An Insight into nd10 Metal Cyanide-based Coordination Polymers Through ab-initio Calculations: Electronic Properties and Optical Response.

Semiconductors are essential for modern life since they are the basis of many current technologies that are related to better living standards. Some of them, characterized by the periodic assembling of metal cyanides with filled d-shell (nd10 ) constitute an interesting series of cyanide-based coordination polymers with physical properties such like anomalous anisotropic thermal expansion and quantum confinement effects related to the polymer's width that can be exploited for technological applications. Herein, the electronic structure of nd10 metal cyanide-based systems were studied both experimentally and through Density Functional Theory. The band gap found for one-dimensional (1D) -M-C≡N- (M=Cu, Ag, Au) and tetrahedral M-(C≡N)2 (M=Zn, Cd, Hg) systems can be attributed to Laporte-allowed π → ${\to }$ π* (Metal to Ligand Charge Transfer mechanism) combined with metal center (d → ${\to }$ s,p) electronic transitions. Aurophilic bonding was found on the AuCN structure, and a new forbidden electronic transition associated to its band gap is reported. Computed effective and reduced masses from carriers revealed that carrier mobility and quantum confinement effects are greater in 1D systems.

Rodlike Particles of Polydopamine-CdTe Quantum Dots: An Actuator As a Photothermal Agent and Reactive Oxygen Species-Generating Nanoplatform for Cancer Therapy.

Herein, novel rodlike CdTe@MPA-PDA particles based on polydopamine (PDA) loaded with CdTe quantum dots (QDs) capped with mercaptopropionic acid (CdTe@MPA QDs) with atypical chemical features are evaluated as a potential actuator for photothermal therapy and oxidative stress induction. Under mild conditions established for the safe and efficient use of lasers, temperature increases of 10.2 and 7.8 °C, photothermal conversion efficiencies of 37.7 and 26.2%, and specific absorption rates of 99 and 69 W/g were obtained for CdTe@MPA-PDA and traditional PDA particles in water, respectively. The particles were set to interact with the human breast adenocarcinoma cell line MDA-MB-231. A significant cellular uptake with the majority of particles colocalized into the lysosomes was obtained at a concentration of 100 µg/mL after 24 h. Additionally, CdTe@MPA-PDA and CdTe@MPA QDs showed significantly different internalization levels and loading kinetics profiles. For the first time, the thermal lens technique was used to demonstrate the stability of particle-like CdTe@MPA-PDA after heating at pH 7 and their migration within the heating region due to the thermodiffusion effect. However, under acidic pH-type lysosomes, a performance decrease in heating was observed, and the chemical feature of the particles was damaged as well. Besides, the internalized rodlike CdTe@MPA-PDA notably enhanced the induction of oxidative stress compared with PDA alone and CdTe@MPA QDs in MDA-MB-231 cells initiating apoptosis. Combining these effects suggests that after meticulous optimizations of the conditions, the CdTe@MPA-PDA particles could be used as a photothermal agent under mild conditions and short incubation time, allowing cytoplasmatic subcellular localization. On the other hand, the same particles act as cell killers by triggering reactive oxygen species after a longer incubation time and lysosomal subcellular localization due to the pH effect on the chemical morphology features of the CdTe@MPA-PDA particles.

Different behavior of two iso-structural zeolitic imidazolate frameworks in ethane-ethylene separation: Study of H2 -CO2 and CH4 -CO2 separation capacity.

The separation of ethane-ethylene mixtures was evaluated using two zeolitic imidazolate frameworks, which are only different from the assemble metal, as stationary phase from inverse gas chromatography data. The chromatographic profiles exhibited peaks adequately resolved. Separation is attributed to the pore sizes of the adsorbents that discern between ethane and ethylene molecule shapes and closed kinetic diameters. The adsorption heats were estimated for each probe molecule from the slopes of the straight lines at four temperatures. The evaluated materials are iso-structural compounds with the unique difference of assembling metal (cobalt and zinc). Cobalt material showed atypical adsorption of ethane over ethylene, which was observed taking into account the retarded elution of the paraffin. Therefore, the anomalous behavior could be ascribed to the presence of cobalt(II). Structural characterization of both materials was performed by X-ray powder diffraction, X-ray photoelectronic spectroscopy, and thermogravimetry, while morphological characterization was performed by scanning electron microscopy. H2 -CO2 and CH4 -CO2 mixtures separation were also evaluated by inverse gas chromatography. Both materials were able to separate these two mixtures. CO2 was the highest retained probe molecule due to the presence of quadrupole moment.

On the CN-K coordination modes in Kn[M6-n(CN)6]·xH2O: first evidence of CN-K electron-deficient bonding.

Based on the determination of single crystal XRD structures of potassium hexacyanidometallates and on IR, and Raman data, here we propose for the first time the occurrence of an electron-deficient bonding between the N end of the CN- ligand and the K+ metal center. The crystal structures of Kn[M6-n(CN)6]·xH2O (M = Fe(ii), Ru(ii), Os(ii), Co(iii), Rh(iii), Ir(iii), Pt(iv)) reveal the presence of four types of CN-K interactions: (i) a linear CN-K bond, (ii) the N ends in a bipodal coordination involving two K atoms, (iii) the N ends in a tripodal coordination mode involving three K atoms and (iv) the N ends and the K atoms with the largest K-N distances within the subseries that can be attributed to the electrostatic interactions. The bi- and tripodal coordination modes between the N end of the CN- ligand and K+ ions are atypical and their nature is discussed in this contribution. The CN- ligand N end can behave as a two-electron donor that participates in a three-center two-electron bonding (i.e. Class II µ-L 3c-2e) for a N-bipodal coordination mode or as a two-electron donor that participates in a four-center two-electron bonding (4c-2e) for an N-tripodal coordination mode. Such a possibility is closely related to the π-back donation ability of the CN- ligand, which results in a charge density accumulation on the N end, which could be partially donated to the K atom through an σ-mechanism. For the divalent metals (Fe, Ru, Os), the solids crystallize with a monoclinic unit cell in the C2/c space group, while for the trivalent ones (Co, Rh, Ir), the crystal structure corresponds to an orthorhombic unit cell in the Pbcn space group. Potassium hexacyanidoplatinate(iv) crystallizes with a trigonal unit cell, in the P3[combining macron]1m space group, where each N end is always found coordinating two K atoms. The finding of these novel coordination modes of the CN- ligands, relying on an electron-deficient bonding behavior, paves the way for the design of functional materials based on hexacyanidometallates. The experimental results and the proposed electron-deficient bonding model herein discussed were appropriately supported by the computational calculations.

Understanding the interaction between heteroatom-doped carbon matrix and Sb2S3 for efficient sodium-ion battery anodes.

Increasing the electrochemical performance of electrode materials in sodium ion batteries (NIBs) remains a major challenge. Here, a combined experimental and theoretical investigation on the modification induced by Sb2S3 embedded in a heteroatom-doped 3D carbon matrix (CM) for efficient anodes in NIBs is presented. The structural and chemical characterization demonstrates the successful doping of 3D CM with S and Sb atoms. When evaluated as anode materials for NIBs, the heteroatom-doped nanocomposites delivered a better cycling stability and superior rate capability than those of undoped Sb2S3/CM anodes. First principle calculations were used at the Density Functional Theory level to systematically study the Sb2S3/CM and Sb2S3/heteroatom doped-CM composites, as NIBs anodes. Doping the carbon substrate by heteroatoms improved the adsorption of Sb2S3 on the matrix and allowed for ionic/covalent attraction with the Sb2S3 nanoparticle, respectively. Such results could be used to model the stabilty of the composite architectures observed in the experiment, for superior cycling stability.

Synthesis, Characterization and Magnetic Hyperthermia of Monodispersed Cobalt Ferrite Nanoparticles for Cancer Therapeutics.

Magnetic nanoparticles such as cobalt ferrite are investigated under clinical hyperthermia conditions for the treatment of cancer. Cobalt ferrite nanoparticles (CFNPs) synthesized by the thermal decomposition method, using nonionic surfactant Triton-X100, possess hydrophilic polyethylene oxide chains acting as reducing agents for the cobalt and iron precursors. The monodispersed nanoparticles were of 10 nm size, as confirmed by high-resolution transmission electron microscopy (HR-TEM). The X-ray diffraction patterns of CFNPs prove the existence of cubic spinel cobalt ferrites. Cs-corrected scanning transmission electron microscopy-high-angle annular dark-field imaging (STEM-HAADF) of CFNPs confirmed their multi-twinned crystallinity due to the presence of atomic columns and defects in the nanostructure. Magnetic measurements proved that the CFNPs possess reduced remnant magnetization (MR/MS) (0.86), which justifies cubic anisotropy in the system. Microwave-based hyperthermia studies performed at 2.45 GHz under clinical conditions in physiological saline increased the temperature of the CFNP samples due to the transformation of radiation energy to heat. The specific absorption rate of CFNPs in physiological saline was 68.28 W/g. Furthermore, when triple-negative breast cancer cells (TNBC) in the presence of increasing CFNP concentration (5 mg/mL to 40 mg/mL) were exposed to microwaves, the cell cytotoxicity was enhanced compared to CFNPs alone.

CuICuII and AgIp-isocyanobenzoates as novel 1D semiconducting coordination oligomers.

Two novel semiconducting coordination oligomers with 1D chain structures, namely [H0.07 CuI0.65CuII0.14(µ-p-CNC6H4CO2)·0.9H2O]n and [Ag(µ-p-CNC6H4CO2)]n, were obtained and characterized by XRD powder patterns, and XPS, EPR, UV-vis-NIR, IR and Raman spectroscopy. According to XRD analysis, CuICuII-ICNBA is an amorphous solid, while AgI-ICNBA crystalizes with a monoclinic unit cell in the C2/c space group (Z = 4). The composition and further information of CuICuII-ICNBA were obtained from the spectroscopic data. In correspondence with the quantification of terminal groups from high-resolution XPS spectra, CuICuII-ICNBA and AgI-ICNBA are composed of an average of 9 and 7 monomer units, respectively, resulting in 1D-oligomers. The spectroscopic evidence indicates that CuICuII-ICNBA is better described as a non-stoichiometric coordination oligomer (where non-integer ratios of metal ions can be accommodated), while AgI-ICNBA is stoichiometric. In both materials, each metal center is linked by two µ-η1:η1-p-isocyanobenzoate ligands forming microfibers of around 120 nm (CuICuII-material) and 310 nm (AgI-material) in average diameters with optical band gaps of 2.60 eV and 2.17 eV, respectively.

From 3D to 2D Transition Metal Nitroprussides by Selective Rupture of Axial Bonds.

1-methyl-2-pyrrolidone (1m2p) is a solvent with proven abilities for 2D-solid exfoliation due to its extremely high surface tension. In principle, such a feature could be used also to induce the selective breaking of certain bonds in solids to obtain new materials. Such a hypothesis is demonstrated in this study for transition metal nitroprussides, where 2D solids are obtained from 3D frameworks by selective rupture of axial bonds. This contribution discusses the mechanism involved in such molecular manufacture. The crystal structure for the formed 2D solids was solved and refined from XRD powder patterns recorded using synchrotron radiation. Mössbauer, IR and Raman spectra provided fine details on the electronic structure of the resulting new series of layered materials. The experimental information was complemented with calculations for the molecule configuration in its non-activated and activated forms. In the obtained 2D solids, neighboring layers of about 1 nm of thickness remain separated by activated 1m2p molecules. The interaction between neighboring layers is of a physical nature, without the presence of a chemical bond between them, as corresponds to a 2D material.

Electrochemical immunoassay for the detection of IgM antibodies using polydopamine particles loaded with PbS quantum dots as labels.

Here, we report for the first time, an electrochemical immunoassay to detect IgM antibodies using lead sulfide quantum dots (PbS QDs) as electrochemical labels. In this sense, dendritic-like polydopamine particles loaded with PbS QDs were synthesized by the self-polymerization of dopamine in basic media in the presence of QDs (PbS@PDA) and further tagged with anti-IgM antibodies, dengue specific antigens, and streptavidin moieties. The analytical features of the sandwich immunoassay on ELISA microplate were carried out with the PbS@PDA-labeled anti-IgM as secondary antibody. The system was interrogated by acid dissolution of PbS@PDA, followed by differential pulse anodic stripping voltammetry in the presence of Bi(III) ions using carbon screen-printed electrodes. The results indicate that the voltammetric current increased with the increasing of the concentration of target IgM within a range of 0-0.5 mg mL-1. The limit of detection of this electrochemical immunoassay was evaluated to 130 ng. The measures of satisfactory recoveries from 88.5% to 114% of spiked samples indicate that such a method has good specificity and is applicable to the quantification of IgM antibodies in complex biological samples. No significant differences at the 0.05 significance level were encountered in the analysis of IgM samples between the electrochemical immunoassay and a Bradford assay.

The intrinsic antimicrobial activity of citric acid-coated manganese ferrite nanoparticles is enhanced after conjugation with the antifungal peptide Cm-p5.

Diseases caused by bacterial and fungal pathogens are among the major health problems in the world. Newer antimicrobial therapies based on novel molecules urgently need to be developed, and this includes the antimicrobial peptides. In spite of the potential of antimicrobial peptides, very few of them were able to be successfully developed into therapeutics. The major problems they present are molecule stability, toxicity in host cells, and production costs. A novel strategy to overcome these obstacles is conjugation to nanomaterial preparations. The antimicrobial activity of different types of nanoparticles has been previously demonstrated. Specifically, magnetic nanoparticles have been widely studied in biomedicine due to their physicochemical properties. The citric acid-modified manganese ferrite nanoparticles used in this study were characterized by high-resolution transmission electron microscopy, which confirmed the formation of nanocrystals of approximately 5 nm diameter. These nanoparticles were able to inhibit Candida albicans growth in vitro. The minimal inhibitory concentration was 250 µg/mL. However, the nanoparticles were not capable of inhibiting Gram-negative bacteria (Escherichia coli) or Gram-positive bacteria (Staphylococcus aureus). Finally, an antifungal peptide (Cm-p5) from the sea animal Cenchritis muricatus (Gastropoda: Littorinidae) was conjugated to the modified manganese ferrite nanoparticles. The antifungal activity of the conjugated nanoparticles was higher than their bulk counterparts, showing a minimal inhibitory concentration of 100 µg/mL. This conjugate proved to be nontoxic to a macrophage cell line at concentrations that showed antimicrobial activity.

Dehydration Process of Hofmann-Type Layered Solids.

In the present work the dehydration process of layered solids with formula unit M(H2O)2[Ni(CN)4]·nH2O, M = Ni, Co, Mn; n = 1, 2, 4 is studied using modulated thermogravimetry. The results show that water molecules need to overcome an energetic barrier (activation energy between 63 and 500 kJ/mol) in order to diffuse through the interlayer region. The related kinetic parameters show a dependence on the water partial pressure. On the other hand, X-ray diffraction results provide evidence that the dehydration process is accompanied by framework collapse, limiting the structural reversibility, except for heating below 80 °C where the ordered structure remains. Removal of water molecules from the interlayer region disrupts the long-range structural order of the solid.

Colloidal photonic crystal pigments with low angle dependence.

Poly(methyl methacrylate) (PMMA)-based colloidal photonic crystals have an incomplete photonic band gap (PBG) and typically appear iridescent in the visible range. As powders, synthetic PMMA opals are white, but when infiltrated with carbon black nanoparticles, they exhibit a well-defined color that shows little dependence on the viewing angle. The quantity of black pigment determines the lightness of the color by controlling scattering. The combined effects of internal order within each particle and random orientation among the particles in the powder are responsible for this behavior. These pigments were employed as paints, using a mixture of polyvinyl acetate as a binder and deionized water as the solvent, and were applied to wood and paper surfaces for color analysis.

Instantaneous synthesis of stable zerovalent metal nanoparticles under standard reaction conditions.

In this report is discussed a novel, easy, and general synthesis method to prepare zerovalent iron (ZVI) and copper (ZV Cu) nanoparticles (NPs), from colloid dispersions in an environmental friendly organic solvent, ethylene glycol (EG). Conventional metallic salts are used as nanoparticle precursors; sodium borohydride (NaBH4) is the reducing agent, and triethylamine (TEA) is used as the nanoparticle stabilizer. The chemical changes take place instantaneously under normal reaction conditions. Small iron (alpha-Fe0 phase) and copper (fcc phase) NPs with average diameters of 10.2 +/- 3.3 and 9.5 +/- 2.5 nm, respectively, were obtained. In both cases, the experimental evidence reveals the absence of any metal oxide shell coating the particle surfaces, and their powders remain stable, under aerobic conditions at least for 3 weeks. ZVI NPs were characterized by X-RD, Mössbauer, and Raman spectroscopies and by EELS coupled to HR-TEM. Otherwise, copper NPs were characterized by X-RD, Z-contrast, and HR-TEM. This synthesis pathway is particularly suitable for large-scale and high-quality zerovalent metallic nanoparticle (ZV M NP) production due to its simple process and low cost.

1-(2-Furo-yl)-3-(1-naphth-yl)thio-urea.

In the title compound, C(16)H(12)N(2)O(2)S, the carbonyl-thio-urea group forms dihedral angles of 75.4 (1) and 13.1 (2)°, respectively, with the naphthalene ring system and furan ring. The mol-ecule adopts a trans-cis configuration with respect to the positions of the furoyl and naphthyl groups relative to the S atom across the thio-urea C-N bonds. This geometry is stabilized by an N-H⋯·O intra-molecular hydrogen bond. In the crystal structure, mol-ecules are linked by N-H⋯S hydrogen bonds, forming centrosymmetric dimers which are inter-linked through C-H⋯π inter-actions.

Role of the anion in the alkali halides interaction with D-ribose: a 1H and 13C NMR spectroscopy study.

The alkali halides interaction with d-ribose in D2O solutions was studied by 1H and 13C NMR spectroscopy. The observed changes in the NMR spectra are interpreted according to a model in which the hydroxyls rich region, from C1 to C4, interacts with the cation while the CH2 group at C5 on the opposite side of the sugar interacts with the anion. It seems, during the salt-sugar interaction, cation and anion preserve, at least partially, their ion-pair character. The cooperative interaction of the sugar hydroxyl groups with the cation leads to a polarization within the sugar molecule, which favors the anion interaction with its most positive region. A correlation between the chemical shift of C5 atom and the atomic number of the anion was observed, which is discussed as a neighboring paramagnetic effect; as higher is the halogen atom more pronounced is the resulting shift of the C5 signal. The anion effect is weak but also observed in the 13C signals of those carbon atoms bound to hydroxyl groups where the interaction is predominant with the cation. The 1H signal of the anomeric protons and the relative population of isomers in the alkali halide solution also show an anion dependence.

Physicochemical changes in the hull of corn grains during their alkaline cooking.

The alkaline cooking of corn in a solution of Ca(OH)2 to produce corn-based foods is oriented to make corn proteins available, to incorporate Ca to the cooked grains, and also to remove the corn hull. This process (nixtamalization) is known in Mexico and Guatemala from prehispanic times; however, the effect of the alkaline cooking on the corn hull remains poorly documented. In this work, the physicochemical changes that take place in the corn hull during its cooking in a saturated solution of Ca(OH)2 were studied using infrared, X-ray diffraction, 13C cross-polarization/magic-angle spinning (CP/MAS) NMR, confocal imaging microscopy, differential scanning calorimetry, and thermogravimetry techniques. The main effect of this treatment on the hull is the removal of hemicelluloses and lignin, increasing the hull permeability and, as a consequence, facilitating the entry of the alkaline solution into the corn kernel. No significant changes were observed in the cellulose fiber network, which remains as native cellulose I, with a crystalline index, according to 13C CP/MAS NMR spectra, of 0.60. The alkaline treatment does not allow the cellulose fibers to swell and their regeneration in the form of cellulose(II). It seems any attempt to make use of the Ca binding capacity of the hull to increase the Ca availability in nixtamalized corn-based foods requires a separated treatment for the hull and kernel. On alkaline cooking, the hull hemicellulose fraction dissolves, losing its ability to bind Ca as a way to incorporate this element into foods elaborated from nixtamalized corn.