Localized Surface Plasmon Resonance Absorption Research Articles

Ultra-broadband, high absorption, polarization-insensitive microwave absorbers designed based on multi-scale fractal metasurfaces

Microwave absorbers play an essential role in radar stealth applications. However, conventional microwave absorbers are hindered by limitations such as narrow bandwidth, large size, and inadequate absorption rates. Leveraging metasurfaces presents an ideal approach for creating microwave absorbers, but metasurface-based broadband absorbers typically entail intricate structures, natural absorbing materials, or electronic components, posing challenges in terms of fabrication and expansion. Here, we numerically demonstrate a simple multi-scale fractal metasurface microwave absorber, with the full width at half-maximum of band exceeding one optical octave. By integrating the localized surface plasmon resonance absorption band and the Salisbury-Screen-type absorption band, we achieve an average absorption of 90% ranging from 11.5 GHz to 27.1 GHz. Furthermore, this absorber exhibits excellent polarization insensitivity and maintains high absorption even at large incident angles. The device, offering both broadband absorption and a straightforward structure, holds significant promise for practical applications and widespread adoption.

Infrared light driven overall water vapor splitting on a plasmonic semiconductor p-n heterojunction photocatalyst

Photocatalytic overall water splitting (OWS) has yet to be realized on plasmonic semiconductor photocatalysts. In this work, we reported a plasmonic heterojunction of p-Cu1.81S/n-CdS with homogeneously distributed p-type and n-type domains in a single nanoparticle. The plasmonic heterojunction displays a strong localized surface plasmon resonance (LSPR) absorption peak at 1480 nm and can drive the OWS into hydrogen and oxygen under infrared light (IR) irradiation. The IR light-induced hot electrons and holes in Cu1.81S nanodisks alone can split water vapor into hydrogen and oxygen, but with poor efficiency. Surprisingly, the plasmonic p-Cu1.81S/n-CdS heterojunction shows significantly improved IR light-driven OWS performance. Under the irradiation of IR light (λ > 800 nm), the hydrogen and oxygen production rates were 0.73 mmol gcat−1 h−1 and 0.33 mmol gcat−1 h−1, respectively. The heterojunction photocatalyst delivered a solar-to-hydrogen conversion efficiency (STH) of 0.02 % under AM 1.5G irradiation. The present study has demonstrated that plasmonic semiconductors are promising photocatalysts for harvesting IR light for green hydrogen generation.

Light erasable surface-enhanced Raman scattering substrates based on the metallic molybdenum dioxide nanospheres

Surface-enhanced Raman scattering (SERS) is a powerful label-free technique for the identification of molecules and molecular structures at extremely low concentrations. However, in most cases, the analytes will remain on SERS substrates, making the substrate a disposable consumable. Here, we propose a light erasable SERS substrate based on the metallic molybdenum dioxide (MoO2) nanospheres. The MoO2 nanospheres present a remarkable localized surface plasmon resonance (LSPR) absorption peak centered at 800 nm. Profiting from the local field magnification induced by the LSPR, MoO2 exhibits excellent SERS detection sensitivity towards rhodamine 6 G (R6G), rhodamine B (RhB), methyl blue (MB), crystal violet (CV) and Malachite Green (MG), with a detection limit of 10−7 M and a maximum enhancement factor up to 5.4 × 104. Moreover, the metallic MoO2 nanospheres possess a high photothermal conversion efficiency of 70.1% and good photothermal stability. The temperature of the MoO2 surface can reach 438 °C under 808 nm laser irradiation with a power density of 2.5 W cm−2, exceeding the decomposition temperature of most organic molecules. Thus, the residual probe molecules can be completely removed from the MoO2 substrate in less than 7.5 min under laser irradiation without compromising its SERS sensitivity and reproducibility. We anticipate our work will pave a new avenue for the development of reusable and highly sensitive SERS substrates.

Scalable synthesis of Au@CeO2 nanozyme for development of colorimetric lateral flow immunochromatographic assay to sensitively detect heart-type fatty acid binding protein

Nanozymes with core@shell nanostructure are considered promising biolabeling materials for their multifunctional properties. In this work, a simple one-pot strategy has been proposed for scalable synthesis of gold@cerium dioxide core@shell nanoparticles (Au@CeO2 NPs) with strong localized surface plasmon resonance (LSPR) absorption and high peroxidase-like catalytic activity by redox reactions of Ce3+ ions and AuCl4− ions in diluted ammonia solution under room temperature. A colorimetric lateral flow immunochromatographic assay (LFIA) has been successfully fabricated for sensitive detection of heart-type fatty acid binding protein (H-FABP, an early cardiac biomarker) by using the Au@CeO2 NPs as reporters. The as-developed LFIA with Au@CeO2 NP reporter (termed as Au@CeO2-LFIA) exhibits a dynamic range of nearly two orders of magnitude, and a limit of detection (LOD) as low as 0.35 ng mL−1 H-FABP with nanozyme-triggered 3,3′,5,5′-tetramethylbenzidine (TMB) colorimetric amplification. Furthermore, the practicality of Au@CeO2-LFIA has been demonstrated by profiling the concentrations of H-FABP in 156 blood samples of acute myocardial infarction (AMI) patients, and satisfactory results are obtained.

A semi-solid, polychromatic dual-band electrochromic smart window: Visualizing sunlight and solar heat transmission

In this paper, a novel semi-solid, polychromatic dual-band electrochromic smart window was constructed by organically assembling monoclinic WO3-x nanowires (m-WO3-x NWs), AlCl3-polyvinyl alcohol (PVA) and polyaniline (PANI). The device not only presented the independent regulation of “bright”, “cool” and “dark”, but also exhibited excellent comprehensive performance, including large optical modulation (74.9 % and 79.1 % at 700 and 2000 nm, respectively.), short coloring/bleaching times (7.6/2.7 and 6.7/3.9 s at 700 and 1200 nm, respectively), and good stability and reversibility (the capacity decreased by 4.3 % and the coulombic efficiency stabled at 99.2 % after 1000 cycles). In addition, the multi-colored PANI endowed the window with the ability to visually monitor modulation modes, as well as indoor sunlight and thermal transmittance. The transparent, green, and blue represented “bright”, “cool”, and “dark” modes, and the depth of the color stood for the control effect in a certain mode. Moreover, the dual-band modulation and polychromatic conversion mechanisms of individual electrodes and the smart window prototype were also elucidated in detail. The modulation of near-infrared light mainly comes from the localized surface plasmon resonance (LSPR) absorption and the phase transition of m-WO3-x NWs, as well as the generated polarons and bipolarons of PANI. While the selective absorption of visible light was related to the bandgap transition of m-WO3-x NWs and the electronic transition of the quinone unit. Surprisingly, the smart window could achieve a maximum decrease of 4.3 °C by controlling the “bright-dark” mode transition in real application simulations, significantly boosting the process of low carbon environmental protection and the construction of energy-saving buildings.

Redox Chemistries for Vacancy Modulation in Plasmonic Copper Phosphide Nanocrystals.

Copper phosphide (Cu3-xP) nanocrystals are promising materials for nanoplasmonics due to their substoichiometric composition, enabling the generation and stabilization of excess delocalized holes and leading to localized surface plasmon resonance (LSPR) absorption in the near-IR. We present three Cu-coupled redox chemistries that allow postsynthetic modulation of the delocalized hole concentrations and corresponding LSPR absorption in colloidal Cu3-xP nanocrystals. Changes in the structural, optical, and compositional properties are evaluated by powder X-ray diffraction, electronic absorption spectroscopy, 31P magic-angle spinning solid-state nuclear magnetic resonance spectroscopy, and elemental analysis. The redox chemistries presented herein can be used to access nanocrystals with LSPR energies of 660-890 meV, a larger range than has been possible through synthetic tuning alone. In addition to utilizing previously reported redox chemistries used for copper chalcogenide nanocrystals, we show that the largest structural and LSPR modulation is achieved using a divalent metal halide and trioctylphosphine. Specifically, nanocrystals treated with zinc iodide and trioctylphosphine have the smallest unit-cell volume (295.2 Å3) reported for P63cm Cu3-xP, indicating more Cu vacancies than have been previously observed. Overall, these redox chemistries present valuable insight into controlling the optical and structural properties of Cu3-xP.

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.

Exploring the interplay of LSPR and CT: Hierarchical shell thickness optimization for advanced SERS sensing using AgNW@ZIF-8 Core@Shell substrates

Synergistic surface-enhanced Raman spectroscopy (SERS) substrates, leveraging the combined strengths of electromagnetic enhancement (EM) and chemical enhancement (CM), have been extensively explored in the literature. In this study, we introduce a distinctive approach to fabricating core@shell structures, specifically employing silver nanowire @ zeolite imidazole framework-8 (AgNW@ZIF-8) as synergistic SERS substrates. Notably, these substrates offer meticulous control over shell thickness through a straightforward post-synthesis procedure. Utilizing Ag nanowires as the plasmonic core, selected for their broader localized surface plasmon resonance (LSPR) absorption range compared to nanoparticles, we encapsulate them within ZIF-8, a metal-organic framework (MOF) recognized for its proficient charge transfer (CT) properties. Our investigation encompasses the SERS performance across various Raman-active molecules, considering their diverse sizes and distinct frontier molecular orbitals (FMO) energy levels. Additionally, we systematically explore the influence of alterations in shell thickness on SERS outcomes and scrutinize the impact of probe orientation. This comprehensive study not only advances the understanding of synergistic effects intrinsic to MOFs-metal SERS substrates but also provides valuable insights for the rational design of highly sensitive substrates tailored for practical applications.

Hybridization chain reaction assisted multicolor immunosensor for sensitively detection of human chorionic gonadotropin

The level of human chorionic gonadotropin (HCG) is an important indicator for early pregnancy, pregnancy-related diseases trophoblastic diseases and even cancer diagnosis. Therefore, sensitive detection of HCG has crucial significance in clinical, especially in gynaecology and obstetrics. Herein, a hybridization chain reaction (HCR) assisted multicolor immunosensor have been developed for HCG analysis. The proposed method introduced HCR after the immunoreaction between antibody and HCG protein, and produced long double strand DNA (dsDNA) that contain biotin sites. The streptavidin-horseradish peroxidase was linked on the dsDNA by the interaction between biotin and streptavidin, and can further mediated gold nanobipyramids (Au NBPs) etching. The localized surface plasmon resonance absorption peaks of Au NBPs blue shift and accompanied a vivid color change after etching effect. Based on this color change, HCG could be qualitative and semi-quantitative detected. Because of the introduction of HCR and enzyme amplification technique, the proposed method exhibited high sensitivity with a linear range of 0.1–2000 pg/mL and limit of detection (LOD) of 0.1 pg/mL. Finally, the proposed immunosensor was used to detect clinical serum samples. The results show there are no significant differences between clinical results and the test results by this method, indicating the practicability of the proposed method.

Synthesis Optimization and Antibacterial Performance of Colloidal Silver Nanoparticles in Chitosan

Colloidal silver nanoparticles were successfully synthesized via the chemical reduction method. The synthesis used AgNO3 as the precursor, chitosan as the reducing and stabilizing agents, and NaOH as the accelerator. The synthesis parameters were optimized. The samples were tested with a UV-vis spectrophotometer to observe their localized surface plasmon resonance (LSPR) phenomenon, a transmission electron microscope (TEM), and a particle size analyzer (PSA) to investigate their particle shape and size distribution. Further, silver nanoparticles were tested for their storage stability and antibacterial performance. The UV-vis spectroscopy data exhibited that the silver nanoparticles have been successfully synthesized, validating via the emergence of the LSPR absorption band at 402–418 nm. At 50 °C, the optimum synthesis was achieved for 100 min of reaction time by adding 0.033 M NaOH and AgNO3 4.00% (w/w, AgNO3/chitosan). TEM results showed spherical silver nanoparticles of 1–8 nm, while the PSA results exhibited particles sizes of about 12–59 nm. The colloidal silver nanoparticles were stable in storage for 8 weeks and had good antibacterial performance against E. coli, S. aureus, extended-spectrum beta-lactamases (ESBL), and methicillin-resistant S. aureus (MRSA). Therefore, colloidal silver nanoparticles have the potential as a material for medical applications.

Gold-Nanorod-Assisted Live Cell Nuclear Imaging Based on Near-Infrared II Dark-Field Microscopy.

Dark-field microscopy offers several advantages, including high image contrast, minimal cell damage, and the absence of photobleaching of nanoprobes, which make it highly advantageous for cell imaging. The NIR-II window has emerged as a prominent research focus in optical imaging in recent years, with its low autofluorescence background in biological samples and high imaging SBR. In this study, we initially compared dark-field imaging results of colorectal cancer cells in both visible and NIR-II wavelengths, confirming the superior performance of NIR-II imaging. Subsequently, we synthesized gold nanorods with localized surface plasmon resonance (LSPR) absorption peaks in the NIR-II window. After bio-compatible modification, we non-specifically labeled colorectal cancer cells for NIR-II dark-field scattering imaging. The imaging results revealed a sixfold increase in SBR, especially in the 1425-1475 nm wavelength range. Finally, we applied this imaging system to perform dark-field imaging of cell nuclei in the NIR-II region and used GNRs for specific nuclear labeling in colorectal cancer cells. The resulting images exhibited higher SBR than non-specifically-labeled cell imaging, and the probe's labeling was precise, confirming the potential application of this system in photothermal therapy and drug delivery for cancer cells.

Dual signal AA detection based on fluorescence and local surface plasmon resonance absorption technology

The core/shell Au@MnO2 nanoparticles (Au@MnO2 NPs) were prepared and characterized by UV–vis spectrum, transmission electron microscopy (TEM) and X-ray photoelectron spectrum (XPS). It was found that MnO2 in the shell of Au@MnO2 NPs could oxidize thiamine (VB1) into blue fluorescent thiochrome (TC). The reduction of MnO2 in the shell layer could lead to a decrease of Au@MnO2 NPs size along with a blue shift of the localized surface plasmon resonance (LSPR) peak. Once ascorbic acid (AA) was introduced, MnO2 in the shell was rapidly reduced to Mn2+ ions. Accordingly, the oxidation of VB1 was inhibited and the fluorescence of TC was weakened. Based on these phenomena, we have established a dual signal method for AA determination with the help of UV–vis and fluorescence spectrophotometer. Under the optimum conditions, the LSPR absorption peak shift (Δλ) of Au@MnO2 NPs and the decrease in fluorescence of TC correlated well with AA concentration ranging from 0.75 to 17.5 μM. The detection limits of LSPR absorption assay and fluorescence assay were 0.18 and 0.47 μM, respectively. More importantly, this dual-signal detection method has been used for the determination of AA in vitamin C tablets with high accuracy and precision, indicating its promising potential applications.

An ultrahigh-resolution multicolor sensing platform via target-induced etching of gold nanorods for multi-colorimetric analysis of trace silver ions

Heavy metal ion pollution is a pressing global concern with detrimental effects on the environment and human health. To address this issue, we have developed an ultrahigh-resolution multicolor sensing platform for the specific detection of silver ions (Ag(I)). The method employs the nanozyme of platinum nanoparticles (PtNPs) as a link to control the etching of gold nanorods (AuNRs). Through specific binding with Ag(I), the PtNPs hinder the catalase-like activity responsible for hydrogen peroxide (H2O2) decomposition. This inhibition enables the Fenton reaction between H2O2 and ferrous ions, generating highly oxidizing hydroxyl free radicals (·OH). The resulting etching of AuNRs induces a blue-shift in their local surface plasmon resonance (LSPR) absorption spectra. The degree of blue-shift is directly proportional to the Ag(I) concentration, facilitating trace-level detection. Furthermore, the aspect ratio change of the AuNRs yields distinguishable colors. In contrast to common multicolor sensors relying on nanozyme horseradish peroxidase (HRP) activity, which exhibits an inverse relationship between AuNR etching and target concentration, our approach demonstrates a proportional response. This unique characteristic enables ultrahigh-resolution multicolor detection of Ag(I) visible to the naked eye. We anticipate that this innovative sensing platform will pave the way for nanosensor development in environmental monitoring and food safety detection.

Effect of Postdeposition Heat Treatment on the Nanoplasmonic Behavior of Glancing Angle‐Deposited Silver Nanostructures

Postdeposition heat treatment‐induced modifications of nanoplasmonic response in glancing angle‐deposited (GLAD) Ag nanostructures are systematically investigated. The as‐deposited GLAD Ag thin films are annealed at various temperatures namely 200, 250, 300, and 350 °C in air atmosphere. The reduction in localized surface plasmon resonance (LSPR) absorption peak width is detected with annealing. Morphological characterization of the as‐deposited and annealed films reveals reduction in grain size and shape distributions responsible for narrowing of the LSPR peak width. The refractive index sensitivities of the as‐deposited and annealed films are measured using an in‐house‐developed optical setup and figure of merit (FOM) of the sensors is also estimated. An increase in FOM of the sensors is observed upon annealing while sensitivity is found to be reduced. E‐field profile surrounding the Ag nanoparticles is also simulated to explain the experimental observations on refractive index sensitivity of the films.

Facile phytosynthesis of gold nanoparticles using Nepeta bodeana Bunge: Evaluation of its therapeutics and potential catalytic activities

In the present study, the ethanol extract of leaves of Nepeta bodeana Bunge was utilized in environmentally friendly synthesis of gold nanoparticles (AuNPs) via an immediate, one-step, and cost-effective process. The biosynthesized AuNPs were characterized using a variety of techniques, including UV–visible spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and laser Doppler electrophoresis (zeta potential), among others. Pink in hue, the manufactured AuNPs were practically spherical and had<20.5 nm in diameter. The peak of the localized surface plasmon resonance absorption band at 547 nm helped to explain the biogenic synthesis of AuNPs, which used the ethanolic extract of the Nepeta bodeana leaves. In addition to this, the biosynthesized AuNPs possessed the remarkable stability as a result of their zeta potential value of − 22.3 mV. The green synthesized AuNPs demonstrated the excellent catalytic activity because they were able to catalytically degrade methylene blue (MB) at a variety of concentrations. The results indicated that 94.2% of MB were degraded after 10 min. They also showed a remarkable antibacterial activity against both Gram-nrgative (Pseudomonas aeruginosa and Escherichia coli) and Gram-positive (Staphylococcus aureus and Bacillus cereus) bacteria. In addition, a proper antifungal activity with the minimum inhibitory concentration (MIC) values of 50 and 25 μg/mL against Candida albicans and Aspergillus niger, respectively, were determined. The phytosynthesized AuNPs indicated a considerable antioxidant activity of 83% and 74% in the applied DPPH and ABTS radical scavenging activity tests, respectively. The anti-inflammatory properties of the synthesized AuNPs were established to be dose-dependent and varied from 11% to 76%. The green synthesized AuNPs also exhibited a concentration-dependent cytotoxicity on human liver (HepG2) and breast (MCF-7) cancer cells, which were around 77.4 and 71.2% at 300 µg/mL, respectively. They showed as well a notable anti-diabetic activity with the 52% inhibition of α-amylase and the 62% glucose uptake activity by yeast cells at 300 µg/mL. All these findings suggested that the produced AuNPs could be explored for developing many therapeutic as well as catalytic useful products.

Dynamically modulating the mid-infrared localized surface plasmon resonance of Al-doped ZnO nanocrystals

The localized surface plasmon resonance (LSPR) regulation of semiconductor oxide nanocrystals (NCs) in the near-infrared region (0.8–2.5 μm) of the solar spectrum has attracted much attention for its potential in applications such as electrochromism and sensing. However, the LSPR modulation properties of doped semiconductor oxide NCs in the mid-infrared region (2.5–25 μm) have rarely been reported. Here, we synthesized aluminum-doped zinc oxide (AZO) NCs with various nominal Al doping contents (1–20at%). The LSPR absorption peaks of these films were regulated between ∼3.8 and 6.57 μm depending on the doping content. AZO NC films with 1at% nominal Al doping and a 1316 nm film thickness exhibited the highest electrochemical infrared absorption regulation, achieving 35.9% regulation at 3–5 μm and 32.5% at 7.5–13 μm. The infrared absorption regulation mechanism of the AZO NCs involved changes in the LSPR absorption intensity caused by electron injection/extraction into/from the surface depletion layer of the AZO NCs. After applying different voltages, the AZO NC film on the Al substrates exhibited different apparent temperatures, demonstrating its potential applications in infrared displays and camouflage.

(Invited) New Class of Plasmonic Alloy Nanoparticles

The past 150 years of research on inorganic nanomaterials that exhibit intrinsic localized surface plasmon resonance (LSPR) in the visible region has focused on well-disperse nanoparticles (NPs) composed of coinage metals (Au, Ag, and Cu). Recent theoretical studies on photo-excited electron dynamics in Au NPs have revealed that not only the interband transition but also the screening caused by the vibrations of bound electrons by visible light are important for visible LSPR [1]. However, the correlation between the electronic and crystal structure (as a means to control the screening effect) remains unclear because most alloys based on coinage metals have a face-centred cubic (fcc)-based structure. Here, we show that well-disperse pseudospherical intermetallic Pd-based alloy NPs with a B2 structure and PtIn2 NPs with a C1 (CaF2-type) structure intrinsically exhibit LSPR absorption in the visible region.It is well known that chemical conversion of inorganic NPs via element substitution reactions, such as ion exchange reactions [2] and galvanic replacement reactions, can overcome the difficulties associated with controlling the size, shape, chemical composition, and crystal structure in conventional syntheses [3-5]. Especially, alloying enables us to drastically modulate the electronic properties of metallic NPs. The retained shape of the parent-NPs in element replacement reactions provides an opportunity to obtain non-equilibrium unique structures and even new structures of inorganic NPs. We demonstrate that various Pd-based alloy NPs with a B2 structure were synthesized by the element replacement reactions with Pd–P NPs and showed LSPR in the visible region [6]. This is an alchemy in nanoplasmonics in the sense that the plasmonic properties of group 11 elements are reproduced by using non-group 11 elements. On the other hand, we successfully synthesized pseudospherical PtIn2 intermetallic NPs with a C1 structure as uncommon types of visible plasmonic NPs [7].Simulations of above alloy NPs and fcc-Au NPs indicate that both the reduction in the interband transition and the strong screening by a small number of bound d-electrons are the main origins of the visible plasmonic features of alloy NPs. Our results demonstrate that the composition and crystal structure of the intermetallic NPs of our work determine the interband transition and the screening effect. Our findings dramatically expand the plasmonic NP library and highlight remarkable NPs that are far superior, in terms of physical and chemical properties, to conventional plasmonic NPs.[1] Iida, K.; Noda, M.; Ishihara, K.; Nobusada, K. J. Phys. Chem. A 2014, 118, 11317–11322.[2] Saruyama, M.; Sato, R.; Teranishi, T. Acc. Chem. Res. 2021, 54, 765–775.[3] Wu, H.-L.; Sato, R.; Teranishi, T. et al., Science 2016, 351, 1306–1310.[4] Li, Z.; Saruyama, M.; Asaka, T.; Tatetsu, Y.; Teranishi, T. Science 2021, 373, 332–337.[5] Matsumoto, K.; Sato, R.; Tatetsu, Y.; Teranishi, T. et al., Nat. Commun. 2022, 13, 1047.[6] Sato, R.; Takekuma, H.; Teranishi T. et al., to be submitted.[7] Takekuma, H.; Sato, R.; Iida, K.; Teranishi, T. et al., submitted.

Surface grafted gold nanorods (GNRDs) using thermosensitive copolymers with various transition temperatures: Nanomaterials with potential application for photothermal therapy

A series of diblock copolymers containing a biocompatible polyethylene glycol (PEG) block and a thermoresponsive poly(N-vinyl caprolactam) (PNVCL) based block, were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The cloud point temperature (Tcp) in water of the diblocks was adjusted from 35 to 42 °C by adding N-vinyl pyrrolidone (NVP) units in the thermoresponsive block. The terminal trithiocarbonate group evolving from the RAFT agent used in the synthesis, was modified to thiol to stabilize gold nanorods (GNRDs) via a “grafting-to” approach. Stability of the PEG-b-P(NVCL-co-NVP)@GNRDs nanomaterials was monitored during 8 days; where the localized surface plasmon resonance (LSPR) absorption band did not shifted or showed any broadening. Aqueous dispersed samples were irradiated with near-infrared laser light for 10 min, observing a temperature increase from 25 to 50 °C depending on the laser optical power (between 100 and 500 mW); while no precipitation was observed. For temperatures above the cloud point temperature of the copolymers (Tcp), the formation of aggregates in sizes around 200 nm was observed without precipitation. This study demonstrates that the stabilization of gold nanorods by grafting with the title thermoresponsive block copolymers, and the observed temperature-dependent block-copolymer@GNRD aggregation, has potential uses in drug-delivery applications for photothermal therapy.

PH regulated lactose inspired fabrication of zinc oxide nanoparticles for insulin sensing by LSPR absorption

Nanostructured metal oxide particles with diversified morphologies are in high demand in nanotechnology. The particle size, shape, and overall geometry mainly depend on the fabrication method. This study reports synthesis of zinc oxide nanoparticles (ZnO NPs) from zinc nitrate hexahydrate [Zn(NO3)2.6H2O] precursor in aqueous media at 65 °C by using lactose from cow milk as a reducing agent and regulating pH from 6 to 10. UV–visible absorption gave maximum absorbance (λmax) at 371–375 nm in ethanol for localized surface plasmon resonance (LSPR), FTIR exhibited bands at ca. 439–481 cm−1 for stretching mode Zn–O bonds, and XRD peaks at 2 θ values at 31.8, 34.45, and 36.28° confirmed the fabricated ZnO NPs. The XRD spectra also indicated that the ZnO crystallite (20–30 nm) has a hexagonal wurtzite structure. The average particle sizes measured by DLS were ca. 50–837 nm, and SEM microphotographs demonstrated the morphology of ZnO NPs with a hexagonal, rod-shaped, or spike-like structure. The ZnO NPs were used to investigate the LSPR absorption at various concentrations of insulin, ranging from 2.5 μM to 50 μM. The ZnO NPs fabricated at pH 7 and 10 showed better insulin sensing performance with high precision. The synthesis approach of ZnO NPs with variable morphologies would play a significant function in biomedical science especially real time monitoring of glucose for efficient management of diabetes.

Development of Nano-Micro Fused LSPR Chip for In Situ Single-Cell Secretion Analysis.

Single-cell analysis has become increasingly important in uncovering cell heterogeneity, which has great implications in medicine and biology for a deep understanding of cell characteristics. Owing to its significance, it is vital to create novel devices that can reveal special or unique cells. In this work, we developed a single-cell secretion detection chip consisting of microwells that can trap single cells. Each well is surrounded by Au nanopillars capable of localized surface plasmon resonance (LSPR) measurement. Using microfabrication and nanofabrication techniques, Au nanopillar and microwell structures were fabricated on a COP film. The Au nanopillar was modified with IL-6 antibodies for the direct detection of single-cell secreted IL-6 via LSPR absorbance peak shift. Specific IL-6 detection was successfully demonstrated using a null and IL-6 oversecreting Jurkat cell. A high single-cell trapping efficiency of over 80% was also achieved. Overall, the development of this single-cell secretion detection chip with a simple LSPR measurement setup represents a significant development in the field of cell biology and immunology, providing researchers with a powerful tool for studying individual cells and their secreted cytokines, and is useful for point-of-care testing (POCT) diagnostics.