Intrinsic Permeation and Anti-Inflammatory Evaluation of Curcumin, Bisdemethoxycurcumin and Bisdemethylcurcumin by a Validated HPLC-UV Method.

Curcumin shows anti-inflammatory activity, and it has been widely investigated for neurodegenerative diseases, adjuvant treatment in AIDS and antitumor activity against different tumors, among other activities. The goal of this work was to evaluate the capacity of curcumin and its derivatives (bisdemethoxycurcumin and bisdemethylcurcumin) in preventing the irritant effects of topically applied xylol and to assess the intrinsic capacity of curcuminoids in permeating human skin by ex vivo permeation tests. Its secondary goal was to validate an HPLC method to simultaneously determine the curcuminoids in the samples from the ex vivo permeation studies and drug extraction from the skin. Curcuminoid quantification was performed using an RP-C18 column, at isocratic conditions of elution and a detection wavelength of 265 nm. The method was specific with a suitable peak resolution, as well as linear, precise, and accurate in the range of 0.195-3.125 µg/mL for the three curcuminoids. Bisdemethylcurcumin showed the greatest permeation through the human skin, and it was the curcuminoid that was most retained within the human skin. The anti-inflammatory activity of the curcuminoids was evaluated in vivo using a xylol-induced inflammation model in rats. Histological studies were performed to observe any changes in morphology at the microscopic level, and these three curcuminoids were found to be respectful within the skin structure. These results show that these three curcuminoids are suitable for anti-inflammatory formulations for dermal applications, and they can be properly quantified using HPLC-UV.

Dielectric behavior of curcuminoid polymorphs on different substrates by direct soft vacuum deposition.

Our work examines the structural-electronic correlation of a new curcuminoid, AlkCCMoid, as a dielectric material on different substrates. For this purpose, we show a homemade sublimation method that allows the direct deposition of molecules on any type of matrix. The electronic properties of AlkCCMoid have been evaluated by measurements on single crystals, microcrystalline powder, and sublimated samples, respectively. GIWAXS studies on surfaces and XRD studies on powder have revealed the existence of polymorphs and the effect that substrates have on curcuminoid organization. We describe the dielectric nature of our system and identify how different polymorphs can affect electronic parameters such as permittivity, all corroborated by DFT calculations.

Luminescence of Macrocyclic Mononuclear DyIII Complexes and Their Immobilization on Functionalized Silicon-Based Surfaces.

Two mononuclear DyIII complexes, [Dy(L1)(NCS)3] (Dy-EDA) and [Dy(L2)(NCS)3] (Dy-DAP), where Ln (n = 1-2) corresponds to a macrocyclic ligand derived from 2,6-pyridinedicarboxaldehyde and ethylenediamine (L1) and 1,3-diaminepropane (L2) were immobilized on functionalized silicon-based surfaces. This was achieved by the microcontact printing (µCP) technique, generating patterns on a functionalized surface via covalent bond formation through the auxiliary -NCS ligands present in the macrocyclic complex species. With this strategy, it was possible to control the position of the immobilized molecules on the surface. Water contact angle measurements, X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectra (IRRAS), and atomic force microscopy (AFM) confirmed that the surfaces were successfully functionalized. Furthermore, the optical properties in a broad temperature range were investigated for the as-prepared compounds. At room temperature, Dy-EDA was shown to emit in the deep blue region (Commission Internationald'Eclairage (CIE): (0.175, 0.128)), while Dy-DAP in the white region (CIE: (0.252, 0.312)). The different CIE values were due to the contribution of the strong emission of the ligand in the case of Dy-EDA. Besides, surface photoluminescence measurements showed that the immobilized complexes retained their bulk emissive properties.

Emergent Insulator-Metal Transition with Tunable Optical and Electrical Gap in Thin Films of a Molecular Conducting Composite.

Composites exhibit unique synergistic properties emerging when components with different properties are combined. The tuning of the energy bandgap in the electronic structure of the material allows designing tailor-made systems with desirable mechanical, electrical, optical, and/or thermal properties. Here, we study an emergent insulator-metal transition at room temperature in bilayered (BL) thin-films comprised of polycarbonate/molecular-metal composites. Temperature-dependent resistance measurements allow monitoring of the electrical bandgap, which is in agreement with the optical bandgap extracted by optical absorption spectroscopy. The semiconductor-like properties of BL films, made with bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF or ET) α-ET2I3 (nano)microcrystals as two-dimensional molecular conductor on one side and insulator polycarbonate as a second ingredient, are attributed to an emergent phenomenon equivalent to the transition from an insulator to a metal. This made it possible to obtain semiconducting BL films with tunable electrical/optical bandgaps ranging from 0 to 2.9 eV. A remarkable aspect is the similarity close to room temperature of the thermal and mechanical properties of both composite components, making these materials ideal candidates to fabricate flexible and soft sensors for stress, pressure, and temperature aiming at applications in wearable human health care and bioelectronics.

Room-Temperature Spin-Dependent Transport in Metalloporphyrin-Based Supramolecular Wires.

Here we present room-temperature spin-dependent charge transport measurements in single-molecule junctions made of metalloporphyrin-based supramolecular assemblies. They display large conductance switching for magnetoresistance in a single-molecule junction. The magnetoresistance depends acutely on the probed electron pathway through the supramolecular wire: those involving the metal center showed marked magnetoresistance effects as opposed to those exclusively involving the porphyrin ring which present nearly complete absence of spin-dependent charge transport. The molecular junction magnetoresistance is highly anisotropic, being observable when the magnetization of the ferromagnetic junction electrode is oriented along the main molecular junction axis, and almost suppressed when it is perpendicular. The key ingredients for the above effect to manifest are the electronic structure of the paramagnetic metalloporphyrin, and the spinterface created at the molecule-electrode contact.

Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium.

We report the spin dynamic properties of non-substituted ferrocenium complexes. Ferrocenium shows a field-induced single-molecule magnet behaviour in DMF solution while cobaltocene lacks slow spin relaxation neither in powder nor in solution. Multireference quantum mechanical calculations give a non-Aufbau orbital occupation for ferrocenium with small first excitation energy that agrees with the relatively large measured magnetic anisotropy for a transition metal S=1/2 system. The analysis of the spin relaxation shows an important participation of quantum tunnelling, Raman, direct and local-mode mechanisms which depend on temperature and the external field conditions. The calculation of spin-phonon coupling constants for the vibrational modes shows that the first vibrational mode, despite having a low spin-phonon constant, is the most efficient process for the spin relaxation at low temperatures. In such conditions, vibrational modes with higher spin-phonon coupling constants are not populated. Additionally, the vibrational energy of this first mode is in excellent agreement with the experimental fitted value obtained from the local-mode mechanism.

Broadening the scope of high structural dimensionality nanomaterials using pyridine-based curcuminoids.

We present a new heteroditopic ligand (3pyCCMoid) that contains the typical skeleton of a curcuminoid (CCMoid) decorated with two 3-pyridyl groups. The coordination of 3pyCCMoid with ZnII centres results in a set of novel coordination polymers (CPs) that display different architectures and dimensionalities (from 1D to 3D). Our work analyses how synthetic methods and slight changes in the reaction conditions affect the formation of the final materials. Great efforts have been devoted toward understanding the coordination entities that provide high dimensional systems, with emphasis on the characterization of 2D materials, including analyses of different types of substrates, stability and exfoliation in water. Here, we foresee the great use of CCMoids in the field of CPs and emphasize 3pyCCMoid as a new-born linker.

Single molecule magnets of cobalt and zinc homo- and heterometallic coordination polymers prepared by a one-step synthetic procedure.

The synthesis of 1D cobalt and zinc monometallic and heterometallic coordination polymers (CPs) was carried out applying one-pot synthetic methods by using either supercritical carbon dioxide or ethanol as the solvent. A collection of four 1D CPs were thus obtained by the combination of a metal (or a mixture of metals) with the linker 1,4-bis(4-pyridylmethyl)benzene. The used metallic complexes were zinc and cobalt hexafluoroacetylacetonate, which can easily incorporate pyridine ligands in the coordination sphere of the metal centre. Independently of the used solvent, the precipitated phases involving Zn(ii), i.e., homometallic CP of Zn(ii) and bimetallic CP of Zn(ii)/Co(ii), were isostructural. Contrarily, homometallic CPs of Co(ii) were precipitated as an isostructural phase of Zn(ii) or with a different structure, depending on the used solvent. All the structures were resolved by XRD using synchrotron radiation. In addition, the magnetic properties of the new CPs involving Co(ii) were studied. Remarkably, at low temperatures with the application of an external field, they acted as field-induced single molecule magnets.

Tuning Single-Molecule Conductance in Metalloporphyrin-Based Wires via Supramolecular Interactions.

Nature has developed supramolecular constructs to deliver outstanding charge-transport capabilities using metalloporphyrin-based supramolecular arrays. Herein we incorporate simple, naturally inspired supramolecular interactions via the axial complexation of metalloporphyrins into the formation of a single-molecule wire in a nanoscale gap. Small structural changes in the axial coordinating linkers result in dramatic changes in the transport properties of the metalloporphyrin-based wire. The increased flexibility of a pyridine-4-yl-methanethiol ligand due to an extra methyl group, as compared to a more rigid 4-pyridinethiol linker, allows the pyridine-4-yl-methanethiol ligand to adopt an unexpected highly conductive stacked structure between the two junction electrodes and the metalloporphyrin ring. DFT calculations reveal a molecular junction structure composed of a shifted stack of the two pyridinic linkers and the metalloporphyrin ring. In contrast, the more rigid 4-mercaptopyridine ligand presents a more classical lifted octahedral coordination of the metalloporphyrin metal center, leading to a longer electron pathway of lower conductance. This works opens to supramolecular electronics, a concept already exploited in natural organisms.

Slow-spin relaxation of a low-spin S = 1/2 FeIII carborane complex.

In this communication, we report the first evidence of slow-spin relaxation of a low-spin FeIII carborane complex. Iron S = 1/2 complexes showing such behaviour are particularly appealing as qubit candidates because they fulfil some of the main requirements to reach long decoherence times, such as moderate magnetic anisotropy, small spin, metal element mainly with zero-nuclear spin and furthermore, large versatility to introduce chemical modifications.

Correction: A new family of fullerene derivatives: fullerene-curcumin conjugates for biological and photovoltaic applications.

[This corrects the article DOI: 10.1039/C8RA08334G.].

Electric-field induced bistability in single-molecule conductance measurements for boron coordinated curcuminoid compounds.

We have studied the single-molecule conductance of a family of curcuminoid molecules (CCMs) using the mechanically controlled break junction (MCBJ) technique. The CCMs under study contain methylthio (MeS-) as anchoring groups: MeS-CCM (1), the free-ligand organic molecule, and two coordination compounds, MeS-CCM-BF2 (2) and MeS-CCM-Cu (3), where ligand 1 coordinates to a boron center (BF2 group) and to a CuII moiety, respectively. We found that the three molecules present stable molecular junctions allowing detailed statistical analysis of their electronic properties. Compound 3 shows a slight increase in the conductance with respect to free ligand 1, whereas incorporation of BF2 (compound 2) promotes the presence of two conductance states in the measurements. Additional experiments with control molecules point out that this bistability is related to the combination of MeS- anchoring groups and the BF2 moiety within the structure of the molecules. Theoretical calculations show that this can be explained by the presence of two conformers once compound 2 is anchored between the gold electrodes. An energy minimum is found for a flat structure but there is a dramatic change in the magnitude and orientation of dipole moment (favouring a non-flat conformer in the presence of an external electric field) due to a conformational change of one of the terminal MeS- groups. The results thus point to an intricate interplay between the applied bias voltage and the molecule dipole moment which could be the basis for designing new molecules aiming at controlling their conformation in devices.

Boosting Self-Assembly Diversity in the Solid-State by Chiral/Non-Chiral ZnII -Porphyrin Crystallization.

A chiral ZnII porphyrin derivative 1 and its achiral analogue 2 were studied in the solid state. Considering the rich molecular recognition of designed metalloporphyrins 1 and 2 and their tendency to crystallize, they were recrystallized from two solvent mixtures (CH2 Cl2 /CH3 OH and CH2 Cl2 /hexane). As a result, four different crystalline arrangements (1 a,b and 2 a,b, from 0D to 2D) were obtained. Solid-state studies were performed on all the species to analyze the role played by chirality, solvent mixtures, and surfaces (mica and HOPG) in the supramolecular arrangements. By means of combinations of solvents and substrates a variety of microsized species was obtained, from vesicles to flower-shaped arrays, including geometrical microcrystals. Overall, the results emphasize the environmental susceptibility of metalloporphyrins and how this feature must be taken into account in their design.

Coumarin Derivative Directly Coordinated to Lanthanides Acts as an Excellent Antenna for UV-Vis and Near-IR Emission.

A chelating coumarin-derived ligand sensitizes all emitting lanthanide ions in the solid state and gives high absolute quantum yields for ethanol solutions of complexes of Sm, Eu, Tb, and Dy, above 20% for the last two. Crystal structures of these four complexes are [Ln(Cum)3(H2O)(X)]·X where X = MeOH or EtOH.

A new family of fullerene derivatives: Fullerene-curcumin conjugates for biological and photovoltaic applications.

The synthesis and characterization of a family of [60]fullerocurcuminoids obtained via Bingel reactions is reported. The new C60 derivatives include curcumin and curcuminoids with a variety of end groups. Preliminary biological experiments show the potential activity of the compound containing a curcumin addend, which exhibits moderate anti-HIV-1 and radical scavenger properties, but no anti-cancer activity. In addition, the new fullerocurcuminoids exhibit HOMO/LUMO energy levels that are reasonably matched with those of perovskites and when they were tested in perovskite solar cells (PSCs) as the electron transporting material (ETM), photoconversion efficiencies ranging from 14.04%-14.95% were obtained, whereas a value of 16.23% was obtained for [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) based devices.

Hetero-bimetallic paddlewheel clusters in coordination polymers formed by a water-induced single-crystal-to-single-crystal transformation.

Herein we report a water-induced single-crystal to single-crystal transformation that involves the formation of hetero-bimetallic paddlewheel clusters in coordination polymers. Through this transformation, which involves the cleavage and formation of different coordination bonds, two different Cu(ii)-Zn(ii) and Cu(ii)-Ni(ii) paddlewheel units exhibiting a 1 : 1 metal ratio were created.

Multiscale Approach to the Study of the Electronic Properties of Two Thiophene Curcuminoid Molecules.

We studied the electronic and conductance properties of two thiophene-curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), in which the only structural difference is the position of the sulfur atoms in the thiophene terminal groups. We used electrochemical techniques as well as UV/Vis absorption studies to obtain the values of the HOMO-LUMO band gap energies, showing that molecule 1 has lower values than 2. Theoretical calculations show the same trend. Self-assembled monolayers (SAMs) of these molecules were studied by using electrochemistry, showing that the interaction with gold reduces drastically the HOMO-LUMO gap in both molecules to almost the same value. Single-molecule conductance measurements show that molecule 2 has two different conductance values, whereas molecule 1 exhibits only one. Based on theoretical calculations, we conclude that the lowest conductance value, similar in both molecules, corresponds to a van der Waals interaction between the thiophene ring and the electrodes. The one order of magnitude higher conductance value for molecule 2 corresponds to a coordinate (dative covalent) interaction between the sulfur atoms and the gold electrodes.

Carving a 1D Co(II)-carboranylcarboxylate system by using organic solvents to create stable trinuclear molecular analogues: complete structural and magnetic studies.

This work presents a straightforward methodology to achieve small linear trinuclear molecules based on the Co(II)-carboranylcarboxylate system obtained by carving a 1D polynuclear analogous system with the use of diethylether. The reaction of the carboranylcarboxylic ligand, 1-CH3-2-CO2H-1,2-closo-C2B10H10 (LH) with different cobalt salts leads to the polynuclear compound [Co2(µ-H2O)(1-CH3-2-CO2-1,2-closo-C2B10H10)4(THF)4], and the polymeric [Co(µ-H2O)(1-CH3-2-CO2-1,2-closo-C2B10H10)2]n(H2O)n. This latter 1D chain has been obtained by an unprecedented synthetic strategy for the isolation of cobalt(ii) compounds. [Co3(µ-H2O)2(1-CH3-2-CO2-1,2-closo-C2B10H10)6(H2O)2(C4H10O)2], is formed by the dissociation of the polymeric structure that forms when a mild coordinating solvent such as diethylether is added. These compounds have been characterized by analytical and spectroscopic techniques. X-ray analysis of and revealed that presents a dinuclear structure whereas is trinuclear; in both cases a six-coordinated Co(II) compound with water molecules bridging each of the two Co(II) centres has been observed. The magnetic properties of and show a weak antiferromagnetic behaviour, respectively, between the Co(II) centres mediated by two carboxylate ligands and a molecule of water.

Sequential Electron Transport and Vibrational Excitations in an Organic Molecule Coupled to Few-Layer Graphene Electrodes.

Graphene electrodes are promising candidates to improve reproducibility and stability in molecular electronics through new electrode-molecule anchoring strategies. Here we report sequential electron transport in few-layer graphene transistors containing individual curcuminoid-based molecules anchored to the electrodes via π-π orbital bonding. We show the coexistence of inelastic co-tunneling excitations with single-electron transport physics due to an intermediate molecule-electrode coupling; we argue that an intermediate electron-phonon coupling is the origin of these vibrational-assisted excitations. These experimental observations are complemented with density functional theory calculations to model electron transport and the interaction between electrons and vibrational modes of the curcuminoid molecule. We find that the calculated vibrational modes of the molecule are in agreement with the experimentally observed excitations.

Multiscale study of mononuclear CoII SMMs based on curcuminoid ligands.

This work introduces a novel family of CoII species having a curcuminoid (CCMoid) ligand, 9Accm, attached, namely [Co(9Accm)2(py)2] (1) and [Co(9Accm)2(2,2'-bpy)] (2), achieved in high yields by the use of a microwave reactor, and exhibiting two different arrangements for the 9Accm ligands, described as "cis"(2) and "trans"(1). The study of the similarities/differences of the magnetic, luminescent and surface behaviors of the two new species, 1 and 2, is the main objective of the present work. The determined single-crystal structures of both compounds are the only CoII-CCMoid structures described in the literature so far. Both compounds exhibit large positive D values, that of 1 (D = +74 cm-1) being three times larger than that of 2 (D = +24 cm-1), and behave as mononuclear Single-Molecule Magnets (SMMs) in the presence of an external magnetic field. Their similar structures but different anisotropy and SMM characteristics provide, for the first time, deep insight on the spin-orbital effects thanks to the use of CASSCF/NEVPT2 calculations implementing such contributions. Further magnetic studies were performed in solution by means of paramagnetic 1H NMR, where both compounds (1 and 2) are stable in CDCl3 and display high symmetry. Paramagnetic NMR appears to be a useful diagnostic tool for the identification of such molecules in solution, where the resonance values found for the methine group (-CH-) of 9Accm vary significantly depending on the cis or trans disposition of the ligands. Fluorescence studies show that both systems display chelation enhancement of quenching (CHEQ) with regard to the free ligand, while 1 and 2 display similar quantum yields. Deposition of 1-2 on HOPG and Si(100) surfaces using spin-coating was studied using AFM; UV photoemission experiments under the same conditions display 2 as the most robust system. The measured occupied density of states of 2 with UV photoemission is in excellent agreement with theoretical DFT calculations.