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1.
Artigo em Inglês | MEDLINE | ID: mdl-38552989

RESUMO

PURPOSE: The POP-RT phase 3 randomized trial showed improved biochemical failure-free survival and metastasis-free survival with whole pelvic radiation therapy versus prostate-only radiation therapy for high and very high-risk prostate cancer, albeit with worse RTOG late urinary toxicity. We report updated late urinary adverse effects and bladder dose-effect relations within this trial. METHODS AND MATERIALS: Late urinary toxicity and the cumulative severity of each symptom during the follow-up period were graded using the Common Terminology Criteria for Adverse Events (CTCAE), version 5.0. Bladder dosimetry in 5-Gy increments (V5, V10, V15, V65, V68Gy) in the approved radiation therapy plans was compared with urinary symptoms and overall grade 2+ toxicity. Potential factors influencing urinary toxicity were tested using multivariable logistic regression analysis. Updated urinary quality of life (QOL) scores were compared between the trial arms. RESULTS: Complete combined data for late urinary symptoms and dosimetry was available for 193 of 224 patients. At a median follow-up of 75 months, cumulative late urinary CTCAE grade 3 toxicity was low and similar for whole pelvic radiation therapy and prostate-only radiation therapy (5.2% vs 4.1%, P = .49), and grade 2 toxicity was 31.3% versus 22.7%, respectively (P = .12). Cumulative rates of each urinary symptom were similar between both arms. Multivariable analysis with age at diagnosis, known diabetes, tumor stage, trial arm, prior transurethral resection of prostate, grade 2+ acute urinary toxicity, low bladder dose (V10Gy), and moderate bladder dose (V40Gy) did not identify any significant association with late urinary toxicity. Urinary QOL scores was similar between both the arms for all the symptoms. CONCLUSIONS: During long-term follow-up, whole pelvic radiation therapy resulted in low (∼5%) and similar grade 3 cumulative urinary toxicity as prostate-only radiation therapy. The long-term patient-reported QOL scores were similar. No causative factors affecting the late urinary toxicity were identified.

2.
Anal Methods ; 16(3): 344-370, 2024 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-38167884

RESUMO

This review focuses on the results of synthetic ratiometric fluorescent and colorimetric probes, which have been applied to qualitatively and quantitatively detect fluoride anions in cells, living organisms, and real samples. Primary attention is given to progress made in the working mechanism and applications of these probes to detect fluoride ions in living systems. In addition, design strategies and detection limit for these probes are discussed. This review aims to deliver a comprehensive compilation of the examples reported from 2005 to 2021 on the developments of ratiometric chromogenic and fluorogenic chemosensors for fluoride anions. A total of 20 different ratiometric/colorimetric sensors have been selected for the novelty in their design, sensitivity, detection limit, dynamic range, and speed of detection based on the three fundamental principles of F- ion detection, namely Si-O bond cleavage; excimer emission; and intramolecular charge transfer emission through the B-F monomer, B-F-B bridged dimers, and deprotonation of the amide N-H. Special emphasis has been given to categorize the fluorophores that work in aqueous media, and possible strategies that might be adopted to design green sensors are discussed. Finally, a tabular summary of the comparative studies of all the sensors based on their sensitivity, detection limit, working solvent, and applications is provided. This extensive review may expedite improvements in the development of advanced fluorescent probes for vast and stimulating applications in the future.


Assuntos
Corantes Fluorescentes , Fluoretos , Fluoretos/química , Espectrometria de Fluorescência , Ânions , Corantes Fluorescentes/química , Colorimetria/métodos
3.
Saudi J Kidney Dis Transpl ; 34(Suppl 1): S226-S229, 2023 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-38995288

RESUMO

Pulmonary mucormycosis is rare in kidney transplant recipients and has a high mortality rate. We report a case of pulmonary mucormycosis presenting as round pneumonia 1 year and 1 month after the transplant. The diagnosis was confirmed by a percutaneous lung biopsy. A complete resection of the lung mass, followed by intravenous liposomal amphotericin B therapy, saved the life of the patient. In conclusion, early and prompt diagnosis followed by complete resection of the lesion in pulmonary mucormycosis is lifesaving.


Assuntos
Anfotericina B , Antifúngicos , Transplante de Rim , Pneumopatias Fúngicas , Mucormicose , Pneumonectomia , Humanos , Mucormicose/diagnóstico , Mucormicose/tratamento farmacológico , Mucormicose/cirurgia , Transplante de Rim/efeitos adversos , Pneumopatias Fúngicas/tratamento farmacológico , Pneumopatias Fúngicas/diagnóstico , Pneumopatias Fúngicas/microbiologia , Pneumopatias Fúngicas/cirurgia , Antifúngicos/uso terapêutico , Anfotericina B/uso terapêutico , Masculino , Resultado do Tratamento , Pneumonia/microbiologia , Pneumonia/tratamento farmacológico , Pneumonia/diagnóstico , Biópsia , Tomografia Computadorizada por Raios X , Pessoa de Meia-Idade , Hospedeiro Imunocomprometido
4.
Artigo em Inglês | MEDLINE | ID: mdl-25847788

RESUMO

The ligand 2,6-bis[(N-phenyl)amido]-4-methylphenol (receptor 1) and its copper(II) complex (receptor 2) having amide moiety have been designed and synthesized for selective sensing of anions. The anion recognition behavior of the receptor 1 and its copper complex (receptor 2) has been studied in acetonitrile. Quenching of fluorescence was observed for both receptors in presence of HSO4(-) anion whereas other physiologically and environmentally important anions such as F(-), Cl(-), Br(-), I(-), CN(-), OAc(-), HCO3(-), H2PO4(-), NO3(-), NO2(-) and SO4(2-) show fluorescence enhancement behavior. The sensing protocol has been studied both spectrophotometrically as well as spectrofluorometrically. Fluorescence quenching is suggested to proceed via both dynamic and static processes.


Assuntos
Complexos de Coordenação/química , Cobre/química , Sulfatos/análise , Ligantes , Fenóis/química , Receptores Artificiais/química , Espectrometria de Fluorescência/métodos , Espectrofotometria/métodos
5.
Dalton Trans ; 41(12): 3414-23, 2012 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-22301883

RESUMO

A series of mononuclear lanthanide(III) complexes [Ln(LH(2))(H(2)O)(3)Cl](ClO(4))(2) (Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate macrocyclic ligand (LH(2)) in 95 : 5 (v/v) methanol-water solution fix atmospheric carbon dioxide to produce the carbonato-bridged trinuclear complexes [{Ln(LH(2))(H(2)O)Cl}(3)(µ(3)-CO(3))](ClO(4))(4)·nH(2)O. Under similar conditions, the mononuclear Y(III) complex forms the dimeric compound [{Y(LH(2))(H(2)O)Cl}(µ(2)-CO(3)){Y(LH(2))(H(2)O)(2)}](ClO(4))(3)·4H(2)O. These complexes have been characterized by their IR and NMR ((1)H, (13)C) spectra. The X-ray crystal structures have been determined for the trinuclear carbonato-bridged compounds of Nd(III), Gd(III) and Tb(III) and the dinuclear compound of Y(III). In all cases, each of the metal centers are 8-coordinate involving two imine nitrogens and two phenolate oxygens of the macrocyclic ligand (LH(2)) whose two other imines are protonated and intramolecularly hydrogen-bonded with the phenolate oxygens. The oxygen atoms of the carbonate anion in the trinuclear complexes are bonded to the metal ions in tris-bidentate µ(3)-η(2):η(2):η(2) fashion, while they are in bis-bidentate µ(2)-η(2):η(2) mode in the Y(III) complex. The magnetic properties of the Gd(III) complex have been studied over the temperature range 2 to 300 K and the magnetic susceptibility data indicate a very weak antiferromagnetic exchange interaction (J = -0.042 cm(-1)) between the Gd(III) centers (S = 7/2) in the metal triangle through the carbonate bridge. The luminescence spectral behaviors of the complexes of Sm(III), Eu(III), and Tb(III) have been studied. The ligand LH(2) acts as a sensitizer for the metal ions in an acetonitrile-toluene glassy matrix (at 77 K) and luminescence intensities of the complexes decrease in the order Eu(3+) > Sm(3+) > Tb(3+).

6.
Inorg Chem ; 50(15): 7257-67, 2011 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-21699147

RESUMO

This investigation presents the syntheses, crystal structures, magnetic properties, and density functional theoretical modeling of magnetic behavior of two heterobridged µ-phenoxo-µ(1,1)-azido dinickel(II) compounds [Ni(II)(2)(L(1))(2)(µ(1,1)-N(3))(N(3))(H(2)O)]·CH(3)CH(2)OH (1) and [Ni(II)(2)(L(2))(2)(µ(1,1)-N(3))(CH(3)CN)(H(2)O)](ClO(4))·H(2)O·CH(3)CN (2), where HL(1) and HL(2) are the [1+1] condensation products of 3-methoxysalicylaldehyde and 1-(2-aminoethyl)-piperidine (for HL(1))/4-(2-aminoethyl)-morpholine (for HL(2)), along with density functional theoretical magneto-structural correlations of µ-phenoxo-µ(1,1)-azido dinickel(II) systems. Compounds 1 and 2 crystallize in orthorhombic (space group Pbca) and monoclinic (space group P2(1)/c) systems, respectively. The coordination environments of both metal centers are distorted octahedral. The variable-temperature (2-300 K) magnetic susceptibilities at 0.7 T of both compounds have been measured. The interaction between the metal centers is moderately ferromagnetic; J = 16.6 cm(-1), g = 2.2, and D = -7.3 cm(-1) for 1 and J = 16.92 cm(-1), g = 2.2, and D(Ni1) = D(Ni2) = -6.41 cm(-1) for 2. Broken symmetry density functional calculations of exchange interaction have been performed on complexes 1 and 2 and provide a good numerical estimate of J values (15.8 cm(-1) for 1 and 15.35 cm(-1) for 2) compared to experiments. The role of Ni-N bond length asymmetry on the magnetic coupling has been noted by comparing the structures and J values of complexes 1 and 2 together with previously published dimers 3 (Eur. J. Inorg. Chem. 2009, 4982), 4 (Inorg. Chem. 2004, 43, 2427), and 5 (Dalton Trans. 2008, 6539). Our extensive DFT calculations reveal an important clue to the mechanism of coupling where the orientation of the magnetic orbitals seems to differ with asymmetry in the Ni-N bond lengths. This difference in orientation leads to a large change in the overlap integral between the magnetic orbitals and thus the magnetic coupling. DFT calculations have also been extended to develop several magneto-structural correlations in this type of complexes and the correlation aim to focus on the asymmetry of the Ni-N bond lengths reveal that the asymmetry plays a proactive role in governing the magnitude of the coupling. From a completely symmetric Ni-N bond length, two behaviors have been noted: with a decrease in bond length there is an increase in the ferromagnetic coupling, while an increase in the bond lengths leads to a decrease in ferromagnetic interaction. The later correlation is supported by experiments. The magnetic properties of 1, 2, and three previously reported related compounds have been discussed in light of the structural parameters and also in light of the theoretical correlations determined here.

7.
Inorg Chem ; 50(1): 46-61, 2011 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-21114281

RESUMO

Homo- and heterobimetallic complexes of composition [(bpy)(2)M(II)(H(2)Imbzim)M'(II)(bpy)(2)](ClO(4))(3)·nH(2)O, where M(II) = M'(II) = Os (1), M(II) = Ru and M'(II) = Os (2), H(3)Imbzim = 4,5-bis(benzimidazole-2-yl)imidazole, and bpy = 2,2'-bipyridine, have been synthesized and characterized using standard analytical and spectroscopic techniques. Both of the complexes crystallized in monoclinic form with the space group P2(1)/m for 1 and P2(1)/n for 2. The absorption spectra, redox behavior, and luminescence properties of the complexes have been thoroughly investigated. The complexes display very intense, ligand-centered absorption bands in the UV region and moderately intense metal-to-ligand charge-transfer (MLCT) bands in the visible region. The bimetallic complexes show two successive one-electron reversible metal-centered oxidations. The strong fluorescence of free H(3)Imbzim is completely quenched in the metal complexes by energy transfer to the metal-based units, which exhibit their characteristic MLCT phosphorescence. The luminescence data of the heterometallic complex 2 show that electronic energy transfer takes place from the ruthenium center to the osmium-based component. The anion binding properties of the complexes have been studied in solutions using absorption, emission, and (1)H NMR spectral measurements. The metalloreceptors act as sensors for F(-) and AcO(-) ions. Sensing studies indicate the presence of two successive anion-induced deprotonation steps, leading to the formation of [(bpy)(2)M(HImbzim)M'(bpy)(2)](2+) and [(bpy)(2)M(Imbzim)M'(bpy)(2)](+) species. Double deprotonation is also observed in the presence of hydroxide. The binding affinities of different anions toward the receptors have been evaluated. Cyclic voltammetry measurements carried out in acetonitrile have provided evidence in favor of anion-dependent electrochemical responses of the bimetallic metalloreceptors with F(-) and AcO(-) ions.

8.
Inorg Chem ; 49(19): 9012-25, 2010 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-20812685

RESUMO

Syntheses, characterization, and magnetic properties of a series of diphenoxo-bridged discrete dinuclear M(II)Ln(III) complexes (M = Cu or Ni, Ln = Ce-Yb) derived from the compartmental Schiff base ligand, H(2)L, obtained on condensation of 3-ethoxysalicylaldehyde with trans-1,2-diaminocyclohexane, are described. Single crystal X-ray structures of eight Cu(II)Ln(III) compounds (Ln = Ce (1), Pr (2), Nd (3), Sm (4), Tb (7), Ho (9), Er (10), and Yb (12)) and three Ni(II)Ln(III) (Ln = Ce (13), Sm (16), and Gd (18)) compounds have been determined. Considering the previously reported structure of the Cu(II)Gd(III) (6) compound (Eur. J. Inorg. Chem. 2005, 1500), a total of twelve structures are discussed/compared in this study. Four types of composition are observed in the Cu(II)Ln(III) complexes: [Cu(II)LLn(III) (NO(3))(3)(H(2)O)] (1-3: Ln = Ce-Nd), [Cu(II)LSm(III)(NO(3))(3)]·CH(3)COCH(3) (4), [Cu(II)(H(2)O)LLn(III)(NO(3))(3)] (5: Ln = Eu; 6: Ln = Gd), and [Cu(II)LLn(III)(NO(3))(3)] (4A: Ln = Sm; 7-12: Ln = Tb-Yb). On the other hand, the Ni(II)Ln(III) complexes are characterized to have two types of composition: [Ni(II)LLn(III)(H(2)O)(NO(3))(3)] (13-15: Ln = Ce-Nd) and [Ni(II)LLn(III)(NO(3))(3)]·0.5CH(3)COCH(3) (16-24: Ln = Sm-Yb). Among twelve X-ray structures, seven belong to three different isomorphous sets (Cu(II)Ce(III) (1), Cu(II)Pr(III) (2), Cu(II)Nd(III) (3), and Ni(II)Ce(III) (13); Cu(II)Tb(III) (7), Cu(II)Ho(III) (9), Cu(II)Er(III) (10), and Cu(II)Yb(III) (12); Ni(II)Sm(III) (16) and Ni(II)Gd(III) (18)), whereas space group/unit cell parameters of two others (Cu(II)Sm(III) (4) and Cu(II)Gd(III) (6)) are of different types. The lanthanide(III) centers in Cu(II)Ce(III) (1), Cu(II)Pr(III) (2), Cu(II)Nd(III) (3), and Ni(II)Ce(III) (13) complexes are eleven-coordinated, while the lanthanide(III) centers in other compounds are ten-coordinated. As evidenced from the dihedral angle (δ) between the CuO(phenoxo)(2) and LnO(phenoxo)(2) planes, variation in the extent of planarity of the bridging moiety in the Cu(II)Ln(III) compounds takes place; the ranges of δ values are 0.8-6.2° in the 4f(1-7) analogues and 17.6-19.1° in the 4f(8-13) analogues. The Cu(II)Gd(III) (6) compound exhibits ferromagnetic interaction (Eur. J. Inorg. Chem. 2005, 1500). The nature of the magnetic exchange interaction in the Cu(II)Ln(III) complexes has been understood by utilizing the empirical approach; the Ni(II)Ln(III) complexes have been used as references. The metal centers in the Eu(III) complex are uncorrelated, while other 4f(1-6) analogues (Ce(III), Pr(III), Nd(III), and Sm(III)) exhibit antiferromagnetic interaction. Among the higher analogues (4f(7-13)), only Yb(III) exhibits antiferromagnetic interaction, while interaction in other analogues (Gd(III), Tb(III), Dy(III), Ho(III), Er(III), and Tm(III)) is ferromagnetic. An important aspect of the present study is the measurement of the magnetic susceptibility of the unblocked samples as well as on blocking the samples with grease to avoid powder reorientation, if any. Comparison of the two sets of data reveals significant difference in some cases.


Assuntos
Cobre/química , Elementos da Série dos Lantanídeos/química , Magnetismo , Níquel/química , Compostos Organometálicos/química , Compostos Organometálicos/síntese química , Cristalografia por Raios X , Ligantes , Modelos Moleculares , Estrutura Molecular , Estereoisomerismo
9.
Inorg Chem ; 49(16): 7382-400, 2010 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-20690748

RESUMO

The tetrapodal ligand 1,1,1,1-tetrakis[(salicylaldimino)methyl]methane (H(4)L) has been used to synthesize a number of divalent metal complexes, which include (i) the trinuclear compounds [Mg(3)(HL)(2)].nH(2)O (1), [Ni(3)(HL)(2)].2C(7)H(8) (3), [Ni(3)L'(2)].0.5C(7)H(8) (4), [Co(3)(HL)(2)] (5), and [Co(3)L'(2)].C(6)H(6) (6); (ii) the dinuclear compounds [Ni(2)L] (2), [Cu(2)L].CH(3)CN (8), and [Pd(2)L] (9); (iii) an unusual dimeric compound [{Ni(H(2.5)L)}(2)](ClO(4)).2H(2)O (7); and (iv) the inclusion compounds [Ni(2)L subset NaClO(4)].CH(3)CN (10) and [Cu(2)L subset NaClO(4)] (11). The molecular structures of compounds 1, 3, 4, 6, 7, and 10 have been determined. In [M(3)(HL)(2)] complexes, one of the salicylaldimine chelating units remains uncoordinated, which on being hydrolyzed is transformed to the amine-ending complex [M(3)L'(2)]. All of the trinuclear complexes have the same core coordination sphere [N(3)M(mu-O(phenolate))(3)M(mu-O(phenolate))(3)MN(3)] where the terminal metals are connected to the central metal via face-shared phenolate oxygens. In the trinuclear compounds, the terminal metals are distorted from octahedral to trigonal prismatic to different extents in 1 and 6, while in 3 and 4 they are trigonal antiprismatically distorted. The stereochemical configurations obtained by the terminal metals in 3 and 6 are homochiral (Delta...Delta), but heterochiral (Lambda...Delta) in 1 and 4. In compound 7, the two mononuclear complex units are held together by three equivalent O...H...O bridges, indicating 50% deprotonation of all the metal-coordinated phenols. The temperature-dependent magnetic behavior of 7 has indicated the presence of very weak antiferromagnetic exchange coupling (J = -0.2 cm(-1)) between the two nickel(II) centers. Very similar magnetic behavior observed for the trinuclear nickel(II) compounds 3 and 4 is attributed to a ferromagnetic exchange interaction between the adjacent metals (J = 7.6 cm(-1)), although an interaction between the terminal metals is absent; in contrast, the adjacent cobalt(II) centers in 6, however, are involved in an antiferromagnetic exchange interaction (J = -5.7 cm(-1)). The dinuclear complexes [M(2)L], in which each of the metal centers are chelated with a pair of salicylaldimines, act as hosts (when M = Ni and Cu) for alkali metals (Li(+), Na(+), and K(+)). The host-guest binding constants (K) have been determined in (CH(3))(2)SO solution, and the results show that [Ni(2)L] is a better host compared to [Cu(2)L]. The decreasing order of K values for both hosts is Na(+) > Li(+) > K(+). [Ni(2)L subsetNaClO(4)].CH(3)CN (10) has been shown to have a polymeric structure in which sodium is octahedrally surrounded by four nickel-coordinated phenolate and two perchlorate oxygens. The magnesium(II) complex 1 exhibits strong fluorescence in CH(2)Cl(2) at room temperature with lambda(em) = 425 nm, and the lifetime for fluorescent decay is 18.5 ns. The thermal behaviors of 3 and 6 with regard to their loss of aromatic solvent molecules have been studied. The evolution of the toluene molecules from 3 takes place between 140 degrees and 230 degrees C, while the benzene is evolved between 100 degrees and 180 degrees C in 6. The enthalpy of desolvation of 3 is 43.4 kJ mol(-1).

10.
Inorg Chem ; 49(11): 5049-62, 2010 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-20469925

RESUMO

A series of heteroleptic tridentate ruthenium(II) complexes of composition [(H(2)pbbzim)Ru(tpy-X)](PF(6))(2) (1-7), where H(2)pbbzim = 2,6-bis(benzimidazole-2-yl)pyridine and tpy-X = 4'-substituted terpyridine ligands with X = H, p-methyl phenyl (PhCH(3)), p-bromomethylphenyl (PhCH(2)Br), p-dibromomethylphenyl (PhCHBr(2)), p-cyanomethylphenyl (PhCH(2)CN), p-triphenylphosphonium methylphenyl bromide (PhCH(2)PPh(3)Br), and 4'-phenylformyl (PhCHO) groups, has been synthesized and characterized by using standard analytical and spectroscopic techniques. These compounds were designed to increase the excited-state lifetime of ruthenium(II) bisterpyridine-type complexes. The X-ray crystal structure of a representative compound 2, which crystallized with monoclinic space group P2(1)/c, has been determined. The absorption spectra, redox behavior, and luminescence properties of the ruthenium(II) complexes have been thoroughly investigated. All of the complexes display moderately strong luminescence at room temperature with lifetimes in the range of 10-58 ns. Correlations have been obtained for the Hammett sigma(p) parameter with their MLCT emission energies, lifetimes, redox potentials, proton NMR chemical shifts, etc. The anion binding properties of all the complexes as well as the parent ligand H(2)pbbzim have been studied in acetonitrile using absorption, emission, and (1)H NMR spectral studies, and it has been observed that the metalloreceptors act as sensors for F(-), AcO(-), and to some extent H(2)PO(4)(-). At a relatively lower concentration of anions, a 1:1 H-bonded adduct is formed; however, in the presence of an excess of anions, stepwise deprotonation of the two benzimidazole N-H fragments occurs, an event which is signaled by the development of vivid colors visible with the naked eye. The receptor-anion binding constants have been evaluated. Cyclic voltammetric (CV) measurements carried out in acetonitrile-dimethylformamide (9:1) provided evidence in favor of anion (F(-), AcO(-)) concentration dependent electrochemical responses, enabling 1 - 7 to act as suitable electrochemical sensors for F(-) and AcO(-) ions.


Assuntos
Benzimidazóis/química , Luminescência , Compostos Organometálicos/química , Compostos Organometálicos/síntese química , Piridinas/química , Rutênio/química , Ânions/química , Sítios de Ligação , Estrutura Molecular , Fotoquímica , Estereoisomerismo
11.
Dalton Trans ; 39(17): 4162-9, 2010 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-20390179

RESUMO

Mixed-ligand monometallic ruthenium(II) and osmium(II) complexes of composition [(bipy)(2)M(H(2)Imdc)](ClO(4)), where H(3)Imdc = imidazole-4,5-dicarboxylic acid and bipy = 2,2'-bipyridine, have been synthesized and characterized using standard analytical and spectroscopic techniques. The X-ray crystal structures of the ruthenium(II) complexes, [(bipy)(2)Ru(H(2)Imdc)](ClO(4)) (1) and its corresponding N-H deprotonated form [(bipy)(2)Ru(HImdc)] (3) have been determined. Compound 1 crystallizes in monoclinic form with space group P2(1)/c while 3 is obtained in triclinic form with the space group P1. The anion binding properties of the complexes 1 and 2 have been thoroughly investigated in acetonitrile solution using absorption, emission, and (1)H NMR spectral measurements. Both of the metalloreceptors act as sensors for F(-), AcO(-) and H(2)PO(4)(-) anions. Although at relatively lower concentration of anions, the 1 : 1 H-bonded adduct is formed, in the presence of excess of anions, deprotonation of the imidazole N-H fragment occurs and is accompanied by distinct change of colour. Cyclic voltammetry (CV) measurements carried out in acetonitrile have provided evidence in favour of anion-dependent electrochemical responses of 1 and 2 with F(-) and AcO(-) ions.

12.
Inorg Chem ; 49(5): 2334-48, 2010 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-20170201

RESUMO

Mixed-ligand monometallic and bimetallic ruthenium(II) complexes of compositions [(bpy)(2)Ru(H(3)Imbzim)](ClO(4))(2) x 2 H(2)O (1) and [(bpy)(2)Ru(H(2)Imbzim)Ru(bpy)(2)](ClO(4))(3) x CH(2)Cl(2) (2), where H(3)Imbzim = 4,5-bis(benzimidazol-2-yl)imidazole and bpy = 2,2'-bipyridine, have been synthesized and characterized using standard analytical and spectroscopic techniques. The X-ray crystal structures of both compounds have been determined and showed that 1 crystallized in the triclinic form with space group P1 and 2 is in the monoclinic form with space group P2(1)/m. The anion binding properties of complexes 1 and 2, as well as those of the parent H(3)Imbzim, were thoroughly investigated in an acetonitrile solution using absorption, emission, and (1)H NMR spectral studies, which revealed that both of the metalloreceptors act as sensors for F(-), for AcO(-), and, to some extent, for H(2)PO(4)(-). At a relatively lower concentration of anions, a 1:1 hydrogen-bonded adduct was formed; however, in the presence of an excess of anions, stepwise deprotonation of the two benzimidazole NH fragments occurred, an event that was signaled by the development of vivid colors visible with the naked eye. Double deprotonation was also observed in the presence of hydroxide. Less basic anions (AcO(-) and H(2)PO(4)(-)) induce deprotonation of only one NH. The effect of solvents on the absorption and emission spectral behavior has also been studied in detail. The binding affinities of different anions toward the receptors were evaluated and showed that the binding constants of 1 and 2 are substantially enhanced relative to free H(3)Imbzim because upon coordination to the Ru(II) center(s), H(3)Imbzim/H(2)Imbzim(-) becomes electron-deficient, thereby rendering the imidazole NH protons more available for hydrogen bonding to the anions. Cyclic voltammetry studies carried out in acetonitrile provided evidence of an anion-dependent electrochemical response with F(-) and AcO(-). Anion-induced lifetime shortening makes complex 2 a suitable lifetime-based sensor for anions.

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