tail arranged molecules., The authors thank the Spanish Ministerio de Economia y Competitividad (MINECO) and Fondo Europeo para el Desarrollo Regional (FEDER) (project numbers CTQ2012-35692, CTQ2011-22516, CTQ2014-53033-P, and MAT2012-38538-CO3-01), the Gobierno de Aragón and Fondo Social Europeo (FSE) (research group E04), and Catedra IQE for financial support.