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1.
Colloids Surf B Biointerfaces ; 182: 110366, 2019 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-31351273

RESUMO

Targeted delivery of vitamins to a desirable area is an active branch in a modern pharmacology. The most important and difficult delivery of vitamin B12 is that to bone marrow and nerve cells. Herein we present a first step towards the development of two types of smart carriers, polymer capsules and lyotropic liquid-crystalline nanosystems, for vitamin B12 targeted delivery and induced release. A vitamin B12 encapsulation technique into nanoengineered polymeric capsules produced by layer-by-layer assembling of polymeric shells on CaCO3 templates has been developed. The effectiveness of the process was demonstrated by optical absorption spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM) and small-angle X-ray diffraction. TEM and AFM analyses performed on capsules after their drying, confirmed the presence of the vitamin B12 inside the capsules in the form of crystalline nanoaggregates, 50-300 nm in diameter. Soft lipid nanovectors consisting of amphiphilic phytantriol molecules, which in water excess spontaneously self-assembly in 3D well-ordered inverse bicontinuous cubic bulk phase, were used as alternative carriers for vitamin B12. It was shown that about 30% of the vitamin added in the preparation of the soft lipid system was actually encapsulated in cubosomes and that no structural changes occurred upon loading. The Vitamin stabilizes the lipid system playing the role of its structure-forming element. The biocompatible nature, the stability and the feasibility of these systems make them good candidates as carriers for hydrophilic vitamins.


Assuntos
Sistemas de Liberação de Medicamentos/métodos , Álcoois Graxos/química , Nanocápsulas/química , Poloxâmero/química , Vitamina B 12/química , Carbonato de Cálcio/química , Cristalização , Composição de Medicamentos/métodos , Humanos , Nanocápsulas/ultraestrutura
2.
Chem Sci ; 10(5): 1539-1548, 2019 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-30809372

RESUMO

Chiral electroanalysis could be regarded as the highest recognition degree in electrochemical sensing, implying the ability to discriminate between specular images of an electroactive molecule, particularly in terms of significant peak potential difference. A groundbreaking strategy was recently proposed, based on the use of "inherently chiral" molecular selectors, with chirality and key functional properties originating from the same structural element. Large differences in peak potentials have been observed for the enantiomers of different chiral molecules, also of applicative interest, using different selectors, all of them based on atropisomeric biheteroaromatic scaffolds of axial stereogenicity. However, helicene systems also provide inherently chiral building blocks with attractive features. In this paper the enantiodiscrimination performances of enantiopure inherently chiral films obtained by electrooxidation of a thiahelicene monomer with helicoidal stereogenicity are presented for the first time. The outstanding potentialities of this novel approach are evaluated towards chiral probes with different chemical nature and bulkiness, in comparison with a representative case of the so far exploited class of inherently chiral selectors with axial stereogenicity. It is also verified that the high enantiodiscrimination ability holds as well for electron spins, as for atropisomeric selectors.

3.
Chem Commun (Camb) ; 54(43): 5490-5493, 2018 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-29756620

RESUMO

The n-type organic semiconductor phenyl-C61-butyric acid methyl ester (PCBM), a soluble fullerene derivative well investigated for organic solar cells and transistors, can undergo several successive reversible, diffusion-controlled, one-electron reduction processes. We exploited such processes to shed light on the correlation between electron transfer properties, ionic and electronic transport as well as device performance in ionic liquid (IL)-gated transistors. Two ILs were considered, based on bis(trifluoromethylsulfonyl)imide [TFSI] as the anion and 1-ethyl-3-methylimidazolium [EMIM] or 1-butyl-1-methylpyrrolidinium [PYR14] as the cation. The aromatic structure of [EMIM] and its lower steric hindrance with respect to [PYR14] favor a 3D (bulk) electrochemical doping. As opposed to this, for [PYR14] the doping seems to be 2D (surface-confined). If the n-doping of the PCBM is pursued beyond the first electrochemical process, the transistor current vs. gate-source voltage plots in [PYR14][TFSI] feature a maximum that points to the presence of finite windows of high conductivity in IL-gated PCBM transistors.

4.
Chemistry ; 24(46): 11954-11960, 2018 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-29603481

RESUMO

Salophens and Salens are Schiff bases generated through the condensation of two equivalents of salicylaldehyde with either 1,2-phenylenediamines or aliphatic diamines, respectively. Both ligands have been extensively exploited as key building blocks in coordination chemistry and catalysis. In particular, their metal complexes have been widely used for various catalytical transformations with high yield and selectivity. Through the modification of the phenol unit it is possible to tune the steric hindrance and electronic properties of Salophen and Salen. The introduction of long aliphatic chains in salicylaldehydes can be used to promote their self-assembly into ordered supramolecular structures on solid surfaces. Herein, we report a novel method towards the facile synthesis of robust and air-stable [Al(Salophen)] derivatives capable of undergoing spontaneous self-assembly at the graphite/solution interface forming highly-ordered nanopatterns. The new synthetic approach relies on the use of [MeAlIII (Salophen)] as a building unit to introduce, via a simple acid/base reaction with functionalized acidic phenol derivatives, selected frameworks integrating multiple functions for efficient surface decoration. STM imaging at the solid/liquid interface made it possible to monitor the formation of ordered supramolecular structures. In addition, the redox properties of the Salophen derivatives functionalized with ferrocene units in solution and on surface were unraveled by cyclic voltammetry. The use of a five-coordinate aluminum alkyl Salophen precursor enables the tailoring of new Salophen molecules capable of undergoing controlled self-assembly on HOPG, and thereby it can be exploited to introduce multiple functionalities with subnanometer precision at surfaces, ultimately forming ordered functional patterns.

5.
Chemistry ; 24(14): 3455-3463, 2018 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-29328530

RESUMO

Molecular and electronic structure, reduction electron transfer and coordination abilities of a polycyclic aromatic hydrocarbon (PAH) having a planar naphtho-group fused to the corannulene bowl have been investigated for the first time using a combination of theoretical and experimental tools. A direct comparison of naphtho[2,3-a]corannulene (C28 H14 , 1) with parent corannulene (C20 H10 , 2) revealed the effect of framework topology change on electronic properties and aromaticity of 1. The presence of two reduction steps for 1 was predicted theoretically and confirmed experimentally. Two reversible one-electron reduction processes with the formal reduction potentials at -2.30 and -2.77 V versus Fc+/0 were detected by cyclic voltammetry (CV) measurements, demonstrating accessibility of the corresponding mono- and dianionic states of 1. The products of the singly and doubly reduced napththocorannulene were prepared using chemical reduction with Group 1 metals and isolated as sodium and rubidium salts. Their X-ray diffraction study revealed the formation of "naked" mono- and dianions crystallized as solvent-separated ion products with one or two sodium cations as [Na+ (18-crown-6)(THF)2 ][C28 H14- ] and [Na+ (18-crown-6)(THF)2 ]2 [C28 H142- ] (3⋅THF and 4⋅THF, respectively). The dianion of 1 was also isolated as a contact-ion complex with two rubidium countercations, [{Rb+ (18-crown-6)}2 (C28 H142- )] (5⋅THF). The structural consequences of adding one and two electrons to the carbon framework of 1 are compared for 3, 4 and 5. Changes in aromaticity and charge distribution stemming from the stepwise electron acquisition are discussed based on DFT computational study.

6.
ACS Sens ; 2(9): 1310-1318, 2017 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-28836760

RESUMO

With the aim of developing miniaturized enzymatic biosensors suitable for in vitro diagnostic applications, such as monitoring of metabolites at single cell level, glucose and lactate biosensors were fabricated by immobilizing enzymes (glucose oxidase and lactate oxidase, respectively) on 10 µm Pt ultramicroelectrodes. These electrodes are meant to be employed as probes for scanning electrochemical microscopy (SECM), which is a unique technique for high-spatial-resolution electrochemical-based analysis. The use of enzymatic moieties improves sensitivity, time scale response, and information content of the microprobes; however, protein immobilization is a key step in the biosensor preparation that greatly affects the overall performance. A crucial aspect is the miniaturization of the sensing, preserving their sensitivity. In this work, we investigated the most common enzyme immobilization techniques. Several fabrication routes are reported and the main figures of merit, such as sensitivity, detection limit, response time, reproducibility, spatial resolution, biosensor efficiency, permeability, selectivity, and the ability to block electro-active interfering species, are investigated and compared. With the intent of using the microprobes for in vitro functional imaging of single living cells, we carefully evaluate the spatial resolution achieved by our modified electrodes on 2D SECM imaging. Metabolic activity of single MCF10A cells were obtained by monitoring the glucose concentrations in close proximity of single living cell, using the UME-based biosensor probes prepared. A voltage-switch approach was implemented to disentangle the topographical contribution of the cells enabling quantitative measurements of cellular uptakes.

7.
J Am Chem Soc ; 138(49): 15935-15942, 2016 12 14.
Artigo em Inglês | MEDLINE | ID: mdl-27960352

RESUMO

The impact of nanotechnology on analytical science is hardly overlooked. In the search for ever-increasing sensitivity in biomedical sensors, nanoparticles have been playing a unique role as, for instance, ultrabright labels, and unravelling the intimate mechanisms which govern their functioning is mandatory for the design of ultrasentitive devices. Herein, we investigated the mechanism of electrogenerated chemiluminescence (ECL) in a family of core-shell silica-PEG nanoparticles (DDSNs), variously doped with a Ru(bpy)32+ triethoxysilane derivative, and displaying homogeneous morphological, hydrodynamic, and photophysical properties. ECL experiments, performed in the presence of 2-(dibutylamino)ethanol (DBAE) as coreactant, showed two parallel mechanisms of ECL generation: one mechanism (I) which involves exclusively the radicals deriving from the coreactant oxidation and a second one (II) involving also the direct anodic oxidation of the Ru(II) moieties. The latter mechanism includes electron (hole) hopping between neighboring redox centers as evidenced in our previous studies and supported by a theoretical model we have recently proposed. Quite unexpectedly, however, we found that the efficiency of the two mechanisms varies in opposite directions within the DDSNs series, with mechanism I or mechanism II prevailing at low and high doping levels, respectively. Since mechanism II has an intrinsically lower efficiency, the ECL emission intensity was also found to grow linearly with doping only at relatively low doping levels while it deviates negatively at higher ones. As the ζ-potential of DDSNs increases with the doping level from negative to slightly positive values, as a likely consequence of the accumulating cationic charge within the silica core, we attributed the observed change in the ECL generation mechanism along the DDSN series to a modulation of the electrostatic and hydrophobic/hydrophilic interactions between the DDSNs and the radical cationic species involved in the ECL generation. The results we report therefore show that the ECL intensity of a nanosized system cannot be merely incremented acting on doping, since other parameters come into play. We think that these results could serve as valuable indications to design more efficient ECL nano- and microsized labels for ultrasensitive bioanalysis.

8.
Nat Commun ; 7: 13549, 2016 12 12.
Artigo em Inglês | MEDLINE | ID: mdl-27941752

RESUMO

Considering the depletion of fossil-fuel reserves and their negative environmental impact, new energy schemes must point towards alternative ecological processes. Efficient hydrogen evolution from water is one promising route towards a renewable energy economy and sustainable development. Here we show a tridimensional electrocatalytic interface, featuring a hierarchical, co-axial arrangement of a palladium/titanium dioxide layer on functionalized multi-walled carbon nanotubes. The resulting morphology leads to a merging of the conductive nanocarbon core with the active inorganic phase. A mechanistic synergy is envisioned by a cascade of catalytic events promoting water dissociation, hydride formation and hydrogen evolution. The nanohybrid exhibits a performance exceeding that of state-of-the-art electrocatalysts (turnover frequency of 15000 H2 per hour at 50 mV overpotential). The Tafel slope of ∼130 mV per decade points to a rate-determining step comprised of water dissociation and formation of hydride. Comparative activities of the isolated components or their physical mixtures demonstrate that the good performance evolves from the synergistic hierarchical structure.

9.
Phys Chem Chem Phys ; 18(22): 15025-38, 2016 06 01.
Artigo em Inglês | MEDLINE | ID: mdl-27194584

RESUMO

The synthesis of two A2B2 porphyrins, {5,15-bis-[4-(octyloxy)phenyl]-porphyrinato}zinc(ii) () and {5,15-bis-(carbazol-3-yl-ethynyl)-10,20-bis-[4-(octyloxy)phenyl]-porphinato}-zinc(ii) (), is reported. Their photophysical properties were studied by steady-state absorption and emission. Substituting the carbazolylethynyl moieties at two of the meso positions results in a large bathochromic shift of all the absorption bands, a notable increase in the absorption coefficient of the Q(0,0) band, and higher fluorescence quantum yield compared to porphyrin , with two unsubstituted meso positions. Cyclic voltammetry and digital simulation show that electrogenerated radical ions of are more stable than those of . The lack of substituents at the meso positions of leads to dimerization reactions of the radical cation. Despite this, the annihilation reaction of and produces very similar electrogenerated chemiluminescence (ECL) intensity. Spectroelectrochemical experiments demonstrate that the electroreduction of leads to a strong absorption band that might quench the ECL.

10.
Faraday Discuss ; 185: 299-309, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26394608

RESUMO

Monitoring Prostate Cancer (PCa) biomarkers is an efficient way to diagnosis this disease early, since it improves the therapeutic success rate and suppresses PCa patient mortality: for this reason a powerful analytical technique such as electrochemiluminescence (ECL) is already used for this application, but its widespread usability is still hampered by the high cost of commercial ECL equipment. We describe an innovative approach for the selective and sensitive detection of the PCa biomarker sarcosine, obtained by a synergistic ECL-supramolecular approach, in which the free base form of sarcosine acts as co-reagent in a Ru(bpy)3(2+)-ECL process. We used magnetic micro-beads decorated with a supramolecular tetraphosphonate cavitand (Tiiii) for the selective capture of sarcosine hydrochloride in a complex matrix like urine. Sarcosine determination was then obtained with ECL measurements thanks to the complexation properties of Tiiii, with a protocol involving simple pH changes - to drive the capture-release process of sarcosine from the receptor - and magnetic micro-bead technology. With this approach we were able to measure sarcosine in the µM to mM window, a concentration range that encompasses the diagnostic urinary value of sarcosine in healthy subjects and PCa patients, respectively. These results indicate how this ECL-supramolecular approach is extremely promising for the detection of sarcosine and for PCa diagnosis and monitoring, and for the development of portable and more affordable devices.


Assuntos
Detecção Precoce de Câncer/métodos , Técnicas Eletroquímicas , Neoplasias da Próstata/diagnóstico , Sarcosina/urina , Urinálise/métodos , Detecção Precoce de Câncer/economia , Humanos , Limite de Detecção , Luminescência , Masculino , Microesferas
11.
ChemistryOpen ; 4(3): 268-73, 2015 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-26246987

RESUMO

Graphene-metal composites have potential as novel catalysts due to their unique electrical properties. Here, we report the synthesis of a composite material comprised of monodispersed platinum nanoparticles on high-quality graphene obtained by using two different exfoliation techniques. The material, prepared via an easy, low-cost and reproducible procedure, was evaluated as an electrocatalyst for the hydrogen evolution reaction. The turnover frequency at zero overpotential (TOF0 in 0.1 m phosphate buffer, pH 6.8) was determined to be approximately 4600 h(-1). This remarkably high value is likely due to the optimal dispersion of the platinum nanoparticles on the graphene substrate, which enables the material to be loaded with only very small amounts of the noble metal (i.e., Pt) despite the very highly active surface. This study provides a new outlook on the design of novel materials for the development of robust and scalable water-splitting devices.

12.
Chemistry ; 21(7): 2936-47, 2015 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-25538028

RESUMO

The electrochemistry, photophysics, and electrochemically generated chemiluminescence (ECL) of a family of polysulfurated dendrimers with a pyrene core have been thoroughly investigated and complemented by theoretical calculations. The redox and luminescence properties of dendrimers are dependent on the generation number. From low to higher generation it is both easier to reduce and oxidize them and the emission efficiency increases along the family, with respect to the polysulfurated pyrene core. The analysis of such data evidences that the formation of the singlet excited state by cation-anion annihilation is an energy-deficient process and, thus, the ECL has been justified through the triplet-triplet annihilation pathway. The study of the dynamics of the ECL emission was achieved both experimentally and theoretically by molecular mechanics and quantum chemical calculations. It has allowed rationalization of a possible mechanism and the experimental dependence of the transient ECL on the dendrimer generation. The theoretically calculated Marcus electron-transfer rate constant compares very well with that obtained by the finite element simulation of the whole ECL mechanism. This highlights the role played by the thioether dendrons in modulating the redox and photophysical properties, responsible for the occurrence and dynamics of the electron transfer involved in the ECL. Thus, the combination of experimental and computational results allows understanding of the dendrimer size dependence of the ECL transient signal as a result of factors affecting the annihilation electron transfer.

14.
Chem Commun (Camb) ; 50(86): 13117-20, 2014 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-25224581

RESUMO

Scanning electrochemical microscopy (SECM) can image graphene oxide (GO) flakes on insulating and conducting substrates. The contrast between GO and the substrate is controlled by the electrostatic interactions that are established between the charges of the molecular redox mediator and the charges present in the sheet/substrate. SECM also allows quantitative measurement - at the nano/microscale - of the charge transfer kinetics between single monolayer sheets and agent molecules.


Assuntos
Grafite/química , Microscopia Eletroquímica de Varredura , Ouro/química , Cinética , Óxidos/química , Compostos de Silício/química
15.
Anal Chim Acta ; 831: 31-7, 2014 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-24861969

RESUMO

The qualitative identification of proteinaceous substances, as well as their location within a complex paint stratigraphy, is one of the most challenging issues in the characterization of painting materials. Nevertheless, information on paint components represent a crucial task for studies concerning both the ancient painting techniques adopted and the state of conservation, being fundamental investigations for the selection of appropriate conservation actions. The present research was aimed at developing a new detection approach for the immunochemical localization of ovalbumin in paint cross-sections based on the use of scanning electrochemical microscopy (SECM). The immunochemical analyses were performed using an anti-ovalbumin primary antibody and a secondary antibody labelled with horseradish peroxidase (HRP). SECM measurements were performed in feedback mode using benzoquinone (BQ)/hydroquinone (H2Q) redox couple. In presence of hydrogen peroxide (H2O2), HRP catalyzes the re-oxidation of H2Q to BQ and the increment of BQ concentration in correspondence of the target protein was detected by SECM through the electrochemical reduction of the regenerated BQ at the microelectrode. Indeed, the localization of ovalbumin was possible thanks to a clear discrimination of SECM currents, achieved by the comparison of the measurements recorded before and after H2O2 administration, based on the HRP on/off approach. The method was evaluated both on samples from standard mocks-up and on a historical sample, collected from a Renaissance wood painting. The obtained results were promising, foreseeing a wider application of SECM on cultural heritage researches.


Assuntos
Peroxidase do Rábano Silvestre/química , Microscopia Eletroquímica de Varredura , Proteínas/análise , Anticorpos/química , Anticorpos/imunologia , Benzoquinonas/química , Peroxidase do Rábano Silvestre/metabolismo , Peróxido de Hidrogênio/química , Hidroquinonas/química , Ovalbumina/análise , Ovalbumina/imunologia , Oxirredução , Proteínas/imunologia
16.
Chemistry ; 19(18): 5566-77, 2013 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-23564495

RESUMO

Rotaxane molecular shuttles were studied in which a tetralactam macrocyclic ring moves between a succinamide station and a second station in which the structure is varied. Station 2 in all cases is an aromatic imide, which is a poor hydrogen-bond acceptor in the neutral form, but a strong one when reduced with one or two electrons. When the charge density on the hydrogen-bond-accepting carbonyl groups in station 2 is reduced by changing a naphthalimide into a naphthalene diimide radical anion, the shuttling rate changes only slightly. When station 2 is a pyromellitimide radical anion, however, the shuttling rate is significantly reduced. This implies that the shuttling rate is not only determined by the initial unbinding of the ring from the first station, as previously supposed. An alternative reaction mechanism is proposed in which the ring binds to both stations in the transition state.


Assuntos
Amidas/química , Imidas/química , Rotaxanos/síntese química , Succinatos/química , Ânions , Eletroquímica , Elétrons , Ligação de Hidrogênio , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Movimento (Física) , Naftalenos/química , Rotaxanos/química
17.
Langmuir ; 29(11): 3791-6, 2013 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-23421711

RESUMO

We describe for the first time the electro-oxidative synthesis and passivating properties of surface films of poly(allylamine) and copolymers of allylamine and diallylamine. Cyclic voltammetry and impedance spectra show that the films exhibit high charge-transfer resistance and that the addition of diallylamine causes improvements in the compactness and stability toward swelling of the films when compared to both allylamine and diallyamine, leading to coatings with high charge-transfer resistance up to 70 MΩ. We also show that removing oxygen before the polymerization further improves the films' passivating properties.


Assuntos
Alilamina/química , Polimerização , Eletroquímica , Oxigênio/química , Poliaminas/química
18.
Int J Nanomedicine ; 8: 307-14, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23355777

RESUMO

Titanium plates treated in vitro with a mouthwash containing amine fluoride (100 ppm F-) and another containing zinc-substituted carbonate-hydroxyapatite have been analyzed by scanning electron microscopy and atomic force microscopy to evaluate the modification of the surface roughness induced by treatment with these two different mouthwashes. The treatment with F--based mouthwash produces a roughness characterized by higher peaks and deeper valleys in the streaks on the titanium bracket surface compared with those observed in the reference polished titanium plates. This effect causes a mechanical weakness in the metallic dental implant causing bacterial growth and therefore promotes infection and prosthesis contamination. However, the in vitro treatment with a mouthwash containing zinc-substituted carbonate-hydroxyapatite reduced the surface roughness by filling the streaks with an apatitic phase. This treatment counteracts the surface oxidative process that can affect the mechanical behavior of the titanium dental implant, which inhibits the bacterial growth contaminating prostheses.


Assuntos
Implantes Dentários , Durapatita/química , Fluoretos/química , Antissépticos Bucais/química , Nanopartículas/química , Titânio/química , Durapatita/farmacologia , Fluoretos/farmacologia , Teste de Materiais , Microscopia de Força Atômica , Propriedades de Superfície/efeitos dos fármacos
19.
ACS Nano ; 7(1): 811-7, 2013 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-23244166

RESUMO

The artificial leaf project calls for new materials enabling multielectron catalysis with minimal overpotential, high turnover frequency, and long-term stability. Is graphene a better material than carbon nanotubes to enhance water oxidation catalysis for energy applications? Here we show that functionalized graphene with a tailored distribution of polycationic, quaternized, ammonium pendants provides an sp(2) carbon nanoplatform to anchor a totally inorganic tetraruthenate catalyst, mimicking the oxygen evolving center of natural PSII. The resulting hybrid material displays oxygen evolution at overpotential as low as 300 mV at neutral pH with negligible loss of performance after 4 h testing. This multilayer electroactive asset enhances the turnover frequency by 1 order of magnitude with respect to the isolated catalyst, and provides a definite up-grade of the carbon nanotube material, with a similar surface functionalization. Our innovation is based on a noninvasive, synthetic protocol for graphene functionalization that goes beyond the ill-defined oxidation-reduction methods, allowing a definite control of the surface properties.


Assuntos
Materiais Biomiméticos/química , Grafite/química , Grafite/efeitos da radiação , Nanoestruturas/química , Fotossíntese , Complexo de Proteína do Fotossistema II/química , Folhas de Planta/química , Materiais Biomiméticos/efeitos da radiação , Luz , Teste de Materiais , Nanoestruturas/efeitos da radiação , Nanoestruturas/ultraestrutura , Propriedades de Superfície
20.
Dalton Trans ; 42(4): 997-1010, 2013 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-23108182

RESUMO

Four Cu(I) complexes with general formulas [Cu(N^N)(2)][BF(4)] and [(P^P)Cu(N^N)][BF(4)] were prepared, where N^N stands for 2-(2-tert-butyl-2H-tetrazol-5-yl)pyridine and P^P is a chelating diphosphine, namely bis-(diphenylphosphino)methane (dppm), bis-(diphenylphosphino)ethane (dppe) or bis[2-(diphenylphosphino)phenyl]ether (POP). In an acetonitrile medium, the Electro-Spray Ionization Mass Spectrometry (ESI-MS) determination provided the preliminary evidence for the occurrence of the dppm-containing complex as a mixture of a cationic mononuclear [Cu(N^N)(dppm)](+) species and a bis-cationic dinuclear [Cu(2)(N^N)(2)(dppm)(2)](2+)-type compound. Definitive evidence of peculiar structural features came from X-ray crystallography, which showed both the dppm- and, unexpectedly, the dppe-based heteroleptic compounds to crystallize as diphosphine-bridged Cu(I) dimers, unlike [Cu(N^N)(2)](+) and [(POP)Cu(N^N)](+) which are mononuclear species. In solutions of non-coordinating solvents, (31)P NMR studies at variable temperatures and dilution titrations confirmed that the dppm-based complex undergoes a monomer-dimer dynamic equilibrium, while the dppe-containing complex occurs as the bis-cationic dinuclear species, [Cu(2)(N^N)(2)(dppe)(2)](2+), within a concentration range comprised between 10(-2) and 10(-4) M. Differences among heteroleptic complexes might be related to the smaller natural bite angle displayed by dppm and dppe phosphine ligands (72° and 85°, respectively), with respect to that reported for POP (102°). The electrochemical features of the new species have been investigated by cyclic voltammetry. Despite the irreversible and complicated redox behaviour, which is typical for copper complexes, the reductions have been attributed to the tetrazole ligand whereas the oxidations are characterized as Cu(I/II) processes with a substantial contribution from the P^P-based ligands in the case of the heteroleptic species. All the four complexes are weakly or not luminescent in CH(2)Cl(2) solution, but heteroleptic complexes are bright green luminophores in a solid matrix, with quantum yields as high as 45% (dppm complex) even at room temperature. This makes them potential candidates as cheap emitting materials for electroluminescent devices.

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