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1.
Rev. cub. inf. cienc. salud ; 33: e1769, 2022. tab, graf
Artigo em Espanhol | LILACS, CUMED | ID: biblio-1408138

RESUMO

Enfocados en el ámbito del periodismo hipermedia por sus posibilidades de monitoreo mediante el teletrabajo, y por el énfasis que está haciendo el país en la utilización creciente de las TIC, un equipo de investigadores de perfiles diversos, con representación en todas las regiones de Cuba, identificaron 35 experiencias de periodismo hipermedia publicadas en los medios públicos cubanos hasta el 5 de junio de 2020. De esta muestra, se seleccionaron 20 propuestas empleando la técnica del grupo nominal en variante virtual, a las cuales se le realizó un análisis más detallado, a partir de 13 criterios identificados entre las recomendaciones internacionales para el abordaje de la pandemia en la prensa. Tanto el análisis de la muestra, como el de un foro debate realizado con periodistas de todo el archipiélago a partir de la publicación del informe resultante de esta investigación, arrojaron pautas interesantes acerca de las prácticas comunicativas positivas detectadas, potencialmente aplicables en las dinámicas productivas de los medios públicos cubanos(AU)


Focused on the field of hypermedia journalism due to its possibilities of monitoring through teleworking, and because of the emphasis that the country is placing on the increasing use of ICTs, a team of researchers with diverse profiles, with representation in all regions of Cuba, identified 35 experiences of hypermedia journalism published in the Cuban public media until June 5th, 2020. From this sample, 20 proposals were selected using the nominal group technique in virtual variant, to which a more detailed analysis was carried out, based on 13 criteria identified among the international recommendations for dealing with the pandemic in the press. Both the analysis of the sample, as well as a discussion forum held with journalists from all over the archipelago from the publication of the report resulting from this research, yielded interesting guidelines about the positive communicative practices detected, potentially applicable in the productive dynamics of Cuban public media(AU)


Assuntos
Humanos , Masculino , Feminino , Hipermídia , Jornalismo/ética , COVID-19/epidemiologia , Meios de Comunicação de Massa , Cuba
2.
Arch Pharm (Weinheim) ; 354(10): e2100095, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-34128249

RESUMO

Purines are ubiquitous structures in cell biology involved in a multitude of cellular processes, because of which substituted purines and analogs are considered excellent scaffolds in drug design. In this study, we explored the key structural features of a purine-based proapoptotic hit, 8-tert-butyl-9-phenyl-6-benzyloxy-9H-purine (1), by setting up a library of 6-alkoxy purines with the aim of elucidating the structural requirements that govern its biological activity and to study the cell selectivity of this chemotype. This was done by a phenotypic screening approach based on cell cycle analysis of a panel of six human cancer cell lines, including T cell leukemia Jurkat cells. From this study, two derivatives (12 and 13) were identified as Jurkat-selective proapoptotic compounds, displaying superior potency and cell selectivity than hit 1.


Assuntos
Antineoplásicos/farmacologia , Leucemia de Células T/tratamento farmacológico , Purinas/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/química , Apoptose/efeitos dos fármacos , Linhagem Celular Tumoral , Humanos , Células Jurkat , Leucemia de Células T/patologia , Purinas/síntese química , Purinas/química , Relação Estrutura-Atividade
3.
Pharmaceutics ; 12(2)2020 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-32098204

RESUMO

Structural maintenance of chromosomes protein 2 (SMC2) is a central component of the condensin complex involved in DNA supercoiling, an essential process for embryonic stem cell survival. SMC2 over-expression has been related with tumorigenesis and cancer malignancy and its inhibition is regarded as a potential therapeutic strategy even though no drugs are currently available. Here, we propose to inhibit SMC2 by intracellular delivery of specific antibodies against the SMC2 protein. This strategy aims to reduce cancer malignancy by targeting cancer stem cells (CSC), the tumoral subpopulation responsible of tumor recurrence and metastasis. In order to prevent degradation and improve cellular internalization, anti-SMC2 antibodies (Ab-SMC2) were delivered by polymeric micelles (PM) based on Pluronic® F127 amphiphilic polymers. Importantly, scaffolding the Ab-SMC2 onto nanoparticles allowed its cellular internalization and highly increased its efficacy in terms of cytotoxicity and inhibition of tumorsphere formation in MDA-MB-231 and HCT116 breast and colon cancer cell lines, respectively. Moreover, in the case of the HCT116 cell line G1, cell-cycle arrest was also observed. In contrast, no effects from free Ab-SMC2 were detected in any case. Further, combination therapy of anti-SMC2 micelles with paclitaxel (PTX) and 5-Fluorouracil (5-FU) was also explored. For this, PTX and 5-FU were respectively loaded into an anti-SMC2 decorated PM. The efficacy of both encapsulated drugs was higher than their free forms in both the HCT116 and MDA-MB-231 cell lines. Remarkably, micelles loaded with Ab-SMC2 and PTX showed the highest efficacy in terms of inhibition of tumorsphere formation in HCT116 cells. Accordingly, our data clearly suggest an effective intracellular release of antibodies targeting SMC2 in these cell models and, further, strong cytotoxicity against CSC, alone and in combined treatments with Standard-of-Care drugs.

5.
Chem Sci ; 8(1): 689-696, 2017 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-28451218

RESUMO

A new approach is presented to form self-supported bimetallic nanosized solids with acid and redox catalytic properties. They are water-, air- and H2-stable, and are able to activate demanding C-C and C-H reactions. A detailed mechanistic study on the formation of the Ag-Fe bimetallic system shows that a rapid redox-coupled sequence between Ag+, O2 (air) and Fe2+ occurs, giving monodisperse Ag nanoparticles supported by O-bridged diatomic Fe3+ triflimides. The system can be expanded to Ag nanoparticles embedded within a matrix of Cu2+, Bi3+ and Yb3+ triflimide.

6.
CorSalud ; 8(1)ene.-mar. 2016. tab, graf
Artigo em Espanhol | CUMED | ID: cum-66687

RESUMO

Introducción: La fibrilación auricular es un serio problema de salud y los paísescentroamericanos no escapan de este flagelo. Objetivo: Caracterizar la fibrilación auricular, precisar sus variables clínico-epidemiológicas y determinar el riesgo de accidente cerebrovascular, a partir del uso dela escala CHA 2 DS 2 -VASc. Método: Se realizó un estudio descriptivo y prospectivo en 107 pacientes que in-gresaron, con diagnóstico de fibrilación auricular, en el servicio de Medicina Interna del Hospital Nacional San Rafael de la ciudad de Santa Tecla, La Libertad, El Salvador; en el período de enero a julio de 2013. Se analizaron las variables clínico-epidemiológicas, se realizó ecocardiograma a todos los pacientes y se calculó la escala de riesgo CHA 2 DS 2 -VASc. Se utilizaron métodos para establecer las relacio-nes entre las variables. Resultados: Más de la mitad de los pacientes con fibrilación auricular (57,0 por ciento; p=0,015) son mujeres, el 51,4 por ciento tiene color blanco de piel y una edad media de 74,7 ± 13,8 años. El 80,4 por ciento de los pacientes tiene una fibrilación auricular no asociada a valvulopatía. Predominaron la hipertensión arterial (54,2 por ciento), las cardiopatías isquémica (28,0 por ciento) e hipertensiva (23,4 por ciento), la miocardiopatía dilatada (24,3 por ciento) y la fibrilación auricular permanente (49,5 por ciento). Conclusiones: La menor fracción de eyección y el mayor diámetro diastólico del ventrículo izquierdo se relacionaron con la fibrilación auricular. La mayoría de los pacientes presenta un riesgo elevado de accidente cerebrovascular, las variables que se le asocian son: la mayor edad, el sexo femenino y el mayor grosor del septum interventricular(AU)


Assuntos
Humanos , Adulto , Fibrilação Atrial , Acidente Vascular Cerebral , Anticoagulantes
7.
Philos Trans A Math Phys Eng Sci ; 372(2027)2014 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-25246675

RESUMO

We present a review, together with new results, of a universal forcing of oscillatory systems, termed 'rocking', which leads to the emergence of a phase bistability and to the kind of pattern formation associated with it, characterized by the presence of phase domains, phase spatial solitons and phase-bistable extended patterns. The effects of rocking are thus similar to those observed in the classic 2 : 1 resonance (the parametric resonance) of spatially extended systems of oscillators, which occurs under a spatially uniform, time-periodic forcing at twice the oscillations' frequency. The rocking, however, has a frequency close to that of the oscillations (it is a 1 : 1 resonant forcing) and hence is a good alternative to the parametric forcing when the latter is inefficient (e.g. in optics). The key ingredient is that the rocking amplitude is modulated either in time or in space, such that its sign alternates (exhibits π-phase jumps). We present new results concerning a paradigmatic nonlinear optical system (the two-level laser) and show that phase domains and dark-ring (phase) solitons replace the ubiquitous vortices that characterize the emission of free-running, broad area lasers.

8.
Dalton Trans ; 41(31): 9286-96, 2012 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-22555652

RESUMO

Combined chemo and photothermal therapy in in vitro testing has been achieved by means of multifunctional nanoparticles formed by plasmonic gold nanoclusters with a protecting shell of porous silica that contains an antitumor drug. We propose a therapeutic nanoplatform that associates the optical activity of small gold nanoparticles aggregates with the cytotoxic activity of 20(S)-camptothecin simultaneously released for the efficient destruction of cancer cells. For this purpose, a method was used for the controlled assembly of gold nanoparticles into stable clusters with a tailored absorption cross-section in the vis/NIR spectrum, which involves aggregation in alkaline medium of 15 nm diameter gold colloids protected with a thin silica layer. Clusters were further encapsulated in an ordered homogeneous mesoporous silica coating that provides biocompatibility and stability in physiological fluids. After internalization in 42-MG-BA human glioma cells, these protected gold nanoclusters were able to produce effective photothermolysis under femtosecond pulse laser irradiation of 790 nm. Cell death occurred by combination of a thermal mechanism and mechanical disruption of the membrane cell due to induced generation of micrometer-scale bubbles by vaporizing the water inside the channels of the mesoporous silica coating. Moreover, the incorporation of 20(S)-camptothecin within the pores of the external shell, which was released during the process, provoked significant cell death increase. This therapeutic model could be of interest for application in the treatment and suppression of non-solid tumors.


Assuntos
Antineoplásicos Fitogênicos/administração & dosagem , Camptotecina/administração & dosagem , Ouro/administração & dosagem , Nanopartículas Metálicas/administração & dosagem , Dióxido de Silício/administração & dosagem , Antineoplásicos Fitogênicos/química , Camptotecina/química , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos da radiação , Terapia Combinada , Ouro/química , Temperatura Alta , Humanos , Terapia a Laser , Nanopartículas Metálicas/química , Nanopartículas Metálicas/ultraestrutura , Microscopia Eletrônica de Transmissão , Neoplasias/terapia , Dióxido de Silício/química
9.
Inorg Chem ; 50(19): 9243-55, 2011 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-21902227

RESUMO

The newly synthesized dinuclear complex [Fe(III)(2)(µ-OH)(2)(bik)(4)](NO(3))(4) (1) (bik, bis(1-methylimidazol-2-yl)ketone) shows rather short Fe···Fe (3.0723(6) Å) and Fe-O distances (1.941(2)/1.949(2) Å) compared to other unsupported Fe(III)(2)(µ-OH)(2) complexes. The bridging hydroxide groups of 1 are strongly hydrogen-bonded to a nitrate anion. The (57)Fe isomer shift (δ = 0.45 mm s(-1)) and quadrupole splitting (ΔE(Q) = 0.26 mm s(-1)) obtained from Mössbauer spectroscopy are consistent with the presence of two identical high-spin iron(III) sites. Variable-temperature magnetic susceptibility studies revealed antiferromagnetic exchange (J = 35.9 cm(-1) and H = JS(1)·S(2)) of the metal ions. The optimized DFT geometry of the cation of 1 in the gas phase agrees well with the crystal structure, but both the Fe···Fe and Fe-OH distances are overestimated (3.281 and 2.034 Å, respectively). The agreement in these parameters improves dramatically (3.074 and 1.966 Å) when the hydrogen-bonded nitrate groups are included, reducing the value calculated for J by 35%. Spontaneous reduction of 1 was observed in methanol, yielding a blue [Fe(II)(bik)(3)](2+) species. Variable-temperature magnetic susceptibility measurements of [Fe(II)(bik)(3)](OTf)(2) (2) revealed spin-crossover behavior. Thermal hysteresis was observed with 2, due to a loss of cocrystallized solvent molecules, as monitored by thermogravimetric analysis. The hysteresis disappears once the solvent is fully depleted by thermal cycling. [Fe(II)(bik)(3)](OTf)(2) (2) catalyzes the oxidation of alkanes with t-BuOOH. High selectivity for tertiary C-H bond oxidation was observed with adamantane (3°/2° value of 29.6); low alcohol/ketone ratios in cyclohexane and ethylbenzene oxidation, a strong dependence of total turnover number on the presence of O(2), and a low retention of configuration in cis-1,2-dimethylcyclohexane oxidation were observed. Stereoselective oxidation of olefins with dihydrogen peroxide yielding epoxides was observed under both limiting oxidant and substrate conditions.


Assuntos
Adamantano/química , Complexos de Coordenação/síntese química , Compostos Férricos/síntese química , Imidazóis/síntese química , Cetonas/síntese química , Catálise , Complexos de Coordenação/química , Compostos Férricos/química , Imidazóis/química , Cetonas/química , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Simulação de Dinâmica Molecular , Espectrometria de Massas por Ionização por Electrospray , Espectrofotometria Ultravioleta , Espectroscopia de Infravermelho com Transformada de Fourier , Espectroscopia de Mossbauer , Difração de Raios X
10.
J Control Release ; 156(2): 246-57, 2011 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-21756949

RESUMO

Here we report the design, synthesis and biological evaluation of surface-modified silica nanoparticles (SNP) for the delivery of camptothecin (CPT). Drug has been covalently linked to the nanoparticle through an ester bond with the 20-hydroxy moiety, in order to stabilize its lactone ring and to avoid unspecific release of the drug. The obtained material is highly stable in plasma, with low release of the cargo at physiological pH. Cell internalization and in vitro efficacy assays demonstrated that nanoparticles carrying CPT (SNP-CPT) entered cells via endocytosis and the intracellular release of the cargo induced cell death with half maximal inhibitory concentration (IC50) values and cell cycle distribution profiles similar to those observed for the naked drug. Further, in vivo biodistribution, therapeutic efficacy and biocompatibility of the SNP-CPT were evaluated in human colorectal cancer xenografts using in vivo fluorescence or bioluminescence optical imaging. In vivo tumor-accumulation and whole-body tissue distribution were carried out based on the acquisition of fluorescence emission of a fluorophore (Cy5.5) conjugated to the SNP-CPT, as well as by HPLC quantification of tissue CPT levels. The results showed that, although SNP-CPT tended to accumulate in organs of the reticulo-endothelial system, nanoparticles boost CPT concentration in tumor vs administration of the free drug. Accordingly, SNP-CPT treatment delayed the growth of subcutaneous tumors while significantly reducing the systemic toxicity associated with CPT administration. These results indicate that the SNP-CPT could be used as a robust drug delivery system for antitumoral treatments based on CPT.


Assuntos
Antineoplásicos/administração & dosagem , Antineoplásicos/uso terapêutico , Camptotecina/administração & dosagem , Camptotecina/uso terapêutico , Neoplasias Colorretais/tratamento farmacológico , Nanopartículas/química , Dióxido de Silício/química , Animais , Antineoplásicos/farmacocinética , Camptotecina/farmacocinética , Linhagem Celular Tumoral , Neoplasias Colorretais/patologia , Humanos , Camundongos , Modelos Moleculares , Nanopartículas/ultraestrutura , Propriedades de Superfície , Distribuição Tecidual
11.
Inorg Chem ; 48(22): 10643-51, 2009 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-19817402

RESUMO

Reaction of 2,4-(2,2'-dipyridylamino)-6-(2-pyridylhydrazino)-1,3,5-triazine, abbreviated dppht (5), with copper(II) chloride in methanol yields a mixed-valent Cu(II)(4)Cu(I) compound (6), also involving the presence of a radical anion. The single-crystal structure determination for [Cu(5)(5(M))(5(MR))Cl(8)] (6) reveals that the original dppht ligand (5) has been monochlorinated at one of its pyridine rings and oxidized at its hydrazyl moiety, generating the ligand 2,4-(2,2'-dipyridylamino)-6-(2-(5-chloropyridyl)azo)-1,3,5-triazine (5(M)). Moreover, the molecular structure of 6 indicates that one of the two coordinated ligands 5(M) is in a radical-anion state, symbolized as 5(MR), characterized by a typical N-N bond length of about 1.33 A for a one-electron reduced azo group. The nature of this unique [Cu(II)(4)Cu(I)(radical)] assembly is corroborated by X-ray absorption spectroscopy, electron paramagnetic resonance, and magnetic susceptibility measurements. Density-functional theory calculations are consistent with the unprecedented structural features and support the spectroscopic data.


Assuntos
Cobre/química , Cristalografia por Raios X , Espectroscopia de Ressonância de Spin Eletrônica , Ligantes , Magnetismo , Modelos Moleculares , Conformação Molecular , Compostos Organometálicos/química , Triazinas/química , Espectroscopia por Absorção de Raios X
12.
Dalton Trans ; (38): 7845-53, 2009 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-19771343

RESUMO

Over the past five years, the spin-crossover (SCO) phenomenon has experienced a clear new lease of interest from the scientific community coinciding with the recent publication of remarkable new advances. This perspective paper describes five illustrative examples of SCO systems, published during the past twelve months, showing new aspects of the unique and very appealing behaviour of these molecular switches, which may find interesting applications in the near future.

13.
Chemistry ; 14(28): 8486-99, 2008.
Artigo em Inglês | MEDLINE | ID: mdl-18780381

RESUMO

The influence of the counteranion on the structure and the spin-transition properties of original 1D bis(tetrazole) Fe(II) systems, namely [Fe(btzx)(3)]X(2) (X=PF(6) (-) (1), CF(3)SO(3) (-) (2) and ClO(4) (-) (3); btzx=m-xylylenebis(tetrazole)) is studied. The X-ray crystal structures of compounds 1 and 2 are described in detail. These structures present a solvent molecule encapsulated within pockets formed by btzx ligands along the 1D coordination chains. Compound 2 is shown to be the first structurally characterised alternating HS-LS 1D spin-transition system (HS=high spin, LS=low spin). The magnetic susceptibility measurements of all three compounds are compared. The degree of completion and the transition temperature are both drastically influenced by the counterion used, while surprisingly, the cooperative nature of the transition is not affected by the choice of counterion. Compounds 1 and 2 are further studied by Mössbauer spectroscopy and their distinct LIESST properties are compared.


Assuntos
Compostos Férricos/química , Tetrazóis/química , Cátions , Magnetismo , Modelos Moleculares , Espectroscopia de Mossbauer
14.
Dalton Trans ; (46): 5434-40, 2007 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-18026593

RESUMO

The reaction of btzmp (1,2-bis(tetrazol-1-yl)-2-methylpropane) with Fe(ClO4)2 generates a 1D polymeric species, [Fe(mu-btzmp)2(btzmp)2](ClO4)2, showing a steep spin transition (T(1/2) / =136 K and T(1/2) / =133 K) with a 3 K thermal hysteresis. The crystal structure at 100 and 200 K reveals that, in contrast to other bistetrazole based spin-transition systems such as [Fe(endi)3](BF4)2 and [Fe(btzp)3](ClO4)2, the present compound has only two ligands bridging the metallic centres, while the other two coordination positions are occupied by two mono-coordinated (non-bridging) btzmp ligands. This peculiarity confers an unprecedented crystal packing in the series of 1D bistetrazole based polymers. The change in spin state is accompanied by an order/disorder transition of the ClO4* counterion. A careful examination of the structural changes occurring upon the spin transition indicates that this order/disorder is most likely affected by the modification of the [tetrazole-centroid]-ND-Fe angle (which is typical of bistetrazole spin-transition materials). Apart from X-ray analysis, also magnetic susceptibility, Mössbauer and UV-vis spectroscopies have been used to characterise the HS and the LS states of [Fe(mu-btzmp)2(btzmp)2](ClO4)2.


Assuntos
Compostos Férricos/química , Propano/análogos & derivados , Tetrazóis/química , Cristalografia por Raios X , Magnetismo , Modelos Moleculares , Percloratos/síntese química , Percloratos/química , Polímeros/síntese química , Polímeros/química , Propano/síntese química , Espectrofotometria Ultravioleta , Espectroscopia de Mossbauer , Tetrazóis/síntese química
15.
Inorg Chem ; 46(10): 4079-89, 2007 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-17441713

RESUMO

Iron(II) complexes obtained from tetradentate, rigid, linear N4 ligands have been investigated to appraise the influence of steric effects and the impact of trans-coordinated anions on the spin-transition behavior. As expected, the well-designed ligands embrace the metal center, resulting in octahedral iron(II) complexes where the basal plane is fully occupied by the pyridine/pyrazole N4 ligand, while anions or solvent molecules are exclusively axially coordinated. Precursor complexes, namely, [Fe(bpzbpy)(MeOH)2](BF4)2 (where bpzbpy symbolizes the ligand 6,6'-bis(N-pyrazolylmethyl)-2,2'-bipyridine) and [Fe(mbpzbpy)(MeOH)2](BF4)2 (where mbpzbpy symbolizes the ligand 6,6'-bis(3,5-dimethyl-N-pyrazolmethyl)-2,2'-bipyridine), have been used for the in situ preparation of a series of structural analogues via the exchange of the weakly coordinated trans methanol molecules by various anions, such as thiocyanate, selenocyanate, or dicyanamide. The magnetic properties of all seven iron(II) compounds thus obtained have been investigated. Two iron(II) complexes, i.e., [Fe(bpzbpy)(NCS)2] and [Fe(bpzbpy)(NCSe)2], exhibit gradual spin-crossover (SCO) properties typical of isolated mononuclear species with weak cooperative interaction. These two SCO materials have been studied by Mössbauer spectroscopy, and the light-induced excited spin state trapping effect has been investigated, revealing the possibility to induce the spin-transition both by temperature variation and by light irradiation. A correlation between steric/anion effect and SCO behavior is suggested.

16.
Phys Rev Lett ; 97(9): 093903, 2006 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-17026364

RESUMO

We report the experimental observation of the conversion of a phase-invariant nonlinear system into a bistable phase-locked one via rocking [G. J. de Valcárcel and K. Staliunas, Phys. Rev. E 67, 026604 (2003)10.1103/PhysRevE.67.026604]. This conversion results in vortices of the phase-invariant system being replaced by phase patterns such as domain walls. A model for the experimental device, a photorefractive oscillator, is given that reproduces the observed behavior.

17.
Chem Commun (Camb) ; (35): 3723-5, 2006 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-17047824

RESUMO

The first crystallographic evidences of the theoretically suggested C2-symmetric cyclohexameric form of liquid methanol and the S6-symmetric cyclohexameric form of liquid ethanol are reported, trapped inside a hydrophilic pocket shielded by tert-butyl groups.

18.
J Phys Chem A ; 110(13): 4348-58, 2006 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-16571037

RESUMO

The six multichromophoric species 1-6, containing the potentially luminescent Ru(II) polypyridine subunits and 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene fluorophores (dipyrromethene-BF(2) dyes, herein after called bodipy), have been prepared and their absorption spectra, luminescence properties (both at room temperature in fluid solution and at 77 K in rigid matrix), and redox properties have been investigated (for the structuralformulas of all the compounds, see Figure 1). For comparison purposes, also the same properties of the bodipy-based free ligands have been examined. Three of the multichromophoric species (1-3) are based on the Ru(bpy)(3)-type metal subunit, whereas 4-6 are based on the Ru(terpy)(2)-type metal subunit. Transient absorption spectroscopy at room temperature of all the compounds has also been performed. The absorption spectra of all the metal complexes show features that can be assigned to the Ru(II) polypyridine subunits and to the bodipy centers. In particular, the lowest energy spin-allowed pi-pi* transition of the bodipy groups dominates the visible region, peaking at about 530 nm. All the new complexes exhibit a rich redox behavior, with reversible processes attributed to specific sites, indicating a small perturbation of each redox center and therefore highlighting the supramolecular nature of the multichromophoric assemblies. Despite the good luminescence properties of the separated components, 1-6 do not exhibit any luminescence at room temperature; however, transient absorption spectroscopy evidences that for all of them a long-lived (microsecond time scale) excited state is formed, which is identified as the bodipy-based triplet state. Pump-probe transient absorption spectroscopy suggests that such a triplet state is formed from the promptly prepared bodipy-based (1)pi-pi* state in most cases by the intervention of a charge-separated level. At 77 K, all the complexes except complex 1 exhibit the bodipy-based fluorescence, although with a slightly shortened lifetime compared to the corresponding free ligand(s), and 4-6 also exhibit a phosphorescence assigned to the bodipy subunits. Phosphorescence of bodipy species had never been reported in the literature to the best of our knowledge: in the present cases we propose that it is an effective decay process thanks to the presence of the ruthenium heavy atom and of the closely lying (3)MLCT state of the Ru(terpy)(2)-type subunits.

19.
Chem Commun (Camb) ; (33): 4222-4, 2005 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-16100610

RESUMO

The triplet emitting state of an indacene at 774 nm (of 50 ms life-time) was observed for the first time in new ruthenium(II) complexes based on bipartite ligands carrying one or two indacene subunits linked via phenylethynyl connectors to terpyridine fragments.

20.
Inorg Chem ; 43(23): 7359-68, 2004 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-15530086

RESUMO

The syntheses, structural features, electrochemical behavior, absorption spectra, and photophysical properties of five mononuclear complexes [(terpy)Ru(terpy-DEDBT(n)-terpy)](2+), RuT(n), and five binuclear complexes [(terpy)Ru(terpy-DEDBT(n)-terpy)Ru(terpy)](4+), RuT(n)Ru, are reported, where n varies from 1 to 5 so that the metal-metal distance is estimated to be 42 A for the largest binuclear complex, RuT(5)Ru (terpy is 2,2':6',2"-terpyridine and DEDBT is 2,5-diethynyl-3,4-dibutylthiophene). The metal-centered oxidation potentials for the mononuclear and binuclear species are slightly more positive than for the reference [Ru(terpy)(2)](2+) complex, owing to the withdrawing nature of the back-to-back terpyridine ligands incorporating the repeat diethynyl-thiophene units. Comparison of the reduction potentials for the mononuclear and binuclear complexes reveals that the reduction steps are localized either at the terpy fragments of the T(n) ligands or at the terpy peripheral ligands. The spectroscopic results (absorption spectra at room temperature, luminescence spectra and lifetimes at room temperature and at 77 K) in acetonitrile solvent are consistent with the establishment of electronic delocalization within the oligomeric diethynyl-thiophene fragments (DEDBT(n)) of the T(n) ligands; however, the results also indicate that the terpy units of these ligands and the DEDBT(n)fragments are not strongly coupled. Both at room temperature and at 77 K, the (3)metal-to-ligand charge-transfer luminescence of RuT(n) and RuT(n)Ru complexes is strongly depressed in the larger species with respect to what happens for n < or = 2 (where the luminescence quantum yield is phi approximately 10(-4)); this is discussed in terms of the possible intervention of triplet levels localized at the oligothiophene DEDBT(n)(fragments.

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