Near-Infrared Responsive Ag@Au Nanoplates with Exceptional Stability for Highly Sensitive Colorimetric and Photothermal Dual-Mode Lateral Flow Immunoassay.

Lateral flow immunoassay (LFIA) has played a vital role in point-of-care (POC) testing on account of its simplicity, rapidity, and low cost. However, the low sensitivity and difficulty of quantitation limit its further development. Sensitive markers with new detection modes are being developed to dramatically improve LFIA's performance. Herein, a ligand-complex approach was proposed to uniformly coat a thin layer of Au onto Ag triangular nanoplates (Ag TNPs) without etching the Ag cores, which not only retain the unique optical properties from Ag TNPs but also acquire the surface stability and biocompatibility of gold. The localized surface plasmon resonance absorption of these Ag@Au TNPs could be finely adjusted from visible (550 nm) to the second near-infrared region (NIR-II) (1100 nm), and even longer, by simply adjusting the ratio between edge length and thickness. Utilizing the Ag@Au TNPs as new markers for LFIA, a highly sensitive colorimetric and photothermal dual-mode detection of the SARS-CoV-2 nucleocapsid protein was achieved with a very low background. The Ag@Au TNPs showed an exceedingly high photothermal conversion efficiency of 61.4% (ca. 2 times higher than that of Au nanorods), endowing the LFIA method with a low photothermal detection limit (40 pg/mL), which was 25-fold lower than that of the colorimetric results. The generality of the method was further verified by the sensitive and accurate analysis of cardiac troponin I (cTnI). This method is robust, reproducible, and highly specific and has been successfully applied to SARS-COV-2 detection in 35 clinical samples with satisfactory results, demonstrating its potential for POC applications.

PEI-Mediated Assembly of Fe3O4 onto SiO2-Encapsulated CsPbBr3 for Highly Sensitive Fluorescent Lateral Flow Immunoassay.

The conventional lateral flow immunoassay (LFIA) method using colloidal gold nanoparticles (Au NPs) as labeling agents faces two inherent limitations, including restricted sensitivity and poor quantitative capability, which impede early viral infection detection. Herein, we designed and synthesized CsPbBr3 perovskite quantum dot-based composite nanoparticles, CsPbBr3@SiO2@Fe3O4 (CSF), which integrated fluorescence detection and magnetic enrichment properties into LFIA technology and achieved rapid, sensitive, and convenient quantitative detection of the SARS-CoV-2 virus N protein. In this study, CsPbBr3 served as a high-quantum-yield fluorescent signaling probe, while SiO2 significantly enhanced the stability and biomodifiability of CsPbBr3. Importantly, the SiO2 shell shows relatively low absorption or scattering toward fluorescence, maintaining a quantum yield of up to 74.4% in CsPbBr3@SiO2. Assembly of Fe3O4 nanoparticles mediated by PEI further enhanced the method's sensitivity and reduced matrix interference through magnetic enrichment. Consequently, the method achieved a fluorescent detection range of 1 × 102 to 5 × 106 pg·mL-1 after magnetic enrichment, with a limit of detection (LOD) of 58.8 pg·mL-1, representing a 13.3-fold improvement compared to nonenriched samples (7.58 × 102 pg·mL-1) and a 2-orders-of-magnitude improvement over commercial colloidal gold kits. Furthermore, the method exhibited 80% positive and 100% negative detection rates in clinical samples. This approach holds promise for on-site diagnosis, home-based quantitative tests, and disease procession evaluation.

A highly sensitive point-of-care detection platform for Salmonella typhimurium by integrating magnetic enrichment and fluorescent CsPbBr3@SiO2.

A platform was designed based on Fe3O4 and CsPbBr3@SiO2 for integrated magnetic enrichment-fluorescence detection of Salmonella typhimurium, which significantly simplifies the detection process and enhances the working efficiency. Fe3O4 served as a magnetic enrichment unit for the capture of S. typhimurium. CsPbBr3@SiO2 was employed as a fluorescence-sensing unit for quantitative signal output, where SiO2 was introduced to strengthen the stability of CsPbBr3, improve its biomodificability, and prevent lead leakage. More importantly, the SiO2 shell shows neglectable absorption or scattering towards fluorescence, making the CsPbBr3@SiO2 exhibit a high quantum yield of 74.4%. After magnetic enrichment, the decreasing rate of the fluorescence emission intensity of the CsPbBr3@SiO2 supernatant at 527 nm under excitation light at UV 365 nm showed a strong linear correlation with S. typhimurium concentration of 1 × 102~1 × 108 CFU∙mL-1, and the limit of detection (LOD) reached 12.72 CFU∙mL-1. This platform has demonstrated outstanding stability, reproducibility, and resistance to interference, which provides an alternative for convenient and quantitative detection of S. typhimurium.

Single-Probe-Based Colorimetric and Photothermal Dual-Mode Identification of Multiple Bacteria.

Effective identification of multiple pathogenic bacteria in unknown samples is important for disease prevention and control but remains a challenge yet. A single-mode array-based sensing approach is simple and sensitive, but it usually relies on the use of multiple cross-reactive receptors to construct sensor arrays, which is cumbersome and insufficiently accurate. Here, we developed a sensor array with colorimetric and photothermal dual mode of differentiating multiple pathogenic bacteria. The sensor array was based on boronic acid-functionalized Au-Fe3O4 nanoparticles (BA-GMNPs), which not only possess localized surface plasmon resonance properties, showing a burgundy color similar to that of AuNPs, but also exhibit mild superparamagnetism, allowing for the differentiation of bacteria before and after binding to the nanoparticles. Immobilization of BA-GMNPs on the bacterial cell surface by covalent bonding would diminish NaCl-induced assembly of BA-GMNPs. Different BA-GMNPs@bacterial complexes differed in their ability to resist assembly and produced different colorimetric and photothermal response signals. A unique molecular fingerprint of each bacterium was obtained by linear discriminant analysis of the response patterns, demonstrating an effective differentiation among the six species studied. Compared with single-mode sensing arrays based on multiple receptors, this method only requires the preparation of a single nanomaterial, which produces two signal outputs for the identification of multiple bacteria with better differentiation. It can distinguish not only multiple pathogenic bacteria but also Gram-negative and Gram-positive bacteria, and, more importantly, it can perform preliminary discrimination of unknown samples.

Functional Zonation Strategy of Heterodimer Nanozyme for Multiple Chemiluminescence Imaging Immunoassay.

Although nanozymes with intrinsic enzyme-like characteristics have aroused great interest in the biosensing field, the challenge is to keep high enzyme-like activity of the nanozyme after the modification of biomolecules onto nanozymes. Herein, a functional zonation strategy of a heterodimer nanozyme was proposed to tackle the challenge and further construct a multiple chemiluminescence (CL) imaging immunoassay. Here Fe3O4-Au as a heterodimer nanozyme model was divided into two zones, in which Fe3O4 nanoparticles (NPs) were regarded as a nanozyme zone and AuNPs were defined as an antibody immobilization zone. A signal amplification probe (Fe3O4-Au-Ab2) was prepared by modifying the secondary antibody (Ab2) on AuNPs of the Fe3O4-Au heterodimer owing to the Au-S bond. The exposed Fe3O4 of the Fe3O4-Au-Ab2 probe shows very high peroxidase-like activity and can efficiently catalyze H2O2-luminol to produce strong CL imaging signals for multiple antigens detection. Using chicken interleukin-4 (ChIL-4) and chicken gamma interferon (ChIFN-γ) as models, the proposed CL imaging immunoassay shows wide linear ranges (0.005-0.10 ng/mL for both ChIL-4 and ChIFN-γ) and low detection limits (0.58 pg/mL for ChIL-4, 0.47 pg/mL for ChIFN-γ) with the characteristics of high sensitivity, high specificity, and good stability. This work provides a promising functional zonation concept for nanozymes to construct new types of nanozyme probes for immunoassay of multiple biomolecules.

Multifunctional Nanoprobe-Amplified Enzyme-Linked Immunosorbent Assay on Capillary: A Universal Platform for Simple, Rapid, and Ultrasensitive Dual-Mode Pathogen Detection.

Although the traditional enzyme-linked immunosorbent assay (ELISA) has been widely applied in pathogen detection and clinical diagnostics, it always suffers from complex procedures, a long incubation time, unsatisfying sensitivity, and a single signal readout. Here, we developed a simple, rapid, and ultrasensitive platform for dual-mode pathogen detection based on a multifunctional nanoprobe integrated with a capillary ELISA (CLISA) platform. The novel capture antibodies-modified capillaries can act as a swab to combine in situ trace sampling and detection procedures, eliminating the dissociation between sampling and detection in traditional ELISA assays. With excellent photothermal and peroxidase-like activity, the Fe3O4@MoS2 nanoprobe with a unique p-n heterojunction was chosen as an enzyme substitute and amplified signal tag to label the detection antibody for further sandwich immune sensing. As the analyte concentration increased, the Fe3O4@MoS2 probe could generate dual-mode signals, including remarkable color changes from the chromogenic substrate oxidation as well as photothermal enhancement. Moreover, to avoid false negative results, the excellent magnetic capability of the Fe3O4@MoS2 probe can be used to pre-enrich the trace analytes, amplifying the detection signal and enhancing the immunoassay's sensitivity. Under optimal conditions, specific and rapid detection of SARS-CoV-2 has been realized successfully based on this integrated nanoprobe-enhanced CLISA platform. The detection limits were 5.41 pg·mL-1 for the photothermal assay and 150 pg·mL-1 for the visual colorimetric assay. More importantly, the simple, affordable, and portable platform can also be expanded to rapidly detect other targets such as Staphylococcus aureus and Salmonella typhimurium in practical samples, making it a universal and attractive tool for multiple pathogen analysis and clinical testing in the post COVID-19 era.

Quantitative Time-Resolved Visualization of Catalytic Degradation Reactions of Environmental Pollutants by Integrating Single-Drop Microextraction and Fluorescence Sensing.

Current methods for evaluating catalytic degradation reactions of environmental pollutants primarily rely on chromatography that often suffers from intermittent analysis, a long turnaround period, and complex sample pretreatment. Herein, we propose a quantitative time-resolved visualization method to evaluate the progress of catalytic degradation reactions by integrating sample pretreatment [single-drop microextraction, (SDME)], fluorescence sensing, and a smartphone detection platform. The dechlorination reaction of chlorobenzene derivatives was first investigated to validate the feasibility of this approach, in which SDME plays a critical role in direct sample pretreatment, and inorganic CsPbBr3 perovskite encapsulated in a metal-organic framework (MOF-5) was utilized as the fluorescent chromogenic agent (FLCA) in SDME to realize fast in situ colorimetric detection via the color switching from green (CsPbBr3) to blue (chlorine lead bromide, inorganic CsPbCl3 perovskite). The smartphone, which can calculate the B/G value of FLCA, serves as a data output window for quantitative time-resolved visualization. Further, a [Eu(PMA)]n (PMA= pyromellitic acid) fluorescent probe was constructed to use as an FLCA for the in situ evaluation of cinnamaldehyde and p-nitrophenol catalytic reduction. This approach not only minimizes the utilization of organic solvents and achieves quantitively efficient time-resolved visualization but also provides a feasible method for in situ monitoring of the progress of catalytic degradation reactions.

Colorimetric and Raman dual-mode lateral flow immunoassay detection of SARS-CoV-2 N protein antibody based on Ag nanoparticles with ultrathin Au shell assembled onto Fe3O4 nanoparticles.

Serological antibody tests are useful complements of nuclei acid detection for SARS-CoV-2 diagnosis, which can significantly improve diagnostic accuracy. However, antibody detection in serum or plasma remains challenging to do with high sensitivity. In this study, Ag nanoparticles with ultra-thin Au shells embedded with 4-mercaptobenzoic acid (MBA) (AgMBA@Au) were manufactured and then assembled onto Fe3O4 surface by electrostatic interaction to construct the Fe3O4-AgMBA@Au nanoparticles (NPs) with magnetic-Raman-colorimetric properties. Based on the composite nanoparticles, a colorimetric and Raman dual-mode lateral flow immunoassay (LFIA) for ultrasensitive identification of SARS-CoV-2 nucleocapsid (N) protein antibody was constructed. The magnetic nanoparticles (Fe3O4 NPs) were acted as the core and coated a layer of AgMBA@Au particles on the surface by electrostatic interaction to prepare Fe3O4-AgMBA@Au NPs, which can amplify the SERS signal due to multiple AgMBA@Au particles concentrated on a single magnetic nanoparticle. Moreover, the Fe3O4-AgMBA@Au NPs facilitated pre-purifying sample using magnetic separation, and complex matrix interference would be greatly decreased in the detection. The Fe3O4-AgMBA@Au NPs modified with N protein recognized and bound with N protein antibodies, which were trapped on the T-line, forming color band for observing detection. Under optimal conditions, the N protein antibodies could be qualitatively detected in colorimetric mode with the visual limit of 10-8 mg/mL and quantitatively detected by SERS signals between 10-6 and 10-10 mg /mL with 0.08 pg/mL detection limit. The coefficients variations (CV) of intra-assay was 8.0%, whereas of inter-assay was 11.7%, confirming of good reproducibility. Finally, this approach was able to discriminate between positive, negative, and weakly positive samples when detecting 107 clinical serum samples. The process enables highly sensitive quantitative assays that are valuable for evaluating disease processes and guiding treatment. Colorimetric and Raman dual-mode LFIA detection of SARS-CoV-2 N protein antibody based on Fe3O4-AgMBA@Au nanoparticles.

Colorimetric and photothermal dual-mode lateral flow immunoassay based on Au-Fe3O4 multifunctional nanoparticles for detection of Salmonella typhimurium.

Au-Fe3O4 multifunctional nanoparticles (NPs) were synthesized and integrated with lateral flow immunoassay (LFIA) for dual-mode detection of Salmonella typhimurium. The Au-Fe3O4 NPs not only combined excellent local surface plasmon resonance characteristics and superparamagnetic properties, but also exhibited good photothermal effect. In the detection, antibody-conjugated Au-Fe3O4 NPs first captured S. typhimurium from complex matrix, which was then loaded on the LFIA strip and trapped by the T-line. By observing the color bands with the naked eyes, qualitative detection was performed free of instrument. By measuring the photothermal signal, quantification was achieved with a portable infrared thermal camera. The introduction of magnetic separation achieved the enrichment and purification of target bacteria, thus enhancing the detection sensitivity and reducing interference. This dual-mode LFIA achieved a visual detection limit of 5 × 105 CFU/mL and a photothermal detection limit of 5 × 104 CFU/mL. Compared with traditional Au-based LFIA, this dual-mode LFIA increased the detection sensitivity by 2 orders of magnitude and could be directly applied to unprocessed milk sample. Besides, this dual-mode LFIA showed good reproducibility and specificity. The intra-assay and inter-assay variation coefficients were 3.0% and 7.9%, and with this dual-mode LFIA, other bacteria hardly produced distinguishable signals. Thus, the Au-Fe3O4 NPs-based LFIA has potential to increase the efficiency of pandemic prevention and control. Au-Fe3O4 nanoparticle proved to be a promising alternative reporter for LFIA, achieving multifunctions: target purification, target enrichment, visual qualitation, and instrumental quantification, which improved the limitations of traditional LFIA.

Ag Nanoparticles with Ultrathin Au Shell-Based Lateral Flow Immunoassay for Colorimetric and SERS Dual-Mode Detection of SARS-CoV-2 IgG.

Immunoglobulin detection is essential for diagnosing progression of SARS-CoV-2 infection, for which SARS-CoV-2 IgG is one of the most important indexes. In this paper, Ag nanoparticles with ultrathin Au shells (∼2 nm) embedded with 4-mercaptobenzoic acid (MBA) (AgMBA@Au) were manufactured via a ligand-assisted epitaxial growth method and integrated into lateral flow immunoassay (LFIA) for colorimetric and SERS dual-mode detection of SARS-CoV-2 IgG. AgMBA@Au possessed not only the surface chemistry advantages of Au but also the superior optical characteristics of Ag. Moreover, the nanogap between the Ag core and the Au shell also greatly enhanced the Raman signal. After being modified with anti-human antibodies, AgMBA@Au recognized and combined with SARS-CoV-2 IgG, which was captured by the SARS-CoV-2 spike protein on the T line. Qualitative analysis was achieved by visually observing the color of the T line, and quantitative analysis was conducted by measuring the SERS signal with a sensitivity four orders of magnitude higher (detection limit: 0.22 pg/mL). The intra-assay and inter-assay variation coefficients were 7.7 and 10.3%, respectively, and other proteins at concentrations of 10 to 20 times higher than those of SARS-CoV-2 IgG could hardly produce distinguishable signals, confirming good reproducibility and specificity. Finally, this method was used to detect 107 clinical serum samples. The results agreed well with those obtained from enzyme-linked immunosorbent assay kits and were significantly better than those of the colloidal gold test strips. Therefore, this dual-mode LFIA has great potential in clinical practical applications and can be used to screen and trace the early immune response of SARS-CoV-2.

Fatigue Resistant Aerogel/Hydrogel Nanostructured Hybrid for Highly Sensitive and Ultrabroad Pressure Sensing.

Achieving high sensitivity over a broad pressure range remains a great challenge in designing piezoresistive pressure sensors due to the irreconcilable requirements in structural deformability against extremely high pressures and piezoresistive sensitivity to very low pressures. This work proposes a hybrid aerogel/hydrogel sensor by integrating a nanotube structured polypyrrole aerogel with a polyacrylamide (PAAm) hydrogel. The aerogel is composed of durable twined polypyrrole nanotubes fabricated through a sacrificial templating approach. Its electromechanical performance can be regulated by controlling the thickness of the tube shell. A thicker shell enhances the charge mobility between tube walls and thus expedites current responses, making it highly sensitive in detecting low pressure. Moreover, a nucleotide-doped PAAm hydrogel with a reversible noncovalent interaction network is harnessed as the flexible substrate to assemble the aerogel/hydrogel hybrid sensor and overcome sensing saturation under extreme pressures. This highly stretchable and self-healable hybrid polymer sensor exhibits linear response with high sensitivity (Smin  > 1.1 kPa-1 ), ultrabroad sensing range (0.12-≈400 kPa), and stable sensing performance over 10 000 cycles at the pressure of 150 kPa, making it an ideal sensing device to monitor pressures from human physiological signals to significant stress exerted by vehicles.

Highly Specific Colorimetric Probe for Fluoride by Triggering the Intrinsic Catalytic Activity of a AgPt-Fe3O4 Hybrid Nanozyme Encapsulated in SiO2 Shells.

Current colorimetric probes for fluoride (F-) primarily rely on organic chromophores that often suffer from unsatisfactory selectivity, complex organic synthesis, and low aqueous compatibility. Herein, we proposed a highly specific colorimetric method for F- with 100% aqueous compatibility by triggering the intrinsic peroxidase-like activity of a AgPt-Fe3O4 nanozyme encapsulated in SiO2 shells. The excellent catalytic performance of the AgPt-Fe3O4 nanozyme serves as an ideal platform for sensitive colorimetric sensing. After being encapsulated in SiO2, the enzyme-like activity of AgPt-Fe3O4 is inhibited and only F- can exclusively etch the SiO2 shell to expose the active site of the nanozyme, thereby inducing color changes via oxidation of the chromogenic substrate. The limit of detection of the proposed method can reach as low as 13.73 µM in aqueous solution, which is lower than the maximum allowable concentration (79 µM) stipulated in the World Health Organization drinking water regulation. More importantly, this method is highly specific toward F- over other types of anions commonly found in environmental water, making it capable of analyzing sewage samples with very complex matrices. Finally, the nanoprobe is embedded into a test strip by electrostatic spinning to enable the rapid, visual, and on-site detection of F-.

Magnetic Relaxation Switching Immunoassay Based on Hydrogen Peroxide-Mediated Assembly of Ag@Au-Fe3 O4 Nanoprobe for Detection of Aflatoxin B1.

Magnetic relaxation switching (MRS) sensors have shown great potential in food safety monitoring due to their high signal-to-noise ratio and simplicity, but they often suffer from insufficient sensitivity and stability due to the lack of excellent magnetic nanoprobes. Herein, dumbbell-like Au-Fe3 O4 nanoparticles are designed as magnetic nanoprobes for developing an aflatoxin B1-MRS immunosensor. The Fe3 O4 portion in the Au-Fe3 O4 nanoparticles functions as the magnetic probe to provide transverse relaxation signals, while the Au segments serve as a bridge to grow Ag shell and assemble the Au-Fe3 O4 nanoparticles, thus modulating transverse relaxation time of surrounding water molecular. The formation of Ag@Au-Fe3 O4 is triggered by hydrogen peroxide. After degraded by horseradish peroxidase, hydrogen peroxide reduces Ag+ to Ag nanoparticles which assemble dispersed Au-Fe3 O4 to aggregated Ag@Au-Fe3 O4 , thus dramatically improving the sensitivity of traditional MRS sensor. Combined with competitive immunoreaction, this Ag@Au-Fe3 O4 -MRS immunosensor can detect aflatoxin B1 with a high sensitivity (3.81 pg mL-1 ), which improved about 21 folds and 9 folds than those of enzyme-linked immunosorbent assay and high-performance liquid chromatography (HPLC), respectively. The good consistency with HPLC in real samples detection indicates the good accuracy of this immunosensor. This Ag@Au-Fe3 O4 -MRS immunosensor offers an attractive tool for detection of harmful substances.

Direct Synthesis of Nanosheet-Stacked Hierarchical "Honey Stick-like" MFI Zeolites by an Aromatic Heterocyclic Dual-Functional Organic Structure-Directing Agent.

Soft template designing is the most promising strategy for the synthesis of zeolite nanosheets. MFI nanosheets directed by soft templates (containing long-chain alkyl groups or aromatic groups as hydrophobic component) can be found frequently; however, so far, MFI nanosheets synthesized by soft templates with aromatic heterocycle groups (e. g., s-triazine groups) are rare. Herein, a nanosheet-stacked hierarchical MFI zeolite (NSHM) has been synthesized by using a triply branched s-triazine-based surfactant as a bifunctional organic structure-directing agent. On the basis of a geometrical match relationship, a formation model has been proposed. Synthesized NSHM had abundant mesopores stacked by nanosheets and exhibited a high surface area (430 m2 ⋅ g-1 ). The 1 wt% Pd/NSHM attained a significant increase in yield of cyclohexanol/cyclohexanone mixture (from 66 to 85 %) in the oxidation of cyclohexane compared with Silicalite-1 and SBA-15 as supports.

In Situ Catalysis and Extraction Approach for Fast Evaluation of Heterogeneous Catalytic Efficiency.

In situ monitoring of products generated by important heterogeneous catalytic reactions is of great significance for chemical industry, particularly when the products or intermediates are not sufficiently stable or occur at trace-level concentrations. It is therefore highly desirable to develop an integrated in situ catalysis and extraction method, which can simultaneously catalyze the reaction and enrich products while maintaining compatibility with analytical instrumentation. Herein, we propose an approach by depositing different types of metal nanocrystals, including gold, platinum, and palladium nanoparticles, onto fibrous silica microspheres coated fibers for integrated in situ catalysis and extraction. As a proof-of-concept, several typical chemical reactions, including the reduction of p-nitrophenol, epoxidation of styrene, oxidation of benzyl alcohol, and dechlorination of p-chlorophenol, were investigated to validate the feasibility of this method. Our results show that these coatings not only function as catalysts to accelerate the selected reactions but also serve as adsorbents to extract the reactants, intermediates, and products for direct gas chromatographic analysis, suggesting the viability of this approach for the in situ evaluation of catalytic processes. By this approach, the yield, selectivity, and kinetics of a reaction can be readily assessed. This approach can also be extended to investigate the catalytic performance of the same metal nanocrystals with different morphology, surface facet, structure, or surface functionalization. This approach will find broad generality for assessing the catalytic efficiency and selectivity of new catalysts or new chemical reactions and dynamic processes in these reactions.

Direct Synthesis of Water-Dispersible Magnetic/Plasmonic Heteronanostructures for Multimodality Biomedical Imaging.

Magnetic/plasmonic hybrid nanoparticles are highly desirable for multimodal bioimaging and biosensing. Although the synthesis of heterodimeric nanoparticles has been reported, the products are usually hydrophobic so that post-treatment procedures are required to transfer them into water which are often difficult to perform and cause damages to the structures. Direct synthesis of hydrophilic hybrid nanostructures has remained a grand challenge albeit its immediate advantage of biocompatibility. Herein we report a general seed-mediated approach to the synthesis of hydrophilic and biocompatible M-Fe3O4 (M = Au, Ag, and Pd) heterodimers, in which the size of metals and Fe3O4 can be independently regulated in a wide range. Benefiting from the aqueous synthesis, this approach can be further extended to design more complex heterodimeric structures such as AgPtalloy-Fe3O4, Aucore@Pdshell-Fe3O4, and Aushell-Fe3O4. The hydrophilic nature of our heterodimers makes them readily useful for biomedical applications without the need of additional ligand exchange processes in contrast to those prepared in nonpolar solvents. These nanoscale magnetic/plasmonic heterostructures were shown to be ideally suited for integrated biomedical diagnoses, such as magnetic resonance imaging, photoacoustic imaging, optical coherence tomography, and computed tomography, in virtue of their biocompatibility and combined tunable magnetic and plasmonic properties.

Controllable Transformation of Aligned ZnO Nanorods to ZIF-8 as Solid-Phase Microextraction Coatings with Tunable Porosity, Polarity, and Conductivity.

While a growing number of solid-phase microextraction (SPME) coatings have been developed, a generalized protocol is still needed to tailor-make SPME coatings with desirable properties for efficient extraction of diverse analytes from sample matrixes. In this work, we developed a versatile approach to prepare SPME coatings with tunable properties by controllable in situ transformation of well-aligned ZNRs into zeolitic imidazolate frameworks-8 (ZIF-8) via reaction with 2-methylimidazole (2-MI). During this process, ZNRs supplied Zn2+ and served as a "hard template" for the in situ growth of well-aligned ZIF-8 with enhanced surface area for adsorption. Because ZNRs and ZIF-8 exhibit markedly different properties, we obtained a series of ZNRs/ZIF-8 hybrid composites, whose morphology, porosity, polarity, and charge transfer resistance can be fine-tuned by simply controlling the concentration of 2-MI. Preparing ZNRs/ZIF-8 SPME coatings with desired properties enabled effective extraction of a wide range of polar and nonpolar compounds including aliphatic hydrocarbons, polycyclic aromatic hydrocarbons, alcohols, phenols, anilines, and ionic drugs.

Toward ultrasensitive and fast colorimetric detection of indoor formaldehyde across the visible region using cetyltrimethylammonium chloride-capped bone-shaped gold nanorods as "chromophores".

Plasmonic nanostructures have been broadly used for chemical detections, but their applications are limited by slow detection rates, insufficient visual resolution and sensitivity due to the chemical and structural stability of conventional plasmonic nanomaterials. It is thus essential to develop strategies to enhance the detection kinetics while promoting their excellent plasmonic properties. In this work, a colorimetric assay for HCHO measurement is developed based on the fact that HCHO can react with Tollens' reagent to anisotropically deposit a layer of silver shells onto the bone-shaped gold nanorod (Au NR) cores. Compared to the routine rod-shaped Au NRs, the bone-shaped Au NRs facilitate the deposition of Ag onto the sunken section due to their unique concave structures, giving rise to fast reaction kinetics and detection rate. It is also important to point out that the surface ligand exchange from CTAB to CTAC is helpful to accelerate the deposition of silver onto Au NRs, which significantly shortens the reaction time. The preferential deposition of Ag on the concave Au NRs induces more dramatic morphology changes and therefore promotes the plasmonic shift of the bone-shaped Au NRs and improves the sensing efficiency. Correspondingly, the apparent color of the solution changes from light gray to dark blue, purple, red, orange and finally to yellow as the longitudinal localized surface plasmon resonance (LSPR) band shifts from 710 to 500 nm along with the emergence of a new LSPR band at 400 nm almost covering the full visible region. The colorimetric method developed enables sensitive detection of HCHO with a low detection limit (1 nM), wide linear range (0.1-50 µM), high visual resolution and good specificity against other common indoor gases. It was successfully applied to the detection of gaseous HCHO present in the air collected from a furniture plaza, showing its potential practicality for on-site HCHO analysis.

Aptamer-functionalized magnetic and fluorescent nanospheres for one-step sensitive detection of thrombin.

A one-step sandwich method is described for detecting proteins with magnetic nanospheres (MNs) and fluorescent nanospheres (FNs). Thrombin is selected as a model analyte to validate the method. Two DNA aptamers (Apt 29 and Apt 15 targeting two different exosites of thrombin) are chosen as recognition elements to modify MNs and FNs. The superparamagnetic MN-Apt 29 conjugate is used to separate and concentrate thrombin. The FN-Apt 15 conjugate encapsulates hundreds of fluorescent quantum dots and is used as reporter to provide a stable signal. Magnetic capture and fluorescence identification are performed simultaneously to form a sandwich complex (MN-Apt 29-thrombin-FN-Apt 15) for fluorescence determination (at excitation/emission wavelengths of 380/622 nm). The method is convenient, time saving, and gives a strong signal (compared to the two-step method where capture and identification are performed in two steps). The one-step method presented here is completed within 30 min and has a 3.5 ng·mL-1 (97 pM) detection limit. The method is reproducible, has an intra-assay variability of 1.5%, and an inter-assay variability of 4.9%. Other serum proteins (HSA, CEA, PSA, and AFP) do not interfere. The method was also applied to analyze serum samples. Almost the same fluorescence intensity was measured when analyzing 1% serum samples (compared to buffer samples). Graphical abstract Magnetic nanospheres with excellent superparamagnetic property and fluorescent QD-based nanospheres were prepared and used in a one-step sensitive method for detecting thrombin. The method exhibits good reproducibility, high specificity, and good selectivity.

Determination of the Absolute Number Concentration of Nanoparticles and the Active Affinity Sites on Their Surfaces.

Number concentration of nanoparticles is a critical and challenging parameter to be identified. Recently, gravimetric strategy is a fundamental method for absolute quantification, which is widely accepted and used by researchers, yet limited by the inaccuracy in measuring related parameters (e.g, density). Hence, we introduced isopycnic gradient centrifugation to determine the nanopartices' density and improved the current gravimetric method for more accuracy. In this work, polymer nanospheres were used as a model to validate this method. Through isopycnic gradient centrifugation, nanospheres finally reached the zone of equal density as them. By measuring the density of the medium solution in this zone, the nanospheres' density was identified. Then, the density was multiplied by the volume of a single nanosphere characterized by transmission electron microscopy (TEM), and the average weight of a single nanosphere was obtained. Using total weight of the nanospheres divided by the unit weight, their number concentration was quantified. Directly using the real density of the nanoparticles achieved more accurate quantification than the current gravimetric method which used the density of the bulk material counterparts for calculation. Besides, compared with the viscosity/light scattering method and the high-sensitivity flow cytometry (HSFCM) method (another two kinds of typical methods respectively based on light measurements and single particle counting), the improved gravimetric method showed better reproducibility and more convenience. Further, we modified the nanospheres with streptavidin (SA) and antibody, and through biorecognition interaction, we determined the amount of the active affinity sites on each biofunctional nanosphere. Moreover, their bioactivity in different storage conditions was monitored, which showed good stability even in PBS at 4 °C over one year. Our work provided a promising method for more accurately determining the absolute number concentration of nanoparticles and the active affinity sites on their surfaces, which would greatly facilitate their downstream applications.