Optical Nanoprobe Research Articles

Nitrogen self-doped desiccated coconut–derived carbon dots as optical nanoprobe sensor for the detection of heavy metal ion Hg2+

Nitrogen self-doped desiccated coconut–derived carbon dots as optical nanoprobe sensor for the detection of heavy metal ion Hg2+

One-drop micro-array towards accelerated optical quantification of dopamine in human biofluids using triangular silver nanoparticles: Smartphone-assisted biomedical analysis by colorimetric sensing and Lab-on-paper technology

Trace-level detection of Dopamine (DA) in human body fluids is crucial for diagnosing neurological disorders, understanding mental health, and advancing drug discovery, but found challenging with rapid and low-cost detection technologies. Herein, an innovative paper-based photochemical method has been developed for the detection of DA using triangular silver nanoprism (AgNPrs), as an optical nanoprobe, in human blood plasma and urine samples. The redox reaction between DA and AgNPrs was evaluated through a color change at two pHs (5.35and 6.14), which can be analyzed by UV–Vis spectrophotometry and microfluidic paper-based colorimetric device (µPCD) with low limit of quantification of 0.01 µM. This study presents pioneering work with the potential to inspire the development of simple and effective on-site semi quantifying recognition devices for other neurotransmitters, requiring only a lightweight piece of paper and a single drop of the necessary reagent.

Tailored peptide nanomaterials for receptor targeted prostate cancer imaging.

We report the development of a peptide-based optical nanoprobe specifically tailored for prostate cancer imaging. The imaging probe is comprised of cyclic peptide nanotubes, formed via the aqueous co-assembly of four cyclic D,L-alternating octapeptides. The inherent properties of these cyclic building blocks have been carefully selected to enhance their efficacy in imaging applications, through the addition of a cancer targeting peptide and a fluorescent dye. Comprehensive characterization using scanning electron microscopy (FESEM) and low-voltage transmission electron microscopy (LV-TEM) confirms the formation of nanotubes through co-assembly of the cyclic peptides. The resulting nanotubes show an average diameter of 28 nm. Circular dichroism (CD) spectroscopy validates the formation of stable beta-sheet hydrogen bonding structures at both 20 and 37 °C, ensuring their suitability for biomedical applications. Evaluation of PSMA-binding specificity of the resulting peptide nanotubes is assessed using confocal fluorescence microscopy demonstrating receptor-mediated uptake in prostate cancer cells. We anticipate this strategy will provide the basis for the utilization of co-assembled systems for advancing molecular imaging techniques in prostate cancer and other cancers.

Optical nanoprobe imaging and spectroscopy

Optical nanoprobe imaging and spectroscopy

Bimetallic nanodisk-based fiber-optic plasmonic nanoprobe for gas detection

In this study, gold-palladium bimetallic nanodisks were patterned on optical fibers via nanosphere lithography and chemical growth. The conditions related to the density of the structures, concentration of the growth solution, and growth time were modified. The structural features of nanodisks with a large surface area and enhancement of plasmonic efficiency owing to the palladium shell resulted in a high refractive index sensitivity. Additionally, based on palladium's sensitivity to hydrogen, hydrogen sensing was performed at various concentrations with a detection limit of 0.125 % and signal-to-noise ratio of 24.2 dB. The response time and hysteresis showed a good performance relative to those of other hydrogen sensors. The high throughput of the nanosphere lithography and simple seed-mediated growth make this system a cost-effective fiber-optic plasmonic nanoprobe. Based on these investigations, the optical fiber-based plasmonic nanoprobe can be actively applied to detect dangerous environments using remote sensing for safety management in the clean energy era.

Encaved optical fiber nano-probe exciting whispering gallery mode resonance with focused far off-axis beam.

This paper demonstrates whispering gallery mode (WGM) resonance with the help of an encaved optical nano-probe developed inside an optical fiber tip cavity. The nano-probe generates a tightly focused beam with a spot-size of ∼3 µm. A barium titanate microsphere is placed besides the optical axis inside the cavity. The focused beam remains off-axis of the microresonator and excites the WGM. The off-axis excitation shows unique resonating properties depending on the location of the resonator. A resonant peak with quality factor as high as Q ∼7 × 104 is achieved experimentally. Another design with a shorter cavity length for a bigger resonator is also demonstrated by embedding a bigger microsphere on the cleaved fiber tip surface. The optical probe holds great potential for photonic devices and is ideal for studying morphology-based scattering problems.

An innovative synthesis of (Ag0-pullulan-Ag+) as an optical nanoprobe for sensitive and selective detection of Fe2+ ion based on redox reaction

Herein, we Synthesized an efficacious optical nanoprobe (Ag0-pullulan-Ag+) for sensitive and discriminative detection of ferrous ions (Fe2+) over ferric ions (Fe3+) in solution. Pullulan (PUL) biopolymer was used as the reductant of excess AgNO3, at moderate heating, so that stable and dispersed silver nanoparticles (AgNPs or Ag0) were formed, which also contained an unreduced silver ion (Ag+), all intertwined in the pullulan polymeric matrix. Extensive characterization confirmed the role of PUL as a capping agent, while sharp Ag0 and Ag+ peaks were validated using X-ray photoelectron spectroscopy (XPS). The Ag0-PUL-Ag+ probe showed a sharp absorption maximum at 415 nm, having a majority size distribution around 20–30 nm, from TEM. The addition of Ag0-PUL-Ag+, acetate buffer pH 5.0, and Fe2+ under room temperature incubation led to Fe2+ reduction of available Ag+ to more AgNPs, based on redox reaction, with color progression from light yellow to yellow, orange, and brownish yellow. The ΔA@411 plotted against Fe2+ concentration was linear within 1.0–20.0 and 20.0–125.0 μM, with a limit of detection (LOD) of 0.15 μM. The assay was selective to only Fe2+ over other metal ions and was applied to Fe2+ detection in tap water and in ferrous fumarate tablets with satisfactory accuracy/precision. Our work showed that with careful control of nanomaterial synthesis conditions, a sensitive detection probe could be obtained for impressive analyte sensing/detection.

Construction and application of thrombin-activated fluorescence-SERS dual-mode optical nanoprobes

Thrombin (TB) plays a key role in the pathological and physiological coagulation of diseases. In this work, a TB-activated fluorescence-surface-enhanced Raman spectroscopy (SERS) dual-mode optical nanoprobe (MRAu) was constructed by linking rhodamine B (RB)-modified magnetic fluorescent nanospheres with AuNPs through TB-specific recognition peptides. In the presence of TB, the polypeptide substrate could specifically be cleaved by TB, resulting in the weakening of SERS hotspot effect and the reduction of Raman signal. Meanwhile, the fluorescence resonance energy transfer (FRET) system was destroyed, and the RB fluorescence signal originally quenched by AuNPs was recovered. Using MRAu, SERS and fluorescence methods were combined to extend the TB detection range to 1–150 pM, and the detection limit was as low as 0.35 pM. In addition, the ability to detect TB in human serum also verified the effectiveness and practicality of the nanoprobe. The probe was also successfully employed to evaluate the inhibitory effect against TB of active components in Panax notoginseng. This study provides a new technical means for the diagnosis and drug development of abnormal TB-related diseases.

Ascorbic acid supported Carboxymethyl cellulose stabilized silver nanoparticles as optical nanoprobe for Au3+ detection in environmental sample

Heavy metals (HMs), pollution of major environmental matrices and its attendant effects on human health and the environment, continue to generate huge scientific interest, particularly in monitoring and detection. Herein, the optical property of carboxymethyl cellulose stabilized silver nanoparticles (CMC-AgNPs), supported with ascorbic acid, is exploited as a colorimetric probe for the detection of toxic Au3+ ion in solution. The as-synthesized CMC-AgNPs showed sharp absorption maximum at 403 nm, with sparkling yellow color and average particles size distribution less than 10 nm. It was further characterized using ATR-FTIR, TEM, FESEM/EDS, XRD and DLS/zeta potential analyzer. Au3+ ion detection strategy involves the addition of ascorbic acid (AA) to a pH adjusted CMC-AgNPs, followed by the analyte addition. AA would facilitate the reduction of Au3+ on CMC-AgNPs (seed), with resultant color perturbations from light yellow to yellow, orange, ruby red and purple red, under 8 min incubation, at room temperature (RT). The CMC-AgNPs could also serve as a catalyst, by promoting AA mediated reduction of Au3+, in-situ. Moreover, we propose, that the color and the absorption spectra change is attributed to the deposition of gold nanoparticles (AuNPs), on the CMC-AgNPs/AA probe, to form (CMC-Ag@Au) nanostructures, depending on the analyte concentration. Absorbance ratio (A540/A403) showed good linearity with Au3+ concentration from 0.25 to 100.0 µM, and an estimated LOD of 0.061 µM. The assay was applied to Au3+ detection in environmental wastewater sample, showing satisfactory real sample detection potentiality.

Differential near-infrared imaging of heterocysts using single-walled carbon nanotubes

The internalization of near-infrared (NIR) optical nanoprobes in photosynthetic microbes can be exploited for applications ranging from energy conversion to biomolecule delivery. However, the intrinsic, species-dependent properties of microbial cell walls, including their surface charge density, composition, thickness, and elasticity, can severely impact nanoprobe uptake and affect the cellular response. An examination of the interaction of the optical nanoprobe in various species and its impact on cell viability is, therefore, imperative for the development of new imaging technologies. Herein, we extend the technology recently developed for internalizing fluorescent single-walled carbon nanotubes (SWCNTs) in prokaryotes, specifically unicellular Synechocystis sp. PCC 6803, to a filamentous cyanobacterial strain, Nostoc punctiforme. Using a combination of NIR fluorescence, scanning electron microscopy (SEM), and Raman spectroscopy, we investigate uptake in vegetative cells as well as differentiated heterocysts. We demonstrate a strong dependence of long-term cell integrity, activity, and viability on SWCNT surface functionalization. We further show differential uptake of SWCNTs across a single filament, with positively charged functionalized SWCNTs preferentially localizing within the heterocysts of the filament. This cell dependency of the nanoparticle internalization motivates the use of SWCNTs as a NIR stain for monitoring cell differentiation.Graphical abstract

SERS/NIR‐II Optical Nanoprobes for Multidimensional Tumor Imaging from Living Subjects, Pathology, and Single Cells and Guided NIR‐II Photothermal Therapy

AbstractMolecular imaging‐guided precision photothermal therapy has shown tremendous potential for invasively thermal ablation with solid tumors. However, it is still a pressing clinical need to develop precise and deep‐tissue multi‐scale imaging technologies easily integrated into a single system to boost accurate photothermal treatments. Herein, a SERS/NIR‐II optical nanoprobe assembled by gold nanostars, Raman molecular tags, and silver sulfide quantum dots through silica bridges (named AuDAg2S) is reported that allows the combination of the fingerprint‐style surface‐enhanced Raman scattering (SERS) imaging and second region near‐infrared (NIR‐II) in‐depth biological fluorescence imaging. It can also yield strong localized surface plasmon resonance for a satisfactory photothermal conversion efficiency of 67.1% at 1064 nm to effectively kill CT26 colon cancer cells. Moreover, the AuDAg2S nanoprobes can enhance the detection sensitivity up to the picomolar level and increase the depth of the NIR‐II fluorescence signal up to 1 cm under the excitation of the near‐infrared laser. As a result, the AuDAg2S nanoprobes can achieve multidimensional tumor imaging in levels of living subjects, histology, and single cell, and further guided deep NIR‐II photothermal anti‐tumor therapy in vivo. This study offers a promising approach for SERS/NIR‐II whole optical imaging for deep tumor photothermal treatment in future clinical applications.

Synchronous enhancement of upconversion and NIR-IIb photoluminescence of rare-earth nanoprobes for theranostics.

This study develops a multifunctional molecular optical nanoprobe (SiO2@Gd2O3: Yb3+/Er3+/Li+@Ce6/MC540) with a unique core-satellite form. The rare-earth doped nanodots with good crystallinity are uniformly embedded on the surface of a hydrophilic silica core, and the nanoprobe can emit near-infrared-IIb (NIR-IIb) luminescence for imaging as well as visible light that perfectly matches the absorption bands of two included photosensitizers under 980 nm irradiation. The optimal NIR-IIb emission and upconversion efficiency are attainable via regulating the doping ratios of Yb3+, Er3+ and Li+ ions. The relevant energy transfer mechanism was addressed theoretically that underpins rare-earth photoluminescence where energy back-transfer and cross relaxation processes play pivotal roles. The nanoprobe can achieve an excellent dual-drive photodynamic treatment performance, verified by singlet oxygen detections and live-dead cells imaging assays, with a synergistic effect. And a brightest NIR-IIb imaging was attained in tumoral site of mouse. The nanoprobe has a high potential to serve as a new type of optical theranostic agent for tumor.

Scattering Cancellation Coating Composed of Periodical Subwavelength Structures

We propose to cancel the scattered wave using two layers of periodical subwavelength structures by coating the scattering object with the designed composite material. As a demonstration, it is possible to obtain such scattering cancellation effect for a fiber optical nanoprobe, and fabricate the coating layers by simply etching cylinders or doping elements in silicon/SOI wafer. The required quasistatic parameters of the coating material are homogeneous and isotropic. The simulation results show that the 632.8 nm TE polarized light travels through the coated fiber optical nanoprobe with the wavefront undisturbed, and serve as evidence of the effectiveness of the designed invisibility coating. The proposed scattering cancellation scheme could be useful in non-invasive probing applications at visible and near-infrared wavelengths.

Nanoscale chemical heterogeneity dominates the optoelectronic response of alloyed perovskite solar cells.

Halide perovskites perform remarkably in optoelectronic devices. However, this exceptional performance is striking given that perovskites exhibit deep charge-carrier traps and spatial compositional and structural heterogeneity, all of which should be detrimental to performance. Here, we resolve this long-standing paradox by providing a global visualization of the nanoscale chemical, structural and optoelectronic landscape in halide perovskite devices, made possible through the development of a new suite of correlative, multimodal microscopy measurements combining quantitative optical spectroscopic techniques and synchrotron nanoprobe measurements. We show that compositional disorder dominates the optoelectronic response over a weaker influence of nanoscale strain variations even of large magnitude. Nanoscale compositional gradients drive carrier funnelling onto local regions associated with low electronic disorder, drawing carrier recombination away from trap clusters associated with electronic disorder and leading to high local photoluminescence quantum efficiency. These measurements reveal a global picture of the competitive nanoscale landscape, which endows enhanced defect tolerance in devices through spatial chemical disorder that outcompetes both electronic and structural disorder.

FITC characterization of a cathepsin B-responsive nanoprobe for report of differentiation of HL60 cells into macrophages.

A cathepsin B (Cat B)-responsive optical nanoprobe is designed and prepared for report of HL60 differentiation into macrophage. A peptide sequence FRFK is linked to fluorescein (FITC) via the distant amino group of its lysine and N-terminated with acrylic acid (AA) to yield a molecular fluorescent probe AA-FRFK (FITC). The molecular probe is further embedded in poly(lactic-co-glycolic acid) (PLGA) to form a fluorescent nanoprobe AA-FRFK (FITC)@PLGA. The resultant optical nanoprobe is degradable by lysosomal Cat B, which is expressed in macrophages with a level of 5-10 times of that in HL60 cells. As a result, a significant decrease in fluorescence intensity is associated with the differentiation process of HL60 to macrophage and can be used as an indication of the differentiation process. The findings may pave a way toward the development of a universal in vitro labeling strategy of exogenous stem cells for report of in vivo cell differentiation by a dual-mode imaging modality involving optical imaging and magnetic resonance imaging.

A H2S-Triggered Dual-Modal Second Near-Infrared/Photoacoustic Intelligent Nanoprobe for Highly Specific Imaging of Colorectal Cancer.

An endogenous H2S-triggered intelligent optical nanoprobe combining second near-infrared (NIR-II) fluorescence with photoacoustic (PA) imaging can provide more comprehensive information to further improve the sensitivity and reliability of diagnosis for colorectal tumor, which is rarely explored. Herein, an endogenous H2S-triggered SiO2@Ag nanoprobe was designed for in situ dual-modal NIR-II/PA imaging of colorectal cancer. The designed dual-modal nanoprobe can be converted to SiO2@Ag2S after in situ biosynthesis via a sulfuration reaction with the over-expressed endogenous H2S in the colorectal tumor. More importantly, the designed SiO2@Ag nanoprobe exhibits high sensitivity and specificity for diagnosing colorectal cancer in vivo via dual-modal NIR-II/PA imaging. These results provide a new NIR-II/PA dual-modal imaging strategy for noninvasive intelligent detection of colorectal cancer.

Plasmon-induced double-field-enhanced upconversion nanoprobes with near-infrared resonances for high-sensitivity optical bio-imaging

High-sensitivity optical imaging can be achieved through improving upconversion photoluminescence (UCPL) efficiency of localized surface plasmon resonance (LSPR)-enhanced excitation and emission. Herein, we report a type of UCPL nanoprobe, Au nanospheres assemblage@Gd2O3:Yb3+/Ln3+ (Ln = Er, Ho, Tm), which exhibits emission enhancements from 46- to 96-fold as compared with its Au-free counterparts. The aggregation and interaction among Au nanospheres embedded inside the nanoprobe brings about three characteristic LSPR peaks in visible and near-infrared regions according to simulated and experimental absorption spectra, resulting in both excitation and emission fields simultaneously intensified all through the entire nanoprobe. We addressed a characteristic wavelength dependence on emission amplifications, which could be elucidated by a LSPR-enhanced UCPL mechanism and relevant rate equations that we addressed. The nanoprobe was verified to have a superior capability for optical bio-imaging with a negligible toxicity in vitro and in vivo. This study realizes a synchronous double-field-enhanced upconversion of optical nanoprobe in situ, and may gain an insight into its mechanism underlying for LSPR-induced UCPL enhancement.

"Switch-on" fluorescence sensing platform based on porphyrin metal-organic frameworks for rapid and specific detection of zinc ion.

Zinc ion (Zn2+) is a necessary transition metal ion in the human body and plays a vital role in biological systems. Therefore, it is meaningful for rapid, sensitive, and specific detection of Zn2+. Herein, a "switch-on" fluorescence sensing platform for the detection of Zn2+ was successfully established. In this work, we report an optical nanoprobe with amino functional groups based on porphyrin metal-organic frameworks (PCN-NH2) through a simple treatment method. The modification of the salicylaldehyde (SA) through the C=N acts as a quencher of PCN-NH2 and the ligand of Zn2+ can effectively inhibit the fluorescence emission of PCN-NH2. The complex of porphyrin-based metal-organic framework and salicylaldehyde (PCN/SA) acts as the fluorescence sensing probe. The presence of Zn2+ results in the new emission peak at 448 nm due to the formation of a complex between Zn2+ and SA. The corresponding fluorescence signal changes were used to accurately detect the concentration of Zn2+. The fluorescence sensing platform shows advantages, including rapid response, high sensitivity, and excellent specificity with a linear detection range of Zn2+ between 0.1 and 250 μM, and a low detection limit (LOD) of 0.07 μM. And the feasibility of the method was verified for the quantification of Zn2+ in cell lysate, environmental water, and plasma.

Radial basis function-artificial neural network (RBF-ANN) for simultaneous fluorescent determination of cysteine enantiomers in mixtures

The determination of chiral compounds is critically important in chemical and pharmaceutical sciences. Cysteine amino acid is one of the important chiral compounds where each enantiomer (L and D) has different effects on fundamental physiological processes. The unique optical properties of nanoparticles make them a suitable probe for the determination of different analytes. In this work, the water-soluble thioglycolic acid (TGA)-capped cadmium-telluride (CdTe) quantum dots (QDs) were applied as optical nanoprobe for the simultaneous determination of cysteine enantiomers. The difference in the kinetics of the interactions between L- and D-cysteine with CdTe QDs is used for multivariate quantitative analysis. Multivariate methods are superior to univariate methods in determining the concentration of each enantiomer in the mixture without the information about the total chiral analyte concentration. As a nonlinear calibration method the radial basis function -artificial neural network (RBF-ANN) model was more successful in predicting L-and D-cysteine concentrations than the linear partial least squares regression (PLS) model.

Fluorescent and Colorimetric Dual-signal Enantiomers Recognition via Enzyme Catalysis: The Case of Glucose Enantiomers Using Nitrogen-doped Silicon Quantum Dots/Silver Probe Coupled with β-D-Glucose Oxidase.

Chiral enantiomer recognition is important but facing tough challenges in the direct quantitative determination for complex samples. In this work, via chosing nitrogen-doped silicon quantum dots (N-SiQD) as optical nanoprobe and constructing N-SiQD/silver (N-SiQD/Ag NPs) complex, β-D-GOx as model enzyme and glucose enantiomers as analytes, a fluorescent and colorimetric dual-signal chiral sensing strategy was proposed herein for chiral recognition based on specific enzyme-catalyzed reaction. N-SiQD can exhibit intense fluorescence, while it can be quenched by Ag NPs owing to the formation of N-SiQD/Ag NPs. In the presence of glucose isomer, D-glucose is catalytically hydrolyzed by β-D-GOx to form H2O2 owing to the specific enzyme catalyzed reaction between D-glucose and β-D-GOx, and H2O2 can etch Ag NPs from the N-SiQD/Ag NPs probe to change the solution color from brown to colorless and restore the N-SiQD fluorescence; while these phenomena cannot be caused by L-glucose, a dual-signal sensing method was thus constructed for recognizing glucose enantiomers. It is believed that the chiral enantiomers recognition strategy via enzyme catalysis has great application for selective and quantificational detection of enantiomers in the complex sample system.