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Core-shell micro/nanomotors have garnered significant interest in biomedicine owing to their versatile task-performing capabilities. However, their effectiveness for photothermal therapy (PTT) still faces challenges because of their poor tumor accumulation, lower light-to-heat conversion, and due to the limited penetration of near-infrared (NIR) light. In this study, we present a novel core-shell micromotor that combines magnetic and photothermal properties. It is synthesized via the template-assisted electrodeposition of iron (Fe) and reduced graphene oxide (rGO) on a microtubular pore-shaped membrane. The resulting Fe-rGO micromotor consists of a core of oval-shaped zero-valent iron nanoparticles with large magnetization. At the same time, the outer layer has a uniform reduced graphene oxide (rGO) topography. Combined, these Fe-rGO core-shell micromotors respond to magnetic forces and near-infrared (NIR) light (1064 nm), achieving a remarkable photothermal conversion efficiency of 78% at a concentration of 434 µg mL -1 . They can also carry doxorubicin (DOX) and rapidly release it upon NIR irradiation. Additionally, preliminary results regarding the biocompatibility of these micromotors through in vitro tests on a 3D breast cancer model demonstrate low cytotoxicity and strong accumulation. These promising results suggest that such Fe-rGO core-shell micromotors could hold great potential for combined photothermal therapy., Competing Interests: The authors declare no conflicts of interest.

Skin has a preventive role against any damage raised by harmful microorganisms and physical and chemical assaults from the external environment that could affect the body's internal organs. Dermis represents the main section of the skin, and its contribution to skin physiology is critical due to its diverse cellularity, vasculature, and release of molecular mediators involved in the extracellular matrix maintenance and modulation of the immune response. Skin structure and complexity limit the transport of substances, promoting the study of different types of nanoparticles that penetrate the skin layers under different mechanisms intended for skin illness treatments and dermo-cosmetic applications. In this work, we present a detailed morphological description of the dermis in terms of its structures and resident cells. Furthermore, we analyze the role of the dermis in regulating skin homeostasis and its alterations in pathophysiological conditions, highlighting its potential as a therapeutic target. Additionally, we describe the use of nanoparticles for skin illness treatments focused on dermis release and promote the use of metal-organic frameworks (MOFs) as an integrative strategy for skin treatments., Competing Interests: The authors declare no conflict of interest. The authors have no other relevant affiliations or financial involvement with any organization or entity with a financial interest in or financial conflict with the subject matter or materials discussed in the manuscript apart from those disclosed.

Cobalt (Co) is one of the most promising materials in nanotechnology due to its superior magnetic properties. However, due to the high cytotoxicity of cobalt, the activity in biological systems has been little studied. In this work, we report the structural, morphological, and magnetic properties of cobalt nanoparticles stabilized with an organic layer (Co 0 @C-NPs) and its potential antimicrobial activity. The Co 0 @C-NPs were obtained from solvothermal conditions and characterized by X-ray powder diffraction, electronic microscopy, and magnetic measurements. The organic layer was analysed by thermogravimetric analysis, Scanning Electron Microscopy, Energy Dispersive Spectrometer, and Fourier Transform Infrared Spectroscopy. From the TEM image, an organic coating layer is observed around Co 0 where this coating prevents NPs from oxidation allowing it to remain stable until 400 °C. Surface composition studies by SEM/EDS allowed the identification of carbon, oxygen, and cobalt elements present in the organic layer. This result was corroborated later by FITR analysis. Preliminary antibacterial properties were also investigated, which showed that the cobalt nanoparticles are active against Staphylococcus aureus after 1 h of exposure. The superparamagnetic properties and organic coating Co 0 @C-NPs could be biocompatible with biological systems, but more research is needed to apply these nanoparticles in biomedical products., Competing Interests: The authors declare that they have no competing interest., (This journal is © The Royal Society of Chemistry.)

In this work, we report a new octanuclear cluster based on Fe III and the ligand 1 H -imidazole-4,5-dicarboxylic acid, [Et 3 NH] 12 [Fe 8 (IDC) 12 ]·10DMF·13H 2 O ( 1 ), with a metal core containing eight Fe III connected by only one type of organic ligand. A peak at 573 m / z in the mass spectra of the compound suggests the adduct species {[Fe 8 (IDC) 12 ]+8H} 4- . By X-ray photoelectron spectroscopy, the oxidation state of the iron cation was confirmed to be 3+, also identifying the presence of a quaternary nitrogen species, which act as a countercation of the anionic metal core [Fe 8 (IDC) 12 ] 12- . Mössbauer spectra recorded at different temperatures show an isomer shift and quadrupole splitting parameters that confirm the existence of only Fe III -HS in the structure of 1 . X-ray analysis reveals that compound 1 crystallizes in the orthorhombic system space group Ibam , confirming a molecular cluster structure with an almost regular cube as geometry, with the Fe III atoms located at the corners of the cube and connected by μ-1κ 2 N , O :2κ 2 N ', O ‴-IDC 3- bridges. Additionally, the magnetic measurements reveal a weak antiferromagnetic coupling in the Fe 8 III coordination cluster ( J = -3.8 cm -1 ). To the best of our knowledge, 1 is the first member of the family of cubes assembled with 1 H -imidazole-4,5-dicarboxylic acid and Fe III cation, exhibiting high pH stability over a broad pH range, making it an ideal candidate for the design of supramolecular structures and metal-organic frameworks., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Two new aromatic organo-imido polyoxometalates with an electron donor triazole group ([ n -Bu₄N]₂[Mo₆O 18 NC₆H₄N₃C₂H₂]) ( 1 ) and a highly conjugated fluorene ([ n -Bu₄N]₂[Mo₆O 18 NC 13 H₉]) ( 2 ) have been obtained. The electrochemical and spectroscopic properties of several organo-imido systems were studied. These properties were analysed by the theoretical study of the redox potentials and by means of the excitation analysis, in order to understand the effect on the substitution of the organo-imido fragment and the effect of the interaction to a metal centre. Our results show a bathochromic shift related to the charge transfer processes induced by the increase of the conjugated character of the organic fragment. The cathodic shift obtained from the electrochemical studies reflects that the electronic communication and conjugation between the organic and inorganic fragments is the main reason of this phenomenon.

We report the synthesis and structural diversity of Zn(II) metal-organic framework (MOF) with in situ formation of tetrazole ligand 3-ptz [ 3-ptz = 5-(3-pyridyl)tetrazolate] as a function pH. By varying the initial reaction pH, we obtain high-quality crystals of the noncentrosymmetric three-dimensional MOF Zn(3-ptz) 2 , mixed phases involving the zinc-aqua complex [Zn(H 2 O) 4 (3-ptz) 2 ]·4H 2 O, and two-dimensional MOF crystals Zn(OH)(3-ptz) with a tunable microrod morphology, keeping reaction time, temperature, and metal-ligand molar ratio constant. Structures are characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and UV-vis spectroscopy. We discuss the observed structural diversity in terms of the relative abundance of hydroxo-zinc species in solution for different values of pH., Competing Interests: The authors declare no competing financial interest.

The finding of high-spin molecules that could behave as conventional magnets has been one of the main challenges in Molecular Magnetism. Here, the exchange interactions, present in the highest-spin molecule published in the literature, Fe42, have been analysed using theoretical methods based on Density Functional Theory. The system with a total spin value S = 45 is formed by 42 iron centres containing 18 high-spin Fe(III) ferromagnetically coupled and 24 diamagnetic low-spin Fe(II) ions. The bridging ligands between the two paramagnetic centres are two cyanide ligands coordinated to the diamagnetic Fe(II) cations. Calculations were performed using either small Fe4 or Fe3 models or the whole Fe42 complex, showing the presence of two different ferromagnetic couplings between the paramagnetic Fe(III) centres. Finally, Quantum Monte Carlo simulations for the whole system were carried out in order to compare the experimental and simulated magnetic susceptibility curves from the calculated exchange coupling constants with the experimental one. This comparison allows for the evaluation of the accuracy of different exchange-correlation functionals to reproduce such magnetic properties.

In the structure of the title compound, {[Cu2(C10H2O8)(H2O)6]·4H2O}n, the benzene-1,2,4,5-tetracarboxylate ligand, (btec)(4-), is located on a crystallographic inversion centre in a μ4-coordination mode. The coordination environment of each pentacoordinated Cu(II) centre is square pyramidal (SBP), formed by three water molecules and two carboxylate O atoms from two different (btec)(4-) ligands. The completely deprotonated (btec)(4-) ligand coordinates in a monodentate mode to four Cu(II) atoms. The alternation of (btec)(4-) ligands and SBP Cu(II) centres leads to the formation of a planar two-dimensional covalent network of parallelograms, parallel to the ab plane. Hydrogen bonds between a basal water molecule and an apical one from an adjacent [Cu(btec)0.5(H2O)3] unit exist in the intralayer space. Hydrogen bonds are also present between the two-dimensional network and the water molecules filling the channels in the structure.

A theoretical study of the magnetic properties, using density functional theory, of a family of trinuclear μ3-OH copper(II) complexes reported in the literature is presented. The reported X-ray crystal structures of [Cu3(μ3-OH)(aat)3(H2O)3](NO3)2 · H2O (HUKDUM), where aat: 3-acetylamine-1,2,4-triazole; [Cu3(μ3-OH)(aaat)3(H2SO4)(HSO4)(H2O)] (HUKDOG), where aaat: 3-acetylamine-5-amine-1,2,4-triazole; [Cu3(μ3-OH)(PhPyCNO)3(tchlphac)2] (HOHQUR), where PhPyCNO: phenyl 2-pyridyl-ketoxime and tchlphac: acid 2,4,5-trichlorophenoxyacetic; [Cu3(μ3-OH)(PhPyCNO)3(NO3)2(CH3OH)] (ILEGEM); [Cu3(μ3-OH)(pz)3(Hpz)3(ClO4)2] (QOPJIP), where Hpz = pyrazole; [Cu3(μ3-OH)(pz)3(Hpz)(Me3CCOO)2] ∙ 2Me3CCOOH (DEFSEN) and [Cu3(μ3-OH)(8-amino-4-methyl-5-azaoct-3-en-2-one)3][CuI3] (RITXUO), were used in the calculations. The magnetic exchange constants were calculated using the broken-symmetry approach. The calculated J values are for HUKDUM J1 = -68.6 cm(-1), J2 = -69.9 cm(-1), J3 = -70.4 cm(-1); for HUKDOG, J1 = -73.5 cm(-1), J2 = -58.9 cm(-1), J3 = -62.1 cm(-1); for HOHQUR J1 = -128.3 cm(-1), J2 = -134.1 cm(-1), J3 = -120.4 cm(-1); for ILEGEM J1 = -151.6 cm(-1), J2 = -173.9 cm(-1), J3 = -186.9 cm(-1); for QOPJIP J1 = -118.3 cm(-1), J2 = -106.0 cm(-1), J3 = -120.6 cm(-1); for DEFSEN J1 = -74.9 cm(-1), J2 = -64.0 cm(-1), J3 = -57.7 cm(-1) and for RITXUO J1 = -10.9 cm(-1), J2 = +14.3 cm(-1), J3 = -35.4 cm(-1). The Kahn-Briat model was used to correlate the calculated magnetic properties with the overlap of the magnetic orbitals. Spin density surfaces show that the delocalization mechanism is predominant in all the studied compounds.

The title complex, [NaNi(C5H7O2)3]n, contains an anionic tris(acetylacetonato)nickelate(II) unit, [Ni(acac)3](-) (acac is acetylacetonate), with a highly regular octahedral coordination geometry. The Ni(II) cation lies on a Wyckoff a site, resulting in D3 symmetry of the anion. Charge balance is provided by sodium cations, which occupy Wyckoff type b sites. Each sodium cation is surrounded by two [Ni(acac)3](-) anions, each of which is connected to the alkali metal through three O atoms, in a fac configuration. This arrangement leads to the formation of linear [Na{Ni(acac)3}]n chains along the c axis. The Ni···Na distance is 2.9211 (10) Å. The title complex is one of the few examples of heterometallic systems based on alkali and transition metal cations bridged by acetylacetonate ligands.

The structure of the title compound, poly[(dihydrogenphosphato-κO)(μ(3)-hydrogenphosphato)di-μ-oxido-(1,10-phenanthroline)copper(II)vanadium(V)], [CuV(HPO(4))(H(2)PO(4))O(2)(C(12)H(8)N(2))](n), is defined by [(phen)Cu-μ-(κ(2)O:O'-VP(2)O(10)H(3))(2)-Cu(phen)] units (phen is 1,10-phenanthroline), which are connected to neighbouring units through vanadyl bridges. Neighbouring chains have no covalent bonds between them, although they interdigitate through the phen groups via π-π interactions.

The structure of the title compound, (C(10)H(10)N(3))(2)[ZnCl(4)], is composed of C(10)H(9)N(3)H(+) (DPAH(+)) cations and [ZnCl(4)](2-) anions. The two pyridyl rings of DPAH(+) are approximately coplanar, with a dihedral angle of 7.2 (2)° between their corresponding least-squares planes. The proton is disordered in a one-to-one ratio over the two chemically equivalent pyridyl N atoms. An intra-molecular hydrogen bond is formed between the pyridinium H atom and the pyridyl N atom of the other pyridyl ring. The Zn atom lies on a twofold rotation axis. There are also some weak N-H⋯Cl hydrogen bonds. These inter-actions lead to the formation of an alternating zigzag chain in the solid state. The results clearly show that reducing agents normally used in hydro-thermal syntheses, such as metallic zinc employed here, are also active in terms of coordination chemistry.

The hydrazine oxidation by iron(II) phthalocyanine (Fe(II)Pc) has been studied using an energy profile framework through quantum chemistry theoretical models calculated in the gas phase at the density functional theory B3LYP/LACVP(d) level. We applied two models of charge-transfer mechanisms previously reported (J. Phys. Chem. A 2005, 109, 1196) for the hydrazine oxidation mediated by Co(II)Pc. Model 1 consists of an alternated loss of one electron and one proton, involving anionic and neutral species. Model 2 considers an alternated loss of two electrons and two protons and includes anionic, neutral, and cationic species. Both applied models describe how the charge-transfer process occurs. In contrast with the obtained results for Co(II)Pc, we found that the hydrazine oxidation mediated by Fe(II)Pc is a fully through-bond charge-transfer mechanism. On the other hand, the use of different charge-transfer descriptors (spin density, electronic population, condensed Fukui function) showed a major contribution of the iron atom in comparison with the cobalt atom in the above-mentioned process. These results could explain the higher catalytic activity observed experimentally for Fe(II)Pc in comparison with Co(II)Pc. The applied theoretical models are a good starting point to rationalize the charge-transfer process of hydrazine oxidation mediated by Fe(II)Pc.

The Ru atom in the title compound, [RuCl(CH(3)CN){P(C(6)H(5))(3)}(2){C(6)H(4)(NH)(2)}]PF(6).0.25H(2)O, has a six-coordinate octahedral geometry, with a trans arrangement of the triphenylphosphine groups. The asymmetric unit contains two complex molecules and a partially occupied water site. Principal dimensions include Ru-N 1.958 (4)-2.044 (5), Ru-P 2.3897 (16)-2.4092 (15), and Ru-Cl 2.4280 (15) and 2.4295 (16) A

The Ru atom in the title compound, [RuCl(2){P(C(6)H(5))(3)}(2){C(6)H(4)(NH)(2)}].1.33CH(3)OH.0.33CH(2)Cl(2), shows a six-coordinate octahedral geometry, with a trans arrangement of the triphenylphosphine groups. One and a half molecules of complex, two molecules of methanol and a half molecule of dichloromethane form the asymmetric unit, with crystallographic twofold rotation symmetry for the complex molecule in a special position.