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Stimuli-responsive nanoplatforms have been popular in controlled drug delivery research because of their ability to differentiate the tumor microenvironment from the normal tissue environment in a spatiotemporally controllable manner. The synergistic therapeutic approach of combining cancer chemotherapy with photothermal tumor ablation has improved the therapeutic efficacy of cancer therapeutics. In this study, a UiO-66 metal organic framework (MOF)-based system loaded with doxorubicin (DOX), surface decorated with the photothermal agents indocyanine green (ICG) and polydopamine (PDA), and conjugated with transferrin (TF) was successfully designed to operate as a responsive system to pH changes, featuring photothermal capabilities and target specificity for the purpose of treating breast cancer. The synthesized nanoplatform benefits from its uniform size, excellent DOX encapsulation efficiency (91.66 %), and efficient pH/NIR-mediated controlled release of the drug. In vitro photothermal studies indicate excellent photothermal stability of the formulation even after 6 on-off cycles of NIR irradiation. The in vitro cytotoxicity assessment using an NIR laser (808 nm) revealed that the DOX-loaded functionalized UiO-66 nanocarriers had outstanding inhibitory effects on 4T1 cells because of synergistic chemo-photo therapies, with no substantial toxicity by the carriers. In addition, cellular uptake evaluations revealed that UiO-DOX-ICG@PDA-TF could specifically target 4T1 cells on the basis of receptor-mediated internalization of transferrin receptors. Additionally, in vivo toxicity studies in Wistar rats indicated no signs of significant toxicity. The UiO-based nanoformulations effectively inhibited and destroyed cancer cells under 808 nm laser irradiation because of their minimal toxicity, strong biocompatibility, and outstanding synergistic chemo/photothermal/photodynamic treatment.
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Microplastics are one of the concerning environmental pollutants because of their ubiquity. Their capability to adsorb other environmental pollutants increases the risk even further. Existing identification approaches for microplastic characterization for polymer class and their surface-adsorbed heavy metal detection require the utilization of multiple resources and expertise. The article discusses the applicability of a custom-made hyphenated Laser Induced Breakdown Spectroscopy (LIBS)-Raman spectroscopic system in characterizing microplastics by comparing the analytical performance with conventional methods such as Attenuated Total Reflectance- Fourier Transform Infrared (ATR-FTIR) spectroscopy, confocal Raman spectroscopy, and Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy (SEM-EDS). Raman analysis identified polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET) plastics, which is confirmed by confocal Raman and FTIR study of the same. LIBS study of microplastics detected heavy metals such as Al, Ni, Co, and Zn, along with Ca and Mg trace elements. The cross-examination with EDS validates these trace elements' presence on the microplastics' surface. The results of the reported LIBS-Raman analysis and its validity evaluated using conventional gold-standard methods show the applicability of the proposed methodology in characterizing microplastics from environmental resources with less or no sample preparation in short time.
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BACKGROUND: Precise localized printing of plasmonic nanoparticles at desired locations can find a plethora of applications in diverse areas, including nanophotonics, nanomedicine, and microelectronics. The focused laser beam-assisted optical printing technique has illustrated its potential for the localized printing of differently shaped plasmonic particles. However, the technique is either time-consuming or often requires focused optical radiation, limiting its practical applications. While the optothermal printing technique has recently emerged as a promising technique for the direct and rapid printing of plasmonic nanoparticles onto transparent substrates at lower laser intensities, its potential to print the plasmonic nanoparticles to the core of the optical fiber platforms and utilize it for biological cell trapping as well as an analytical platform remains unexplored. RESULTS: Herein, we demonstrate the thermal-convection-assisted printing of the Ag plasmonic nanoparticles from the plasmonic colloidal solution onto the core of single-mode optical fiber and its multi-functional applications. The direct printing of plasmonic structure on the fiber core via the thermal-convection mechanism is devoid of the requirement of any additional chemical ligand to the fiber core. Further, we demonstrated the potential of the developed plasmonic fiber probe as a multifunctional surface-enhanced Raman spectroscopic (SERS) platform for sensing, chemical reaction monitoring, and single-cell studies. The developed SERS fiber probe is found to detect crystal violet in an aqueous solution as low as 100 pM, with a plasmonic enhancement of 107. Additionally, the capability of the fiber-tip platform to monitor the surface plasmon-driven chemical reaction of 4-nitrothiophenol (4NTP) dimerizing into p, p'-dimercaptoazobenzene (DMAB) is demonstrated. Further, the versatility of the fiber probe as an effective platform for opto-thermophoretic trapping of single biological cells such as yeast, along with its Raman spectroscopic studies, is also shown here. SIGNIFICANCE: In this study, we illustrate for the first time the optothermal direct printing of plasmonic nanoparticles onto the core of a single-mode fiber. Further, the study demonstrates that such plasmonic nanoparticle printed fiber tip can act as a multi-functional analytical platform for optothermally trap biological particles as well as monitoring plasmon-driven chemical reactions. In addition, the plasmonic fiber tip can be used as a cost-effective SERS analytical platform and is thus expected to find applications in diverse areas.
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Nanopartículas Metálicas , Fibras Ópticas , Prata , Análise de Célula Única , Análise Espectral Raman , Análise Espectral Raman/métodos , Nanopartículas Metálicas/química , Prata/química , Compostos de Sulfidrila/química , Fenóis/análise , Fenóis/química , Humanos , ImpressãoRESUMO
Droplet assay platforms have emerged as a significant methodology, providing distinct advantages such as sample compartmentalization, high throughput, and minimal analyte consumption. However, inherent complexities, especially in multiplexed detection, remain a challenge. We demonstrate a novel strategy to fabricate a plasmonic droplet assay platform (PDAP) for multiplexed analyte detection, enabling surface-enhanced Raman spectroscopy (SERS). PDAP efficiently splits a microliter droplet into submicroliter to nanoliter droplets under gravity-driven flow by wettability contrast between two distinct regions. The desired hydrophobicity and adhesive contrast between the silicone oil-grafted nonadhesive hydrophilic zone with gold nanoparticles is attained through (3-aminopropyl) triethoxysilane (APTES) functionalization of gold nanoparticles (AuNPs) using a scotch-tape mask. The wettability contrast surface facilitates the splitting of aqueous droplets with various surface tensions (ranging from 39.08 to 72 mN/m) into ultralow volumes of nanoliters. The developed PDAP was used for the multiplexed detection of Rhodamine 6G (Rh6G) and Crystal Violet (CV) dyes. The limit of detection for 120 nL droplet using PDAP was found to be 134 pM and 10.1 nM for Rh6G and CV, respectively. These results align with those from previously reported platforms, highlighting the comparable sensitivity of the developed PDAP. We have also demonstrated the competence of PDAP by testing adulterant spiked milk and obtained very good sensitivity. Thus, PDAP has the potential to be used for the multiplexed screening of food adulterants.
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Ouro , Nanopartículas Metálicas , Análise Espectral Raman , Molhabilidade , Análise Espectral Raman/métodos , Ouro/química , Nanopartículas Metálicas/química , Rodaminas/química , Silanos/química , Limite de Detecção , Animais , Leite/química , Propriedades de Superfície , Tamanho da PartículaRESUMO
The eyes provide rich physiological information and offer diagnostic potential as a sensing site, and probing tear constituents via the wearable contact lens could be explored for healthcare monitoring. Herein, we propose a novel adhesive contrast contact lens platform that can split tear film by natural means of tear secretion and blinking. The adhesive contrast is realized by selective grafting of a lubricant onto a polydimethylsiloxane (PDMS)-based contact lens, leading to high pinning zones on a non-adhesive background. The difference in contact angle hysteresis facilitates the liquid splitting. Further, the method offers control over the droplet volume by controlling the zone dimension. The adhesive contrast contact lens is coupled with fluorescent spectroscopic as well as colorimetric techniques to realize its potential as a diagnostic platform. The adhesive contrast contact lens is exploited to detect the level of lactoferrin in tear by sensitizing split droplets with Tb3+ ions. The adhesive contrast contact lens integrated with a fluorescence spectrometer was able to detect the lactoferrin level up to a concentration of 0.25 mg mL-1. Additionally, a colorimetric detection based on the fluorescence of the lactoferrin-terbium complex is demonstrated for the measurement of lactoferrin, with a limit of detection in the physiological range up to 0.5 mg mL-1.
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Lentes de Contato Hidrofílicas , Lactoferrina/análise , Olho , Lágrimas/química , PiscadelaRESUMO
MXenes are two-dimensional transition metal carbides, nitrides, and carbonitrides that have become important materials in nanotechnology because of their remarkable mechanical, electrical, and thermal characteristics. This review emphasizes how crucial MXene conjugates are for several biomedical applications, especially in the field of cancer. These two-dimensional (2D) nanoconjugates with photothermal, chemotherapeutic, and photodynamic activities have demonstrated promise for highly effective and noninvasive anticancer therapy. MXene conjugates, with their distinctive optical capabilities, have been employed for bioimaging and biosensing, and their excellent light-to-heat conversion efficiency makes them perfect biocompatible and notably proficient nanoscale agents for photothermal applications. The synthesis and characterization of MXenes provide a framework for an in-depth understanding of various fabrication techniques and their importance in the customized formation of MXene conjugates. The following sections explore MXene-based conjugates for nanotheranostics and demonstrate their enormous potential for biomedical applications. Nanoconjugates, such as polymers, metals, graphene, hydrogels, biomimetics, quantum dots, and radio conjugates, exhibit unique properties that can be used for various therapeutic and diagnostic applications in the field of cancer nanotheranostics. An additional layer of understanding into the safety concerns of MXene nanoconjugates is provided by detailing their toxicity viewpoints. Furthermore, the review concludes by addressing the opportunities and challenges in the clinical translation of MXene-based nanoconjugates, emphasizing their potential in real-world medical practices.
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PURPOSE: The study showcased the application of the lab-assembled HPLC-LED-IF system to analyze proteins in tear fluid samples collected from individuals diagnosed with primary open-angle glaucoma (POAG). METHODS: Clinical application of the said technique was evaluated by recording chromatograms of tear fluid samples from control and POAG subjects and by analyzing the protein profile using multivariate analysis. The data analysis methods involved are principal component analysis (PCA), Match/No-Match, and artificial neural network (ANN) based binary classification for disease diagnosis. RESULTS: Mahalanobis distance and spectral residual values calculated using a standard calibration set of clinically confirmed POAG samples for the Match/No-Match test gave 86.9% sensitivity and 81.8% specificity. ANN with leaving one out procedure has given 87.1% sensitivity and 81.8% specificity. CONCLUSION: The results of the study revealed that the utilization of a 278 nm LED excitation in the HPLC system offers good sensitivity for detecting proteins at low concentrations allowing to obtain reliable protein profiles for the diagnosis of POAG.
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Glaucoma de Ângulo Aberto , Humanos , Glaucoma de Ângulo Aberto/diagnóstico , Cromatografia Líquida de Alta Pressão , Projetos de Pesquisa , Análise Multivariada , Redes Neurais de ComputaçãoRESUMO
[This corrects the article DOI: 10.1039/D3RA04389D.].
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In recent years, the application of lasers for modifying the surface topography of dental biomaterials has received increased attention. This review paper aims to provide an overview of the current status on the utilization of lasers as a potential tool for surface modification of dental biomaterials such as implants, ceramics, and other materials used for restorative purposes. A literature search was done for articles related to the use of lasers for surface modification of dental biomaterials in English language published between October 2000 and March 2023 in Scopus, Pubmed and web of science, and relevant articles were reviewed. Lasers have been mainly used for surface modification of implant materials (71%), especially titanium and its alloys, to promote osseointegration. In recent years, laser texturing has also emerged as a promising technique to reduce bacterial adhesion on titanium implant surfaces. Currently, lasers are being widely used for surface modifications to improve osseointegration and reduce peri-implant inflammation of ceramic implants and to enhance the retention of ceramic restorations to the tooth. The studies considered in this review seem to suggest laser texturing to be more proficient than the conventional methods of surface modification. Lasers can alter the surface characteristics of dental biomaterials by creating innovative surface patterns without significantly affecting their bulk properties. With advances in laser technology and availability of newer wavelengths and modes, laser as a tool for surface modification of dental biomaterials is a promising field, with excellent potential for future research.
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BACKGROUND: The thermally coupled energy states that contribute to the upconversion luminescence of rare earth element-doped nanoparticles have been the subject of intense research due to their potential nanoscale temperature probing. However, the inherent low quantum efficiency of these particles often limits their practical applications, and currently, surface passivation and incorporation of plasmonic particles are being explored to improve the inherent quantum efficiency of the particle. However, the role of these surface passivating layers and the attached plasmonic particles in the temperature sensitivity of upconverting nanoparticles while probing the intercellular temperature has not been investigated thus far, particularly at the single nanoparticle level. RESULTS: The analysis of the study on the thermal sensitivity of oleate-free UCNP, UCNP@SiO2, and UCNP@SiO2@Au particles is carried out at a single particle level in a physiologically relevant temperature range (299 K-319 K) by optically trapping the particle. The thermal relative sensitivity of the as-prepared upconversion nanoparticle (UCNP) is found to be greater than that of UCNP@SiO2 and UCNP@SiO2@Au particles in an aqueous medium. An optically trapped single luminescence particle inside the cell is used to monitor the temperature inside the cell by measuring the luminescence from the thermally coupled states. The absolute sensitivity of optically trapped particles inside the biological cell increases with temperature, with a greater impact on the bare UCNP, which exhibits higher values for thermal sensitivity than UCNP@SiO2 and UCNP@SiO2@Au. The thermal sensitivity of the trapped particle inside the biological cell at 317 K indicates the thermal sensitivity of UCNP > UCNP@SiO2@Au > UCNP@SiO2 particles. SIGNIFICANCE AND NOVELTY: Compared to bulk sample-based temperature probing, the present study demonstrates temperature measurement at the single particle level by optically trapping the particle and further explores the role of the passivating silica shell and the incorporation of plasmonic particles on thermal sensitivity. Furthermore, thermal sensitivity measurements inside a biological cell at the single particle level are investigated and illustrated that thermal sensitivity at a single particle is sensitive to the measuring environment.
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Tear fluid contains organic and inorganic constituents, variations in their relative concentrations could provide valuable information and can be useful for the detection of several ophthalmological diseases. This report describes the application of the lab-assembled light-emitting diode (LED)-based high-performance liquid chromatography system for protein profiling of tear fluids to diagnose dry eye disease. Principal Component Analysis (PCA), match/no-match, and Artificial Neural Network (ANN) based binary classification of protein profile data were performed for disease diagnosis. Results from the match/no-match test of the protein profile data showed 94.4% sensitivity and 87.8% specificity. ANN with the leaving one out procedure has given 91.6% sensitivity and 93.9% specificity.
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Raman spectroscopy offers the potential for fingerprinting biological molecules at ultra-low concentration and therefore has potential for the detection of viruses. Here we review various Raman techniques employed for the investigation of viruses. Different Raman techniques are discussed including conventional Raman spectroscopy, surface-enhanced Raman spectroscopy, Raman tweezer, tip-enhanced Raman Spectroscopy, and coherent anti-Stokes Raman scattering. Surface-enhanced Raman scattering can play an essential role in viral detection by multiplexing nanotechnology, microfluidics, and machine learning for ensuring spectral reproducibility and efficient workflow in sample processing and detection. The application of these techniques to diagnose the SARS-CoV-2 virus is also reviewed. Supplementary Information: The online version contains supplementary material available at 10.1007/s12551-023-01059-4.
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The quenching in luminescence emission of an optically trapped ligand-free hydrophilic NaYF4:Yb, Er upconversion nanoparticle (UCNP) as a function of rose Bengal dye molecule is investigated here. The removal of oleate capping of the as-prepared UCNPs was achieved via acid treatment and characterized via FTIR and Raman spectroscopic techniques. Further, the capping removed hydrophilic single UCNP is optically trapped and the emission studies were carried out as a function of excitation laser power. Compared to the studies using the bulk solution, the single UCNP luminescence spectrum exhibited additional spectral lines. The excitation laser power-dependent studies using the bulk solution yield a slope value between 1 and 2 for Blue, Green 1, Green 2, and Red emission and thus indicate that upconversion is a two-photon upconversion process. On the other hand, in the case of laser power-dependent studies on an optically trapped single-particle study, Blue and Green 1 yield a slope value of less than 1 whereas Green 2 and Red emission gave a slope value between 1 and 2. The energy transfer studies between an optically trapped ligand-free single UCNP and the rose Bengal dye show a concentration-dependent quenching in the emission of Green emissions and illustrate the potential of developing sensor platforms.
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Wettability-tailored tracks are emerging as an efficient approach to collecting and transporting underwater air bubbles as well as water from the mist. However, tailoring the surface wettability by modifying the surface structural features via physiochemical methods to create superhydrophilic-superhydrophobic contrast tracks suffers from long-term durability issues, while the emerging liquid-infused slippery surface has inherent design engineering limitations and issues from infused oil depletion. Herein, we demonstrate that by selective silicone oil grafting onto the glass substrate, it is possible to create a wettability contrast of â¼ 43°. Further, we illustrate the application of such tracks for underwater air bubble capturing and transportation in an aqueous medium with surface tension ranging from 72 to 43.5 mN/m. In addition, the potential of these nonadhesive and adhesive tracks for water collection from the mist is shown and the critical effect of the track dimension and intertrack spacing on the water harvesting rate is investigated in detail. The study illustrates that the nonadhesive nature of the oil-grafted region enables the easy transport of underwater air bubbles as well as water from the flow medium and thus offers an easy and facile approach to creating substrates for underwater air bubble collection and water harvesting.
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The selective ultra-sensitive detection of a very low concentration of analyte in a liquid environment using surface-enhanced Raman spectroscopy (SERS) is a challenging task owing to the poor reproducibility of the Raman signals arising from the nonstationary nature of the substrate. However, plasmonic metal particle-incorporated microparticles can be effectively 3-D arrested in a liquid environment that can serve as a stable SERS substrate by employing an optical trapping force. Herein, we demonstrate a 3-D optically trapped Au-attached SiO2 microparticle as an efficient SERS substrate that can detect 512 pM for Rhodamine6G and 6.8 pM for crystal violet. Further, the substrate allows the simultaneous detection of multiple analytes. By utilizing the Raman signal from Rhodamine 6G as the probe beam, the selective detection of Hg2+ ions as low as 100 pM is demonstrated.
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Droplet splitting by exploiting tailored surface wettability is emerging as an important pathway to creating ultralow volumes of samples that can have applications in bioassays, tissue engineering, protein chips, and material synthesis. Reduction of droplet volumes enables the encapsulation of single biological cells which allows high throughput screening. In this work, we demonstrate a facile fabrication approach to create a non-adhesive contrast quartz substrate that allows droplet splitting under gravitational force and its utilization to trap single biological cells for Raman spectroscopic studies. The non-adhesive contrast surface is created by low-power continuous-wave laser-assisted removal of the region of interest from a biocompatible non-adhesive silicone oil grafted quartz substrate. For a given laser spot dimension, the hydrophilic zone dimension is controlled via irradiation with varying laser powers. The fabricated non-adhesive contrast surface can split a microliter droplet into pico- and sub-picolitre daughter droplets. By using the substrate, the trapping of a single polystyrene bead is demonstrated and the recording of Raman spectra is carried out. Additionally, the Raman spectra of two biological cells, yeast cells and human mononuclear cells (MNCs), from a daughter droplet are recorded independently and from a mixture of the solutions. This single-cell Raman analysis could find applications in cell identification and type discrimination, biochemical imaging, metabolic and functional characterization, and clinical and toxicity studies.
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Poliestirenos , Quartzo , Humanos , Óleos de Silicone , Análise Espectral Raman/métodos , Molhabilidade , Análise de Célula Única/métodosRESUMO
In this study, hydrophilic activated carbon has been prepared and used to synthesize innovative activated carbon/polysulfone mixed matrix membranes (MMMs). These membranes were investigated in terms of membrane morphology, hydrophilicity, antifouling ability, and metal ions rejection. The activated carbon (AC) was prepared from a simple chemical activation method using Rhizophora mucronata propagules, which are rich in aerenchyma cells and possess a high surface area. The hydrophilicity of the MMMs is enhanced by the incorporation of activated carbon, which is confirmed by the measurement of equilibrium water contact angle, water uptake and pure water flux. The optimized concentration of 0.625 wt% activated carbon (A2) incorporated mixed matrix membrane exhibits better rejection efficiencies of 98 ± 0.5%, 99 ± 0.5%, 92 ± 2%, and 44 ± 1% for Pb+2, Cd+2, Hg+2, and F- with the permeate flux of 28.27, 31.88, 33.21, 43.82 L/m2/h, respectively. The fabricated mixed matrix membranes demonstrated an excellent flux recovery ratio and reversible fouling, when filtrating a mixed feed solution containing 200 ppm BSA, 10 ppm Pb+2 and 10 ppm Cd+2. The optimized A2 membrane showed excellent long-term stability up to 120 h without compromising in permeate flux and rejection efficiency. Finally, a numerical investigation using a usual transport model has shown that dielectric exclusion was the most probable mechanism that can physically explain experimental trends.
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Rhizophoraceae , Águas Residuárias , Cádmio , Carvão Vegetal , Descontaminação , Chumbo , Membranas Artificiais , ÁguaRESUMO
Anisotropic rare earth ion (RE3+) doped fluoride upconversion particles are emerging as potential candidate in diverse areas, ranging from biomedical imaging to photonics. Here, we develop a facile strategy to synthesize NaYF4: Yb, Gd, Er, and NaYF4: Yb, Gd, Tm upconversion nanorods via microwave synthesis route by controlling the synthesis time and compared the optical properties similar nanorods prepared via solvothermal technique. With the increase in synthesis time, the phase of the particle found to change from mixed phase to purely hexagonal and morphology of the particles change mixed phase of spherical and rod-shaped particles to completely nanorods for a synthesis time of 60 min. Further, the intrinsically hydrophobic particles changed to hydrophilic by removal of oleic capping via acid treatment and the amine functionalized silica coating. The upconversion luminescence as well as laser power dependent emission properties of the surface modified particles elucidate that surface modification route influence the upconversion luminescence as well as solvent dependent emission properties. Moreover, the laser power dependent studies elucidate that the upconversion process in a multi-photon process.
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Luminescência , Nanotubos , Fluoretos , Micro-Ondas , Nanotubos/química , Dióxido de SilícioRESUMO
The fabrication of a thick oxide layer onto an aluminum surface via anodization has been a subject of intense research activity for more than a century, largely due to protective and decorative applications. The capability to create well-defined pores via a cost-effective electrochemical oxidation technique onto the surface has made a major renaissance in the field, as the porous surfaces exhibit remarkably different properties compared to a bulk oxide layer. Amongst the various nanoporous structures being investigated, nanoporous anodic alumina (NAA) with well-organized and highly ordered hexagonal honeycomb-like pores has emerged as the most popular nanomaterial due to its wide range of applications, ranging from corrosion resistance to bacterial repelling surfaces. As compared to conventional nanostructure fabrication, the electrochemical anodization route of NAA with well-controlled pore parameters offers an economical route for fabricating nanoscale materials. The review comprehensively reflects the progress made in the fabrication route of NAA to obtain the material with desired pore properties, with a special emphasis on self-organization and pore growth kinetics. Detailed accounts of the various conditions that can play an important role in pore growth kinetics and pore parameters are presented. Further, recent developments in the field of controlling optical properties of NAA are discussed. A critical outlook on the future trends of the fabrication of NAA and its optical properties on the emerging nanomaterials, sensors, and devices are also outlined.
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The advances in the synthesis of nanoparticles with engineered properties are reported to have profound applications in oncological disease detection via optical and multimodal imaging and therapy. Among the various nanoparticle-assisted imaging techniques, engineered fluorescent nanoparticles show great promise from high contrast images and localized therapeutic applications. Of all the fluorescent nanoparticles available, the gold nanoparticles, carbon dots, and upconversion nanoparticles are emerging recently as the most promising candidates for diagnosis, treatment, and cancer monitoring. This review addresses the recent progress in engineering the properties of these emerging nanoparticles and their application for cancer diagnosis and therapy. In addition, the potential of these particles for subcellular imaging is also reviewed here.