Upconverting nanoparticles for pre‐clinical diffuse optical imaging,microscopy and sensing: Current trends and future challenges

Upconverting nanoparticles (UCNPs) are a class of recently developed luminescent biomarkers that – in several aspects – are superior to organic dyes and quantum dots. UCNPs can emit spectrally narrow anti‐Stokes shifted light with quantum yields which greatly exceed those of two‐photon dyes for fluence rates relevant for deep tissue imaging. Compared with conventionally used Stokes‐shifting fluorophores, UCNP‐based imaging systems can acquire completely autofluorescence‐free data with superb contrast. For diffuse optical imaging, the multi‐photon process involved in the upconversion process can be used to obtain images with unprecedented resolution. These unique properties make UCNPs extremely attractive in the field of biophotonics. UCNPs have already been applied in microscopy, small‐animal imaging, multi‐modal imaging, highly sensitive bioassays, temperature sensing and photodynamic therapy. In this review, the current state‐of‐the‐art UCNPs and their applications for diffuse imaging, microscopy and sensing targeted towards solving essential biological issues are discussed.     

Long‐Term Colloidal and Chemical Stability in Aqueous Media of NaYF4‐Type Upconversion Nanoparticles Modified by Ligand‐Exchange

Surface capping is an essential component of nanoparticles as it provides access to their outstanding properties in the real world. Upconversion nanoparticles are predominantly interesting for use in biological environments, due to their excellent optical properties such as the conversion of near‐infrared excitation light into emissions in the visible or UV range of the spectrum, high photostability, and the absence of any intermittence. One of the most efficient upconversion nanoparticles, consisting of lanthanide doped NaYF₄, suffers from limited stability in aqueous media. This study investigates a set of five types of surface coatings, ranging from small ligands to polymers of different charge and different coordinating groups, on monodisperse 28 ± 0.9 nm sized NaYF₄(Yb,Er) nanoparticles modified by a two‐step ligand exchange mediated by NOBF₄. Information on the long‐term chemical and colloidal stability for highly diluted aqueous dispersions of these particles is acquired by transmission electron microscopy, dynamic light scattering, and luminescence spectroscopy. The findings are of importance for the development of probes and labels based on upconversion nanoparticles for biological applications.     

Copper‐Based Nanomaterials for High‐Performance Lithium‐Ion Batteries

With the increasing energy demands for electronic devices and electrical vehicles, anode materials for lithium‐ion batteries with high specific capacity, good cyclic and rate performance become one of the focal areas of research. A class of them is the copper‐based nanomaterials that have thermal and chemical stability, high theoretical specific capacity, low price and environment friendliness. Now this kind of nanomaterials has been recognized as one of the critical materials for lithium‐ion batteries due to the predicted future market growth. Current status of different copper‐based materials which produced already are discussed. In this review, comprehensive summaries and evaluations are given in synthesis strategies, tailored material properties and different electrochemical performance. Recent progress of general copper‐based nanomaterials for lithium‐ion batteries is carefully presented.     

Recent Advancements in Bulk Metallic Glasses and Their Applications: A Review

Bulk metallic glasses (BMGs), that display extraordinary properties of high strength, corrosion resistance, polymer-like formability, and excellent magnetic properties, are emerging as modern quintessential engineering materials. BMGs have garnered significant research enthusiasm owing to their tremendous technological and scientific standing. In this article, the recent advancements in the field of BMGs and their applications are put in a nutshell. Novel state-of-the-art production routes and nano/microimprinting strategies with salient features capable of circumventing the processing related complexities as well as accelerating modern developments, are briefly summarized. Heterogeneous BMG composite systems that lead to incredible combination of otherwise conflicting properties are highlighted. Biocorrosion studies and recent developments in the field of magnetic BMGs are presented owing to their significance for prospective biomedical and magnetic applications, respectively. In the last section, the current status of BMGs applications in the field of catalysis, biomedical materials, structural materials, functional materials, microelectromechanical systems (MEMS), and micro/macro devices are summed up.     

Chiral Ag and Au Nanomaterials Based Optical Approaches for Analytical Applications

Sensing of chiral compounds has gained great attentions for many decades. Chiral nanomaterials with a greater surface area, optical properties, and stability have however not been well realized in this field. Herein, strategies for the preparation of chiral Ag and Au nanomaterials are focused upon, including Ag and Au nanoparticles conjugated with chiral molecules with/without containing fluorophores, chiral nanoassemblies of Ag and Au nanoparticles, and chiral Ag and Au nanoclusters. The chirality of nanomaterials originates from their core and/or ligand, meanwhile that for nanoassemblies results from their complex spatial configuration. An emphasis is given to circular dichroism, colorimetry/UV–vis absorption, and fluorescence detection modes for sensing enantiomers and achiral analytes using the chiral Ag and Au nanomaterials. Several interesting examples for quantitation of DNA, proteins, peptides, drugs, and pollutants are provided to highlight their potential as sensitive and selective nanomaterials for enantiomer recognition and sensing of achiral analytes. Several important issues to be solved when using chiral nanomaterials for chiral recognition are specified. Some strategies for improving the sensitivity and selectivity of chiral nanomaterials for chiral recognition are suggested. The aim is to bring more attention to the potential of chiral nanomaterials for sensing important analytes such as chiral drugs.     

近红外到近红外Mn2+掺杂NaYF4:Yb3+/Tm3+纳米粒子的制备及其生物成像

在反应温度为200℃、反应时间为8 h的温和条件下,采用水热法合成了近红外到近红外的Mn²⁺掺杂NaYF₄:Yb³⁺/Tm³⁺上转换荧光纳米粒子,再以两亲性聚合物C₁₈PMH-mPEG作为亲水性配体修饰到上转换荧光纳米粒子表面,得到具有水溶性的上转换荧光纳米粒子。然后在980 nm近红外光源激发下,测量了上转换荧光纳米粒子的荧光发射光谱,在（800±10） nm附近,观察到了较强的单近红外光发射（³H₄→³H₆）。对样品进行细胞毒性实验,结果表明制得的水溶性Mn²⁺掺杂NaYF₄:Yb³⁺/Tm³⁺纳米粒子具有良好的生物相容性。并进一步在小鼠体内进行了近红外成像,表明其在生物成像领域将会具有一定的应用前景。     

Red/Near‐Infrared Emissive Metalloporphyrin‐Based Nanodots for Magnetic Resonance Imaging‐Guided Photodynamic Therapy In Vivo

Near‐infrared emissive (NIR) porphyrin‐implanted carbon nanodots (PCNDs or MPCNDs) are prepared by selectively carbonization of free base or metal complexes [M = Zn(II) or Mn(III)] of tetra‐(meso‐aminophenyl)porphyrin in the presence of citric acid. The as‐prepared nanodots exhibit spontaneously NIR emission, small size, good aqueous dispersibility, and favorable biocompatibility characteristic of both porphyrins and pristine carbon nanodots. The subcellular localization experiment of nanodots indicates a lysosome‐targeting feature. And the in vitro photodynamic therapy (PDT) results on HeLa cells indicate the nanodots alone have no adverse effect on tumor cells, but display remarkable photodynamic efficacy upon irradiation. Moreover, MnPCNDs containing paramagnetic Mn(III) ions, which possesses good biocompatibility, NIR luminescence, and magnetic resonance imaging and efficient singlet oxygen production, are further studied in magnetic resonance imaging‐guided photodynamic therapy in vivo.     

Multifunctional Small Molecule Fluorophore for Long‐Duration Tumor‐Targeted Monitoring and Dual Modal Phototherapy

In this work, a specific tumor‐targeted small molecular fluorophore for synchronous long‐duration cancer imaging, photodynamic therapy, and photothermal therapy is synthesized. This novel fluorophore exhibits specific targeting ability in certain tumors (U87MG, MDA‐MB‐231, A549, etc.) based on its inherent structure and efficiently generates local hyperthermia and reactive oxygen species simultaneously for imaging‐guided precise cancer therapy combining the photothermic and photodynamic effects under laser irradiation. Meanwhile, compared to traditional near infrared fluorophore, this novel fluorophore with significantly enhanced stability against photobleaching can prolong the time of tumor imaging and improve the phototherapy efficiency. This work presents a potential strategy to develop small‐molecule‐based cancer theranostic agents for simultaneous cancer targeting, imaging, and therapy.     

Engineering of SERS Substrates Based on Noble Metal Nanomaterials for Chemical and Biomedical Applications

Abstract

Surface-enhanced Raman scattering (SERS) has attracted great interest due to its remarkable enhancement, excellent sensitivity, and the “fingerprinting” ability to produce distinct spectra for detecting various molecules. Noble metal nanomaterials have usually been employed as SERS-active substrates because of their strong SERS enhancement originated from their unique surface plasmon resonance (SPR) properties. Because the SPR property depends on metal material's size, shape, morphology, arrangement, and dielectric environment around metal nanostructures, the key to wider applications of SERS technique is to develop plasmon-resonant structures with novel geometries to enhance Raman signals and to control the periodic ordering of these structures over a large area to obtain reproducible Raman enhancement. This review presents a general view on the theory background of SERS effect and several basic concepts and focuses on recent progress in engineering metallic nanostructures with various morphologies using versatile methods for improving SERS properties. Their potential applications in the field of chemical detection and biological sensing are overviewed.     

Carbon Dots‐Cluster‐DOX Nanocomposites Fabricated by a Co‐Self‐Assembly Strategy for Tumor‐Targeted Bioimaging and Therapy

Carbon‐based nanomaterials could afford versatile potential applications in biomedical optical imaging and as nanoparticle drug carriers, owing to their promising optical and biocompatible capabilities. In this paper, it is first found that amphipathic cetylpyridinium chloride (CPC)‐stabilized oil‐soluble carbon dots (CDs) could self‐assemble into hydrophilic CDs clusters with hydrophobic core under ultrasound, in which CPC acts as carbon source, stabilizer, and phase transfer agent. Next, the size‐control (for size‐dependent passive tumor targeting) and doxorubicin (DOX) uploading of aqueous CDs clusters, and subsequent surface charge modification via overcoating with cRGD‐ and octylamine‐modified polyacrylic acid (cRGD‐PAA‐OA) (reversing their surface charges into negative and introducing active tumor‐targeting ability) are explored systematically. Based on this sequential administration mode, CDs‐cluster‐DOX/cRGD‐PAA‐OA nanocomposites exhibit selective human malignant glioma cell line (U87MG) tumor targeting. In in vitro drug release experiments, the nanocomposites could release DOX timely. Owning to the dual tumor targeting effects and seasonable drug release, CDs‐cluster‐DOX/cRGD‐PAA‐OA show remarkably tumor targetability and enhanced antitumor efficacy (and reduced adverse reaction), comparing to free DOX in animal models. These results indicate that fabricating nanocomposite via co‐self‐assembly strategy is efficient toward drug delivery system for tumor‐targeting theranostic.     

Graphene and Graphene‐Based Materials in Biomedical Science

Graphene and its composite materials are very important in many disciplines of science and have been used enormously by researchers since their discovery in 2004. These are a new group of compounds, and are also wonderful model systems for quantum behavior studies. Their properties like exceptional conductivity, biocompatibility, surface area, mechanical strength, and thermal properties make them rising stars in the scientific community. Graphene and its composite compounds are utilized widely in different medical applications, for example, biosensing of biological compounds responsible for disease development, bioimaging of various cells, tissues, microorganisms, animal models, etc. In addition, they are used for enhancing and supporting the stem cell differentiation, i.e., regenerative medicine for regeneration studies of various human organs, tissue engineering in biology for the development of carrier materials, as well as in bone reformation. This review focuses on the modification procedure involved in the fabrication of graphene‐based biomaterials for various applications and recent developments in research related to graphene and graphene‐based materials in biosensing, optical sensing, gas sensing, drug, gene, protein delivery, tissue engineering, and bioimaging. In addition, the potential toxicological effects of graphene‐based biomaterials are discussed.     

Anthracene‐Based Colloidal Polymer Nanoparticles: Their Photochemical Ligation and Waterborne Coating Applications

In the current work, a linear polymer, with anthracene moieties in the side chain, is prepared via step‐growth polymerization using epoxide‐amine ring opening reaction. The polymer is dispersed in water to form physically crosslinked nanoparticles (NPs), which are formed by π–π stacking of anthracene moieties. Later, the NPs are crosslinked using UV irradiation, where the anthracene units in the core are simply dimerized and crosslinked the individual chain. In this process, no significant interparticle crosslinking is observed. The higher structural integrity of the chemically crosslinked Nps is revelled via a simple swelling test. The colloidal solution is used to coat glass and silica surfaces homogeneously, which enhances the surface roughness significantly as revealed by atomic force microscope and contact angle measurements.     

State‐of‐the‐Art and Trends in Synthesis,Properties, and Application of Quantum Dots‐Based Nanomaterials

Quantum dots (QDs) with a nanoscale size range have attracted significant attention in various areas of nanotechnology due to their unique properties. Different strategies for the synthesis of QD nanoparticles are reported in which various factors, such as size, impurities, shape, and crystallinity, affect the QDs fundamental properties. Consequently, to obtain QDs with appropriate physical properties, it is required to select a synthesis method which allows enough control over the surface chemistry of QDs through fine‐tuning of the synthesis parameters. Moreover, QDs nanocrystals are recently used in multidisciplinary research integrated with biological interfaces. The state‐of‐the‐art methods for synthesizing QDs and bioconjugation strategies to provide insight into various applications of these nanomaterials are discussed herein.     

Recent Advances in the Applications of Nanotechnology and Nanomaterials in the Petroleum Industry: A Descriptive Review

Nanotechnology applications are rapidly expanding in various fields because of its unique qualities, such as a large surface area. Also, the synthetic changes can be utilized to alter nanomaterial to fit into specialized necessities. From the last decade there is a tremendous increase in the utilization of nanotechnology and nanomaterials in the petroleum industry. The current review's main objective is to summarize numerous nanoparticle applications in the field of petroleum, bio-fuel formation, and clean-up treatments of oil spill-related issues with their existing challenges that may help improve further research.     

Synthesis of Blue‐, Green‐, Yellow‐, and Red‐Emitting Graphene‐Quantum‐Dot‐Based Nanomaterials with Excitation‐Independent Emission

A one‐pot method is described for the preparation of graphene quantum dots/graphene oxide (GQDs/GO) hybrid composites with emission in the visible region, through heteroatom doping and hydroxyl‐radical‐induced decomposition of GO. The NH₄OH‐ and thiourea‐mediated dissociation of H₂O₂ produces hydroxyl radicals. Treatment of GO with hydroxyl radicals results in the production of small‐sized GO sheets and GQDs, which self‐assemble to form GQDs/GO through strong π–π interactions. For example, the reaction of GO with a mixture of NH₄OH and H₂O₂ for 40, 120, and 270 min generates yellow‐emitting GQDs/GO (Y‐GQDs/GO), green‐emitting GQDs/GO, and blue‐emitting GQDs, while red‐emitting GQDs/GO (R‐GQDs/GO) are prepared by incubating GO with a mixture of thiourea and H₂O₂. From the analysis of these four GQD‐based nanomaterials by transmission electron microscopy, atomic force microscopy, and fluorescence lifetime spectroscopy, it is found that this tunable fluorescence wavelength results from the differences in particle size. All four GQD‐based nanomaterials exhibit moderate quantum yields (1–10%), nanosecond fluorescence lifetimes, and excitation‐independent emissions. Except for R‐GQDs/GO, the other three GQD‐based nanomaterials are stable in a high‐concentration salt solution (e.g., 1.6 m NaCl) and under high‐power irradiation, enabling the sensitive (high‐temperature resolution and large activation energy) and reversible detection of temperature change. It is further demonstrated that Y‐GQD/GO can be used to image HeLa cells.     

Localized Surface Plasmon Resonance Enhanced Singlet Oxygen Generation and Light Absorption Based on Black Phosphorus@AuNPs Nanosheet for Tumor Photodynamic/Thermal Therapy

Although photodynamic therapy is an efficient therapeutic strategy for cancer treatment, it always suffers from the low singlet oxygen (¹O₂) yields owing to the weak absorption in optical transparent window of biological tissues. Herein, the black phosphorus (BP) nanosheet is integrated with gold nanoparticles (AuNPs) to simultaneously enhance the singlet oxygen generation and hyperthermia by localized surface plasmon resonance (LSPR) in cancer therapy. In the design, BP nanosheet employed as two‐dimension (2D) inorganic photosensitizer is hybridized with AuNPs through polyetherimide (PEI) as bridge to form BP‐PEI/AuNPs hybrid nanosheet. Such hybridation not only significantly increases the ¹O₂ production of BP nanosheet through maximizing the local field enhancement of AuNPs, but also significantly enhances the light absorption of BP nanosheet to promote photothermal effect by LSPR. Accordingly, about 3.9‐fold enhancement of ¹O₂ production and 1.7‐fold increasement of photothermal conversion efficiency are achieved compared with BP‐PEI alone upon single 670 nm laser irradiation. As a proof‐of‐concept model, BP‐PEI/AuNPs hybrid nanosheet with simultaneous dual‐modal phototherapy functions result in effective suppression of tumor growth with minimized side effects both in vitro and in vivo, indicating the great potential of the BP‐PEI/AuNPs hybrid nanosheet as an effective strategy to enhance the cancer therapy efficiency.     

Ion‐ and positron‐acoustic solitons in magnetized dusty plasma with q‐non‐extensive electron and positron velocity distribution

In this study, the properties of ion‐ and positron‐acoustic solitons are investigated in a magnetized multi‐component plasma system consisting of warm fluid ions, warm fluid positrons, q‐non‐extensive distributed positrons, q‐non‐extensive distributed electrons, and immobile dust particles. To drive the Korteweg–de Vries (KdV) equation, the reductive perturbation method is used. The effects of the ratio of the density of positrons to ions, the temperature of the positrons, and ions to electrons, the non‐extensivity parameters q_e and q_p , and the angle of the propagation of the wave with the magnetic field on the potential of ion‐ and positron‐acoustic solitons are also studied. The present investigation is applicable to solitons in fusion plasmas in the edge of tokamak.     

Recent Advances in Common Transition Metal-Based Single-Atom Nanozymes and Their Applications in Pollutant Detection and Degradation

Nanozymes can be used as favorable substitutes for natural enzymes because of their strong catalytic activity and good stability. At the same time, research on single-atom catalysts (SACs) with isolated metal atoms as active centers is also in full swing, showing excellent performance in a variety of catalytic reactions. With the in-depth study of SACs, people have a comprehensive understanding of them and put forward the concept of single-atom nanozymes (SAzymes) by combining nanozymes with SACs. As a new type of nanomaterial, SAzymes have attracted great interest due to their remarkable catalytic activity and rapid energy conversion. However, most applications of SAzymes are mainly in the fields of biomedicine and biosensing, and less research has been done in the field of the environment. Based on the amazing ability of nanozymes to detect and degrade pollutants, SAzymes are also used in the environmental field, and even they will show better capabilities. This review mainly analyses common transition metal-based SAzymes and describes their applications in the field of environmental pollutants.