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.

Nanoparticles as Next-Generation Tooth-Whitening Agents: Progress and Perspectives.

Whitening agents, such as hydrogen peroxide and carbamide peroxide, are currently used in clinical applications for dental esthetic and dental care. However, the free radicals generated by whitening agents cause pathological damage; therefore, their safety issues remain controversial. Furthermore, whitening agents are known to be unstable and short-lived. Since 2001, nanoparticles (NPs) have been researched for use in tooth whitening. Importantly, nanoparticles not only function as abrasives but also release reactive oxygen species and help remineralization. This review outlines the historical development of several NPs based on their whitening effects and side effects. NPs can be categorized into metals or metal oxides, ceramic particles, graphene oxide, and piezoelectric particles. Moreover, the status quo and future prospects are discussed, and recent progress in the development of NPs and their applications in various fields requiring tooth whitening is examined. This review promotes the research and development of next-generation NPs for use in tooth whitening.

Natural bone-mimicking nanopore-incorporated hydroxyapatite scaffolds for enhanced bone tissue regeneration.

BACKGROUND: A considerable number of studies has been carried out to develop alloplastic bone graft materials such as hydroxyapatite (HAP) that mimic the hierarchical structure of natural bones with multiple levels of pores: macro-, micro-, and nanopores. Although nanopores are known to play many essential roles in natural bones, only a few studies have focused on HAPs containing them; none of those studies investigated the functions of nanopores in biological systems. METHOD: We developed a simple yet powerful method to introduce nanopores into alloplastic HAP bone graft materials in large quantities by simply pressing HAP nanoparticles and sintering them at a low temperature. RESULTS: The size of nanopores in HAP scaffolds can be controlled between 16.5 and 30.2 nm by changing the sintering temperature. When nanopores with a size of ~ 30.2 nm, similar to that of nanopores in natural bones, are introduced into HAP scaffolds, the mechanical strength and cell proliferation and differentiation rates are significantly increased. The developed HAP scaffolds containing nanopores (SNPs) are biocompatible, with negligible erythema and inflammatory reactions. In addition, they enhance the bone regeneration when are implanted into a rabbit model. Furthermore, the bone regeneration efficiency of the HAP-based SNP is better than that of a commercially available bone graft material. CONCLUSION: Nanopores of HAP scaffolds are very important for improving the bone regeneration efficiency and may be one of the key factors to consider in designing highly efficient next-generation alloplastic bone graft materials.

Simultaneous Stabilization and Functionalization of Gold Nanoparticles via Biomolecule Conjugation: Progress and Perspectives.

Gold nanoparticles (AuNPs) are used in various biological applications because of their small surface area-to-volume ratios, ease of synthesis and modification, low toxicity, and unique optical properties. These properties can vary significantly with changes in AuNP size, shape, composition, and arrangement. Thus, the stabilization of AuNPs is crucial to preserve the properties required for biological applications. In recent years, various polymer-based physical and chemical methods have been extensively used for AuNP stabilization. However, a new stabilization approach using biomolecules has recently attracted considerable attention. Biomolecules such as DNA, RNA, peptides, and proteins are representative of the biomoieties that can functionalize AuNPs. According to several studies, biomolecules can stabilize AuNPs in biological media; in addition, AuNP-conjugated biomolecules can retain certain biological functions. Furthermore, the presence of biomolecules on AuNPs significantly enhances their biocompatibility. This review provides a representative overview of AuNP functionalization using various biomolecules. The strategies and mechanisms of AuNP functionalization using biomolecules are comprehensively discussed in the context of various biological fields.

Bioinspired Adenosine Triphosphate as an "All-In-One" Green Flame Retardant via Extremely Intumescent Char Formation.

The development of eco-friendly flame retardants is crucial due to the hazardous properties of most conventional flame retardants. Herein, adenosine triphosphate (ATP) is reported to be a highly efficient "all-in-one" green flame retardant as it consists of three essential groups, which lead to the formation of char with extreme intumescence, namely, three phosphate groups, providing an acid source; one ribose sugar, working as a char source; and one adenine, acting as a blowing agent. Polyurethane foam was used as a model flammable material to demonstrate the exceptional flame retardancy of ATP. The direct flammability tests have clearly shown that the ATP-coated polyurethane (PU) foam almost did not burn upon exposure to the torch flame. Importantly, ATP exhibits an extreme volume increase, whereas general phosphorus-based flame retardants show a negligible increase in volume. The PU foam coated with 30 wt % of ATP (PU-ATP 30 wt %) exhibits a significant reduction in the peak heat release rate (94.3%) with a significant increase in the ignition time, compared to bare PU. In addition, PU-ATP 30 wt % exhibits a high limiting oxygen index (LOI) value of 31% and HF-1 rating in the UL94 horizontal burning foamed material test. Additionally, we demonstrated that ATP's flame retardancy is sufficient for other types of matrices such as cotton, as confirmed from the results of the standardized ASTM D6413 test; cotton-ATP 30 wt % exhibits an LOI value of 32% and passes the vertical flame test. These results strongly suggest that ATP has great potential to be used as an "all-in-one" green flame retardant.

Soft, smart contact lenses with integrations of wireless circuits, glucose sensors, and displays.

Recent advances in wearable electronics combined with wireless communications are essential to the realization of medical applications through health monitoring technologies. For example, a smart contact lens, which is capable of monitoring the physiological information of the eye and tear fluid, could provide real-time, noninvasive medical diagnostics. However, previous reports concerning the smart contact lens have indicated that opaque and brittle components have been used to enable the operation of the electronic device, and this could block the user's vision and potentially damage the eye. In addition, the use of expensive and bulky equipment to measure signals from the contact lens sensors could interfere with the user's external activities. Thus, we report an unconventional approach for the fabrication of a soft, smart contact lens in which glucose sensors, wireless power transfer circuits, and display pixels to visualize sensing signals in real time are fully integrated using transparent and stretchable nanostructures. The integration of this display into the smart lens eliminates the need for additional, bulky measurement equipment. This soft, smart contact lens can be transparent, providing a clear view by matching the refractive indices of its locally patterned areas. The resulting soft, smart contact lens provides real-time, wireless operation, and there are in vivo tests to monitor the glucose concentration in tears (suitable for determining the fasting glucose level in the tears of diabetic patients) and, simultaneously, to provide sensing results through the contact lens display.

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.

Stability of a gold nanoparticle-DNA system in seawater.

We investigated the stability of gold nanoparticles (AuNPs) in seawater. The large amount of Na+, Mg2+, K+, and Ca2+ in seawater makes AuNPs unstable resulting in immediate aggregation. We found that AuNPs become much more stable when they were treated with polyethylene glycol (PEG, MW = 20, 000) before exposure to seawater. The AuNPs maintained stability up to 10 days when they were treated with 16.6% PEG 20000. The AuNP-DNA complex formed in the presence of 3.3% PEG 20000 maintained stability when exposed to seawater. We also demonstrated that the AuNP-DNA complexes can be redispersed after centrifugation and show sequence-specific aggregation in seawater. The results show that the both AuNPs and an AuNP-DNA system can be used in seawater and have the potential to be used to study marine systems.