Luminescent Ru(bpy)3 2+-doped silica nanoparticles for imaging of intracellular temperature

Silica nanoparticles doped with the luminescent temperature probe Ru(bpy)₃ ²⁺ were prepared by a modified Stöber method and are shown to enable optical sensing of intracellular temperatures. Based on the regrowth of silica nanoseeds, the ruthenium probe was easily incorporated and then covered with a shell of pure silica. The resulting nanothermometers were immune to the quenching by oxygen owing to the outer silica layer. The nanoparticles were further coated with poly-L-lysine in order to reduce cytotoxicity and to warrant cellular uptake. The luminescence of these nanosensors is rather sensitive to temperature in the physiological range (25–45 °C), with a decrease of ?1.26 % in intensity per °C increase in temperature. The nanosensors were internalized into living cells of a hepatocellular carcinoma cell line along with gold nanorods. These display longitudinal surface plasmon resonance absorption at ~808 nm that causes a local rise in temperature. The microscopically captured luminescence intensity of the nanosensors after 808 nm irradiation of the gold nanorods decayed with increasing temperature, thereby indicating successful imaging of temperature.

Acetone sensor based on solvothermally prepared ZnO doped with Co3O4 nanorods

This paper describes a reliable and sensitive method for sensing dissolved acetone using doped nanomaterials. Large-scale synthesis of ZnO nanorods (NRs) doped with Co₃O₄ was accomplished by a solvothermal method at low temperature. The doped NRs were characterized in terms of their morphological, structural, and optical properties by using field-emission scanning electron microscopy coupled with energy-dispersive system, UV-Vis., Fourier transform IR, X-ray diffraction, and Xray photoelectron spectroscopy. The calcinated (at 400 °C) doped NRs are shown to be an attractive semiconductor nanomaterial for detecting acetone in aqueous solution using silver electrodes. The sensor exhibits excellent sensitivity, stability and reproducibility. The calibration plot is linear over a large concentration range (66.8 μM to 0.133 mM), displays high sensitivity (~3.58 μA cm^?2 mM^?1) and a low detection limit (~14.7?±?0.2 μM; at SNR of 3).

Coating sulfonated polystyrene microspheres with highly dense gold nanoparticle shell for SERS application

The fabrication of highly dense gold nanoparticles (NPs)-coated sulfonated polystyrene (PS) microspheres and their application in surface-enhanced Raman spectroscopy (SERS) were reported. After the preparation of PS microsphere using dispersion polymerization and subsequent sulfonation, [Ag(NH₃)₂]⁺ ions were adsorbed on the surfaces of the sulfonated PS microspheres and then reduced to silver nanoseeds for further growth of gold NPs shell by seeded growth approach. Reaction conditions such as the concentration of the growth solution and growth time were adjusted to achieve nonspherical gold NPs-coated PS microspheres with different coverage degree. The application of the as-prepared spiky gold NPs-coated PS microsphere hybrid composite in SERS was finally investigated by using 4-aminothiophenol as probe molecules. The results showed that as-prepared gold NPs-coated PS microspheres could be used as functional hybrid materials to exhibit excellent enhancement ability in SERS.

Colorimetric determination of ferrous ion via morphology transition of gold nanorods

A colorimetric method is described for the determination of ferrous ion (Fe²⁺) with high sensitivity and selectivity. The method is based on catalytic etching of gold nanorod (NR). In an acid condition, Fe²⁺ reacts with H₂O₂ to produce superoxide radical (O₂ ^??) that etches gold NRs from the low energy surface along the longitudinal direction preferentially. As a result, the changes in the absorption spectrum and color of gold NR can be measured and also can be detected visually. Under the optimal conditions, the assay has very low detection limit (13.5 nM) and a linear response in a concentration range of 75 to 1 μM. The method was applied to the determination of Fe²⁺ in spiked samples of fetal bovine serum and also transferred to a kind of test stripe for use in fast practical applications. A unique colorimetric sensing method is demonstrated for the colorimetric detection of Fe²⁺, again based on the oxidation of gold nanorods which leads to the blue-shift of the absorption.

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Graphical abstract A unique colorimetric sensing method was shown for the colorimetric detection of Fe²⁺. Fe²⁺reacts with H₂O₂ to generate superoxide radical that oxidize gold nanorods. This leads to a color change from blue-green to pink.

     

Simultaneous determination of trace levels of lead(II) and copper(II) by square wave stripping voltammetry using a glassy carbon electrode modified with hierarchical gold dendrites

A glassy carbon electrode was modified with gold hierarchical dendrites (Au HDs) by one-step electrodeposition in the presence of cytosine, which plays an important role in the formation of the Au HDs. This approach is simple, fast, feasible, controllable, without any seed, template, or surfactant. The modified electrodes were used for the simultaneous determination of Pb²⁺ and Cu²⁺ by square wave stripping voltammetry. The peak currents show good linear relationship with concentrations of Pb²⁺ and Cu²⁺ in the range of 5.0 to 15.0 μM. The recoveries of the spiked water samples are in the range of 94.0 %–107.4 % for Pb²⁺ and Cu²⁺, and their relative standard deviation are in the range of 2.7 %–4.3 % for Pb²⁺ and Cu²⁺, respectively (n?=?3).

Sensitive and selective colorimetric detection of cadmium(II) using gold nanoparticles modified with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole

We have developed a simple, sensitive and selective colorimetric method for the detection of cadmium(II) (Cd²⁺) using gold nanoparticles modified with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole. Organic solvents or additives are not required. It is found that Cd²⁺ induces the aggregation of the modified Au-NPs via chelation, leading to a color change from red to blue. This change can be seen with bare eyes, and monitored by UV–vis spectroscopy, transmission electron microscopy and dynamic light scattering. The detection limit is 30 nM (at a signal-to-noise ratio of 3). The new approach was successfully applied to the detection of Cd²⁺ in spiked samples of tap water and lake water, and the results agree well with those obtained by flame atomic absorption spectroscopy.

Emulsification-based dispersive liquid microextraction and HPLC determination of carbazole-based explosives

We have developed a simple method for the highly selective colorimetric detection of dissolved mercury(II) ions via direct formation of gold nanoparticles (AuNPs). The dithia-diaza ligand 2-[3-(2-amino-ethylsulfanyl)-propylsulfanyl]-ethylamine (AEPE) was used as a stabilizer to protect AuNPs from aggregation and to impart highly selective recognition of Hg(II) ion over other metal ions. A solution of Au(III) ion is directly reduced by sodium borohydride in the presence of AEPE and the detergent Triton X-100. This results in the formation of AEPE-AuNPs and a red coloration of the solution. On the other hand, in the presence of Hg(II), the solution turns blue within a few seconds after the addition of borohydride. This can be detected spectrophotometrically or even visually. The method was successfully applied to quantify Hg(II) levels in water sample, with a minimum detectable concentration as low as 35?nM.

A colorimetric assay for measuring iodide using Au@Ag core–shell nanoparticles coupled with Cu

Au@Ag core–shell nanoparticles (NPs) were synthesized and coupled with copper ion (Cu²⁺) for the colorimetric sensing of iodide ion (I⁻). This assay relies on the fact that the absorption spectra and the color of metallic core–shell NPs are sensitive to their chemical ingredient and dimensional core-to-shell ratio. When I⁻ was added to the Au@Ag core–shell NPs-Cu²⁺ system/solution, Cu²⁺ can oxidize I⁻ into iodine (I₂), which can further oxidize silver shells to form silver iodide (AgI). The generated Au@AgI core–shell NPs led to color changes from yellow to purple, which was utilized for the colorimetric sensing of I⁻. The assay only took 10 min with a lowest detectable concentration of 0.5 μM, and it exhibited excellent selectivity for I⁻ over other common anions tested. Furthermore, Au@Ag core–shell NPs-Cu²⁺ was embedded into agarose gels as inexpensive and portable “test strips”, which were successfully used for the semi-quantitation of I⁻ in dried kelps.     

A colorimetric method for the determination of lead(II) ions using gold nanoparticles and a guanine-rich oligonucleotide

We have developed a colorimetric method for the determination of Pb(II) ions. It is based on the use of gold nanoparticles and a guanine-rich synthetic oligonucleotide. On addition of Pb(II), the color of the solution turns from red to blue. The ratio of the UV-vis absorption at 630?nm and 525?nm is proportional to the concentration of Pb(II) ions in the range from 10 to 100?nM, and the detection limit is 20?nM. Other metal ions do not interfere if present in up to a 10-fold molar excess. The method was successfully applied to the detection of Pb(II) in lake water and urine. The recovery in case of spiked samples is 92%. The results show that this method is sensitive, simple and fast.

Visual detection of silver(I) ions by a chromogenic reaction catalyzed by gold nanoparticles

We report on a novel method for visual detection silver(I) ion. It is based on the finding that Ag(I) ions are rapidly reduced by hydroquinone to form a shell of silver on the surface of gold nanoparticles (AuNPs) which act as catalysts for this reaction. This leads to a color change from red to yellow which can be seen with bare eyes. This scheme is sensitive and highly specific for Ag(I) ions. The detection limits are 5 μM for visual inspection and 1 μM for photometric readout, respectively. The method was successfully applied to the determination of Ag(I) ions in spiked lake water and soil.

Synthesis of ZnO/Cu2S core/shell nanorods and their enhanced photoelectric performance

In this work, two kinds of ZnO/Cu₂S core/shell nanorods (NRs) have been successfully synthesized from ZnO NRs for photoelectrochemical (PEC) water splitting by a versatile hydrothermal chemical conversion method (H-ZnO/Cu₂S core/shell NRs) and successive ionic layer adsorption and reaction method (S-ZnO/Cu₂S core/shell NRs), respectively. The photoelectrode is composed of a core/shell structure where the core portion is ZnO NRs and the shell portion is Cu₂S nanoparticles sequentially located on the surface. The ZnO NRs array provides a fast electron transport pathway due to its high electron mobility properties. The optical property of both two kinds of core/shell NRs was characterized, and enhanced absorption spectrum was discovered. Our PEC system produced very high photocurrent density and photoconversion efficiency under 1.5 AM irradiation for hydrogen generation. On the basis of a versatile chemical conversion process based on the ion-by-ion growth mechanism, H-ZnO/Cu₂S core/shell NRs exhibit a much higher photocatalytic activity than S-ZnO/Cu₂S core/shell NRs. The photocurrent density and photoconversion efficiency of H-ZnO/Cu₂S core/shell NRs are up to 20.12 mA cm^?2 at 0.85 V versus SCE and 12.81 % at 0.40 V versus SCE, respectively.     

Non-enzymatic hydrogen peroxide sensor based on a gold electrode modified with granular cuprous oxide nanowires

Granular nanowires with a diameter of about 60 nm were fabricated from cuprous oxide (Cu₂O) by an electrochemical method using anodic aluminium oxide as the template. A non-enzymatic sensor for hydrogen peroxide (H₂O₂) was then developed on the basis of a gold electrode modified with Cu₂O nanowires and Nafion. The resulting sensor enables the determination of H₂O₂ with a sensitivity of 745 μA?mM^?1?cm^?2, over a wide linear range (0.25 μM to 5.0 mM), and with a low detection limit (0.12 μM). The results demonstrate that the use of such granular nanowires provides a promising tool for the design of non-enzymatic chemical sensors.

A colorimetric probe for the rapid and selective determination of mercury(II) based on the disassembly of gold nanorods

We report on a novel mercury(II)-controlled approach for the disassembly of gold nanorods (AuNRs) that has led to a detection system for Hg(II). The modified AuNRs were fabricated by functionalizing AuNRs with L-cysteine via a thiol group chemisorption-type of interaction. L-cysteine induces the assembly of AuNRs through cooperative electrostatic interaction upon which the color of the solution of the AuNRs changes from blue-green to gray dark. The addition of Hg(II), in turn, causes the disassembly of the modified AuNRs and the color of the solution returns to blue-green. This effect enables the optical determination of Hg(II) in aqueous solution, with a linear response in the 0.5 to 250 μM Hg(II) concentration range, an excellent selectivity for Hg(II), and with recoveries ranging from 99 % to 106 % in spiked environmental water samples.

Direct electrochemistry and electrocatalysis of myoglobin using an ionic liquid-modified carbon paste electrode coated with Co3O4 nanorods and gold nanoparticles

A nanohybrid biomaterial was fabricated by mixing Co₃O₄ nanorods, gold nanoparticles (Au-NPs) and myoglobin (Mb), and depositing it on the surface of a carbon paste electrode containing the ionic liquid N-hexylpyridinium hexafluorophosphate as the binder. UV–vis and FT-IR revealed the Mb in the composite film to have remained in its native structure. A pair of well-defined redox peaks appears in cyclic voltammograms and indicates direct electron transfer from the Mb to the underlying electrode. The results are attributed to the favorable orientation of Mb in the composite film, to the synergistic effects of Co₃O₄ nanorods and Au-NPs. The modified electrode shows excellent electrocatalytic ability towards the reduction of substrates such as trichloroacetic acid and nitrite, and displays good stability and reproducibility.

Colorimetric detection of lead (II) based on silver nanoparticles capped with iminodiacetic acid

We report on a colorimetric probe for the determination of Pb(II). It is based on the use of silver nanoparticles that have been functionalizd with iminodiacetic acid (IDA-Ag NPs). The absorption spectrum and solution color of IDA-Ag NPs undergo dramatic changes on exposure to Pb(II) with a new absorption peak appearing at 650 nm and a concomitant color change from yellow to green. This is assumed to result from the aggregation of IDA-Ag NPs induced by Pb(II). Under optimum conditions, there is a linear relationship between the ratio of the absorbances at 650 and 396 nm, respectively, and the concentration of Pb(II) in the 0.4 to 8.0 μM concentration range, with a detection limit of 13 nM. The method was applied to the determination of Pb(II) in tap water and urea samples, and recoveries ranged from 93.7 % to 98.6 %.

Magnetic beads-based multicolor colorimetric immunoassay for ultrasensitive detection of aflatoxin B1

Aflatoxin B₁ (AFB₁) is one of the most toxic, mutagenic and carcinogenic mycotoxin, widely exists in contaminated food, grains and feedstuff products. In this study, a novel magnetic beads multicolor colorimetric immunoassay (MBMCIA) based on Au@Ag nanorods (Au@Ag NRs) is proposed to visual detect ultralow concentration of AFB₁ with high-resolution by the naked-eye. To design the MBMCIA system, AFB₁-BSA conjugates were first coated on the surface of magnetic beads (MBs), then alkaline phosphatase (ALP) as a bridge between immunoassay and color reaction was used for catalytic hydrolysis of ascorbic acid-phosphate to generate reductive ascorbic acid. Finally, the yielded ascorbic acid could reduce silver ions to grow a silver coating on the surface of gold nanorods to generate Au@Ag NRs, which leads to the bule-shifted longitudinal absorption peak of Au NRs, accompanying with a series of perceptible color change. Under the optimal conditions, the proposed MBMCIA exhibited good sensitivity and specificity for the detection of AFB₁ with the detection limit as low as 5.7 pg/mL. Meanwhile, the MBMCIA was also applied for the analysis of AFB₁ in spiked wheat samples, the obtained recoveries range from 99.1% to 104.3% with relative standard deviation (RSD) less than 7.05% were acceptable. The proposed MBMCIA integrates separated, enriched, anti-interference and signal read-out into one, which opens up a new avenue for an on-site visual food safety inspection or environmental monitoring.     

Colorimetric sensing of iodide based on triazole-acetamide functionalized gold nanoparticles

We have modified gold nanoparticles (AuNPs) with triazole acetamide to obtain a material for the sensitive and selective colorimetric determination of iodide. The functionalized AuNPs were prepared by a reductive single chemical step using a Cu(I)-catalyzed click reaction. The presence of iodide ions induces the aggregation of these AuNPs and results in a color change from wine-red to purple. The iodide-induced aggregation can be detected visually with bare eyes, but also by photometry. The detection limit is as low as 15 nM. The method displays excellent selectivity for iodide over other anions due to the selective interaction with the amido groups of the triazole. The method was applied to the determination of iodide in spiked lake waters.

Enhancement of the colorimetric sensitivity of gold nanoparticles with triethanolamine to minimize interparticle repulsion

Cysteine and thioglycolic acid were immobilized on gold nanoparticles via established thiolgold surface chemistry. It is found that calcium ions rapidly induce the aggregation of the functional gold nanoparticles due to the complexation of Ca(II) by immobilized cysteine. It was also found that triethanolamine enhances the effect of calcium ions by decreasing the electrostatic repulsion between the gold nanoparticles. Transmission electron microscopy, electrophoresis, zeta potential measurements and absorptiometry were used to investigate the mechanism. Under the optimum experimental condition, the cysteine/thioglycolate/triethanolamine-modified nanoparticles were highly sensitive (the detection limit being 0.3 ??M) and selective towards calcium and magnesium ions, with a linear detection range between 1.0 ??M and 14 ??M. Based on these findings, a rapid and selective colorimetric method was developed for assaying Ca(II) ions in serum.

Direct electrochemistry of hemoglobin on an ionic liquid carbon electrode modified with zinc tungstate nanorods

We have constructed a new electrochemical biosensor by immobilization of hemoglobin (Hb) and ZnWO₄ nanorods in a thin film of chitosan (CTS) on the surface of carbon ionic liquid electrode. UV–vis and FT-IR spectra reveal that Hb remains in its native conformation in the film. The modified electrode was characterized by scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry. A pair of well-defined redox peaks appears which indicates direct electron transfer from the electrode. The presence of CTS also warrants biocompatibility. The electron transfer coefficient and the apparent heterogeneous electron transfer rate constant were calculated to be 0.35 and 0.757 s^?1, respectively. The modified electrode displays good electrocatalytic activity for the reduction of trichloroacetic acid with the detection limit of 0.613 mmol L^?1 (3σ). The results extend the protein electrochemistry based on the use of ZnWO₄ nanorods.

Cyanido-bridged one-dimensional systems assembled from [ReIVCl4(CN)2]2? and [MII(cyclam)]2+ (M = Ni, Cu) precursors

Three new cyanido-bridged heterometallic Re^IVNi^II and Re^IVCu^II one-dimensional systems were synthesized and extensively characterized both structurally and magnetically. Single-crystal X-ray diffraction analysis revealed that these compounds display a common topology, with chains composed of alternating [Re^IVCl₄(CN)₂]^2? and [M^II(cyclam)]²⁺ (M = Ni in 1, Cu in 2) or [Cu^II(N,N??-dimethylcyclam)]²⁺ (in 3) building units. Two different chain orientations with a tilt angle of ca. 51° to 55° are present in the crystal packing of these compounds. The magnetic susceptibility measurements suggest the presence of intrachain ferromagnetic interactions between the S = 3/2 Re^IV centers and the 3d metal ions: S = 1 Ni^II or S = 1/2 Cu^II. At low temperature, a three-dimensional ordered magnetic phase induced by interchain antiferromagnetic interactions (antiferromagnetic for 1 and 2; canted antiferromagnetic for 3) is detected for the three compounds.