Microwave-assisted rapid extracellular synthesis of stable bio-functionalized silver nanoparticles from guava (<Emphasis Type="Italic">Psidium guajava</Emphasis>) leaf extract

Our research interest centers on microwave-assisted rapid extracellular synthesis of bio-functionalized silver nanoparticles of 26 ± 5 nm from guava (Psidium guajava) leaf extract with control over dimension and composition. The reaction occurs very rapidly as the formation of spherical nanoparticles almost completed within 90 s. The probable pathway of the biosynthesis is suggested. Appearance, crystalline nature, size and shape of nanoparticles are understood by UV–vis (UV–vis spectroscopy), FTIR (fourier transform infrared spectroscopy), XRD (X-ray diffraction), FESEM (field emission scanning electron microscopy) and TEM (transmission electron microscopy) techniques. Microwave-assisted route is selected for the synthesis of silver nanoparticles to carry out the reaction fast, suppress the enzymatic action and to keep the process environmentally clean and green.     

Biosynthesis of silver nanoparticles using <Emphasis Type="Italic">Ocimum sanctum</Emphasis> (Tulsi) leaf extract and screening its antimicrobial activity

Development of green nanotechnology is generating interest of researchers toward ecofriendly biosynthesis of nanoparticles. In this study, biosynthesis of stable silver nanoparticles was done using Tulsi (Ocimum sanctum) leaf extract. These biosynthesized nanoparticles were characterized with the help of UV–vis spectrophotometer, Atomic Absorption Spectroscopy (AAS), Dynamic light scattering (DLS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Transmission electron microscopy (TEM). Stability of bioreduced silver nanoparticles was analyzed using UV–vis absorption spectra, and their antimicrobial activity was screened against both gram-negative and gram-positive microorganisms. It was observed that O. sanctum leaf extract can reduce silver ions into silver nanoparticles within 8 min of reaction time. Thus, this method can be used for rapid and ecofriendly biosynthesis of stable silver nanoparticles of size range 4–30 nm possessing antimicrobial activity suggesting their possible application in medical industry.     

The Role of Intermolecular Interactions in Solid State Fluorescent Conjugated Polymer Chemosensors

A functionalized fluorescent conjugated polymer, tolylterpyridine poly(p-phenyleneethynylene-thienyleneethynylene (ttp-PPETE), was designed and synthesized to detect trace amounts of toxic transition metal pollutants in ground water. Photophysical studies in tetrahydrofuran (THF) successfully demonstrated this polymer as a selective and sensitive chemosensor for Ni²⁺ and Co²⁺ in aqueous solution. Solid state composites of these chemosensors have now been prepared which can be modified to provide for inexpensive and portable field based chemical detection. A solid composite of ttp-PPETE, blended with poly (methyl methacrylate) shows UV–vis absorption and fluorescence emission spectra which are red- shifted when compared to solution phase spectra, suggesting an increase in conjugation in the solid state. An additional absorption peak, not present in solution, is also observed in the solid state. The presence of this new peak provides evidence of interacting FCP chains in the solid state. Concentration dependent experiments were done on the solid composite showing red-shifted emission peaks accompanied by a significant reduction in the fluorescent quantum yield. These observations are consistent with the formation of aggregated polymer species in the solid state. Intermolecular interactions of this type can be manipulated in the design of sensitive and selective solid state fluorescent conjugated polymer sensors.     

Catalytic reduction of organic dyes at gold nanoparticles impregnated silica materials: influence of functional groups and surfactants

Gold nanoparticles (Au NPs) in three different silica based sol–gel matrixes with and without surfactants are prepared. They are characterized by UV–vis absorbance and transmission electron microscopic (TEM) studies. The size and shape of Au NPs varied with the organo-functional group present in the sol–gel matrix. In the presence of mercaptopropyl functionalized organo-silica, large sized (200–280 nm) spherical Au NPs are formed whereas in the presence of aminopropyl functionalized organo-silica small sized (5–15 nm) Au NPs are formed inside the tube like organo-silica. Further, it is found that Au NPs act as efficient catalyst for the reduction of organic dyes. The catalytic rate constant is evaluated from the decrease in absorbance of the dye molecules. Presence of cationic or anionic surfactants greatly influences the catalytic reaction. The other factors like hydrophobicity of the organic dyes, complex formation of the dyes with anionic surfactants, repulsion between dyes and cationic surfactant, adsorption of dyes on the Au NPs also play important role on the reaction rate.     

Fabrication of magnetic gold nanorod particles for immunomagnetic separation and SERS application

The preparation and application of rod-shaped core–shell structured Fe₃O₄–Au nanoparticles for immunomagnetic separation and sensing were described for the first time with this study. To synthesize magnetic gold nanorod particles, the seed-mediated synthetic method was carried out and the resulting nanoparticles were characterized with transmission electron microscopy (TEM), ultraviolet visible spectroscopy (UV–Vis), energy-dispersive X-ray (EDX), and X-ray diffraction (XRD). Magnetic properties of the nanoparticles were also examined. Characterization of the magnetic gold nanorod particles has proven that the resulting nanoparticles were composed of Fe₃O₄ core and the gold shell. The rod-shaped gold-coated iron nanoparticles have an average diameter of 16 ± 2 nm and an average length of about 50 ± 5 nm (corresponding aspect ratio of 3). The saturation magnetization value for the magnetic gold nanorod particles was found to be 37 emu/g at 300 K. Rapid and room temperature reaction synthesis of magnetic gold nanorod particles and subsequent surface modification with E. coli antibodies provide immunomagnetic separation and SERS application. The analytical performance of the SERS-based homogenous sandwich immunoassay system with respect to linear range, detection limit, and response time is also presented.     

Immobilization of platinum nanoparticles on 3,4-diaminobenzoyl-functionalized multi-walled carbon nanotube and its electrocatalytic activity

Abstract  

Multi-walled carbon nanotubes (MWCNTs) are functionalized at the sp² C–H defect sites with 3,4-diaminobenzoic acid by a “direct” Friedel–Crafts acylation reaction in a mild polyphosphoric acid/phosphorous pentoxide medium. Owing to enhanced surface polarity, the resulting 3,4-diaminobenzoyl-functionalized MWCNTs (DAB-MWCNT) are highly dispersible in polar solvents, such as ethanol, N-methyl-2-pyrrolidone, and methanesulfonic acid. The absorption and emission properties of DAB-MWCNT in solution state are qualitatively shown to be sensitive to the pH in the environment. The DAB-MWCNT is used as a stable platform on which to deposit platinum nanoparticles (PNP). The PNP/DAB-MWCNT hybrid displays high electrocatalytic activity with good electrochemical stability for an oxygen reduction reaction under an alkaline condition.     

Size control synthesis of starch capped-gold nanoparticles

Metallic gold nanoparticles have been synthesized by the reduction of chloroaurate anions [AuCl₄]⁻ solution with hydrazine in the aqueous starch and ethylene glycol solution at room temperature and at atmospheric pressure. The characterization of synthesized gold nanoparticles by UV–vis spectroscopy, high resolution transmission electron microscopy (HRTEM), electron diffraction analysis, X-ray diffraction (XRD), and X-rays photoelectron spectroscopy (XPS) indicate that average size of pure gold nanoparticles is 3.5 nm, they are spherical in shape and are pure metallic gold. The concentration effects of [AuCl₄]⁻ anions, starch, ethylene glycol, and hydrazine, on particle size, were investigated, and the stabilization mechanism of Au nanoparticles by starch polymer molecules was also studied by FT-IR and thermogravimetric analysis (TGA). FT-IR and TGA analysis shows that hydroxyl groups of starch are responsible of capping and stabilizing gold nanoparticles. The UV–vis spectrum of these samples shows that there is blue shift in surface plasmon resonance peak with decrease in particle size due to the quantum confinement effect, a supporting evidence of formation of gold nanoparticles and this shift remains stable even after 3 months.     

Membrane Dipole Potential as Measured by Ratiometric 3-Hydroxyflavone Fluorescence Probes: Accounting for Hydration Effects

We previously applied the electrochromic modulation of excited-state intramolecular proton-transfer (ESIPT) reaction for the design of novel 3-hydroxyflavone (3-HF) derivatives as fluorescent probes for measuring the dipole potential, Ψ_D, in lipid bilayers (Klymchenko et al., Proc. Natl. Acad. Sci. USA, 2003, 100, 11219). In the present work, this method was revisited to take into account the influence of the bilayer hydration on the emission ratiometric response of 3-HF probes. For this reason, it was necessary to deconvolute the whole fluorescence spectra into three bands corresponding to the non H-bonded forms, normal N^* and tautomer T^* forms, both participating to the ESIPT reaction, and to the H-bonded H–N^* form, excluded from this reaction. This allowed us to determine the pure N^*/T^* intensity ratio, without any contribution from the H–N^* form emission depending essentially on the bilayer hydration. This new approach allowed us to confirm the correlation we obtained between the response of 3-HF probes on dipole potential modifications and the corresponding response of the reference fluorescent probe di-8-ANEPPS, thus further confirming the potency of 3-HF probes as excellent emission ratiometric probes to measure dipole potential in lipid membranes.     

Stabilizer specific interaction of gold nanoparticles with a thermosensitive polymer hydrogel

We report the experimental results on temperature-dependent studies of interactions between a novel biocompatible thermosensitive polymer hydrogel and different stabilizing agent capped gold nanoparticles (Au NPs) with particle size ranging from 5 to 20 nm. Stabilizing agents such as thioglycolic acid, tryptophan, and phenylalanine have been used as capping agents for Au NPs. The poly-N-isopropyl acrylamide-co-acrylic acid (pNIPAm-AAc) with 3.0 ± 0.7 μm in size was synthesized by radical polymerization of a selected mixture of N-isopropyl acrylamide (NIPAm), methylene-bis-acrylamide and acrylic acid (AAc). The capped Au NPs were mixed with a solution of pNIPAm-AAc hydrogel. The temperature-dependent properties of the mixture were studied by UV–vis spectroscopy, dynamic light scattering based particle size analysis, and transmission electron microscopy (TEM). The observations indicated change in the lower critical solution temperature (LCST) depending on the nature of the stabilizer, with hydrophobic ones lowering the value while hydrophilic stabilizers increasing the same. Also, the optical absorption due to Au NPs, when stabilized with hydrophobic groups, reduced significantly at above LCST along with significant blue shift of wavelength maximum.     

A hybrid electrochemical–thermal method for the preparation of large ZnO nanoparticles

A simple and efficient two-step hybrid electrochemical–thermal route was developed for the synthesis of large quantity of ZnO nanoparticles using aqueous sodium bicarbonate electrolyte and sacrificial Zn anode and cathode in an undivided cell under galvanostatic mode at room temperature. The bath concentration and current density were varied from 30 to 120 mmol and 0.05 to 1.5 A/dm². The electrochemically generated precursor was calcined for an hour at different range of temperature from 140 to 600 °C. The calcined samples were characterized by XRD, SEM/EDX, TEM, TG-DTA, FT-IR, and UV–Vis spectral methods. Rietveld refinement of X-ray data indicates that the calcined compound exhibits hexagonal (Wurtzite) structure with space group of P63mc (No. 186). The crystallite sizes were in the range of 22–75 nm based on Debye–Scherrer equation. The TEM results reveal that the particle sizes were in the order of 30–40 nm. The blue shift was noticed in UV–Vis absorption spectra, the band gaps were found to be 5.40–5.11 eV. Scanning electron micrographs suggest that all the samples were randomly oriented granular morphology.     

Rapid extra-/intracellular biosynthesis of gold nanoparticles by the fungus <Emphasis Type="Italic">Penicillium</Emphasis> sp.

In this work, the fungus Penicillium was used for rapid extra-/intracellular biosynthesis of gold nanoparticles. AuCl₄ ⁻ ions reacted with the cell filtrate of Penicillium sp. resulting in extracellular biosynthesis of gold nanoparticles within 1 min. Intracellular biosynthesis of gold nanoparticles was obtained by incubating AuCl₄ ⁻ solution with fungal biomass for 8 h. The gold nanoparticles were characterized by means of visual observation, UV–Vis absorption spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). The extracellular nanoparticles exhibited maximum absorbance at 545 nm in UV–Vis spectroscopy. The XRD spectrum showed Bragg reflections corresponding to the gold nanocrystals. TEM exhibited the formed spherical gold nanoparticles in the size range from 30 to 50 nm with an average size of 45 nm. SEM and TEM revealed that the intracellular gold nanoparticles were well dispersed on the cell wall and within the cell, and they are mostly spherical in shape with an average diameter of 50 nm. The presence of gold was confirmed by EDX analysis.     

Synthesis of gelatin-capped gold nanoparticles with variable gelatin concentration

Gelatin-stabilized gold nanoparticles (AuNPs-gelatin) with controlled particle size were synthesized with simple variation of concentration of gelatin by reducing in situ tetrachloroauric acid with sodium citrate. The nanoparticles showed excellent colloidal stability. Transmission electron microscopy (TEM) revealed the formation of well-dispersed gold nanoparticles (AuNPs) with different sizes. The methodology produces particles 10–15 nm in size depending on the concentration of gelatin used. The measured AuNPs are 10, 11, 12, 13, 14, and 15 nm for AuNPs-gelatin 1, 0.5, 0.25, 0.1 and 0.05%, and pure AuNPs, respectively. The AuNPs-gelatin exhibit size-dependent localized surface plasmon resonance behavior as measured by UV–visible spectroscopy. UV–vis spectroscopy and TEM results suggest that higher concentration of gelatin favor smaller particle size and vice versa. FTIR spectroscopy analysis of AuNPs-gelatin revealed the amino bands and carboxyl peak of gelatin. The crystalline nature of AuNPs was investigated by X-ray diffraction.     

Synthesis,X-Ray Crystal Structures and Optical Properties of Novel Substituted Pyrazoly 1,3,4-Oxadiazole Derivatives

Novel pyrazoly 1,3,4-oxadiazole derivatives were synthesized and characterized by ¹H NMR, IR, HRMS and X-ray diffraction analysis. UV–vis absorption and fluorescence properties of these compounds in different solutions showed that the maximum absorption wavelength was not significantly changed in different solvents; however, maximal emission wavelength was red-shifted with the increase of solvent polarity. Absorption λ_max and emission λ_max was less correlated with substituent groups on aryl rings.     

Microwave-assisted rapid synthesis of Ag nanoparticles/graphene nanosheet composites and their application for hydrogen peroxide detection

Abstract  

Ag nanoparticles/graphene nanosheet (AgNPs/GN) composites have been rapidly prepared by a one-pot microwave-assisted reduction method, carried out by microwave irradiation of a N,N-dimethylformamide (DMF) solution of graphene oxide (GO) and AgNO₃. Several analytical techniques including UV–vis spectroscopy, FT-IR spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) have been used to characterize the resulting AgNPs/GN composites. It suggests that such composites exhibit good catalytic activity toward reduction of hydrogen peroxide (H₂O₂), leading to a H₂O₂ sensor with a fast amperometric response time of less than 2 s. The linear detection range is estimated to be from 0.1 to 100 mM (r = 0.999), and the detection limit is estimated to be 0.5 μM at a signal-to-noise ratio of 3.     

Rational Design of Novel Benzimidazole-Based Sensor Molecules that Display Positive and Negative Fluorescence Responses to Anions

Two novel and neutral benzimidazole derivatives-based anion receptors bearing a 1,10-phenanthroline fluorophore, N,N′-di-(2′-benzimidazolyl-methylene)-1, 10-phenanthroline-2,9-diamide (1) and N,N′-di-[2′-(benzimidazolyl-2′-) ethyl-]-1,10-phenanthroline-2,9-diamide (2), which exhibited turn-on and turn-off fluorescence responses to various anions, were rationally designed and synthesized and their fluorescent response toward anions was investigated in DMSO solution. In the process of anions binding, there were two different fluorescent responses in presence of anions: a quenching of the fluorescence emission for F^- and AcO^- and an enhancement of the fluorescence emission for Cl⁻, Br⁻ and I⁻. Two different luminescent mechanisms of the receptors 1 and 2 resulting from various anions were exploited to rationalize quenching and enhancement of the fluorescence emission: a photo-induced electronic transfer mechanism (PET) and the increase of the rigidity of the host molecules, respectively. In particular, chloride could be recognized selectively from the anions tested according to changes of fluorescence spectrum. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Plasmon coupling in binary metal core–satellite assemblies

Controlled plasmon coupling is observed in nanoparticle assemblies composed of 20 nm silver ‘satellite’ nanoparticles tethered by reconfigurable duplex DNA linkers to a 50 nm gold ‘core’ particle. The assemblies incorporate silver nanoparticle–oligonucleotide conjugates prepared using a new conjugation method in which the recognition strand is anchored by a 10 base pair, double strand spacer that presents adjacent 3’- and 5’-thiols to the silver surface. Reconfiguration of the DNA linkers from a compact to an extended state results in decreased core–satellite coupling and a blue-shift in the gold core plasmon resonance. The structural basis for the observed resonance modulation is investigated through simulation of the scattering spectra of binary assemblies with various core–satellite separations. Additional simulations of core–satellite assemblies composed of gold satellite particles bound to silver cores and of assemblies composed entirely of silver particles are used to clarify the dependence of the coupling response on the composition of the components and their distribution within the assembly. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

Therapeutic Pretargeting with Gold Nanoparticles as Drug Candidates for Boron Neutron Capture Therapy

Boron neutron capture therapy (BNCT) is a binary approach for cancer treatment in which boron-10 atoms and thermal neutrons need to colocalize to become effective. Recent research in the development of BNCT drug candidates focuses increasingly on nanomaterials, with the advantages of high boron loadings and passive targeting due to the enhanced permeability and retention (EPR) effect. The use of small boron-rich gold nanoparticles (AuNPs) in combination with a pretargeting approach is proposed. Small sized polyethylene glycol–stabilized AuNPs (core size 4.1 ± 1.5 nm), are synthesized and functionalized with thiolated cobalt bis(dicarbollide) and tetrazine. To enable in vivo tracking of the AuNPs by positron emission tomography (PET), the core is doped with [⁶⁴Cu]CuCl₂. For the pretargeting approach, the monoclonal antibody Trastuzumab is functionalized with trans-cyclooctene-N-hydroxysuccinimide ester. After proving in vitro occurrence of the antibody conjugation onto the AuNPs by click reaction and the low toxicity of the AuNPs, the boron delivery system is evaluated in vivo using breast cancer xenograft bearing mice and PET imaging. Tumor uptake due to the EPR effect can be witnessed with ≈5% injected dose (ID) cm⁻³ at 24 h postinjection, but with slower clearance than expected. Therefore, no increased retention can be observed using the pretargeting strategy.     

Characterization and applications of as-grown β-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles prepared by hydrothermal method

The production of low-dimensional nanoparticles (NPs) with appropriate surface modification has attracted increasing attention in biological, biochemical, and environmental applications including chemical sensing, photocatalytic degradation, separation, and purification of toxic molecules from the matrices. In this study, iron oxide NPs have been prepared by hydrothermal method using ferric chloride and urea in aqueous medium under alkaline condition (pH 9 ~ 10). As-grown low-dimensional NPs have been characterized by UV–vis spectroscopy, FT-IR, X-ray diffraction, Field emission scanning electron microscopy, Raman spectroscopy, High-resolution Transmission electron microscopy, and Electron Diffraction System. The uniformity of the NPs size was measured by the scanning electron microscopy, while the single phase of the nanocrystalline β-Fe₂O₃ was characterized using powder X-ray diffraction technique. As-grown NPs were extensively applied for the photocatalytic degradation of acridine orange (AO) and electrochemical sensing of ammonia in liquid phase. Almost 50% photo-catalytic degradation with AO was observed in the presence of UV sources (250 W) with NPs. β-Fe₂O₃ NP-coated gold electrodes (GE, surface area 0.0216 cm²) have enhanced ammonia-sensing performances in their electrical response (I–V characterization) for detecting ammonia in liquid phase. The performances of chemical sensor were investigated, and the results exhibited that the sensitivity, stability, and reproducibility of the sensor improved significantly using β-Fe₂O₃ NPs on GE surface. The sensitivity was approximately 0.5305 ± 0.02 μAcm⁻²mM⁻¹, with a detection limit of 21.8 ± 0.1 μM, based on a signal/noise ratio of 3 with short response time.     

Fluorescent Carbon Dots Capped with PEG<Subscript>200</Subscript> and Mercaptosuccinic Acid

The synthesis and functionalization of carbon nanoparticles with PEG₂₀₀ and mercaptosuccinic acid, rendering fluorescent carbon dots, is described. Fluorescent carbon dots (maximum excitation and emission at 320 and 430 nm, respectively) with average dimension 267 nm were obtained. The lifetime decay of the functionalized carbon dots is complex and a three component decay time model originated a good fit with the following lifetimes: τ ₁ = 2.71 ns; τ ₂ = 7.36 ns; τ ₃ = 0.38 ns. The fluorescence intensity of the carbon dots is affected by the solvent, pH (apparent pK _a of 7.4 ± 0.2) and iodide (Stern-Volmer constant of 78 ± 2 M⁻¹).     

Silver Nanoparticle-Enhanced Chemiluminescence Method for Determining Naproxen Based on Europium(III)-Sensitized Ce(IV)-Na<Subscript>2</Subscript>S<Subscript>2</Subscript>O<Subscript>4</Subscript> Reaction

A simple and sensitive chemiluminescence (CL) method coupled with flow-injection technique is proposed to determine naproxen (NAP). The method is based upon the enhancement of the weak CL signal arising from the reaction of Ce(IV) and Na₂S₂O₄ with Eu³⁺ to form the Eu³⁺-Ce(IV)-Na₂S₂O₄ system. The CL intensity was significantly increased by the introduction of NAP into this system in the presence of silver nanoparticles (Ag NPs). Examination of the recorded UV–vis spectra and fluorescence spectra indicated that the energy of the intermediate SO₂*, which originated from the redox reaction of Ce(IV) and Na₂S₂O₄, was transferred to Eu³⁺ via NAP and that the process was accelerated by Ag NPs due to their catalytic activity. Under the optimum conditions, the CL intensity was increased with increasing NAP concentration and the correlation was linear (r = 0.9992) over the NAP concentration range of 1–420 ng mL⁻¹. The limit of detection (LOD) was 0.11 ng mL⁻¹ with a relative standard deviation (RSD) of 1.15% for 5 replicate determinations of 200 ng mL⁻¹ NAP. The method was successfully applied to determine NAP in pharmaceutical and biological samples.