Gold Nanoparticles as Exquisite Colorimetric Transducers for Water Pollutant Detection.

Gold nanoparticles (AuNPs) are useful nanomaterials as transducers for colorimetric sensors because of their high extinction coefficient and ability to change color depending on aggregation status. Therefore, over the past few decades, AuNP-based colorimetric sensors have been widely applied in several environmental and biological applications, including the detection of water pollutants. According to various studies, water pollutants are classified into heavy metals or cationic metal ions, toxins, and pesticides. Notably, many researchers have been interested in AuNP that detect water pollutants with high sensitivity and selectivity, while offering no adverse environmental issues in terms of AuNP use. This review provides a representative overview of AuNP-based colorimetric sensors for detecting several water pollutants. In particular, we emphasize the advantages of AuNP as colorimetric transducers for water pollutant detection in terms of their low toxicity, high stability, facile processability, and unique optical properties. Next, we discuss the status quo and future prospects of AuNP-based colorimetric sensors for the detection of water pollutants. We believe that this review will promote research and development of AuNP as next-generation colorimetric transducers for water pollutant detection.

Chitosan-reinforced gelatin composite hydrogel as a tough, anti-freezing, and flame-retardant gel polymer electrolyte for flexible supercapacitors.

Hydrogel-based electrolytes for flexible solid-state supercapacitors (SSCs) have received significant attention due to their mechanical robustness and stable electrochemical performance over a wide temperature range. However, achieving flame retardancy in such SSCs at subzero temperatures to increase their practical utility remains challenging. Furthermore, there is a need for sustainable and bio-friendly SSCs that use natural polymer-based hydrogel electrolytes. This study reports a novel approach for developing a chitosan-reinforced anti-freezing ionic conductive gelatin hydrogel to meet these demands. Immersion of chitosan-containing gelatin hydrogels in salt solutions caused chitosan precipitation, resulting in composite hydrogels. The precipitated chitosan contributes to the reinforcement of the gelatin hydrogel network, resulting in a high mechanical toughness of up to 3.81 MJ/m3, a fracture energy of 26 kJ/m2, anti-freezing properties (below -30 °C), and excellent flame retardancy without softening. Furthermore, the hydrogel exhibits excellent electrochemical performance, with an ionic conductivity ranging from 72 mS/cm at room temperature (26 °C) to 39 mS/cm at -30 °C. The proposed hydrogel exhibits potential for use in SSC as a gel polymer electrolyte. This study demonstrates a novel strategy for controlling the mechanical, thermal, and electrochemical characteristics of flexible supercapacitors using biological macromolecules.

Multifunctional Heterogeneous Carbon Nanotube Nanocomposites Assembled by DNA-Binding Peptide Anchors.

Although carbon nanotubes (CNTs) are remarkable materials with many exceptional characteristics, their poor chemical functionality limits their potential applications. Herein, a strategy is proposed for functionalizing CNTs, which can be achieved with any functional group (FG) without degrading their intrinsic structure by using a deoxyribonucleic acid (DNA)-binding peptide (DBP) anchor. By employing a DBP tagged with a certain FG, such as thiol, biotin, and carboxyl acid, it is possible to introduce any FG with a controlled density on DNA-wrapped CNTs. Additionally, different types of FGs can be introduced on CNTs simultaneously, using DBPs tagged with different FGs. This method can be used to prepare CNT nanocomposites containing different types of nanoparticles (NPs), such as Au NPs, magnetic NPs, and quantum dots. The CNT nanocomposites decorated with these NPs can be used as reusable catalase-like nanocomposites with exceptional catalytic activities, owing to the synergistic effects of all the components. Additionally, the unique DBP-DNA interaction allows the on-demand detachment of the NPs attached to the CNT surface; further, it facilitates a CNT chirality-specific NP attachment and separation using the sequence-specific programmable characteristics of oligonucleotides. The proposed method provides a novel chemistry platform for constructing new functional CNTs suitable for diverse applications.

Gold nanostar-mediated neural activity control using plasmonic photothermal effects.

Nanomaterials have emerged as an essential tool for the understanding of cellular level mechanism in the fields of biology and medical science. Recently, researchers have been studying the regulation of neuronal activity using plasmonic nanoparticles and light, and it has been reported that photothermal effects could lead to both excitation and inhibition of neuronal cells. So far, only a few photothermal transducers have been applied to modulate neural activity. In this paper, we synthesized biocompatible gold nanostars (AuNSs) which generate heat by absorbing near-infrared (NIR) light. And we used the AuNS to inhibit the activity of neurons through light stimulation. We have demonstrated that AuNS inhibits the neural activity by NIR laser in both chip-attached mode and cell-attached mode. We also confirmed the suppression of single neuron signal by using digital micromirror device (DMD) set up. This approach is possible to inhibit the neural firing by controlling the intensity of light, and overcome the disadvantages of conventional electrochemical stimulation methods. This method of NIR-mediated stimulating neurons using light sensitive AuNS will be a powerful tool for neuromodulation researches and neuroscience studies.

A significant enhancement of color transition from an on-off type achromatic colorimetric nanosensor for highly sensitive multi-analyte detection with the naked eye.

Here, we report the development of an achromatic nanoparticle-based colorimetric sensor (achromatic nanosensor) with an on-off type color change that significantly enhances the color transition and increases the sensitivity of the sensor for naked-eye inspection. The achromatic nanosensor was prepared via a modified CMYK (CRYK) subtractive color model by combining DNA-functionalized gold nanoparticles (AuNPs-DNA), silver nanoparticles (AgNPs-DNA), and gold nanorods (AuNRs-DNA). The initially black-colored achromatic nanosensor not only allowed multiplexed detection by generating target-specific diverse color changes, but also improved the recognition of color changes by the naked eye. Thus, this on-off type color change enabled analysis near the limit of detection (LOD) with the naked eye. In addition, we developed a new image processing method adapted for this achromatic sensor. By quantifying the saturation value of the color images of the achromatic sensor, we could significantly amplify the color signal of the samples, which is difficult to achieve with general colorimetric sensors. The practical application of this achromatic nanosensor for biomarker detection was demonstrated with thrombin and platelet-derived growth factor (PDGF) in human blood plasma. These results provide a new sensing platform that is applicable to most NP-based colorimetric sensing systems for a wide range of applications, including biomolecular diagnosis, chemical pollutant sensing, environmental monitoring, etc.

A one-step colorimetric acid-base titration sensor using a complementary color changing coordination system.

We report the development of a colorimetric sensor that allows for the quantitative measurement of the acid content via acid-base titration in a single-step. In order to create the sensor, we used a cobalt coordination system (Co-complex sensor) that changes from greenish blue colored Co(H2O)4(OH)2 to pink colored Co(H2O)6(2+) after neutralization. Greenish blue and pink are two complementary colors with a strong contrast. As a certain amount of acid is introduced to the Co-complex sensor, a portion of greenish blue colored Co(H2O)4(OH)2 changes to pink colored Co(H2O)6(2+), producing a different color. As the ratio of greenish blue and pink in the Co-complex sensor is determined by the amount of neutralization reaction occurring between Co(H2O)4(OH)2 and an acid, the sensor produced a spectrum of green, yellow green, brown, orange, and pink colors depending on the acid content. In contrast, the color change appeared only beyond the end point for normal acid-base titration. When we mixed this Co-complex sensor with different concentrations of citric acid, tartaric acid, and malic acid, three representative organic acids in fruits, we observed distinct color changes for each sample. This color change could also be observed in real fruit juice. When we treated the Co-complex sensor with real tangerine juice, it generated diverse colors depending on the concentration of citric acid in each sample. These results provide a new angle on simple but quantitative measurements of analytes for on-site usage in various applications, such as in food, farms, and the drug industry.

Ultrastable-Stealth Large Gold Nanoparticles with DNA Directed Biological Functionality.

The stability of gold nanoparticles (AuNPs) in biological samples is very important for their biomedical applications. Although various molecules such as polystyrenesulfonate (PSS), phosphine, DNA, and polyethylene glycol (PEG) have been used to stabilize AuNPs, it is still very difficult to stabilize large AuNPs. As a result, biomedical applications of large (30-100 nm) AuNPs are limited, even though they possess more favorable optical properties and are easier to be taken up by cells than smaller AuNPs. To overcome this limitation, we herein report a novel method of preparing large (30-100 nm) AuNPs with a high colloidal stability and facile chemical or biological functionality, via surface passivation with an amphiphilic polymer polyvinylpyrrolidone (PVP). This PVP passivation results in an extraordinary colloidal stability for 13, 30, 50, 70, and 100 nm AuNPs to be stabilized in PBS for at least 3 months. More importantly, the PVP capped AuNPs (AuNP-PVP) were also resistant to protein adsorption in the presence of serum containing media and exhibit a negligible cytotoxicity. The AuNP-PVPs functionalized with a DNA aptamer AS1411 remain biologically active, resulting in significant increase in the uptake of the AuNPs (∼12,200 AuNPs per cell) in comparison with AuNPs capped by a control DNA of the same length. The novel method developed in this study to stabilize large AuNPs with high colloidal stability and biological activity will allow much wider applications of these large AuNPs for biomedical applications, such as cellular imaging, molecular diagnosis, and targeted therapy.

Achromatic-chromatic colorimetric sensors for on-off type detection of analytes.

We report the development of achromatic colorimetric sensors; sensors changing their colors from achromatic black to other chromatic colors. An achromatic colorimetric sensor was prepared by mixing a general colorimetric indicator, whose color changes between chromatic colors, and a complementary colored dye with no reaction to the targeted analyte. As the color of an achromatic colorimetric sensor changes from black to a chromatic color, the color change could be much easily recognized than general colorimetric sensors with naked eyes. More importantly, the achromatic colorimetric sensors enable on-off type recognition of the presence of analytes, which have not been achieved from most colorimetric sensors. In addition, the color changes from some achromatic colorimetric sensors (achromatic Eriochrome Black T and achromatic Benedict's solution) could be recognized with naked eyes at much lower concentration ranges than normal chromatic colorimetric sensors. These results provide new opportunities in the use of colorimetric sensors for diverse applications, such as harsh industrial, environmental, and biological detection.

Surfactant-free nanoparticle-DNA complexes with ultrahigh stability against salt for environmental and biological sensing.

We report the development of surfactant free-gold nanoparticle (AuNP)-DNA complexes that remained stable in solutions with extremely high ionic strength, using seawater as a model solution. Although the stability of AuNPs can be increased to a certain degree by functionalizing negatively charged DNA strands on their surfaces, they still have limited stability in highly concentrated salt solutions. However, we found that AuNPs functionalized with poly-T bases have exceptional stability in high ionic strength solutions. For example, AuNPs functionalized with a 5T spacer remained highly stable in seawater, with no color change and no red-shift in absorbance spectra for up to 9 days. Using this surprising property of poly-T spacers, we prepared highly stable AuNP-DNA complexes containing random sequences by introducing 5T spacers on the random sequenced DNA strand. The random sequenced AuNP-DNA complexes remained stable in seawater, several molar concentrations of monovalent metal ion solutions (6.1 M Na(+) or 4.8 M K(+)), and millimolar concentrations of diverse divalent metal ions. In addition, the highly stable AuNP-DNA complex maintained biological activity in seawater, which was demonstrated by complementary reaction and aptamer based biosensing. These results provide important insight into NP use for various applications under harsh biological and environmental conditions.