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Mayara Klimuk Uchiyama,1 Sergio Hiroshi Toma,1 Stephen Fernandes de Paula Rodrigues,2 Ana Lucia Borges Shimada,2 Rodrigo Azevedo Loiola,2 Hernán Joel Cervantes Rodríguez,3 Pedro Vitoriano Oliveira,4 Maciel Santos Luz,4 Said Rahnamaye Rabbani,3 Henrique Eisi Toma,1 Sandra Helena Poliselli Farsky,2 Koiti Araki11Laboratory of Supramolecular Chemistry and Nanotechnology, Department of Fundamental Chemistry, Institute of Chemistry, 2Laboratory of Experimental Toxicology, Department of Clinical and Toxicological Analysis, Faculty of Pharmaceutical Sciences, 3Magnetic Resonance Laboratory, Department of General Physics, Institute of Physics, 4Analysis and Research Group in Spectrometry, Department of Fundamental Chemistry, Institute of Chemistry, University of Sao Paulo, Sao Paulo, SP, BrazilAbstract: Fully dispersible, cationic ultrasmall (7 nm diameter) superparamagnetic iron oxide nanoparticles, exhibiting high relaxivity (178 mM-1s-1 in 0.47 T) and no acute or subchronic toxicity in Wistar rats, were studied and their suitability as contrast agents for magnetic resonance imaging and material for development of new diagnostic and treatment tools demonstrated. After intravenous injection (10 mg/kg body weight), they circulated throughout the vascular system causing no microhemorrhage or thrombus, neither inflammatory processes at the mesentery vascular bed and hepatic sinusoids (leukocyte rolling, adhesion, or migration as evaluated by intravital microscopy), but having been spontaneously concentrated in the liver, spleen, and kidneys, they caused strong negative contrast. The nanoparticles are cleared from kidneys and bladder in few days, whereas the complete elimination from liver and spleen occurred only after 4 weeks. Ex vivo studies demonstrated that cationic ultrasmall superparamagnetic iron oxide nanoparticles caused no effects on hepatic and renal enzymes dosage as well as on leukocyte count. In addition, they were readily concentrated in rat thigh by a magnet showing its potential as magnetically targeted carriers of therapeutic and diagnostic agents. Summarizing, cationic ultrasmall superparamagnetic iron oxide nanoparticles are nontoxic and efficient magnetic resonance imaging contrast agents useful as platform for the development of new materials for application in theranostics.Keywords: cationic USPIOs, MRI, contrast agent, magnetic targeting, in vivo toxicity, intravital microscopy

Inexistent colors have been the inspiring theme of investigation by Israel Pedrosa, a Brazilian artist, who has devoted his life to creative painting, exploiting the chemical and physical effects associated with light, especially those generated in the light refraction domain. In this article, by focusing on the electronic spectra of phthalocyanines and gold nanoparticles, we discuss how such effects can influence the spectroscopic measurements, leading to inexistent bands and transitions.

At the onset of the nanotechnology age, molecular designing of materials and single molecule studies are opening wide possibilities of using molecular systems in electronic and photonic devices, as well as in technological applications based on molecular switching or molecular recognition. In this sense, inorganic chemists are privileged by the possibility of using the basic strategies of coordination chemistry to build up functional supramolecular materials, conveying the remarkable chemical properties of the metal centers and the characteristics of the ancillary ligands. Coordination chemistry also provides effective self-assembly strategies based on specific metal-ligand affinity and stereochemistry. Several molecular based materials, derived from inorganic and metal-organic compounds are focused on this article, with emphasis on new supramolecular porphyrins and porphyrazines, metal-clusters and metal-polyimine complexes. Such systems are also discussed in terms of their applications in catalysis, sensors and molecular devices.

The isomorphic series of double sulfites with empirical formula Cu2SO3.MSO3.2H 2O (where M is Cu, Fe, Mn, or Cd) have been prepared from the Cu(II) replacement by transition metal ions such as Mn(II), Fe(II) and Cd(II) ions in Chevreul's salt, Cu2SO3.CuSO3.2H 2O. As a consequence, the isomorphic species present distinct colors. Molecular modeling calculations were carried out for the dimeric [CuI2(SO3) 2(SO3)2]6- center. The electronic spectra of the Chevreul's salt consist of a charge-transfer band around 425 nm associated with the [CuI2(SO3) 2(SO3)2]6- chromophore and two ligand field transitions at 785 and 1000 nm involving the Jahn-Teller splitting of the Cu(II) levels. An additional intervalence-transfer band, responsible for its characteristic red color, can be found at 500 nm. The replacement of the Cu(II) ions for Fe(II), Mn(II) and Cd(II) does not eliminate the absorption band at 425 nm, supporting its assignment as a charge-transfer transition centered on the Cu(I) sites; while the original band at 500 nm disappears, in agreement with its intervalence transfer nature.

Iron and ruthenium complexes of the type [M-LH]n (where M = RuII,III(NH3)5(2+,3+), RuII,III(edta)2-,- [edta = ethylenedinitrilotetraacetate], or FeII,III(CN)5(3-,2-) and LH = benzotriazole or benzimidazole) were prepared and characterized in aqueous solutions by means of electrochemical and spectroelectrochemical methods. Special emphasis was given to the pH-dependent redox processes, exhibited by all the investigated complexes. From their related Pourbaix diagrams, which displayed a typically Nernstian behavior, the pKa and formal reduction potential values were extracted. In addition, these E1/2 versus pH curves were also used to illustrate the partitioning relationship concerning the redox and acid-base species, and their interconversion equilibria. The active area in which the dependence of the M III/M II couple on the pH takes place, as delimited by pKaIII and pKaII, was taken into account in order to evaluate the usefulness of such simple complexes as models for proton-coupled electron transfer (PCET). The results were interpreted in terms of the acceptor/donor electronic character of the ligands and sigma,pi-metal-ligand interactions in both redox states of the metal ion.

A review with 94 references focusing on mu3-oxo-triruthenium carboxylate clusters is presented. The electronic, magnetic, electrochemical, and catalytic properties of these compounds are discussed. Main synthetic routes and structural characteristics, including their use as building blocks in supramolecular systems are described.

Microplastics are commonly referred to as tiny plastic fragments polluting our environment, although their nanometric forms have also been found in our drinking water supplies and many living systems. Their removal is relevant for preserving our health and sustainability and is being pursued according to many different strategies, including filtration through selective porous materials or agglomeration using flocculant agents. An alternative nanotechnological approach described in this paper deals with the capture and degradation of micro and nanoplastics by enzyme-immobilized magnetic nanoparticles. Magnetic nanoparticles (Fe 3 O 4 ) were functionalized with polydopamine (PDA) and Lipase enzyme straightforwardly to generate agents capable of removing and degrading µPET from an aqueous solution. In addition to synthesizing and characterizing the Fe3O4@PDA-Lipase nanoparticles and performing the µPET degradation, the novelty encompassed in this work is the successful use of confocal Raman microscopy to monitor the process, in real-time, through in situ hyperspectral images., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Henrique Eisi Toma reports financial support was provided by University of Sao Paulo, Institute of Chemistry. Henrique Eisi Toma reports a relationship with Instito de Quimica Universidade de São Paulo that includes: employment. Henrique Eisi Toma has patent pending to none. Nothing to declare If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Nanoporous gold electrodes are of great interest in electroanalytical chemistry, because of their unusual activity and large surface area. The electrochemical activity can be further improved by coating with molecular catalysts such as the tetraruthenated cobalt-tetrapyridylporphyrazines investigated in this work. The plasmonic enhancement of the scattered light at the nanoholes and borders modifies the electrode's optical characteristics, improving the transmission through the surface-enhanced Raman scattering (SERS) effect. When monitored by hyperspectral dark-field and confocal Raman microscopy, this effect allows probing of the porphyrazine species at the plasmonic nanholes, improving the understanding of the chemically modified gold electrodes., (© 2024 Royal Microscopical Society.)

Jacobsite is a relatively rare mineral of composition MnFe2O4, found in Urandi (Bahia State) in Brazil. It is also a common species in the deep-sea manganese nodules, attracting the interest of many mineral-extracting companies. Because of its spinel constitution similar to magnetite, Jacobsite is commonly called a manganese-ferrite. However, the manganese/iron content may vary substantially according to its origin, demanding specific studies in each case. The Jacobsite mineral inspired our laboratory synthesis of the analogous manganese ferrite nanoparticles. The direct synthesis by the coprecipitation method has not been successful; however, it can be carried in the presence of citrate ions, yielding strongly magnetic nanoparticles, with a maximum magnetization of 45.6 emu.g1. Although they were structurally identical to Jacobsite, the mineral from Bahia exhibited a rather weak magnetism, because it involves a ferrimagnetic coupling. For this reason, the synthetic method seems to provide a better way of obtaining strongly magnetic manganese ferrites. These magnetic nanoparticles have been investigated in detail, including their interaction with diatoms, providing interesting magnetic bio-silicate carriers in drug delivery.

A supramolecular complex μ- meso -tetra(4-pyridyl) porphyrinate nickel(ii)tetrakis[bis(bipyridine)(chloro)ruthenium(ii)] ([NiTPyP{Ru(bipy) 2 Cl} 4 ] 4+ ) was intercalated into the interlayer space of natural smectite clay (shortened as Ba) collected in a Cameroonian deposit at Bagba hill. Physicochemical characterization of the resulting material using ultraviolet-visible spectroscopy (UV-vis), Fourier transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD) confirmed the intercalation of the porphyrin within the interlayer space of the clay. The intercalated clay was then used to form a stable thin film onto a glassy carbon electrode (GCE) by drop casting a suspension of the hybrid material. The GCE modified with the intercalated organoclay endowed the electrode with a larger electrochemically active surface area, good stability, high selectivity, and sensitivity toward dopamine (DA), acetaminophen (AC) and tryptophan (Trp). In addition, it was observed that the modified electrodes exhibited good and pH-dependent electrocatalytic properties toward these analytes. The simultaneous determination of DA, AC and Trp at [NiTPyP{Ru(bipy) 2 Cl} 4 ] 4+ -Ba/GCE was thus possible without the interference of one analyte on the others, and the resulting calibration curve exhibits two segments for the three analytes. For DA, AC and Trp, the detection limits were found to be 0.8 μM, 0.3 μM and 0.3 μM, respectively. The [NiTPyP{Ru(bipy) 2 Cl} 4 ] 4+ -Ba/GCE modified electrodes were successfully applied for the determination of AC in Paracetamol, a commercial product, and Trp in real pharmaceutical formulation samples., Competing Interests: There is no conflict to declare., (This journal is © The Royal Society of Chemistry.)

Co-abietate and Cu-abietate complexes were obtained by a low-cost and eco-friendly route. The synthesis process used Pinus elliottii resin and an aqueous solution of CuSO 4 /CoSO 4 at a mild temperature (80 °C) without organic solvents. The obtained complexes are functional pigments for commercial architectural paints with antipathogenic activity. The pigments were characterized by Fourier-transform infrared spectroscopy (FTIR), mass spectrometry (MS), thermogravimetry (TG), near-edge X-ray absorption fine structure (NEXAFS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and colorimetric analysis. In addition, the antibacterial efficiency was evaluated using the minimum inhibitory concentration (MIC) test, and the antiviral tests followed an adaptation of the ISO 21702:2019 guideline. Finally, virus inactivation was measured using the RT-PCR protocol using 10% ( w / w ) of abietate complex in commercial white paint. The Co-abietate and Cu-abietate showed inactivation of >4 log against SARS-CoV-2 and a MIC value of 4.50 µg·mL -1 against both bacteria Staphylococcus aureus ( S. aureus ) and Escherichia coli ( E. coli ). The results suggest that the obtained Co-abietate and Cu-abietate complexes could be applied as pigments in architectural paints for healthcare centers, homes, and public places.

Urease is an enzyme containing a dinuclear nickel active center responsible for the hydrolysis of urea into carbon dioxide and ammonia. Interestingly, inorganic models of urease are unable to mimic its mechanism despite their similarities to the enzyme active site. The reason behind the discrepancy in urea decomposition mechanisms between inorganic models and urease is still unknown. To evaluate this factor, we synthesized two bis -nickel complexes, [Ni 2 L(OAc)] (1) and [Ni 2 L(Cl)(Et 3 N) 2 ] (2), based on the Trost bis -Pro-Phenol ligand (L) and encompassing different ligand labilities with coordination geometries similar to the active site of jack bean urease. Both mimetic complexes produced ammonia from urea, (1) and (2), were ten- and four-fold slower than urease, respectively. The presence and importance of several reaction intermediates were evaluated both experimentally and theoretically, indicating the aquo intermediate as a key intermediate, coordinating urea in an outer-sphere manner. Both complexes produced isocyanate, revealing an activated water molecule acting as a base. In addition, the reaction with different substrates indicated the biomimetic complexes were able to hydrolyze isocyanate. Thus, our results indicate that the formation of an outer-sphere complex in the urease analogues might be the reason urease performs a different mechanism.

The search for less expensive and viable products is always one of the challenges for research development. Commonly, the synthesis of coordination compounds involves expensive ligands, through expensive and low-yield routes, in addition to generating toxic and unusable residues. In this work, the organic ligand used is derived from the resin of a reforestation tree, Pinus elliottii var. elliottii. The synthesis method used Pinus resin and an aqueous solution of vanadium(III) chloride at a temperature of 80 °C. The procedure does not involve organic solvents and does not generate toxic residues, thus imparting the complex formation reaction a green chemistry character. The synthesis resulted in an unprecedented oxovanadium(IV)-bis(abietate) complex, which was characterized by mass spectrometry (MS), chemical analysis (CHN), vibrational (FTIR) and electronic spectra (VISIBLE), X-ray diffraction (XRD), and thermal analysis (TG/DTA). Colorimetric studies were performed according to the CIELAB color space. The structural formula found, consisted of a complex containing two abietate ligands, [VO(C20H29O2)2]. The VO(IV)-bis(abietate) complex was applied against microorganisms and showed promising results in antibacterial and antifungal activity. The best result of inhibitory action was against the strains of Gram-positive bacteria S. aureus and L. monocytogenes, with minimum inhibitory concentration (MIC) values of 62.5 and 125 μmol L−1, respectively. For Gram-negative strains the results were 500 μmol L−1 for E. coli; and 1000 μmol L−1 for Salmonella enterica Typhimurium. Antifungal activity was performed against Candida albicans, where the MIC was 15.62 μmol L−1, and for C. tropicalis it was 62.5 μmol L−1. According to the MFC analysis, the complex presented, in addition to the fungistatic action, a fungicidal action, as there was no growth of fungi on the plates tested. The results found for the tests demonstrate that the VO(IV)-bis(abietate) complex has great potential as an antimicrobial and mainly antifungal agent. In this way, the pigmented ink with antimicrobial activity could be used in environments with a potential risk of contamination, preventing the spread of microorganisms harmful to health.

Inflammasomes are cytosolic complexes composed of a Nod-like receptor, NLR, the adaptor protein, ASC, and a proteolytic enzyme, caspase-1. Inflammasome activation leads to caspase-1 activation and promotes functional maturation of IL-1β and IL-18, two prototypical inflammatory cytokines. Besides, inflammasome activation leads to pyroptosis, an inflammatory type of cell death. Inflammasomes are vital for the host to cope with foreign pathogens or tissue damage. Herein, we show that quantum-dot-based iron oxide nanoparticles, MNP@QD, trigger NLRP3 inflammasome activation and subsequent release of proinflammatory interleukin IL-1β by murine bone marrow-derived dendritic cells (BMDCs). This activation is more pronounced if these cells endocytose the nanoparticles before receiving inflammatory stimulation. MNP@QD was characterized by using imaging techniques like transmission electron microscopy, fluorescence microscopy, and atomic force microscopy, as well as physical and spectroscopical techniques such as fluorescence spectroscopy and powder diffraction. These findings may open the possibility of using the composite MNP@QD as both an imaging and a therapeutic tool.

Molecular machines, as exemplified by the kinesin and microtubule system, are responsible for molecular transport in cells. The monitoring of the cellular machinery has attracted much attention in recent years, requiring sophisticated techniques such as optical tweezers, and dark field hyperspectral and fluorescence microscopies. It also demands suitable procedures for immobilization and labeling with functional agents such as dyes, plasmonic nanoparticles and quantum dots. In this work, microtubules were co-polymerized by incubating a tubulin mix consisting of 7 biotinylated tubulin to 3 rhodamine tubulin. Rhodamine provided the fluorescent tag, while biotin was the anchoring group for receiving streptavidin containing species. To control the microtubule alignment and consequently, the molecular gliding directions, functionalized iron oxide nanoparticles were employed in the presence of an external magnet field. Such iron oxide nanoparticles, (MagNPs) were previously coated with silica and (3-aminopro-pyl)triethoxysilane (APTS) and then modified with streptavidin (SA) for linking to the biotin-functionalized microtubules. In this way, the binding has been successfully performed, and the magnetic alignment probed by Inverted Fluorescence Microscopy. The proposed strategy has proved promising, as tested with one of the most important biological structures of the cellular machinery.

A new supramolecular electrocatalyst for Oxygen Evolution Reaction (OER) was synthesized from a central multibridging cobalt tetrapyridylporphyrazine (CoTPyPz) species by attaching four [Ru(bpy) 2 Cl] + groups. Both CoTPyPz and the tetraruthenated cobalt porphyrazine species, TRuCoTPyPz, form very homogenous molecular films just by dropcasting their methanol solutions onto GCE electrodes. Such films exhibited low overpotentials for O 2 evolution, e.g., 560 e 340 mV, respectively, displaying high stability, typically exceeding 15 h. The kinetic parameters obtained from the Tafel plots showed that the peripheral complexes are very important for the electrocatalytic activity. Hyperspectral Raman images taken along the electrochemical process demonstrated that the cobalt center is the primary active catalyst site, but its performance is enhanced by the ruthenium complexes, which act as electron-donating groups, in the supramolecular system.

A ranelate ion, an old antiosteoporotic drug, readily reacts with gold(III) ions generating stable gold nanoparticles (AuNP@Ran). The reaction proceeds rapidly under green conditions and is specific for gold ions at room temperature. Their characteristic color associated with the plasmonic resonance effects allows its use in colorimetric/spectrophotometric analysis, as well as in spot test assays. In addition to the color changes, the gold nanoparticles exhibit surface enhanced Raman scattering (SERS), providing another interesting route for the analytical detection of gold ions. Because of the great simplicity, the ranelate method can be very convenient for monitoring gold ions, especially in metal extraction and hydrometallurgical processes.

This data article is associated with the work "Ecofriendly synthesis of Zn-abietate complex derived from Pinus elliottii resin and its application as an antibacterial pigment against S. aureus and E. coli ". The characterization data of the Zn-abietate complex obtained from Pinus elliottii resin and their reactional intermediary (Na-abietate) are reported. The Na-abietate was prepared with purified Pinus resin and sodium hydroxide (≥ 99%) in a stoichiometric ratio of 1:1. For the Zn-abietate synthesis was used ZnSO 4 and Na-abietate solutions were at mild temperature and stirring without using organic solvents to ensuring the green character of the synthesis. Spectroscopic and structural characterization was consistent with an octahedral complex involving three carboxylate ligands per metal ion. X-ray photoelectron spectroscopy (XPS) analysis of the Na-abietate salt confirms the presence of carbonyl groups, carbon-oxygen atoms simple bonds (O-C/O=C), and carboxylate groups oxygen atoms (O-C=O). Analysis of the Zn LMM Auger, for the Zn-abietate complex, indicates the presence of zinc atoms with oxidation state Zn 2+ , this is supported by the distance between Zn 2p 3/2 and 1p 1/2 in the XPS spectrum. Together, these data will be useful for the structural representation of the samples., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2021 The Author(s). Published by Elsevier Inc.)

Inspired on the outstanding behavior of the BODIPY dye, a new fluorescent boron fluoride derivative of the classical 2,2'-dihydroxy-1,1'-naphtalazine or YELLOW 101 dye has been synthesized and investigated in this work. Analogously to YELLOW 101 (λ emission  = 510 nm), the new species, here denoted BYELLOW 101, exhibits strong fluorescence around 570 and 535 nm in the solid form and in organic solvents, respectively. The observed red shift of the luminescence emission can be explored in the superparamagnetic fluorescent materials employed in MPI (magnetic particle inspection) technology, decreasing the influence of the FRET mechanism, - a critical limitation in this type of system. BYELLOW 101 is stable in solid form, but in organic solvents, it hydrolyses very slowly regenerating the initial dye, keeping the fluorescence emission but exhibiting a small blue shift along the time., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The analytical determination of lithium ions is usually performed by atomic absorption and X-ray fluorescence methods. Chemical analysis based on polyfluoroporphyrin chromogenic methods is also being employed, especially for biological samples. However, all existing methods are expensive and not suitable for routine work or field assays. The alternative method proposed here is based on the formation of a LiKFe(IO 6 ) compound which is converted into a tris(1,10-phenanthroline)iron(ii) complex and monitored by spectrophotometric or colorimetric methods, the latter using a smartphone app. Under similar conditions, these two methods proved superior to the X-ray fluorescence method. A one pot analysis of lithium ions is also described, using an Eppendorf microtube previously modified for performing reaction, filtration and detection. This method is simple and very convenient for didactic and field assays.

The production of materials that contain more than one functional constituent, the so-called multifunctional materials, is quite relevant in advanced technology. By acting as building blocks, nanoparticles can be suitably explored for generating higher-order multifunctional structures. In this regard, herein, a special clustered magneto-fluorescent superstructure has been developed for non-destructive detection of flaws and shallow subsurface discontinuities in industrial ferromagnetic materials. The strategy consists of the solvophobic-controlled assembly of organic-based maghemite cores and water-based II-VI quantum dots, in the presence of hexadecyltrimethyl-ammonium bromide, CTAB, as a compatibilizer agent. This composite exhibited a high magnetic response ( σ max = 66 emu g -1 ) and uniform size, in addition to tunable optical properties (QY = 78%). The strategy of utilizing nanoparticles as magneto-fluorescent nanoprobes to identify tiny slits represents a great advance, for improving the capability of precisely revealing the fracture boundary locations by visual real-time inspection. The nanoscale probes exhibit a low signal-to-noise ratio and a higher competitive performance in relation to the existing micrometric detection systems., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

The time scale for interfacial photoinduced electron transfer (PeT) in plasmonic nanoparticles is not well established and the details are still under debate. This has renewed the interest in studying the electron transfer effect from both experimental and theoretical points of view. We present a quantitative analysis of PeT in single spherical gold (Au) and gold@palladium core@shell (Au@Pd) nanoparticles supported on reduced graphene oxide (RGO) using dark-field hyperspectral microscopy (DFHM) and electrochemical impedance spectroscopy (EIS). By studying the plasmon bandwidth in the scattering spectra of single particles and by correlating it to the plasmon damping processes we showed that PeT occurs from the AuNPs to RGO in a 10 fs time scale with a quantum efficiency of 35%. The introduction of a Pd shell on the AuNPs decreases the PeT time, with transfer occurring in as little as 1.7 fs with quantum yield higher than 74%. Furthermore, EIS showed a smaller resistance for PeT on RGO/Au@PdNPs under green light illumination. Our results can improve the understanding of the chemical interface damping process due to PeT in plasmonic nanomaterials and can enable the design of more efficient plasmon enhanced photocatalysts.

Turkevich gold nanoparticles colloidal solutions undergo further changes after ageing for several weeks or months, and in most cases a spongy dark material can be observed suspended in the red solution. CytoViva® dark-field microscopy images and high resolution transmission electron micrographys (HRTEM) of the strange body played a central role and revealed a fibrous structure, consistent with cellulose, as commonly found in the cell-walls of many fungi. Surprisingly, the interior of the fibers are filled with gold nanoparticles, responsible for the high contrasting images obtained in this work. The fungi were replicated in the laboratory, characterized by Infrared Microscopy (FTIR) and revealed an ability to grow in gold-citrate media, even in dark and anaerobical conditions., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Significant differences were found in the proton-coupled redox chemistry and catalytic behavior of the binuclear [{Ru(H2O)(bpz)}2(tpy2ph)](PF6)4 complex [bpz = 2,2'-bipyrazine; tpy2ph = 1,3-bis(4'-2,2':6',2''-terpyridin-4-yl)benzene] as compared with the structurally analogous derivative with 2,2'-bipyridine (bpy) instead of bpz. The differences were assigned to the stronger π-accepting character of bpz relative to bpy as the ancillary ligand. The expectation of a positive shift for the Ru-centered redox potentials was confirmed for the lower oxidation state species, but that trend was reversed in the formation of the high-valence catalytic active species as shown by a negative shift of 0.14 V for the potential of the [RuIV/V[double bond, length as m-dash]O] process. Moreover, DFT calculations indicated a significant decrease of about 15% on the spin density and oxyl character of the [RuV[double bond, length as m-dash]O]3+ fragment. The significantly lower kcat(O2) for the bpz system was attributed to these combined electronic effects.

Pentacyanidoferrate(II) complexes of aromatic N-heterocycles, such as 4-cyanopyridine, exhibit characteristic colors and strong metallochromism associated with the donor-acceptor interactions of the metal ions with the cyanide ligands. In the presence of transition metal ions insoluble polymeric complexes are formed, displaying bright yellow, red, brown and green colors with zinc(II), nickel(II), copper(II) and iron(III) ions, respectively. Such metallochromic response is better observed on filter paper, allowing applications in analytical spot tests. The effects can be explored visually and probed by means of modern instrumental facilities, including spectrophotometric and resonance Raman techniques. In this way, by using the cyanopyridinepentacyanidoferrates, the Prussian Blue test for ferric ions can be extended to the entire row of transition metal elements, providing a new and modern insight of such classical Feigl's spot tests.

Drugs bearing metal-coordinating moieties can alter biological metal distribution. In this work, a complex between iron(II) and diflunisal was prepared in the solid state, exhibiting the following composition: [Fe(diflunisal) 2 (H 2 O) 2 ], (Fe(dif) 2 ). The ability of diflunisal to alter labile pools of both plasmatic and cellular iron was investigated in this work. We found out that diflunisal does not increase the levels of redox-active iron in plasma of iron overloaded patients. However, diflunisal efficiently carries iron into HeLa or HepG2 cells, inducing an iron-catalyzed oxidative stress., (Copyright © 2018 Elsevier GmbH. All rights reserved.)

The Raman spectral profile of p-methylcarbohydrazonethioamide (MCHT) is completely changed due to strong SERS effects upon bonding onto gold nanoparticles surface, but some vibrational modes are further enhanced in the presence of Hg(II) ions. The lack of SERS response for most common metal ions indicates that the coordinating groups are interacting with the gold nanoparticles surface and not available for binding metal ions in solution, except for mercury ions. The selective enhancement of some vibrational modes is consistent with significant conformational changes upon binding of Hg(II) ion onto the AuNP@MCHT hybrid, as confirmed by TEM/EDS measurements, demonstrating its potentiality as a highly selective and sensitive SERS substrate., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The extraction of dysprosium (Dy3+) ions from aqueous solution was carried out successfully, using magnetite (Fe3O4) nanoparticles functionalized with diethylenetriaminepentaacetic acid (MagNP@DTPA). The process was monitored by energy dispersive X-ray fluorescence spectroscopy, as a function of concentration, proceeding according to a Langmuir isotherm with an equilibrium constant of 2.57 × 10-3 g(MagNP) L-1 and a saturation limit of 63.2 mgDy/gMagNP. The presence of paramagnetic Dy3+ ions attached to the superparamagnetic nanoparticles led to an overall decrease of magnetization. By imaging the nanoparticles surface using scanning transmission electron microscopy equipped with high resolution elemental analysis, it was possible to probe the binding of the Dy3+ ions to DTPA, and to show their distribution in a region of negative magnetic field gradients. This finding is coherent with the observed decrease of magnetization, associated with the antiferromagnetic coupling between the lanthanide ions and the Fe3O4 core.

An unusual photooxidation of a coordinated 4-mercaptopyridine ( SpyH) ligand in the [Ru(Hmctpy)(dmbpy)(κ S-SpyH)] 2+ complex (Hmctpy = 4'-carboxy-2,2';6',2″-terpyridine, dmbpy = 4,4'-dimethyl-2,2'-bipyridine) takes place under visible and UV irradiation, in aerated acetonitrile. The [Ru(mctpy)(dmbpy)(κ S-SO 2 py)] sulfinato product has been characterized by a variety of methods, including X-ray diffraction which supports the presence of the Ru-κ S-SpyH isomer in the starting complex. The photooxidation of the 4-mercaptopyridine ligand enhances the back-bonding interactions in the complex by means of the strongly acceptor 4-pyridinesulfinato-SO 2 py species, increasing the redox potential of the Ru(III)/Ru(II) couple significantly from 1.23 to 1.62 V. It also led to pronounced changes in the electronic and NMR spectra of the complexes, corroborated by DFT and ZINDO-S calculations. A possible mechanism based on referenced data of photooxidation has been proposed, which involves the formation of a reactive oxygen species and intermediate endoperoxide species, yielding a very stable Ru-sulfinato product. This novel species exhibits stronger luminescence (Φ f = 0.004) than the starting complex under UV excitation.

The kinesin-microtubule pair has attracted much attention in recent years due to their promising use in the development of synthetic nanotransport machines. One of the challenges to study such system is how to observe the motility of either kinesin or microtubule. The usual technique for observation of the molecular machinery pair is by fluorescence microscopy, where fluorescent probes are bound to one, or both species, through a biotin-avidin linker. Here, the use of mercaptopropionic acid (MPA)-capped cadmium telluride (CdTe) quantum dots (QDs) as a direct fluorescent labeling agent to microtubule biomolecules is reported. QDs are able to not only bind to microtubules in vitro, but also to fluorescently label them in the red spectral region. Surface plasmon resonance (SPR) studies showed the binding of synthesized QDs to microtubules, while quantum dots-labeled microtubules were successfully visualized with fluorescence microscopy. It is believed QDs adsorbs to the microtubule surface mainly through the coordination of Cd with histidine, cysteine and methionine residues, as well as through interactions of the nanocrystal's carboxylated surface with free amino groups on microtubules., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The simultaneous electrochemical detection of mood disorder related substances, such as amitriptyline, melatonin and tryptophan, was successfully achieved by using a novel nano-magnetic electrochemical sensor design, encompassing Fe 3 O 4 nanoparticles decorated with carbon quantum dots (MagNPs/Cdots). The magnetic composite was characterized using HR-TEM microscopy, XRD and Raman spectroscopy, and was applied onto a glassy carbon electrode using a miniature neodymium magnet. The determination of amitriptyline, melatonin and tryptophan was performed by monitoring oxidation promoted by MagNPs/Cdots in BR-buffer at pH 3.0, which proceeded according to well-defined differential pulse voltammetry peaks, with detection limits of 5.9, 4.4 and 4.2 nmol L -1 , respectively. No significant interference was seen from biological interferents such as uric acid, ascorbic acid, dopamine, estriol and 17β-estradiol. The magnetic hybrid material was highly stable in solution, opening exciting opportunities for the development of low cost and practical electrochemical sensors for the determination of mood disorder related substances in real clinical samples., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Measuring lead in the surface dental enamel (SDE) using biopsies is a rapid, safe, and painless procedure. The dental enamel lead levels (DELLs) decrease from the outermost superficial layer to the inner layer of dental enamel, which becomes crucial for the biopsy depth (BD) measurement. However, whether the origin of lead found in SDE is fully endogenous is not yet established. There is also controversy about the biopsy protocol. The aims of this study were to investigate if DELLs are altered by extrinsic contamination (A) and to evaluate the real geometric figure formed by the erosion provoked by biopsy procedure and the respective BD in SDE (B). To accomplish the aim A, lead from 90 bovine incisor crowns lead was determined by graphite furnace atomic absorption spectrometer as a function of exposure time and lead concentration. Two biopsies were performed in each tooth, before and after lead exposure. Six 15-tooth groups differed by exposure time (1 or 30 min) and lead concentrations (A. 0 mg/L-placebo, B. 0.01 mg/L-standard for drinking water, or C. 0.06 mg/L-concentration found in contaminated groundwater). Phosphorus was determined by an inductively coupled plasm optical emission spectrometer to quantify the enamel removed. To compare intakes/losses of lead in SDE among the groups, values of DELL differences between before and after lead exposure were compared by ANOVA (p < 0.05). To attain the objective B, one extracted human permanent tooth was studied by confocal Raman microscopy. Lead measurements and the surface profile were determined. There was no difference in DELL among the groups (p = 0.964). The biopsy bottom surface area, analyzed by microscopy, showed an irregular area, with regions of peaks and valleys, where areas with depth ranging from 0.2 (peaks) to 1.8 μm (valleys) (± 0.1 μm) could be found. BD carried out in vivo is commonly calculated using the cylinder height formula. The real BD was shown to be very similar to already published data. In conclusion, the SDE of erupted teeth does not seem to be susceptible to environmental lead intake, being thus reliable to measure remote exposures to lead.

The conversion of carbon dioxide into important industrial feedstock is a subject of growing interest in modern society. A possible way to achieve this goal is by carrying out the CO2/methanol cascade reaction, allowing the recycle of CO2 using either chemical catalysts or enzymes. Efficient and selective reactions can be performed by enzymes; however, due to their low stability, immobilization protocols are required to improve their performance. The cascade reaction to reduce carbon dioxide into methanol has been explored by the authors, using, sequentially, alcohol dehydrogenase (ADH), formaldehyde dehydrogenase (FalDH), and formate dehydrogenase (FDH), powered by NAD+/NADH and glutamate dehydrogenase (GDH) as the co-enzyme regenerating system. All the enzymes have been immobilized on functionalized magnetite nanoparticles, and their reactions investigated separately in order to establish the best performance conditions. Although the stepwise scheme led to only 2.3% yield of methanol per NADH; in a batch system under CO2 pressure, the combination of the four immobilized enzymes increased the methanol yield by 64 fold. The studies indicated a successful regeneration of NADH in situ, envisaging a real possibility of using immobilized enzymes to perform the cascade CO2-methanol reaction.

Self-supported oligo-layered ZnAlEu LDH nanotubes (∅ 20 nm) self-assemble upon controlled hydrolysis of the metal ions (Zn 2+ , Al 3+ , Eu 3+ ) in the presence of 1,3,5-benzenetricarboxylate anions and non-ionic worm-like micelles. Their high surface area and easily accessible cylindrical mesopores (175 m 2 g -1 ; 0.75 cm 3 g -1 ) facilitate interaction with 5 nm CdTe quantum dots, enhancing the overall luminescence behavior.

We report the unprecedented observation of plasmon coupling between silver nanowires, showing how the surface-enhanced Raman scattering depends upon this interaction and how the spectrum can be shaped by the hot spot. Such observations were accomplished by Raman spectroscopy mapping of silver nanowires modified with rhodamine. The local spectra on the hot spots were measured by darkfield hyperspectral microscopy, a powerful but uncommonly used technique that is capable of determining the location, structure, and spectra of the hot spots. The result obtained by the simulation of two parallel nanowires based on the discrete dipole approximation (DDA) method was in excellent agreement with the results obtained experimentally., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Alcohol dehydrogenase (ADH) from Saccharomyces cerevisiae was covalently attached, via glutaraldehyde, to magnetite nanoparticles (MagNP) previously coated with aminopropyltriethoxysilane (MagNP/APTS), or with a silica shell followed by the APTS coating (MagNP@SiO2/APTS). In both cases, a great improvement of enzymatic activity has been observed for the ethanol-acetaldehyde conversion. The MagNP@SiO2/APTS-ADH system exhibited the best stability with respect to pH and temperature. Its residual activity after 10 successive recovery cycles and 24 h storage, was maintained around 80% in comparison with 20% for the MagNP/APTS system, and a null activity for free ADH. Luminescence measurements for the immobilized enzyme indicated the occurrence of conformational changes on ADH, contributing for its improved catalytic performance.

Surface enhanced Raman spectroelectrochemistry (SERS) spectroelectrochemistry provides a very sensitive technique to investigate the vibrational characteristics of coordination compounds and their particular behavior under the influence of plasmonic surfaces, concomitant with the exploitation of their redox properties and electronic spectra. The results, however, depend upon the mechanisms involved in the intensification of Raman spectra associated with the electromagnetic, resonance Raman and charge-transfer excitation at the Fermi levels. By probing the model complex [(Ru3O)(CH3COO)6(4,4'-bipy)3](n) (n = 1, 0, -1) adsorbed onto rough gold electrode surfaces, contrasting SERS profiles were obtained at several successive redox potentials and oxidation states, which enables a critical discussion on the role of the complex interaction with the gold surface, and the influence of the specific electronic bands in the triruthenium acetate cluster. Density functional theory (DFT) and time-dependent DFT calculations were carried out for the complex bound to an Au20 cluster to show the participation of active lowest unoccupied molecular orbital levels centered on the gold atoms. The corresponding charge-transfer band was predicted around 1200 nm, which supports a charge-transfer interpretation for the SERS response observed at λexc = 1064 nm. The selective enhancement of the vibrational modes was discussed based on the Raman theoretical calculations.

The structure of polytetraruthenated nickel porphyrin was unveiled for the first time by electrochemistry, Raman spectroelectrochemistry, and a hydroxyl radical trapping assay. The electrocatalytic active material, precipitated on the electrode surface after successive cycling of [NiTPyP{Ru(bipy)2Cl}4](4+) species in strong aqueous alkaline solution (pH 13), was found to be a peroxo-bridged coordination polymer. The electropolymerization process involves hydroxyl radicals (as confirmed by the characteristic set of DMPO/(•)OH adduct EPR peaks) as reaction intermediates, electrocatalytically generated in the 0.80-1.10 V range, that induce the formation of Ni-O-O-Ni coordination polymers, as evidenced by Raman spectroelectrochemistry and molecular modeling studies. The film growth is halted above 1.10 V due to the formation of oxygen gas bubbles.

The light scattering properties of hexagonal and triangular gold nanodisks were investigated by means of Cytoviva hyperspectral dark-field microscopy, exploring the huge enhancement of the scattered waves associated with the surface plasmon resonance (SPR) effect. Thanks to the high resolution capability of the dark-field microscope, the SPR effect turned it possible to probe the individual nanoparticles directly from their hyperspectral images, extrapolating the classical optical resolution limit, and providing their corresponding extinction spectra. Blue spectral shifts involving the in-plane dipolar modes were observed for the hexagonal gold nanodisks in relation to the triangular ones, allowing their spectroscopic differentiation in the dark-field images., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

A simple and accessible method for molecular analyses down to the picomolar range was realized using self-assembled hybrid superparamagnetic nanostructured materials, instead of complicated SERS substrates such as core-shell, surface nanostructured, or matrix embedded gold nanoparticles. Good signal-to-noise ratio has been achieved in a reproducible way even at concentrations down to 5×10(-11) M using methylene blue (MB) and phenanthroline (phen) as model species, exploiting the plasmonic properties of conventional citrate protected gold nanoparticles and alkylamine functionalized magnetite nanoparticles. The hot spots were generated by salt induced aggregation of gold nanoparticles (AuNP) in the presence of those analytes. Then, the aggregates of AuNP/analyte were decorated with small magnetite nanoparticles by electrostatic self-assembly forming MagSERS hybrid nanostructured materials. SERS peaks were enhanced up to 100 times after magnetic concentration in a circular spot using a magnet in comparison with the respective dispersion of the nanostructured material., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The most challenging and wanted development in photodynamic therapy is the control of photosensitizer (PS) cytolocalization and the mechanism of cell death. 5,10,15-triphenyl-20-(3-N-methylpyridinium-yl)porphyrin (3MMe) administered to HeLa cells as DMSO solution accumulates in the cytoplasmic membrane (CM) where it causes severe photodamage and cell necrosis. In contrast, when incorporated in marine atelocollagen/xantham gum polymeric nanocapsules, the PS is shuttled through CM allowing its gradual release and accumulation in mitochondria and lysosomes. Little photodamage was caused to cells in this case, but compelling evidences are presented showing that encapsulation changes the cytolocalization and shifts the cell death mechanism from necrosis to apoptosis. In conclusion, both of those challenges can be overcome by encapsulation of typical PSs such as 3MMe by using the new concept of photodynamic treatment with minimal cell damage by targeting specifically some key organelles. We are confident that these findings are important for the development of more efficient photosensitizers tailored to induce apoptosis while minimizing undesirable side effects such as over-inflammation.

A hybrid material with excellent mechanical and biological properties is produced by electrospinning a co-solution of PET and collagen. The fibers are mapped using SEM, confocal Raman microscopy and collagenase digestion assays. Fibers of different compositions and morphologies are intermingled within the same membrane, resulting in a heterogeneous scaffold. The collagen distribution and exposure are found to depend on the PET/collagen ratio. The materials are chemically and mechanically characterized and biologically tested with fibroblasts (3T3-L1) and a HUVEC culture in vitro. All of the hybrid scaffolds show better cell attachment and proliferation than PET. These materials are potential candidates to be used as vascular grafts., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The photochemical cis-trans isomerization of the 4-{4-[2-(pyridin-4-yl)ethenyl]phenyl}-2,2':6',2''-terpyridine ligand (vpytpy) was investigated by UV-vis, NMR and TWIM-MS. Ion mobility mass spectrometry was performed pursuing the quantification of the isomeric composition during photolysis, however an in-source trans-to-cis isomerization process was observed. In order to overcome this inherent phenomenon, the isomerization of the vpytpy species was suppressed by complexation, reacting with iron(II) ions, and forming the [Fe(vpytpy)(2)](2+) complex. The strategy of "freezing" the cis-trans isomerizable ligand at a given geometric conformation was effective, preventing further isomerization, thus allowing the distinction of each one of the isomers in the photolysed mixture. In addition, the experimental drift times were related to the calculated surface areas of the three possible cis-cis, cis-trans and trans-trans iron(II) complex isomers. The stabilization of the ligand in a given conformation also allows us to obtain the cis-cis and cis-trans complexes exhibiting the ligand in the metastable cis-conformation, as well as in the thermodynamically stable trans-conformation.

Sevenfold enhancement of photoconversion efficiency was achieved by incorporation of peripheral ruthenium complexes to a porphyrin dye, generating supramolecular effects capable of playing several key roles (e.g., transferring energy to, inhibiting aggregation, and accepting the hole generated in the porphyrin center after electron injection), providing new insights for the design of better DSSC photosensitizers.

Travelling wave ion mobility mass spectrometry (TWIM-MS) with post-TWIM and pre-TWIM collision-induced dissociation (CID) experiments were used to form, separate and characterize protomers sampled directly from solutions or generated in the gas phase via CID. When in solution equilibria, these species were transferred to the gas phase via electrospray ionization, and then separated by TWIM-MS. CID performed after TWIM separation (post-TWIM) allowed the characterization of both protomers via structurally diagnostic fragments. Protonated aniline (1) sampled from solution was found to be constituted of a ca. 5:1 mixture of two gaseous protomers, that is, the N-protonated (1a) and ring protonated (1b) molecules, respectively. When dissociated, 1a nearly exclusively loses NH(3) , whereas 1b displays a much diverse set of fragments. When formed via CID, varying populations of 1a and 1b were detected. Two co-existing protomers of two isomeric porphyrins were also separated and characterized via post-TWIM CID. A deprotonated porphyrin sampled from a basic methanolic solution was found to be constituted predominantly of the protomer arising from deprotonation at the carboxyl group, which dissociates promptly by CO(2) loss, but a CID-resistant protomer arising from deprotonation at a porphyrinic ring NH was also detected and characterized. The doubly deprotonated porphyrin was found to be constituted predominantly of a single protomer arising from deprotonation of two carboxyl groups., (Copyright © 2012 John Wiley & Sons, Ltd.)

The ability of travelling wave ion mobility mass spectrometry (TWIM-MS) to resolve cationic meta/para and cis/trans isomers of mono-, di-, tri- and tetra-ruthenated supramolecular porphyrins was investigated. All meta isomers were found to be more compact than the para isomers and therefore mixtures of all isomeric pairs could be properly resolved with baseline or close to baseline peak-to-peak resolution (R(p-p)). Di-substituted cis/trans isomers were found, however, to present very similar drift times and could not be resolved. N(2) and CO(2) were tested as the drift gas, and similar α but considerably better values of R(p) and R(p-p) were always observed for CO(2)., (Copyright © 2012 John Wiley & Sons, Ltd.)