FRET-based Solid-state Luminescent Glyphosate Sensor Using Calixarene-grafted Ruthenium(II)bipyridine Doped Silica Nanoparticles.

Calixarene-functionalized luminescent nanoparticles were successfully fabricated for the FRET-based selective and sensitive detection of the organophosphorus pesticide glyphosate (GP). p-Tert-butylcalix[4]arene was grafted on the surface of [Ru(bpy)3 ]2+ incorporated SiNps to produce self-assembled nanosensors (RSC). FRET was switched on in the presence of GP by means of energy transfer due to binding with p-tert-butylcalix[4]arene grafted on the surface of the RSC. The FRET efficiency of the GP-RSC system was increased gradually with the addition of GP. The FRET efficiency was evaluated as 87.69 % and a high binding affinity was established by the binding constant value, 1.16×107  M-1 , using a Langmuir binding isotherm plot. The estimated limit of detection (LOD) was 7.91×10-7  M, which was lower than the Environmental Protection Agency (EPA) recommendation. The probe also effectively responds to real sample analysis. The sensitivity and selectivity was realized due to the efficient FRET towards the fluorescence properties of the [Ru(bpy)3 ]2+ complex.

Aggregation-induced emission enhancement of anthracene-derived Schiff base compounds and their application as a sensor for bovine serum albumin and optical cell imaging.

Three anthracene-based Schiff base complexes, R1-R3 (R1 = (E)-N´-((anthracen-10-yl)methylene)benzohydrazide; R2 = (E)-1-((anthracen-10-yl)methylene)-4-phenylsemicarbazide; and R3 = (E)-1-((anthracen-10-yl)methylene)-4-phenylthiosemicarbazide) were synthesized from 9-anthracenecarboxaldehyde, benzohydrazide, 4-phenylsemicarbazide and 4-phenylthiosemi-carbazide respectively, and characterized by various spectral techniques. The absorption spectral characteristics of R1-R3 were bathochromically tuned to the visible region by extending the π conjugation. These target compounds were weakly fluorescent in tetrahydrofuran (THF) solution because of rapid isomerization of the C=N double bond in the excited state. However, the aqueous dispersion of R1-R3 in the THF/water mixture by the gradual addition of water up to 90% resulted in an increase in the fluorescence intensity mainly due to aggregation-induced emission enhancement (AIEE) properties. The formation of nanoaggregates of R1-R3 were confirmed by scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. The compounds R1-R3 are ideal probes for the fluorescence sensing of bovine serum albumin (BSA) and breast cancer cells by optical cell imaging.

Electron Transfer Studies of Ruthenium(II) Complexes with Biologically Important Phenolic Acids and Tyrosine.

The ruthenium(II) complexes having 2,2'-bipyridine and phenanthroline derivatives are synthesized and characterized. The photophysical properties of these complexes at pH 12.5 are studied. The electron transfer reaction of biologically important phenolic acids and tyrosine are studied using absorption, emission and transient absorption spectral techniques. Semiclassical theory is applied to calculate the rate of electron transfer between ruthenium(II) complexes and biologically important phenolic acids.

A Spectroscopy Approach for the Study of the Interaction of Oxovanadium(IV)-Salen Complexes with Proteins.

Oxovanadium(IV)-salen complexes bind with bovine serum albumin (BSA) and ovalbumin (OVA) strongly with binding constant in the range 10(4)-10(7) M(-1) at physiological pH (7.4) confirmed using UV-visible absorption, fluorescence spectral and circular dichroism (CD) study. CD results show that the binding of oxovanadium(IV) complexes induces the conformational change with the loss of α-helicity in the proteins. Docking studies indicate that mode of binding of oxovanadium(IV)-salen complexes with proteins is hydrophobic in nature.

Photophysical properties of amphiphilic ruthenium(II) complexes in micelles.

Amphiphilic ruthenium(II) complexes II­IV were synthesized and their photophysical properties were investigated in the presence of anionic (SDS), cationic (CTAB) and neutral (Triton X-100) micelles. The absorption and emission spectral data in the presence of micelles show that these Ru(II) complexes are incorporated in the micelles. There are two types of interaction between complexes I­IV and the micelles: hydrophobic and electrostatic. In the case of cationic micelles (CTAB), the hydrophobic interactions are predominant over electrostatic repulsion for the binding of cationic complexes II­IV with CTAB. In the case of anionic micelles (SDS), electrostatic interactions seem to be important in the binding of II­IV to SDS. Hydrophobic interactions play a dominant role in the binding of II­IV to the neutral micelles, Triton X-100. Based on the steady state and luminescence experiments, the enhancement of luminescence intensity and lifetime in the presence of micelles is due to the protection of the complexes from exposure to water in this environment.

Visible-light activation of the bimetallic chromophore-catalyst dyad: analysis of transient intermediates and reactivity toward organic sulfides.

In order to develop a new photocatalytic system, we designed a new redox-active module (5) to hold both a photosensitizer part, [Ru(II)(terpy)(bpy)X](n+) (where terpy = 2,2':6',2''-terpyridine and bpy = 2,2'-bipyridine), and a popular Jacobsen catalytic part, salen-Mn(III), covalently linked through a pyridine-based electron-relay moiety. On the basis of nanosecond laser flash photolysis studies, an intramolecular electron transfer mechanism from salen-Mn(III) to photooxidized Ru(III) chromophore yielding the catalytically active high-valent salen-Mn(IV) species was proposed. To examine the reactivity of such photogenerated salen-Mn(IV), we employed organic sulfide as substrate. Detection of the formation of a Mn(III)-phenoxyl radical and a sulfur radical cation during the course of reaction using time-resolved transient absorption spectroscopy confirms the electron transfer nature of the reaction. This is the first report for the electron transfer reaction of organic sulfide with the photochemically generated salen-Mn(IV) catalytic center.

Electron transfer reactions of ruthenium(II)-bipyridine complexes carrying tyrosine moiety with quinones.

Three ruthenium(II)-bipyridine complexes carrying a tyrosine moiety were synthesized and photophysical and electron transfer studies with quinones were carried out using absorption and emission spectral techniques. The binding efficiency of quinones with ruthenium(II)-bipyridine complexes was also studied using these techniques. The binding efficiency was moderate and similar for all complexes with all quinones. The quenching modes were also similar and efficient for all complexes with all quinones. The quenching processes were diffusion controlled. The rate of electron transfer was calculated using semiclassical theory.

Optical recognition of anions by ruthenium(II)-bipyridine-calix[4]arene system.

The two t-butylcalix[4]arene attached ruthenium(II)-bipyridine complexes (Rubc2 and Rubc3) has been synthesized and the anion recognition studies have been carried out using emission techniques. The binding of anions, which are sensed by the complexes, are studied by UV-visible and emission techniques. The complex Rubc2 recognizes the Cl(-), H2PO4 (-) and AcO(-) anions. The complex Rubc3 recognizes the Br(-) and AcO(-) anions. The AcO(-) quenches the emission intensity of both two complexes but the other anion increases the emission intensity of the complexes. The excited state lifetime and transient absorption studies were carried out the AcO(-) facilitates non radiative pathway. The other anions stabilize the excited state and facilitate the radiative pathway.

Highly sensitive optical biosensor for thrombin based on structure switching aptamer-luminescent silica nanoparticles.

We describe here the construction of a sensitive and selective optical sensor system for the detection of human α-thrombin. The surface functionalized luminescent [Ru(dpsphen)(3)](4-) (dpsphen-4,7-diphenyl-1,10-phenanthroline disulfonate) ion doped silica nanoparticles (SiNPs) with a size ~70 nm have been prepared. The DABCYL (2-(4-dimethylaminophenyl)diazenyl-benzoic acid) quencher labeled thrombin binding aptamer is conjugated to the surface of SiNPs using BS(3) (bis(sulfosuccinimidyl) suberate) as a cross-linker, resulting in the conformational change of aptamer to form G-quadruplex structure upon the addition of thrombin. The binding event is translated into a change in the luminescence intensity of Ru(II) complex via FRET mechanism, due to the close proximity of DABCYL quencher with SiNPs. The selective detection of thrombin using the SiNPs-aptamer system up to 4 nM is confirmed by comparing its sensitivity towards other proteins. This work demonstrates the application of simple aptamer-SiNPs conjugate as a highly sensitive system for the detection of thrombin and also it is highly sensitive towards thrombin in the presence of other proteins and complex medium such as BSA.

Sensitized near-infrared luminescence from Nd(III), Yb(III) and Er(III) complexes by energy-transfer from ruthenium 1,3-Bis([1,10]phenanthroline-[5,6-d]-imidazol-2 -yl)benzene.

The luminescent ruthenium 1,3 -bis([1,10]phenanthroline-[5,6 -d]- imidazol-2 -yl)benzene (bpibH2) complex, a potentially useful bridging ligand with a vacant diimine site, has been used as 'metallo ligand' to make heterodinuclear d-f complexes by attachment of a {Ln(dik)3} fragment (dik = 1,3-diketonate) at the vacant site. When Ln = Nd, Yb, or Er the lanthanide centre has low-energy f-f excited states capable of accepting energy from the (3)MLCT excited state of the Ru(II) centre, there is quenching in the (3)MLCT luminescence of the Ru(II) centre, that affords sensitized lanthanide(III) based luminescence in the near-IR region. Nd(III) was found to be the most effective at quenching the (3)MLCT luminescence of the ruthenium component because of the high density of f-f excited states of the appropriate energy which make it as effective energy-acceptor compared to Er and Yb complexes.

Ruthenium nanocatalysis on redox reactions.

Nanoparticles have generated intense interest over the past 20 years due to their high potential applications in different areas such as catalysis, sensors, nanoscale electronics, fuel and solar cells and optoelectronics. As the large fractions of metal atoms are exposed to the surface, the use of metal nanoparticles as nanocatalysts allows mild reaction conditions and high catalytic efficiency in a large number of chemical transformations. They have emerged as sustainable heterogeneous catalysts and catalyst supports alternative to conventional materials. This review focuses on the synthesis, characterization and catalytic role of ruthenium nanoparticles (RuNPs) on the redox reactions of heteroatom containing organic compounds with the green reagent H2O2, a field that has attracted immense interest among the chemical, materials and industrial communities. We intend to present a broad overview of Ru nanocatalysts for redox reactions with an emphasis on their performance, stability and reusability. The growth in the chemistry of organic sulfoxides and N-oxides during last decade was due to their importance as synthetic intermediates for the production of a wide range of chemically and biologically active molecules. Thus design of efficient methods for the synthesis of sulfoxides and N-oxides becomes important. This review concentrates on the catalysis of RuNPs on the H2O2 oxidation of organic sulfides to sulfoxides and amines to N-oxides. The deoxygenation reactions of sulfoxides to sulfides and reduction of nitro compounds to amines are fundamental reactions in both chemistry and biology. Here, we also highlight the catalysis of metal nanoparticles on the deoxygenation of sulfoxides and sulfones and reduction of nitro compounds with particular emphasis on the mechanistic aspects.

Host-guest interaction studies of polycyclic aromatic hydrocarbons (PAHs) in alkoxy bridged binuclear rhenium (I) complexes.

The interaction of two neutral alkoxy bridged binuclear rhenium(I) complexes, 1 and 2 [{Re(CO)3(1,4-NVP)}2(µ2-OR)2] (1, R = C4H9; 2, R = C10H21; 1,4-NVP = 4-(1-naphthylvinyl)pyridine] with polycyclic aromatic hydrocarbons (PAH) is investigated. UV-vis absorption, emission, 1H NMR spectral titrations, TCSPC lifetime studies and DFT theoretical calculations were carried out to examine the binding responses of complexes 1 and 2 with various PAHs such as pyrene, naphthalene, anthracene and phenanthrene. The UV-Vis absorption spectra showed an increase in absorbance of the metal-to ligand charge-transfer (MLCT) and ligand centered (LC) bands upon addition of various PAH molecules to 1 and 2, whereas the emission behavior was found to show emission quenching, which might occur through energy transfer pathway. The binding constants (K) of complexes 1 and 2 for various PAHs are found to be in the order of 104 M-1 with a 1:1 binding mode, as determined from UV-vis absorption and emission spectral titration studies. 1H NMR spectral studies show that the chemical shifts of pyrene guest and the 1,4-NVP moiety of 2 are shifted up-field, whilst the alkoxy protons do not show any appreciable change in their chemical shifts. It is believed that the open cavities present in the Re(I) complexes may lead to the recognition of PAHs via CH···π interaction.

Oxidation of methionines by oxochromium(V) cations: a kinetic and spectral study.

The oxidation of methionine (Met) plays an important role during biological conditions of oxidative stress as well as for protein stability. By choosing [oxo(salen)chromium(V)] ions, [(salen)Cr(V)=O](+) (where salen = bis(salicylidene)ethylenediamine) as suitable biomimics for the peptide complexes that are formed during the reduction of Cr(VI) with biological reductants, the oxidation of methionine and substituted methionines with five [oxo(salen)chromium(V)] complexes in aqueous acetonitrile has been investigated by spectrophotometric, electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization mass spectrometry (ESI-MS) methods. In aqueous solution [(salen)Cr(V)=O](+) ion is short lived, ligation of H(2)O to the Cr center takes place and [O=Cr(V)(salen)-H(2)O](+) adduct is the active oxidant. The reaction is found to be first order each in the oxidant and the substrate. The presence of water in the reaction system accelerates the reaction rate and an inactive, stable mu-oxo dimer is also formed during the course of the reaction. On the basis of spectral, kinetic and product analysis study a mechanism involving direct oxygen transfer from [O=Cr(V)(salen)-H(2)O](+) to methionine has been proposed as a suitable mechanism for the reaction.

Development of luminescent sensors based on transition metal complexes for the detection of nitroexplosives.

The detection of chemical explosives is a major area of research interest and is essential for the military as well as homeland security to counter the catastrophic effects of global terrorism. In recent years, tremendous effort has been devoted to the development of luminescent materials for the detection of explosives in the vapor, solution, and solid states with a high degree of selectivity and sensitivity and a rapid response time. Apart from the wide range of organic fluorescent chemosensors, transition metal complexes play a prominent role in the sensing of nitroaromatic explosives owing to their rich photophysical characteristics. This review briefly summarizes the salient features of the design and preparation of transition metal (Zn(ii), Ir(iii), Pd(ii), Pt(ii), Re(i) and Ru(ii)) complexes/metallacycles/metallosupramolecules with emphasis on their photophysical properties, sensing behavior, mechanism of action, and the driving forces for detecting explosives and future prospects and challenges. Most of the probes that have been reported to date act as "turn-off" luminescent sensors because their emission (intensity, lifetime, and quantum yield) is eventually quenched upon sensing with nitroaromatic compounds (NACs) through photo-induced electron or energy transfer. These unique properties of transition metal complexes in response to explosives open up new vistas for the development of real world applications such as on-site detection, in-field security, forensic research, etc.

Sensing and inhibition of amyloid-ß based on the simple luminescent aptamer-ruthenium complex system.

Aggregation of amyloid-ß (Aß) peptide has been known to be pathologically associated with Alzheimer and dementia diseases. Amyloid-ß fibrils serve as an important target for the drugs development and diagnosis of neurodegenerative diseases. Herein, we report a new [Ru(dmbpy)(dcbpy)dppz)] complex (dmbpy; 4,4'-dimethyl-2,2'-bipyridine, dcbpy; 4,4'-dicorboxy-2,2'-bipyridine, dppz; dipyridophenazine) intercalated aptamer based recognition of amyloid-ß. Interestingly, aforementioned Ru(II) complex shows weak luminescence intensity in the aqueous medium but it shows strong luminescence intensity in the presence of RNA aptamer. Upon addition of amyloid-ß monomers, the luminescence intensity of Ru(II) complex is reduced due to the strong interaction of aptamer with amyloid-ß monomer/small oligomers. Furthermore, present study implies that our system has ability to inhibit the formation of amyloid-ß fibrils, which is confirmed from the AFM morphological structures in the absence and presence of aptamer. This work may contribute the rapid diagnosis and inhibition of amyloid-ß aggregation in the clinical applications.

Oxygenation Reaction of Organic Sulfides with Oxochromium(V) Ion.

The selective oxidation of 19 alkyl aryl sulfides to sulfoxides with three oxochromium(V) complexes in an acetonitrile-water mixture is overall second order, first order in the oxidant and in the substrate. Sulfides containing electron-attracting substitutents retard the rate while those containing electron-releasing substitutents accelerate the rate of oxidation. The rate constant for the oxygenation reaction, k(2), is better correlated with sigma(+)/sigma(-) than Hammett sigma constants. The reactivity of different alkyl phenyl sulfides C(6)H(5)SR (R = Me, Et, n-Pr, i-Pr, n-Bu, and t-Bu) is accounted for in terms of Taft's polar, sigma, and steric, E(s), substitutent constants. These kinetic results are interpreted in terms of a mechanism involving outer sphere electron transfer from sulfide to Cr(V) as the rate-determining step. The results of Cr(V) oxidation are compared with those of Cr(VI) oxidation.

A selective, long-lived deep-red emissive ruthenium(II) polypyridine complexes for the detection of BSA.

A selective, label free luminescence sensor for bovine serum albumin (BSA) is investigated using ruthenium(II) complexes over the other proteins. Interaction between BSA and ruthenium(II) complexes has been studied using absorption, emission, excited state lifetime and circular dichroism (CD) spectral techniques. The luminescence intensity of ruthenium(II) complexes (I and II), has enhanced at 602 and 613 nm with a large hypsochromic shift of 18 and 5 nm respectively upon addition of BSA. The mode of binding of ruthenium(II) complexes with BSA has analyzed using computational docking studies.

Interaction of oxovanadium(IV)-salphen complexes with bovine serum albumin and their cytotoxicity against cancer.

Vanadyl compounds of clinical significance are recommended as drugs against diseases such as tuberculosis, diabetes, cancer, etc. In order to check the potential of the salphen ligands and oxovanadium(IV)-salphen complexes as drugs their binding with bovine serum albumin (BSA) is investigated. The binding constants measured at pH 7.4 using UV-vis absorption and fluorescence techniques are in the range of 10(3)-10(5) M(-1). The quenching of the fluorescence of BSA and appearance of enhanced luminescence of the salphen ligand/vanadium(IV) complex at the increased [quencher] show efficient FRET from the protein to the quencher and the distance of energy transfer estimated using Forster's theory is in the range of 1.4-3.5 nm. Molecular docking studies (DFT) utilizing oxovanadium(IV)-salphen derivatives show strong binding with BSA and give insight into the binding modes, interaction pattern and stability of synthesized complexes in the target site. The cytotoxicity study shows the ability of these V(IV) complexes to inhibit the growth of AGS gastric cell lines.

Alkoxy bridged binuclear rhenium (I) complexes as a potential sensor for ß-amyloid aggregation.

Alkoxy bridged binuclear rhenium(I) complexes are used as a probe for the selective and sensitive detection of aggregation of ß-amyloid fibrils that are consorted with Alzheimer's disease (AD). The strong binding of the complexes is affirmed by the fluorescence enhancement and calculated binding constant value in the order of 10(5)M(-1) is obtained from the Scatchard plots. The binding of ß-amyloid can be attributed to π-π stacking interaction of naphthalene moiety present in rhenium(I) complexes, and it is supported by docking studies. The selectivity is quite high towards other proteins and the formation of fibrils can be observed in the range of 30-40 nm through the AFM and TEM techniques.

Aggregation-induced emission enhancement in alkoxy-bridged binuclear rhenium(I) complexes: application as sensor for explosives and interaction with microheterogeneous media.

The aggregation-induced emission enhancement (AIEE) characteristics of the two alkoxy-bridged binuclear Re(I) complexes [{Re(CO)3(1,4-NVP)}2(µ2-OR)2] (1, R = C4H9; 2, C10H21) bearing a long alkyl chain with 4-(1-naphthylvinyl)pyridine (1,4-NVP) ligand are illustrated. These complexes in CH2Cl2 (good solvent) are weakly luminescent, but their intensity increased enormously by almost 500 times by the addition of poor solvent (CH3CN) due to aggregation. By tracking this process via UV-vis absorption and emission spectral and TEM techniques, the enhanced emission is attributed to the formation of nanoaggregates. The nanoaggregate of complex 2 is used as a sensor for nitroaromatic compounds. Furthermore, the study of the photophysical properties of these binuclear Re(I) complexes in cationic, cetyltrimethylammonium bromide (CTAB), anionic, sodium dodecyl sulfate (SDS), and nonionic, p-tert-octylphenoxypolyoxyethanol (TritonX-100, TX-100), micelles as well as in CTAB-hexane-water and AOT-isooctane-water reverse micelles using steady-state and time-resolved spectroscopy and TEM analysis reveals that the nanoaggregates became small and compact size.