Recent Advances in Gold Nanocluster-Based Biosensing and Therapy: A Review.

Gold nanoclusters (Au NCs) with bright emission and unique chemical reactivity characters have been widely applied for optical sensing and imaging. With a combination of surface modifications, effective therapeutic treatments of tumors are realized. In this review, we summarize the recently adopted biosensing and therapy events based on Au NCs. Homogeneous and fluorometric biosensing systems toward various targets, including ions, small molecules, reactive oxygen species, biomacromolecules, cancer cells, and bacteria, in vitro and in vivo, are presented by turn-off, turn-on, and ratiometric tactics. The therapy applications are concluded in three aspects: photodynamic therapy, photothermal therapy, and as a drug carrier. The basic mechanisms and performances of these systems are introduced. Finally, this review highlights the challenges and future trend of Au NC-based biosensing and therapy systems.

Probing the Alcoholysis Degree of Polyvinyl Alcohol by Synergistic Coordination-Regulated Fluorescence.

Polyvinyl alcohol (PVA) with abundant hydroxyl groups (-OH) has been widely used for membranes, hydrogels, and films, and its function is largely affected by the alcoholysis degree. Therefore, the development of rapid and accurate methods for alcoholysis degree determination in PVAs is important. In this contribution, we have proposed a novel fluorescence-based platform for probing the alcoholysis degree of PVA by using the (E)-N-(4-methoxyphenyl)-1-(quinolin-2-yl)methanimine (QPM)-Zn2+ complex as the reporter. The mechanism study disclosed that the strong coordination between -OH and Zn2+ induced the capture of the QPM-Zn2+ complex and promoted its subsequent immobilization into the noncrystalline area. The immobilization of the QPM-Zn2+ complex restricted its molecular rotation and reduced the nonirradiative transition, thus yielding bright emissions. In addition, the practical applications of this proposed method were further validated by the accurate alcoholysis degree determination of blind PVA samples with the confirmation of the National Standard protocol. It is expected that the developed fluorescence approach in this work might become an admissive strategy for screening the alcoholysis degree of PVA.

Electron Transfer Efficiency-Regulated Electrochemiluminescence for Rapid Crystallinity Analysis in Layered Materials.

The electrochemiluminescence (ECL) signal is largely determined by the electron transfer efficiency. Therefore, in the nanomaterial-involved ECL system, the structure-related electron distribution could affect the electron transfer efficiency and further alter the ECL intensity. These features make the design of versatile ECL-based analytical techniques for probing the correlated structure possible. And it is generally accepted that the increased crystallinity of nanomaterials usually leads to a uniform electron distribution, which provides higher conductivity. Therefore, the crystallinity-improved conductivity could facilitate electron transfer, promote the electrochemical activity of support materials, and boost the efficiency of the ECL reaction. In this study, we have demonstrated that the ECL signal of the graphitic carbon nitride reporter was proportional to the crystallinity of layered double hydroxides (LDHs), which meets the supposition well. On the basis of this phenomenon, an ECL-based crystallinity analysis approach has been established using CdAl-LDHs as the model materials. The universality of this proposed technique was further validated by the rapid and accurate crystallinity determination of ZnAl-LDH samples with diverse crystallinities. This work not only contributes an alternative to the X-ray diffraction technique for the rapid screening of crystallinity in layered materials but also opens a new avenue for the design of ECL-based structure analysis techniques toward nanomaterials and even organic materials by involving electron transfer regulation correlation.

Probing Coordination Number of Single-Atom Catalysts by d-Band Center-Regulated Luminescence.

It is essential to probe the coordination number (CN) because it is a crucial factor to ensure the catalytic capability of single-atom catalysts (SACs). Currently, synchrotron X-ray absorption spectroscopy (XAS) is widely used to measure the CN. However, the scarcity of synchrotron X-ray source and complicated data analysis restrict its wide applications in determining the CN of SACs. In this contribution, we have developed a d-band center-regulated acetone cataluminescence (CTL) probe for a rapid screening of the CN of Pt-SACs. It is disclosed that the CN-triggered CTL is attributed to the fact that the increased CN could induce the downward shift of d-band center position, which assists the acetone adsorption and promotes the subsequent catalytic reaction. In addition, the universality of the proposed acetone-CTL probe is verified by determining the CN of Fe-SACs. This work has opened a new avenue for exploring an alternative to synchrotron XAS for the determination of CN of SACs and even conventional metal catalysts through d-band center-regulated CTL.

Dopamine-based selective spectrophotometry p-aminosalicylic acid assay by hydrolyzate-triggered formation of azamonardine-like products.

BACKGROUND: The selective recognition of drugs and its metabolism or decomposition products is significant to drug development and drug resistance research. Fluorescence-based techniques provide satisfying sensitivity by target-triggered chemical reaction. However, the interference from the matrix or additives usually restricts the specific detection. It is highly desirable to explore specific chemical reactions for achieving selective perception of these species. RESULTS: We report a specific m-aminophenol (MAP)-dopamine (DA) reaction, which generates highly fluorescent azamonardine-like products. Based on this reaction, fluorometric and indirect detection of p-aminosalicylic acid (typical antituberculosis drug, PAS) can be realized using the DA-based probe with high sensitivity. The acid induces the decarboxylation of PAS and produces MAP, which reacts with DA and generates fluorescent azamonardine-like products. The practical application of the proposed method is validated by the accurate PAS analysis in urine samples and Pasinazid tablets. Interestingly, none of additives in the Pasinazid tablets contribute comparable fluorescence variation. SIGNIFICANCE: This work discovers a new MAP-DA reaction for the first time, it not only explores sensitive PAS drug detection probe, but also demonstrates the feasibility of the development of novel drug analysis platform by recognizing decomposition product with specific reaction. Thus, new avenues for the exploration of simple and rapid spectrophotometric probes toward various drug analytes with high specify and sensitivity based on this tactic might be possible in analytical and drug-related fields.

3,5-Dihydroxybenzoic Acid-Based Selective Dopamine Detection via Subsititution-Enhanced Kinetics Differences.

The selective recognition of dopamine (DA) over other neurotransmitter analogues is difficult due to the similar molecular structure and chemical reactivity. In this study, substitution-regulated chemical reactivity of the sensing substrate is utilized to explore a novel DA detection probe with satisfying selectivity. As a case study, 3,5-dihydroxybenzoic acid (DHBA, carboxy-substituted resorcinol)-based probes have been explored for selective and ratiometric DA sensing. The carboxy substitution benefits the stabilization of the carbanion intermediate and the azamonardine product, which enhances the reaction kinetics and thermodynamics and subsequently facilitates selective DA recognition over other analogues and interferents. By exploring DHBA emission as the internal reference, ratiometric fluorescence variation is realized, which contributes to sensitive DA analysis. With the combination of logic gate and fluorometric analysis, DA detection in both low and high concentrations can be readily achieved. In addition, the DA analysis in biological samples and the enzymatic transformation of DA analogues in cerebrospinal fluid samples are achieved by the proposed DHBA probe.

Recent developments in detection and therapeutic approaches for antibiotic-resistant bacterial infections.

Owing to the widespread emergence and proliferation of antibiotic-resistant bacteria, the therapeutic benefits of antibiotics have been reduced. In addition, the ongoing evolution of multidrug-resistant pathogens poses a challenge for the scientific community to develop sensitive analytical methods and innovative antimicrobial agents for the detection and treatment of drug-resistant bacterial infections. In this review, we have described the antibiotic resistance mechanisms that occur in bacteria and summarized the recent developments in detection strategies for monitoring drug resistance using different diagnostic methods in three aspects, including electrostatic attraction, chemical reaction, and probe-free analysis. Additionally, to understand the effective inhibition of drug-resistant bacterial growth by recent nano-antibiotics, the underlying antimicrobial mechanisms and efficacy of biogenic silver nanoparticles and antimicrobial peptides, which have shown promise, and the rationale, design, and potential improvements to these methods are also highlighted in this review. Finally, the primary challenges and future trends in the rational design of facile sensing platforms and novel antibacterial agents against superbugs are discussed.

Recent Advancements in Natural Plant Colorants Used for Hair Dye Applications: A Review.

There is an on-going demand in recent years for safer and "greener" hair coloring agents with the global consumer awareness of the adverse effects of synthetic hair dyes. The belief in sustainability and health benefits has focused the attention of the scientific community towards natural colorants that serve to replace their synthetic toxic counterparts. This review article encompasses the historical applications of a vast array of natural plant hair dyes and summarizes the possible coloration mechanisms (direct dyeing and mordant dyeing). Current information on phytochemicals (quinones, tannins, flavonoids, indigo, curcuminoids and carotenoids) used for hair dyeing are summarized, including their botanical sources, color chemistry and biological/toxicological activities. A particular focus is given on research into new natural hair dye sources along with eco-friendly, robust and cost-effective technologies for their processing and applications, such as the synthetic biology approach for colorant production, encapsulation techniques for stabilization and the development of inorganic nanocarriers. In addition, innovative in vitro approaches for the toxicological assessments of natural hair dye cosmetics are highlighted.

Visualization of Polymer-Surfactant Interaction by Dual-Emissive Gold Nanocluster Labeling.

Polymer-surfactant interaction decides the performance of corresponding complexes, making its rapid and intuitionistic visualization important for enhancing the performance of products and/or processing in related fields. In this study, the fluorescence visualization of the interaction between cationic hyperbranched polyethyleneimine and anionic sodium dodecyl sulfonate surfactant was realized by dual-emissive gold nanocluster labeling. The sensing mechanism was due to the interaction-induced polymer conformation change, which regulated the molecular structure and subsequent photoradiation process of the gold nanoclusters. All three inflection points of the interactions between the polymers and the surfactants were obtained by the change in fluorescence emission ratio of the designed dual-emissive gold nanoclusters. Moreover, these inflection points are verified by the hydrodynamic diameter and zeta potential measurements.

Gold Nanocluster-Encapsulated Hyperbranched Polyethyleneimine for Selective and Ratiometric Dopamine Analyses by Enhanced Self-Polymerization.

The exploitation of selective and sensitive dopamine (DA) sensors is essential to more deeply understand its biological function and diagnosis of related diseases. In this study, gold nanocluster-encapsulated hyperbranched polyethyleneimine (hPEI-Au NCs) has been explored as the specific and ratiometric DA nanoprobe through hPEI-assisted DA self-polymerization reactions. The Au NCs encapsulation not only provides a fluorescent internal reference but also enhances the DA self-polymerization by weakening the proton sponge effect of the hPEI layer. Rapid and sensitive DA detection is realized through the proposed hPEI-Au NC nanoprobe with a limit of detection of 10 nM. The favorable selectivity over other possible interferents including amino acids, sugars, and salts is due to the specific self-polymerization reaction. The DA analysis in urine samples with small relative standard deviations has been accomplished with an hPEI-Au NC nanoprobe.

Array-based chemical warfare agent discrimination via organophosphorus-H2O2 reaction-regulated chemiluminescence.

It has been a challenge to achieve rapid, simple, and effective discrimination of organophosphorus nerve agents (typical chemical warfare agents) due to the similar chemical properties of the targets such as sarin, soman, cyclosarin and VX. In this study, we propose a chemiluminescence sensor array that can effectively discriminate organophosphorus nerve agents by organophosphorus-H2O2 reaction, which produces peroxyphosphonate intermediate and regulates the chemiluminescence intensity. A simple chemiluminescence sensor array based on different chemiluminescence characteristics of the four organophosphorus nerve agents in the luminol-H2O2 system and layered double hydroxide-luminol-H2O2 system has been constructed. Four agents can be well distinguished at a concentration of 1.0 mg L-1 when linear discriminant analyses and hierarchical cluster analyses are smartly combined. The high accuracy (100%) evaluation of 20 blind samples demonstrates the practicability of this proposed chemiluminescence sensor array.

Cationic AIEgen micelle-improved chemiluminescent H2O2 assay by integrating reactant approach and CRET.

The enhancement of chemiluminescence (CL) intensity is significant in the development of chemiluminescent detection systems with improved sensitivity. In this study, a cationic surfactant with an intrinsic aggregation-induced emission emitter (AIEgen) has been applied to boost the CL signal of the horseradish peroxidase-luminol-H2O2 system. The formed cationic AIEgen micelles enhance the CL signal in two ways: the electrostatic attraction-mediated enrichment and approach of reactants and the high CRET efficiency between excited luminol radicals and AIEgen in the surfactant backbone. As a result, strong CL intensity is produced. Rapid and sensitive H2O2 detection is realized through the proposed cationic AIEgen micelle-containing chemiluminescent system with a limit of detection of 100 nM. The favourable selectivity over other possible interferents including metal ions and anions is due to the specific chemical reaction. Practical H2O2 analysis of thawing water samples with high accuracy using the proposed chemiluminescent platform is realized and is consistent with standard methods.

Catechin-inspired gold nanocluster nanoprobe for selective and ratiometric dopamine detection via forming azamonardine.

The sensitive and selective perception of dopamine (DA, a typical neurotransmitter) is important to evaluate the biological environment. In this study, a catechin-functionalized gold nanocluster (C-Au NC) nanoprobe has been explored for the ratiometric DA sensing. The detection mechanism is based on the formation of azamonardine via selective DA-catechin chemical reaction and subsequent enhanced fluorescence emission. Using Au NC emission as the internal reference, ratiometric fluorescence variation is realized, which allows sensitive DA analysis with a limit of detection of 1.0 nM (S/N = 3) and linear response concentration range from 0 to 500 nM. The characteristic chemical reaction between catechin and DA affords favorable selectivity over other amino acids, metal ions and small molecules. In addition, the practical application of the proposed nanoprobe is validated by the accurate detection of DA content in urea and cell lysate samples.

Recent Progress of Near-Infrared Persistent Phosphors in Bio-related and Emerging Applications.

Near-infrared persistent phosphors (NIR-PPs) are an emerging category of luminescent materials that can continuously emit NIR luminescence with super-long decay time of minutes, hours, or even days after the excitation ceases. Their unique excitation-free long-lasting afterglow, together with the NIR emission, has not only attracted wide research interests in the areas of photochemistry, photophysics, spectroscopy, and materials science, but also stimulated advanced applications in biosensing, bioimaging, biomedicine, and therapy in the past decade. Beyond these bio-related applications, the active research field triggers a number of novel applications recently. In this review, a brief outline of NIR-PPs including the luminescence mechanism, main material systems, and how they were applied into various fields was depicted. Particular emphasis was put on the emerging applications outside the field of biology. Future perspectives in this exploration research area were also presented. We hope this review can help researchers grab the latest information in the fast-growing field of NIR-PPs.

Design of ratiometric monoaromatic fluorescence probe via modulating intramolecular hydrogen bonding: A case study of alkaline phosphatase sensing.

Monoaromatic molecules are a category of molecules containing a single aromatic ring which generally emit light in the ultraviolet (UV) region. Despite their facile preparation, the UV emission greatly limits their application as organic probes. In this study, we developed a general method to red shift the emission of monoaromatic molecules. Significant fluorescence red-shift (∼100 nm per intramolecular hydrogen bonding) can be achieved by introducing intramolecular hydrogen bonding units to benzene, a typical monoaromatic molecule. Upon increasing the number of hydrogen bonding units on the benzene ring, UV, blue, and green emissions are screened, which are switchable by simply breaking/restoration the intramolecular hydrogen bonding. As a demonstration, with the breaking of one intramolecular H-bonding, the green emission (λemmax = 533 nm) of 2,5-dihydroxyterephthalic acid (DHTA) changed to cyan (λemmax = 463 nm) upon the formation of its phosphorylated form (denoted as PDHTA), which, in the presence of alkaline phosphatase (ALP), hydrolyzed and recovered the green emission. By taking advantage of the switchable emission colors, ratiometric in vitro and endogenous ALP sensing was achieved. This general approach offers a great promise to develop organic probes with tunable emissions for fluorescence analysis and imaging by different intramolecular hydrogen bonding.

Ratiometric and sensitive cyanide sensing using dual-emissive gold nanoclusters.

The detection of cyanide anion (CN-), a highly toxic pollutant, has attracted growing attention in the past years. In this work, a nanosensor composed of hyperbranched polyethyleneimine (hPEI)-assisted dual-emissive gold nanoclusters (DE-Au NCs) is proposed for ratiometric detection of CN- based on surface valence state-driving etch. The ratiometric color change of fluorescence is based on a fact that the red-emissive Au NCs with a high content of surface Au(I) can be easily etched by CN-, while the blue-emissive Au NCs with nearly neutral character can resist CN-. Because of the specific gold-CN- chemistry and electrostatic attraction between the positively charged hPEI protecting layer and the negatively charged CN-, the DE-Au NC-based nanosensor provides high selectivity toward CN- over other anions with a limit of detection of 10 nM. Practical application of the proposed DE-Au NC nanosensor is verified by satisfying recoveries of CN- determination in river water and urine samples. Graphical abstract.

Recent advances of plasmonic nanoparticle-based optical analysis in homogeneous solution and at the single-nanoparticle level.

Plasmonic nanoparticles with special localized surface plasmon resonance (LSPR) characters have been widely applied for optical sensing of various targets. With the combination of single nanoparticle imaging techniques, dynamic information of reactions and biological processes is obtained, facilitating the deep understanding of their principle and design of outstanding nanomaterials. In this review, we summarize the recently adopted optical analysis of diverse analytes based on plasmonic nanoparticles both in homogeneous solution and at the single-nanoparticle level. A brief introduction of LSPR is first discussed. Colorimetric and fluorimetric homogeneous detection examples by using different sensing mechanisms and strategies are provided. Single plasmonic nanoparticle-based analysis is concluded in two aspects: visualization of chemical reactions and understanding of biological processes. The basic sensing mechanisms and performances of these systems are introduced. Finally, this review highlights the challenges and future trend of plasmonic nanoparticle-based optical analysis systems.

11-Mercaptoundecanoic acid capped gold nanoclusters with unusual aggregation-enhanced emission for selective fluorometric hydrogen sulfide determination.

In present study, we discovered unusual solvent-mediated aggregation-enhanced emission (AEE) character of 11-mercaptoundecanoic acid capped gold nanoclusters (MUA-Au NCs). When aggregated in aqueous media, the MUA-Au NCs showed strong emission, which was weakened by adding ethanol. Interestingly, the suppressed emission was selectively enhanced in the presence of hydrogen sulfide (H2S) because H2S was absorbed onto Au NCs through the strong sulfur-gold bonding affinity. The hydrolyzed H2S, namely, HS-, made the Au NCs negatively charged, which aggregated again due to decreased solubility. The H2S-mediated fluorescence enhancement can be further amplified by introducing a hydrophilic thiolate (glutathione, GSH) onto the surface of Au NCs (GSH/MUA-Au NCs), which enabled sensitive determination of H2S. Under the optimized condition, a detection limit of 35 nM was achieved. The determination was not interfered by other anions such as F-, Cl-, Br-, I-, OAc-, N3-, NO3-, HCO3-, SCN-, SO32-, and SO42-. This excellent sensing performance allowed practical application of the GSH/MUA-Au NC-based sensing platform to accurate determination of H2S in human serum samples. Graphical abstractUnusual aggregation-enhanced emission character of 11-mercaptoundecanoic acid capped gold nanoclusters is discovered and has been applied for fluorometric hydrogen sulfide detection.

Precisely tuning the longitudinal localized surface plasmon resonance of gold nanorods via additive-regulated overgrowth.

Gold nanorods (GNRs) with desired longitudinal localized surface plasmon resonance (LLSPR) and strong scattering intensity are important for extending their practical applications in bioimaging and sensing. Herein, a simple additive (HCl and Na2S)-regulated overgrowth approach has been proposed for preparing GNRs with tunable LLSPR. In this approach, HCl is used to slow down the growth reaction rate by changing chemical equilibrium, while Na2S is utilized to halt the reaction when LLSPR is reaching the expected wavelength under monitoring by a UV-Vis spectrometer. Under optimal conditions, GNRs with an LLSPR range from 850 to 650 nm could be facilely prepared with a high precision of 3 nm deviation. The TEM images reveal that GNRs have high monodispersity, displaying an increase in both length and diameter but a decrease in the aspect ratio. With the increase in size, the produced GNRs show enhanced scattering intensity and are applicable for single nanoparticle imaging due to the enlarged absorption and scattering cross-section and improved matching efficiency toward the CCD response.

Improved food additive analysis by ever-increasing nanotechnology.

Improper use of food additives may lead to potential threat to human health, making it important to develop sensitive and selective method for their detection. Nanomaterials with unique chemical and electrochemical properties show extensive applications in the design of food additive sensing systems. In this review, we summarize the recently adopted electrochemical and optical analysis of food additives based on nanomaterials. Detection of typical food additives (colorants and preservatives) by using different sensing mechanisms and strategies are provided. In addition, determination of illegal food additives is also briefly introduced. Finally, this review highlights the challenges and future trend of nanomaterial-based food analysis system.