Colloidal Nanoparticles Research Articles

A Rapid and Interference-Resistant Formaldehyde Detection Method Based on Surface-Enhanced Raman Spectroscopy with a Reaction-Induced Self-Amplification Strategy

Formaldehyde is widely utilized across various industries such as food, textiles, and leather, yet its presence raises significant health concerns due to its irritation and carcinogenicity. Numerous methods have been developed to probe it in solution and gas states. Among them, absorption spectroscopy-based methods commonly employed. However, these methods require complex preprocessing for colored solutions to avoid interference. In response to this challenge, a novel interference-resistant detection kit leveraging surface-enhanced Raman spectroscopy (SERS) coupled with reaction-induced self-amplification for rapid and direct detection of formaldehyde was developed. The kit needed only ten minutes and achieved a limit of detection lower than 10−4 μg/mL with a handheld Raman spectrometer. Thanks to the kit’s reaction with formaldehyde, colloidal nanoparticles were linked to form “hot-spots” to further enhance the SERS signals. The signal demonstrated outstanding resistance to interference, including different dyes, ensuring a practical tool for direct detection of formaldehyde in complex solutions.

Structural Color Enhancement through Synchronizing Natural Convection and Marangoni Flow in Pendant Drops.

Structural color, renowned for its enduring vibrancy, has been extensively developed and applied in the fields of display and anticounterfeiting. However, its limitations in brightness and saturation hinder further application in these areas. Herein, we propose a pendant evaporation self-assembly method to address these challenges simultaneously. By leveraging natural convection and Marangoni flow synchronization, the self-assembly process enhances the dynamics and duration of colloidal nanoparticles, thereby enhancing the orderliness of colloidal photonic crystals. On average, this technique boosts the brightness of structural color by 20% and its saturation by 35%. Moreover, pendant evaporation self-assembly is simple and convenient to operate, making it suitable for industrial production. We anticipate that its adoption will remarkably advance the industrialization of structural color, facilitating its engineering applications across various fields, such as display technology and anticounterfeiting identification.

Facile Synthesis of Novel Short-Chain Ligand-Capped Colloidal Metal Oxide Nanoparticles for Printed Flexible Devices.

Colloidal metal oxide nanoparticles are key materials for achieving cost-effective and large-scale production of flexible devices, as they enable the formation of functional oxide thin films at low temperatures (<400 °C) through printing techniques such as inkjet printing, gravure coating, and microcontact printing. The conventional solvothermal synthesis of colloidal metal oxide nanoparticles through the thermal decomposition of precursors results in particles with bulky, long-chain ligands on their surfaces, which hinder the formation of dense oxide films when depositing the colloidal metal oxide nanoparticles. Herein, we have developed a simple and versatile method for synthesizing colloidal metal oxide nanoparticles using base-induced hydrolysis and the condensation of metal acetates as precursors. Various binary and ternary colloidal metal oxide nanoparticles (CuO, Mn3O4, Co3O4, CeO2, In2O3, Co1.8Mn1.2O4) were synthesized using short-chain acetate ligands on their surfaces. The thin acetate ligand-containing colloidal Co1.8Mn1.2O4 nanoparticle film exhibited lower resistivity than the same with long-chain oleate ligands. The films coated onto a polyimide substrate formed a flexible negative temperature coefficient thermistor that exhibited the temperature dependence of resistance comparable to bulk materials with a bending durability of up to 5 mm radius. These findings highlight the effectiveness of utilizing colloidal metal oxide nanoparticles with short-chain ligands in flexible devices.

Impact of colloidal silver nanoparticles (AgNPs) added for their antimicrobial efficacy on the compressive strength of poly(methyl methacrylate)-based acrylic denture base resin subjected to two different curing cycles: An in vitro study

Abstract Introduction: Colloidal silver nanoparticles (AgNPs) have been incorporated into acrylic resins to induce antimicrobial properties. However, as additives, they can influence the mechanical properties of the final product. The aim of the present study was to evaluate compressive strength of acrylic denture base resin incorporated with different concentrations of AgNPs subjected to two different curing cycles. Materials and Methods: Lucitone 199 acrylic denture base resin was used in the present in vitro study design because of its high-impact strength, while AgNPs were incorporated at 0.5% and 5% concentration by polymer mass. Specimens devoid of AgNPs were used as controls. The specimens were fabricated according to the American Dental Association specification No. 12 for denture base resin: Second revision, BS specification 2482 and tested for compressive strength using universal testing machine. Statistical analysis was done using Statistical Package for Social Sciences (SPSS) version 19 (SPSS Inc., Chicago, IL, USA). Descriptive statistics was used to compare two different curing cycles; while one-way analysis of variance and Kruskal–Wallis H-test were used for statistical analysis. P &lt;0.05 was considered statistically significant. Results: Colloidal silver nanoparticles (AgNPs) incorporation at 0.5% concentration increased the mean compressive strength in both the short and long curing cycles by 5.3% and 8.3% respectively when compared with the control group. Conclusions: The findings of the present study suggested that the mean compressive strength of acrylic denture base resin modified with 0.5% concentration of AgNPs was above the control group, both in the short and long curing cycles. However, at 5% concentration of AgNPs, decrease in compressive strength compared to the control group was observed, both in short and long curing cycles, giving it a questionable prognosis, while the results were found to be statistically significant. The following core competencies are addressed in this article: Practice-based learning and improvement, Patient care and procedural skills, Systems-based practice, Medical knowledge.

Plasmonic magnesium arrays with nanosphere lithography

Magnesium is a rising alternative plasmonic metal that is potentially cheaper, more biocompatible, and less lossy in the ultraviolet-blue region of the visible spectrum than the commonly used gold and silver. Recent studies of colloidal magnesium nanoparticles demonstrated the plasmonic resonances of a variety of faceted shapes. However, applications such as refractive index sensing benefit from well-defined arrays, which have been developed for all other plasmonic metals. Here, we implement nanosphere lithography to fabricate metallic magnesium arrays that display attractive plasmonic properties. The deposition process was found to be highly vulnerable to oxidation, recrystallization, kinetic energy of the metal vapor, and substrate properties. The resulting structures obtained with 350, 500, and 750 nm hexagonally packed nanosphere masks exhibit the hallmark light–matter interactions of plasmonic metals, including strong extinction and resonance energy dependence on feature size, further securing Mg’s place as an alternative plasmonic metal.

The mechanism of the influence of ultrasound on the nucleation and growth of A2B6 nanoparticles in a colloidal solution

The mechanism of the influence of ultrasound on the nucleation and growth of A2B6 nanoparticles in a colloidal solution was investigated. The proposed theory is based on an increase in the temperature of the colloidal solution and the diffusion coefficient of the monomer under the influence of ultrasonic cavitation. It was established that ultrasound leads to a decrease in the critical radius of colloidal nanoparticles. And when the radius of nanoparticles exceeds this critical value, their growth is observed. The dependence of the growth rate of CdSe nanoparticles on their radius at different temperatures and intensities of ultrasound was researched. It is shown that at the beginning of nanocrystal growth, an increase in intensity of ultrasound leads to an increase in the growth rate, followed by a sharp decrease. This makes it possible to synthesize colloidal quantum dots that are more uniform in size with the help of ultrasonic treatment.

Spin echo small-angle neutron scattering using superconducting magnetic Wollaston prisms.

We show the implementation of superconducting magnetic Wollaston prisms for spin echo small-angle neutron scattering. Two calibration methods for the spin echo length are presented: one utilizing spin echo modulated small-angle neutron scattering and the other based on the neutron refraction by quartz wedge crystals. Our experimental results with polystyrene nano-particle colloids showcase the system's efficacy in measuring both dilute and concentrated colloidal systems. Additionally, investigations into the pore diameter and pitch of a nano-porous alumina membrane demonstrate its capability in analyzing nano-porous materials. Furthermore, we discuss potential optimizations to further extend the accessible spin echo length.

Synthetic Roadmap to a Large Library of Colloidal High-Entropy Rare Earth Oxyhalide Nanoparticles Containing up to Thirteen Metals.

Nanoparticles of high-entropy materials that incorporate five or more elements randomized on a crystalline lattice often exhibit synergistic properties that can be influenced by both the identity and number of elements combined. These considerations are especially important for structurally and compositionally complex materials such as multimetal multianion compounds, where cation and anion mixing can influence properties in competitive and contradictory ways. Here, we demonstrate the synthesis of a large library of colloidal high-entropy rare earth oxyhalide (REOX) nanoparticles. We begin with the synthesis of (LaCePrNdSmEuGdDyHoErYbScY)OCl, which homogeneously incorporates 13 distinct rare earth elements. Through time point studies, we find that (LaNdSmGdDy)OCl, a 5-metal analogue, forms through in situ generation of compositionally segregated core@shell@shell intermediates that convert to homogeneously mixed products through apparent core-shell interdiffusion. Assuming that all possible combinations of 5 through 13 rare earth metals are synthetically accessible, we propose the existence of a 7099-member REOCl nanoparticle library, of which we synthesize and characterize 40 distinct members. We experimentally validate the incorporation of a large number of rare earth elements using energy dispersive X-ray spectra, despite closely spaced and overlapping X-ray energy lines, using several fingerprint matching strategies to uniquely correlate experimental and simulated spectra. We confirm homogeneous mixing by analyzing elemental distributions in high-entropy nanoparticles versus physical mixtures of their constituent compounds. Finally, we characterize the band gaps of the 5- and 13-metal REOCl nanoparticles and find a significantly narrowed band gap, relative to the constituent REOCl phases, in (LaCePrNdSmEuGdDyHoErYbScY)OCl but not in (LaNdSmGdDy)OCl.

One-step fabrication of a self-driven point-of-care chip by femtosecond laser direct writing and its application in cancer cell H2O2 detection via semiconductor-based SERS

Self-driven microfluidic systems have attracted significant attention and demonstrated great potential in the field of point-of-care (POC) testing due to their device simplicity, low power consumption, increased portability, and reduced sample consumption. To develop POC detection chips with diverse characteristics that meet different requirements, there is a strong demand for feasible strategies that enable easy operation and reduce processing time. Here, a one-step processing approach using femtosecond laser direct writing technology was proposed to fabricate a capillary-actuated POC microfluidic chip. The driving force of the chip is highly dependent on its surface wettability, which can be easily adjusted by changing the laser processing parameters. This POC microfluidic chip allowed for the detection of intracellular H2O2 through a catalytic reaction system that incorporated 5-aminosalicylic acid -sensitized colloidal TiO2 nanoparticles and horse radish peroxidase, with integrating semiconductor-based surface-enhanced Raman scattering (SERS) quantitative technique. The concentration of H2O2 was determined by the SERS signal of the catalytic products in the microfluidic chip, resulting in rapid detection with minimal sample consumption. Our method provides a simple, feasible, and alternative strategy for POC testing of H2O2, with a linear range of 10−2∼10−6 M and a limit of detection of 0.55 μM. This approach was successfully applied to rapid detection of intracellular H2O2 in MCF-7 breast cancer cells with high sensitivity and minimal sample consumption. Additionally, this study not only demonstrates the exceptional advantages of femtosecond laser processing technology in fabricating diverse microfluidic chips for various applications, but also presents an efficient POC testing strategy for detecting cell signaling molecules.

Direct visualization of ligands on gold nanoparticles in a liquid environment.

The interactions between gold nanoparticles, their surface ligands and the solvent critically influence the properties of these nanoparticles. Although spectroscopic and scattering techniques have been used to investigate their ensemble structure, a comprehensive understanding of these processes at the nanoscale remains challenging. Electron microscopy makes it possible to characterize the local structure and composition but is limited by insufficient contrast, electron beam sensitivity and the requirement for ultrahigh-vacuum conditions, which prevent the investigation of dynamic aspects. Here we show that, by exploiting high-quality graphene liquid cells, we can overcome these limitations and investigate the structure of the ligand shell around gold nanoparticles and at the ligand-gold interface in a liquid environment. Using this graphene liquid cell, we visualize the anisotropy, composition and dynamics of ligand distribution on gold nanorod surfaces. Our results indicate a micellar model for surfactant organization. This work provides a reliable and direct visualization of ligand distribution around colloidal nanoparticles.

Multiple Fano Resonances Enabled by the Interference between an Out‐of‐Plane Plasmon Mode and Fabry–Pérot Cavity Modes

AbstractMultiple Fano resonances (mFRs) are arising as a promising optical platform to achieve precise sensing and detection. However, experimentally achieving mFRs by simple structures has remained challenging, which impedes the widespread applications of mFRs. Herein a simple structure composed of a single colloidal metal nanoparticle and a transition metal dichalcogenide flake to simultaneously achieve up to 8 FRs in experiments is demonstrated. Combining theoretical and experimental techniques, that an out‐of‐plane plasmon mode of the metal nanoparticle interferes with the Fabry–Pérot cavity modes from the WS2 flake to form mFRs in the visible region is proved. The simplicity and generality of the method further allow us to systematically study the tunability of the mFRs, in terms of the peak/dip positions and the number of FRs, by changing the structural parameters, which include the thickness of the WS2 flake, size and shape of the plasmonic nanoparticle. In addition, the quality of the mFRs is proved to be adjustable by tuning the reflectivity of the substrate in the system. The highest quality factor and spectral contrast of the achieved resonances are up to ≈180 and ≈0.95, respectively. The simple structure and high‐quality optical modes will prosper applications in precise sensing and light modulation.

Interactions between prokaryotic polysaccharides and colloidal magnetic nanoparticles for bacteria removal: A strategy for circumventing antibiotic resistance

Highly stable, colloidal iron oxide nanoparticles with an oxyhydroxide-like surface were used as bacteria-capturing nano-baits. Peptidoglycan isolated from Listeria spp was used as bacteria polysaccharide model, and the nanoparticle binding was characterized showing a Langmuir isotherm constant, KL, equal to 50 ± 3 mL mg−1. The chemical affinity was further supported by dynamic light scattering, transmission electron microscopy, and infrared and UV–Vis data, pointing at the occurrence of extended, coordinative multiple point bindings. The interaction with Gram (+) (Listeria spp) and Gram (−) (Aeromonas veronii) bacteria was shown to be effective and devoid of any toxic effect. Moreover, a real sample, containing a population of several oligotrophic bacteria strains, was incubated with 1 g L−1 of nanoparticle suspension, in the absence of agitation, showing a 100 % capture efficiency, according to plate count. A nanoparticle regeneration method was developed, despite the known irreversibility of such bacterial-nanosurface binding, restoring the bacteria capture capability. This nanomaterial represents a competitive option to eliminate microbiological contamination in water as an alternative strategy to antibiotics, aimed at reducing microbial resistance dissemination. Finally, beyond their excellent features in terms of colloidal stability, binding performances, and biocompatibility this nanoparticle synthesis is cost effective, scalable, and environmentally sustainable.

Multiparticle Synergistic Electrophoretic Deposition Strategy for High-Efficiency and High-Resolution Displays.

Colloidal nanoparticles offer unique photoelectric properties, making them promising for functional applications. Multiparticle systems exhibit synergistic effects on the functional properties of their individual components. However, precisely controlled assembly of multiparticles to form patterned building blocks for solid-state devices remains challenging. Here, we demonstrate a versatile multiparticle synergistic electrophoretic deposition (EPD) strategy to achieve controlled assembly, high-efficiency, and high-resolution patterns. Through elaborate surface design and charge regulation of nanoparticles, we achieve precise control over the particle distribution (gradient or homogeneous structure) in multiparticle films using the EPD technique. The multiparticle system integrates silicon oxide and titanium oxide nanoparticles, synergistically enhancing the emission efficiency of quantum dots to a high level in the field. Furthermore, we demonstrate the superiority of our strategy to integrate multiparticle into large-area full-color display panels with a high resolution over 1000 pixels per inch. The results suggest great potential for developing multiparticle systems and expanding diverse functional applications.

Fabrication of metallic titanium nanoparticles through ultrasonication assisted by electric current flow

This study was aimed at characterizing metallic Ti electrodes and nanoparticles fabricated from a titanium chloride/deep eutectic solvent (DES) solution by applying electric current between metallic Ti plates used as the anode and cathode under ultrasonic irradiation at room temperature. The cathode was not damaged during the flow of electric current, whereas the anode deteriorated to produce a nanoparticle colloidal solution. The nanoparticle size ranged from 5.3 to 12.2 nm. X-ray diffraction measurements revealed that the Ti nanoparticle powder exhibited a hexagonal crystal structure without any crystalline Ti oxide. However, X-ray photoelectron spectroscopy results indicated the presence of O. Furthermore, the metallic Ti nanoparticles were noted to be covered with Ti oxide layers. These layers acted as a physical barrier, protecting the metallic Ti nanoparticles against further oxidation by exposure to water and air.

Characterization of Mass, Diameter, Density, and Surface Properties of Colloidal Nanoparticles Enabled by Charge Detection Mass Spectrometry.

A variety of scattering-based, microscopy-based, and mobility-based methods are frequently used to probe the size distributions of colloidal nanoparticles with transmission electron microscopy (TEM) often considered to be the "gold standard". Charge detection mass spectrometry (CDMS) is an alternative method for nanoparticle characterization that can rapidly measure the mass and charge of individual nanoparticle ions with high accuracy. Two low polydispersity, ∼100 nm diameter nanoparticle size standards with different compositions (polymethyl methacrylate/polystyrene copolymer and 100% polystyrene) were characterized using both TEM and CDMS to explore the merits and complementary aspects of both methods. Mass and diameter distributions are rapidly obtained from CDMS measurements of thousands of individual ions of known spherical shape, requiring less time than TEM sample preparation and image analysis. TEM image-to-image variations resulted in a ∼1-2 nm range in the determined mean diameters whereas the CDMS mass precision of ∼1% in these experiments leads to a diameter uncertainty of just 0.3 nm. For the 100% polystyrene nanoparticles with known density, the CDMS and TEM particle diameter distributions were in excellent agreement. For the copolymer nanoparticles with unknown density, the diameter from TEM measurements combined with the mass from CDMS measurements enabled an accurate measurement of nanoparticle density. Differing extents of charging for the two nanoparticle standards measured by CDMS show that charging is sensitive to nanoparticle surface properties. A mixture of the two samples was separated based on their different extents of charging despite having overlapping mass distributions centered at 341.5 and 331.0 MDa.

Probing the Adsorption Sites of 5‐amino‐2‐mercaptobenzimidazole Conformations on Colloidal Gold Nanoparticles Investigated by SERS and DFT

AbstractGold nanoparticles (AuNP) have shown great potential in biomedical applications due to their unique and tunable properties. Understanding the ligand conformation on AuNP has profound interest in nanoparticle research leading to a precise drug delivery system. Colloidal AuNPs were synthesized using trisodium citrate as reducing agent. Normal Raman spectrum (NRS) in solid and aqueous phase identifies that 5‐amino‐2‐mercaptobenzimidazole (5A2MBI) mainly exist as thione form. Surface enhanced Raman scattering (SERS) investigation of 5A2MBI depending on pH was performed to explore the adsorption mechanism of thiolate and thione conformations on AuNPs. Density functional theory (DFT) calculations were used to find the band assignments and molecular electrostatic potential (MEP) mapping to identify the electron rich site where metal can interact preferentially. Using SERS spectral analysis and DFT results, surface adsorption scheme was proposed. At basic pH, 5A2MBI adsorbs on AuNP as thiolate form bidentately via Sulfur and nitrogen atom of imidazole ring with tilted geometry. However, in acidic condition the thione form adsorbs on nanosurface with perpendicular orientation.

SERS as a tool for determination of structurally related compounds: The case of sulfanilamide class antibiotics

Analysis of real objects based on surface-enhanced Raman spectroscopy (SERS) often utilizes new SERS substrates and/or complex analysis procedures, and they are optimized for only the determination of a single analyte. Moreover, analysis simplicity and selectivity are often sacrificed for maximum (sometimes unnecessary) sensitivity. Consequently, this trend limits the versatility of SERS analysis and complicates its practical implementation. Thus, we have developed a universal, but simple SERS assay suitable for the determination of structurally related antibiotics (five representatives of the sulfanilamide class) in complex objects (human urine and saliva). The assay involves only mixing of acidified analyzed solution with co-activating agent (polydiallyldimethylammonium chloride – PDDA) and SERS substrate (standard colloidal silver nanoparticles). Acidification promotes the generation of SERS spectra with maximum similarity and intensity, which is explained by the favorable enhancement of the protonated sulfanilamide moiety (a structurally similar part of the studied antibiotics) as a result of its strong electrostatic interaction with the SERS-active surface. Meanwhile, the addition of PDDA improves analysis selectivity by reducing background signal from body fluids, enabling to simplify sample pretreatment (dilution for urine; mucin removal and dilution for saliva). Therefore, the assay allows for rapid (≤10 min), precise, and accurate class-specific determination of sulfanilamides within concentration ranges suitable for non-invasive therapeutic drug monitoring in urine (40–600 μM) and saliva (10–30 μM). We also believe that thorough investigation of structurally related analytes and accompanying effects (e.g., high spectral similarity) is a promising direction to improve the understanding of SERS in general and expand its capabilities as an analytical tool.

Controllable Supramolecular Aggregation of Hydroazaheptacene Tetraimides and Derivatives in Nonpolar and Polar Solvents.

Rational control of the supramolecular aggregation of π-conjugated molecules plays an important role in determining their optoelectronic properties and applications. Here, we report a systematic study of the factors, including solvent polarity, concentration, and surfactants, that affect the aggregation behavior of a brominated hydroazaheptacene tetraimide (HATI) and its thiophene-substituted derivative, Th-HATI, as near-infrared fluorophores, in both nonpolar and polar solvents. The thermal stability of the aggregates is also studied by monitoring their optical absorption against temperature change. Our results indicate that the aggregation of HATI is highly sensitive to the solvent polarity. Moreover, the average aggregation number of HATI inside the colloidal nanoparticles formed in aqueous media can be controlled by surfactants. The substitution of the bromo groups in HATI by thiophene units induces a slight blue shift of the optical absorption, enhanced crystallinity, distinct aggregation behavior in both nonpolar and polar solvents, and improved thermal stability. The multifacet understanding of the supramolecular aggregation of these systems may offer insight for other π-conjugated molecular chromophores with various optoelectronic properties and applications.

Gold nanoparticle-based biosensor for Lysozyme-DNA detection utilizing decomposition Mueller matrix polarimetry

Lysozyme serves as a crucial biomarker in the identification of several diseases, that includes breast cancer, Alzheimer’s disease, meningitis, and rheumatoid arthritis. This study proposes an innovative method for the detection of Lysozyme using a gold nanoparticle based biosensor and decomposition Muller matrix polarimetry. In the proposed study, the DNA aptamer is used as the recognition element, while the gold nanoparticles are used as a sensing element. The sensed signal is taken as the input to a Mueller matrix calculation process, which determines three optical characteristics that yield optimal results of the gold nanoparticle colloidal solution, namely the degree of depolarization, the linear diattenuation, and the depolarization index. The results have shown that all three optical parameters vary linearly with the concentration of Lysozyme throughout a broad dynamic range spanning from 0.01 to 500 pM with a limit of detection of 1.24 fM. Overall, the proposed technique provides potential tool for the detection of Lys.

Active Assembly of CsPbBr3 Nanorods into Microcolumns by Electric Field in Nonpolar Solvent.

High-precision, controllable, mass-producible assembly of nanoparticles into complex structures or devices holds immense importance in the application across various fields but it remains challenging. Here a highly controllable and reversible active assembly of colloidal CsPbBr3 nanorods, driven by an external electric field is achieved. This approach enables the nanorods dynamically orient themselves, assemble into chains, aggregate into columns, and eventually form an ordered column array, with the electric field intensity varying from 0 to 50V µm-1 at 100kHz. The nanorods inside the columns align parallel to the electric field, leading to a well-ordered structure. With the analysis of the interactions among the nanorods, a quantitative interpretation of the assembly is proposed. Monte Carlo calculation is also introduced to simulate the assembly process and the results prove to be in great agreement with the experimental observations. This electric field-driven assembly presents an exciting opportunity to pave the way for next-generation sensors and photonic devices based on well-developed colloidal nanoparticles.