Formulating a TMEM176B blocker in chitosan nanoparticles uncouples its paradoxical roles in innate and adaptive antitumoral immunity.

The immunoregulatory cation channel TMEM176B plays a dual role in tumor immunity. On the one hand, TMEM176B promotes antigen cross-presentation to CD8 T cells by regulating phagosomal pH in dendritic cells (DCs). On the other hand, it inhibits NLRP3 inflammasome activation through ionic mechanisms in DCs, monocytes and macrophages.

Exploring Mixed Ionic-Electronic-Conducting PVA/PEDOT:PSS Hydrogels as Channel Materials for Organic Electrochemical Transistors.

Here, we report the preparation and evaluation of PVA/PEDOT:PSS-conducting hydrogels working as channel materials for OECT applications, focusing on the understanding of their charge transport and transfer properties. Our conducting hydrogels are based on crosslinked PVA with PEDOT:PSS interacting via hydrogen bonding and exhibit an excellent swelling ratio of ~180-200% /. Our electrochemical impedance studies indicate that the charge transport and transfer processes at the channel material based on conducting hydrogels are not trivial compared to conducting polymeric films.

Reverse Phase HPLC Methodology for the Determination of Bay K8644.

Following ICH guidelines for analytical validation, we report a common C18 column stability indicating isocratic reverse phase high performance liquid chromatography method for the determination of the ion channel modulator Bay K8644. Two main forced degradation products and a minor impurity were also tentatively identified by Mass Spectrometry. The mobile phase consisted of a 50/50 acetonitrile/buffer mixture at a flow rate of 2 mL/min.

On the Donor: Acceptor Features for Poly(3-hexylthiophene): TiO Quantum Dots Hybrid Materials Obtained via Water Vapor Flow Assisted Sol-Gel Growth.

Here, we present a novel methodology for the preparation of P3HT:TiO quantum dots hybrid materials via water vapor flow-assisted sol-gel growth focusing on the structural, optical and electrical property characterization complemented with first-principles calculations as a promising donor-acceptor system for polymer and hybrid solar cells. X-ray diffraction and UV-Vis spectroscopy analyses suggest that the increasing concentration of TiO quantum dots leads to the formation of higher amounts of amorphous regions while the crystalline regions exhibited interesting aspect ratio modifications for the P3HT polymer. Raman spectra evidenced the formation of charge carriers in the P3HT with increasing TiO quantum dots content and the P3HT:TiO 50:50 weight ratio resulted in the best composition for optimizing the bulk electronic conductivity, as evidenced by impedance spectroscopy studies.

Hybrid Organic-Inorganic Materials and Interfaces With Mixed Ionic-Electronic Transport Properties: Advances in Experimental and Theoretical Approaches.

The main goal of this mini-review is to provide an updated state-of-the-art of the hybrid organic-inorganic materials focusing mainly on interface phenomena involving ionic and electronic transport properties. First, we review the most relevant preparation techniques and the structural features of hybrid organic-inorganic materials prepared by solution-phase reaction of inorganic/organic precursor into organic/inorganic hosts and vapor-phase infiltration of the inorganic precursor into organic hosts and molecular layer deposition of organic precursor onto the inorganic surface. Particular emphasis is given to the advances in joint experimental and theoretical studies discussing diverse types of computational simulations for hybrid-organic materials and interfaces.

Docetaxel in chitosan-based nanocapsules conjugated with an anti-Tn antigen mouse/human chimeric antibody as a promising targeting strategy of lung tumors.

The aim of this work was to evaluate the physicochemical and biological properties of docetaxel (DCX) loaded chitosan nanocapsules (CS Nc) functionalized with the monoclonal antibody Chi-Tn (CS-PEG-ChiTn mAb Nc) as a potential improvement treatment for cancer therapy. The Tn antigen is highly specific for carcinomas, and this is the first time that such structure is targeted for drug delivery. The nanocapsules (Ncs), formed as a polymeric shell around an oily core, allowed a 99.

From Chain- to Graphene-like Hydroxyl-terminated (ZnO) Clusters with n≤6 Obtained via Zinc Dimethoxide Hydrolysis and Condensation: Ab initio Structural, Electronic, Vibrational and Optical Properties Calculations.

Recent reports are focusing on the structural evolution from the atomic-scale and also at the expenses of alkyl zinc alkoxide precursors towards (ZnO) clusters and nanostructures with different interesting motifs, but still not much is known about their electronic properties. In this manuscript, we present a theoretical study using DFT and TD-DFT methodologies on the hydrolysis and condensation of zinc dimethoxide precursor in its monomeric, dimeric and trimeric forms towards thermodynamically stable hydroxyl-terminated (ZnO) clusters with novel chain- and graphene-like fashions. For all cases, distinct vibrational and optical spectra features were assigned evidencing a global monotonic decrease in the opto-electronic gap with increasing oligomerization and cyclization stages.

Mini-Review: Mixed Ionic-Electronic Charge Carrier Localization and Transport in Hybrid Organic-Inorganic Nanomaterials.

In this mini-review, a comprehensive discussion on the state of the art of hybrid organic-inorganic mixed ionic-electronic conductors (-MIECs) is given, focusing on conducting polymer nanocomposites comprising inorganic nanoparticles ranging from ceramic-in-polymer to polymer-in-ceramic concentration regimes. First, a brief discussion on fundamental aspects of mixed ionic-electronic transport phenomena considering the charge carrier transport at bulk regions together with the effect of the organic-inorganic interphase of hybrid nanocomposites is presented. We also make a recount of updated instrumentation techniques to characterize structure, microstructure, chemical composition, and mixed ionic-electronic transport with special focus on those relevant for -MIECs.

Physico-chemical and antilisterial properties of nisin-incorporated chitosan/carboxymethyl chitosan films.

The objective of this work was to investigate the effect of the addition of carboxymethyl chitosan on the structural properties and antilisterial activity of nisin-incorporated chitosan films. Chitosan and carboxymethyl chitosan solutions were prepared with different mass ratios and bacteriocin nisin was added (0, 1000 and 6000 IU/ml). Filmogenic solutions were cast, dried and their physico-chemical and antimicrobial properties were investigated.

Extremely Large Magnetic-Field-Effects on the Impedance Response of TiO Quantum Dots.

Here, we report large magnetoresistance and magnetocapacitance response of undoped TiO quantum dots weighting the contribution of both grain and grain boundaries by means of impedance spectroscopy. We also performed a complete characterization of the TiO quantum dots (~5 nm) prepared by sol-gel via water vapor diffusion method, using X-ray diffraction, small angle X-ray scattering, transmission electron microscopy and Raman spectroscopy. In addition, we showed a complete theoretical study on the electronic properties of TiO surface and subsurface oxygen and titanium vacancies to shed some light in their electronic and magnetic properties.

Raman Microscopy Insights on the Out-of-Plane Electrical Transport of Carbon Nanotube-Doped PEDOT:PSS Electrodes for Solar Cell Applications.

In the present report, we focused on the study of the out-of-plane electrical transport of multiwalled carbon nanotube (MWCNT)-doped poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) composites (PEDOT:PSS-MWCNTs) as electrodes for solar cell applications. The out-of-plane direct current and alternating current electrical transport, rarely studied but not less relevant, was additionally supported with in-plane and out-of-plane confocal Raman microscopy and grazing incidence small-angle X-ray scattering characterizations. The main relevance of our study is the monitoring of the polymer structure all across the polymeric film by using confocal Raman spectroscopy and its correlation with electrical transport.

Mechanical properties and electronic structure of edge-doped graphene nanoribbons with F, O, and Cl atoms.

In this study, we present the structural, electronic, and mechanical properties of edge-doped zigzag graphene nanoribbons (ZGNRs) doped with fluorine, oxygen, and chlorine atoms. To the best of our knowledge, to date, no experimental results concerning the mechanical properties of graphene-derived nanoribbons have been reported in the literature. Simulations indicate that Cl- and F-doped ZGNRs present an equivalent 2-dimensional Young's modulus E, which seems to be higher than those of graphene and H-doped ZGNRs.

Experimental and Theoretical Study of Ionic Pair Dissociation in a Lithium Ion-Linear Polyethylenimine-Polyacrylonitrile Blend for Solid Polymer Electrolytes.

Herein, we report the preparation and characterization of a novel polymeric blend between linear polyethylene imine (PEI) and polyacrylonitrile (PAN), with the purpose of facilitating the dissociation of lithium perchlorate salt (LiClO) and thus to enhance Li ion transport. It is a joint theoretical and experimental procedure for evaluating and thus demonstrating the lithium salt dissociation. The procedure implies the correlation between the theoretical pair distribution function (PDF) and conventional X-ray diffraction (XRD) by means of a molecular dynamics (MD) approach.

Crystal structure and absolute configuration of (3aS,4S,5R,7aR)-2,2,7-trimethyl-3a,4,5,7a-tetra-hydro-1,3-benzodioxole-4,5-diol.

The absolute configuration of the title compound, C10H16O4, determined as 3aS,4S,5R,7aR on the basis of the synthetic pathway, was confirmed by X-ray diffraction. The mol-ecule contains a five- and a six-membered ring that adopt twisted and envelope conformations, respectively. The dihedral angle between the mean planes of the rings is 76.

Magnetism in multivacancy graphene systems.

Ab initio calculations using density functional theory (DFT) have been performed in order to study defects in graphene. The structural distortions that can be observed when multi-atom vacancies are created in graphene and the net magnetic moment that can eventually appear are characterized for a variety of vacancy sizes and shapes. We conclude that the configuration arising in the construction of multivacancies in graphene can unambiguously indicate whether a magnetic response of the defected system is to be expected.

Bisphosphonate metal complexes as selective inhibitors of Trypanosoma cruzi farnesyl diphosphate synthase.

In the search for a pharmacological answer to treat Chagas disease, eight metal complexes with two bioactive bisphosphonates, alendronate (Ale) and pamidronate (Pam), were described. Complexes of the formula [M(2)(II)(Ale)(4)(H(2)O)(2)]·2H(2)O, with M = Cu, Co, Mn, Ni, and ([CuPam]·H(2)O)(n) as well as [M(II)(Pam)(2)(H(2)O)(2)]·3H(2)O, with M = Co, Mn and Ni, were synthesized and fully characterized. Crystal structure of [Cu(2)(II)(Ale)(4)(H(2)O)(2)]·2H(2)O, [Co(II)(Pam)(2)(H(2)O)(2)] and [Ni(II)(Pam)(2)(H(2)O)(2)] were solved by X-ray single crystal diffraction methods and the structures of [M(2)(II)(Ale)(4)(H(2)O)(2)]·2H(2)O complexes M = Co, Mn and Ni were studied by X-ray powder diffraction methods.

The conformations of two copper(I) complexes of 1H-benzimidazole-2(3H)-thione and thiosaccharinate.

(Acetonitrile-1κN)[μ-1H-benzimidazole-2(3H)-thione-1:2κ(2)S:S][1H-benzimidazole-2(3H)-thione-2κS]bis(μ-1,1-dioxo-1λ(6),2-benzothiazole-3-thiolato)-1:2κ(2)S(3):N;1:2κ(2)S(3):S(3)-dicopper(I)(Cu-Cu), [Cu(2)(C(7)H(4)NO(2)S(2))(2)(C(7)H(6)N(2)S)(2)(CH(3)CN)] or [Cu(2)(tsac)(2)(Sbim)(2)(CH(3)CN)] [tsac is thiosaccharinate and Sbim is 1H-benzimidazole-2(3H)-thione], (I), is a new copper(I) compound that consists of a triply bridged dinuclear Cu-Cu unit. In the complex molecule, two tsac anions and one neutral Sbim ligand bind the metals. One anion bridges via the endocyclic N and exocyclic S atoms (μ-S:N).

Magneto-structural studies on heterobimetallic malonate-bridged M(II)Re(IV) complexes (M = Mn, Co, Ni and Cu).

The mononuclear Re(IV) compound of formula (PPh(4))(2)[ReBr(4)(mal)] (1) was used as a ligand to obtain the heterobimetallic species [ReBr(4)(μ-mal)Co(dmphen)(2)]· MeCN (2), [ReBr(4)(μ-mal)Ni(dmphen)(2)] (3), [ReBr(4)(μ-mal)Mn(dmphen)(2)] (4a), [ReBr(4)(μ-mal)Mn(dmphen)(H(2)O)(2)]·dmphen·MeCN·H(2)O (4b), [ReBr(4)(μ-mal)Cu(phen)(2)]·1/4H(2)O (5) and [ReBr(4)(μ-mal)Cu(bipy)(2)] (6) (mal = malonate dianion, dmphen = 2,9-dimethyl-1,10-phenanthroline, phen = 1,10-phenanthroline and bipy = 2,2'-bipyridine). The structures of 2 and 5 (single-crystal X-ray diffraction) are made up of neutral [ReBr(4)(μ-mal)M(AA)] dinuclear units [AA = dmphen with M = Co (2) and AA = phen with M = Cu (5)] where the metal ions are connected through a malonate ligand which exhibits simultaneously the bidentate [at the Re(IV)] and monodentate [at the M(II)] coordination modes. The carboxylate-malonate group in them adopts the anti-syn conformation with intramolecular ReM separation of 5.

Mechanical properties of graphene nanoribbons.

Herein, we investigate the structural, electronic and mechanical properties of zigzag graphene nanoribbons in the presence of stress by applying density functional theory within the GGA-PBE (generalized gradient approximation-Perdew-Burke-Ernzerhof) approximation. The uniaxial stress is applied along the periodic direction, allowing a unitary deformation in the range of ± 0.02%.

Is it possible to dope single-walled carbon nanotubes and graphene with sulfur?

Herein, we investigate sulfur substitutional defects in single-walled carbon nanotubes (SWCNTs) and graphene by using first-principles calculations. The estimated formation energies for the (3,3), (5,5), and (10,0) SWCNTs and graphene lie between 0.9 and 3.

Synthesis, crystal structure and magnetic properties of novel heterobimetallic malonate-bridged MIIReIV complexes (M = Mn, Fe, Co and Ni).

Five novel ReIV-MII bimetallic complexes of formula [ReCl4(mu-mal)M(dmphen)2].MeCN [M = Co (1), Fe (2) and Ni (3)], [ReCl4(mu-mal)Ni(dmphen)(MeCN)2(H2O)].(MeCN)0.

Tetra-kis[μ-2-(3-phenoxy-phen-yl)propionato-κO:O']bis-[(dimethyl-formamide-κO)copper(II)].

The title compound, [Cu(2)(C(15)H(13)O(3))(4)(C(3)H(7)NO)(2)], is formed by the chelate coordination of four racemic fenoprofenate (fenoprofenate is 2,3-phenoxyphenyl propionate) anions and two dimethyl-formamide mol-ecules to two copper(II) ions, building a paddle-wheel dinuclear mol-ecule. The distorted square-pyramidal coordination of each Cu(II) atom is made up of four O atoms of the four fenoprofenate units and another O atom from a dimethyl-formamide mol-ecule. The two enanti-omeric forms of the fenoprofenate anions are present in the complex, in an optically inactive centrosymmetric arrangement.

Bisabolanes from the red alga Laurencia scoparia.

Three novel halogenated beta-bisabolene sesquiterpenoids (1-3), together with two know triquinane alcohol sesquiterpenes (6 and 7), were isolated from the red alga Laurencia scoparia and their structures elucidated by spectroscopic methods. Single-crystal X-ray crystallography allowed us to confirm the structure of 1 as well as to determine the absolute configuration of all stereocenters. To the best of our knowledge, the isolation of beta-bisabolenes from the genus Laurencia has no precedent in the literature.