Cysteamine-decorated gold nanoparticles for plasmon-based colorimetric on-site sensors for detecting cyanide ions using the smart-phone color ratio and for catalytic reduction of 4-nitrophenol.

In this paper, we have reported the cyanide ions (CN-) sensing in environmental water samples using cysteamine-capped gold nanoparticles (Cyst-AuNPs) by spectrophotometric, colorimetric, and smartphone-based RGB color detection. The surface plasmon resonance shift at around 525 nm for the Cyst-AuNPs could be used to detect quantitatively the amounts of CN- with concomitant alteration of their color from wine red to purple visualized by the naked eye. For the first time, the Cyst-AuNPs-based visual sensing of CN- was performed using smartphone-based detection with its detection limit of 159 × 10-9 M, ten times lower than that of the highest tolerance level (2 × 10-6 M) permitted by the world health organization. The Cyst-AuNPs displayed excellent specificity for detecting the concentration of 30 × 10-6 M even amid the presence of other interfering inorganic anions with their concentrations about five times higher than it. Environmental real water samples were used to arrange the three different CN- concentrations for plasmon-based colorimetric detection and smartphone-based method. Additionally, the catalytic performance of Cyst-AuNPs was demonstrated for the fast catalytic conversion of hazardous 4-nitrophenol (selected environmental contaminant) to the analogous amino aromatic compounds. A chemical kinetic study showed the conversion rate to be estimated as 1.65 × 10-2 s-1. Cyst-AuNPs can find an application in colorimetric sensing of CN- while being able to be utilized as a catalytic nanomaterial for ecological remedies associated with health care.

Gold nanoparticle-decorated earth-abundant clay nanotubes as catalyst for the degradation of phenothiazine dyes and reduction of 4-(4-nitrophenyl)morpholine.

In the present work, halloysite nanotubes modified with gold nanoparticles (AuNPs-HNT) are successfully prepared by wet chemical method for the catalytic degradation of phenothiazine dyes (azure B (AZB) and toluidine blue O (TBO)) and also cleaner reduction of 4-(4-nitrophenyl)morpholine (4NM) in the sodium borohydride (NaBH4) media. The catalyst is formulated by modifying the HNT support with a 0.964% metal loading using the HNT supports modified with 3-aminopropyl-trimethoxysilane (APTMS) coupling agent to facilitate the anchoring sites to trap the AuNPs and to prevent their agglomeration/aggregation. The AuNPs-HNT catalyst is investigated for structural and morphological characterization to get insights about the formation of the catalyst for the effective catalytic reduction of dyes and 4NM. The microscopic studies demonstrate that AuNPs (2.75 nm) are decorated on the outer surface of HNT. The as-prepared AuNPs-HNT catalyst demonstrates AZB and TBO dye degradation efficiency up to 96% in 10 and 11 min, respectively, and catalytic reduction of 4NM to 4-morpholinoaniline (MAN) is achieved up to 97% in 11 min, in the presence of NaBH4 without the formation of any by-products. The pseudo-first-order rate constant (K1) value of the AuNPs-HNT catalyst for AZB, TBO, and 4NM were calculated to be 0.0078, 0.0055, and 0.0066 s-1, respectively. Moreover, the synthesized catalyst shows an excellent reusability with stable catalytic reduction for 7 successive cycles for both the dyes and 4NM. A plausible mechanism for the catalytic dye degradation and reduction of 4NM by AuNPs-HNT catalyst is proposed as well. The obtained results clearly indicate the potential of AuNPs-HNT as an efficient catalyst for the removal of dye contaminants from the aquatic environments and cleaner reduction of 4NM to MAN, insinuating future pharmaceutical applications.

Colorimetric determination of cysteamine based on the aggregation of polyvinylpyrrolidone-stabilized silver nanoparticles.

A simple, colorimetric and visual method is described for the determination of cysteamine (CA) using polyvinylpyrrolidone-stabilized silver nanoparticles (PVP-AgNPs) as a colorimetric probe. The sensing method was based on the aggregation of PVP-AgNPs that led to the changes in the color and absorption profile of the probe. The aggregation of PVP-AgNPs in the presence of CA was evidenced by using transmission electron microscopy (TEM), zeta and dynamic light scattering (DLS) measurements. A distinct color transition could be observed with the naked eye from pale yellow color of PVP-AgNPs to purple. PVP-AgNPs probe showed an excellent selectivity towards CA versus other interfering biomolecules, cations and anions. Furthermore, the colorimetric probe had a linear response for CA from 0.1 to 1.0 µM concentration range with the limit of detection (LOD) of 4.9 nM. The prepared probe was successfully utilized for the determination of CA in blood serum as biological samples.

Liquid Phase Hydrogenation of Pharmaceutical Interest Nitroarenes over Gold-Supported Alumina Nanowires Catalysts.

In this work, Au nanoparticles, supported in Al2O3 nanowires (ANW) modified with (3-aminopropyl)trimethoxysilane were synthetized, for their use as catalysts in the hydrogenation reaction of 4-(2-fluoro-4-nitrophenyl)-morpholine and 4-(4-nitrophenyl)morpholin-3-one. ANW was obtained by hydrothermal techniques and the metal was incorporated by the reduction of the precursor with NaBH4 posterior to superficial modification. The catalysts were prepared at different metal loadings and were characterized by different techniques. The characterization revealed structured materials in the form of nanowires and a successful superficial modification. All catalysts show that Au is in a reduced state and the shape of the nanoparticles is spherical, with high metal dispersion and size distributions from 3.7 to 4.6 nm. The different systems supported in modified-ANW were active and selective in the hydrogenation reaction of both substrates, finding for all catalytic systems a selectivity of almost 100% to the aromatic amine. Catalytic data showed pseudo first-order kinetics with respect to the substrate for all experimental conditions used in this work. The solvent plays an important role in the activity and selectivity of the catalyst, where the highest efficiency and operational stability was achieved when ethanol was used as the solvent.

Water-soluble MoS2 quantum dots as effective fluorescence probe for the determination of bilirubin in human fluids.

Bilirubin is an important biomarker in the diagnosis and prognosis of patients with liver disorders. Herein, we report a simple, rapid, sensitive and selective quantitative determination of bilirubin using molybdenum disulfide quantum dots (MoS2 QDs) as a probe. The MoS2 QDs were synthesized through a hydrothermal route by using sodium molybdate and cysteine as the starting materials. The obtained MoS2 QDs exhibits strong luminescence property and excellent stability. The HR-TEM image shows that the size of the prepared MoS2 QDs was 2.4 nm with a spherical morphology. The MoS2 QDs emit intense blue photoluminescence (with excitation/emission peaks at 310/392 nm) under UV light and the fluorescence of MoS2 QDs was drastically quenched by the addition of bilirubin. The Förster resonance energy transfer (FRET) and inner filter effect (IFE) between MoS2 QDs and bilirubin resulted in the fluorescence quenching of MoS2 QDs. The present method demonstrated high sensitivity towards bilirubin with the limit of detection (LOD) of 2.1 nM (S/N = 3). The MoS2 QDs probe showed remarkable selectivity to bilirubin over other possible interferences. Moreover, the present fluorophore was successfully utilized for the detection of bilirubin in human serum and urine samples. QDs based fluorescence probe for the recognition of bilirubin is reported for the first time.

Elucidation of Binding Mechanism of Photodynamic Therapeutic Agent Toluidine Blue O with Chicken Egg White Lysozyme by Spectroscopic and Molecular Dynamics Studies.

The nature of binding mechanism of toluidine blue O (TBO) with chicken egg white lysozyme was studied comprehensively by various spectroscopic and computational methods. Both steady state and time-resolved fluorescence studies unambiguously point to the prevalence of static quenching mechanism in lysozyme-TBO system. Thermodynamic parameters revealed that the association of TBO with lysozyme was a spontaneous process in which hydrophobic and hydrogen bond interactions played a pivotal role in the binding process. The secondary and tertiary conformational changes of lysozyme in the presence of TBO were unraveled using absorption, Fourier transform infrared spectroscopy (FT-IR) and circular dichroism (CD) techniques. Molecular docking studies of lysozyme-TBO system substantiated the findings of site marker experiment and revealed TBO adjacent to Trp-63 and Trp-108 residues of lysozyme. Molecular dynamics (MD) simulation studies of lysozyme-TBO system indicate a stable and effective complexation of TBO with lysozyme. It is hoped that the results presented here will enable further understanding of TBO toxicity.

Exploring the biophysical aspects and binding mechanism of thionine with bovine hemoglobin by optical spectroscopic and molecular docking methods.

In the present investigation, we have elucidated the interaction between thionine (TH) and bovine hemoglobin (BHb) under physiological conditions by using absorption, emission, time resolved fluorescence, synchronous fluorescence, circular dichroism (CD) and three dimensional emission (3D) spectral studies. Molecular docking experiment was also carried out to establish the possible binding site of TH on BHb. The emission spectral studies revealed that, TH have the ability to bind with BHb and form a ground state complex via static quenching process. The calculated binding constant and the number of binding sites was found to be 3.65×10(4)dm(3)mol(-1) and 1.04, respectively. Förster Resonance Energy Transfer (FRET) theory was employed to calculate the distance (r) between donor (BHb) and acceptor (TH) as 3.64nm. Furthermore, the conformational changes of BHb induced by TH complexation showed some degree of structural unfolding. In addition, molecular docking study confirmed that the most probable binding site of TH was located within the active cavity constituted by α1 and α2 subunits of BHb.