Photoacoustic Imaging: Contrast Agents and Their Biomedical Applications

Photoacoustic (PA) imaging as a fast‐developing imaging technique has great potential in biomedical and clinical applications. It is a noninvasive imaging modality that depends on the light‐absorption coefficient of the imaged tissue and the injected PA‐imaging contrast agents. Furthermore, PA imaging provides superb contrast, super spatial resolution, and high penetrability and sensitivity to tissue functional characteristics by detecting the acoustic wave to construct PA images. In recent years, a series of PA‐imaging contrast agents are developed to improve the PA‐imaging performance in biomedical applications. Here, recent progress of PA contrast agents and their biomedical applications are outlined. PA contrast agents are classified according to their components and function, and gold nanocrystals, gold‐nanocrystal assembly, transition‐metal chalcogenides/MXene‐based nanomaterials, carbon‐based nanomaterials, other inorganic imaging agents, small organic molecules, semiconducting polymer nanoparticles, and nonlinear PA‐imaging contrast agents are discussed. The applications of PA contrast agents as biosensors (in the sensing of metal ions, pH, enzymes, temperature, hypoxia, reactive oxygen species, and reactive nitrogen species) and in bioimaging (lymph nodes, vasculature, tumors, and brain tissue) are discussed in detail. Finally, an outlook on the future research and investigation of PA‐imaging contrast agents and their significance in biomedical research is presented.     

Advancements Toward the Greener Processing of Engineered Nanomaterials—Effect of Core Size on the Dispersibility and Transport of Gold Nanocrystals in Near‐Critical Solvents

The ability to process and purify engineered nanomaterials using near critical or supercritical fluids (NcFs or ScFs) has enormous potential for the application at various stages of the development of green nanomaterials. The dispersibility of octanethiol‐stabilized gold nanocrystals of different core sizes is explored, which were chosen to serve as model nanomaterials of general interest in compressed ethane and propane over a wide range of fluid conditions. Both solvents have enormous potential for the environmentally benign processing and transport of engineered nanomaterials due to their nominal toxicity and high degree of tunability and processability that can essentially eliminate solvent waste. The dispersibility is determined by measuring the absorption spectra of dispersions of various sizes of nanocrystals in NcFs. To better understand the obtained results three models, the total interaction theory, the sedimentation coefficient equation, and the Chrastil method, are discussed. Nanoparticle dispersibility versus density plots are strongly dependent on nanoparticle size and solvent conditions, with the dispersion of larger nanocrystals more dependent on changes of pressure or density at a given temperature. For the range of nanoparticle sizes studied, compressed ethane at 25 °C leads to a greater tunability of nanoparticle dispersion when compared with compressed propane at 65 °C. For equivalent pressures, compressed propane is found to provide better solubility than ethane due to its higher density. The results quantitatively demonstrate that NcFs can offer pressure‐tunable, size‐selective control of nanoparticle solvation and transport at easily obtainable temperature and pressure conditions. These capabilities provide clear advantages over conventional solvents and direct application to various nanomaterials processes, such as synthesis, separation, transport, and purification of nanocrystals.     

High Efficiency Organic Solar Cells Achieved by the Simultaneous Plasmon‐Optical and Plasmon‐Electrical Effects from Plasmonic Asymmetric Modes of Gold Nanostars

The plasmon‐optical effects have been utilized to optically enhance active layer absorption in organic solar cells (OSCs). The exploited plasmonic resonances of metal nanomaterials are typically from the fundamental dipole/high‐order modes with narrow spectral widths for regional OSC absorption improvement. The conventional broadband absorption enhancement (using plasmonic effects) needs linear‐superposition of plasmonic resonances. In this work, through strategic incorporation of gold nanostars (Au NSs) in between hole transport layer (HTL) and active layer, the excited plasmonic asymmetric modes offer a new approach toward broadband enhancement. Remarkably, the improvement is explained by energy transfer of plasmonic asymmetric modes of Au NS. In more detail, after incorporation of Au NSs, the optical power in electron transport layer transfers to active layer for improving OSC absorption, which otherwise will become dissipation or leakage as the role of carrier transport layer is not for photon‐absorption induced carrier generation. Moreover, Au NSs simultaneously deliver plasmon‐electrical effects which shorten transport path length of the typically low‐mobility holes and lengthen that of high‐mobility electrons for better balanced carrier collection. Meanwhile, the resistance of HTL is reduced by Au NSs. Consequently, power conversion efficiency of 10.5% has been achieved through cooperatively plasmon‐optical and plasmon‐electrical effects of Au NSs.     

Programmable Construction of Peptide‐Based Materials in Living Subjects: From Modular Design and Morphological Control to Theranostics

Self‐assembled nanomaterials show potential high efficiency as theranostics for high‐performance bioimaging and disease treatment. However, the superstructures of pre‐assembled nanomaterials may change in the complicated physiological conditions, resulting in compromised properties and/or biofunctions. Taking advantage of chemical self‐assembly and biomedicine, a new strategy of “in vivo self‐assembly” is proposed to in situ construct functional nanomaterials in living subjects to explore new biological effects. Herein, recent advances on peptide‐based nanomaterials constructed by the in vivo self‐assembly strategy are summarized. Modular peptide building blocks with various functions, such as targeting, self‐assembly, tailoring, and biofunctional motifs, are employed for the construction of nanomaterials. Then, self‐assembly of these building blocks in living systems to construct various morphologies of nanostructures and corresponding unique biological effects, such as assembly/aggregation‐induced retention (AIR), are introduced, followed by their applications in high‐performance drug delivery and bioimaging. Finally, an outlook and perspective toward future developments of in vivo self‐assembled peptide‐based nanomaterials for translational medicine are concluded.     

Scanning electron microscopy imaging of single-walled carbon nanotubes on substrates

Scanning electron microscopy (SEM) plays an indispensable role in nanoscience and nanotechnology because of its high efficiency and high spatial resolution in characterizing nanomaterials.Recent progress indicates that the contrast arising from different conductivities or bandgaps can be observed in SEM images if single-walled carbon nanotubes (SWCNTs) are placed on a substrate.In this study,we use SWCNTs on different substrates as model systems to perform SEM imaging of nanomaterials.Substantial SEM observations are conducted at both high and low acceleration voltages,leading to a comprehensive understanding of the effects of the imaging parameters and substrates on the material and surface-charge signals,as well as the SEM imaging.This unified picture of SEM imaging not only furthers our understanding of SEM images of SWCNTs on a variety of substrates but also provides a basis for developing new imaging recipes for other important nanomaterials used in nanoelectronics and nanophotonics.     

Charge Transfer from Carbon Nanotubes to Silicon in Flexible Carbon Nanotube/Silicon Solar Cells

Mechanical fragility and insufficient light absorption are two major challenges for thin flexible crystalline Si‐based solar cells. Flexible hybrid single‐walled carbon nanotube (SWNT)/Si solar cells are demonstrated by applying scalable room‐temperature processes for the fabrication of solar‐cell components (e.g., preparation of SWNT thin films and SWNT/Si p–n junctions). The flexible SWNT/Si solar cells present an intrinsic efficiency ≈7.5% without any additional light‐trapping structures. By using these solar cells as model systems, the charge transport mechanisms at the SWNT/Si interface are investigated using femtosecond transient absorption. Although primary photon absorption occurs in Si, transient absorption measurements show that SWNTs also generate and inject excited charge carriers to Si. Such effects can be tuned by controlling the thickness of the SWNTs. Findings from this study could open a new pathway for designing and improving the efficiency of photocarrier generation and absorption for high‐performance ultrathin hybrid SWNT/Si solar cells.     

基于SEM图像的低维纳米材料自动分类方法

针对传统方法在低维纳米材料形貌检测和分类鉴别方面的不足,提出了一种基于扫描电子显微镜（SEM）图像的低维纳米材料自动分类方法．以纳米材料的SEM图像为基础,利用小波包分解技术对材料表面纹理特征进行提取,通过将纹理特征与支持向量机（SVM）相结合,实现了纳米材料的自动分类．该方法具有检测速度快、精度高、无损耗等诸多优点,可用于纳米材料大规模生产中的自动检测．对16种不同类别材料的SEM图像仿真结果表明,该方法的分类精度能够达到93．75％,证明了其在实际工程中的有效性．     

Two‐Dimensional Nanomaterials for Biomedical Applications: Emerging Trends and Future Prospects

Two‐dimensional (2D) nanomaterials are ultrathin nanomaterials with a high degree of anisotropy and chemical functionality. Research on 2D nanomaterials is still in its infancy, with the majority of research focusing on elucidating unique material characteristics and few reports focusing on biomedical applications of 2D nanomaterials. Nevertheless, recent rapid advances in 2D nanomaterials have raised important and exciting questions about their interactions with biological moieties. 2D nanoparticles such as carbon‐based 2D materials, silicate clays, transition metal dichalcogenides (TMDs), and transition metal oxides (TMOs) provide enhanced physical, chemical, and biological functionality owing to their uniform shapes, high surface‐to‐volume ratios, and surface charge. Here, we focus on state‐of‐the‐art biomedical applications of 2D nanomaterials as well as recent developments that are shaping this emerging field. Specifically, we describe the unique characteristics that make 2D nanoparticles so valuable, as well as the biocompatibility framework that has been investigated so far. Finally, to both capture the growing trend of 2D nanomaterials for biomedical applications and to identify promising new research directions, we provide a critical evaluation of potential applications of recently developed 2D nanomaterials.     

Production of Two‐Dimensional Nanomaterials via Liquid‐Based Direct Exfoliation

Tremendous efforts have been devoted to the synthesis and application of two‐dimensional (2D) nanomaterials due to their extraordinary and unique properties in electronics, photonics, catalysis, etc., upon exfoliation from their bulk counterparts. One of the greatest challenges that scientists are confronted with is how to produce large quantities of 2D nanomaterials of high quality in a commercially viable way. This review summarizes the state‐of‐the‐art of the production of 2D nanomaterials using liquid‐based direct exfoliation (LBE), a very promising and highly scalable wet approach for synthesizing high quality 2D nanomaterials in mild conditions. LBE is a collection of methods that directly exfoliates bulk layered materials into thin flakes of 2D nanomaterials in liquid media without any, or with a minimum degree of, chemical reactions, so as to maintain the high crystallinity of 2D nanomaterials. Different synthetic methods are categorized in the following, in which material characteristics including dispersion concentration, flake thickness, flake size and some applications are discussed in detail. At the end, we provide an overview of the advantages and disadvantages of such synthetic methods of LBE and propose future perspectives.     

Self‐Assembled Peptide‐Based Nanomaterials for Biomedical Imaging and Therapy

Peptide‐based materials are one of the most important biomaterials, with diverse structures and functionalities. Over the past few decades, a self‐assembly strategy is introduced to construct peptide‐based nanomaterials, which can form well‐controlled superstructures with high stability and multivalent effect. More recently, peptide‐based functional biomaterials are widely utilized in clinical applications. However, there is no comprehensive review article that summarizes this growing area, from fundamental research to clinic translation. In this review, the recent progress of peptide‐based materials, from molecular building block peptides and self‐assembly driving forces, to biomedical and clinical applications is systematically summarized. Ex situ and in situ constructed nanomaterials based on functional peptides are presented. The advantages of intelligent in situ construction of peptide‐based nanomaterials in vivo are emphasized, including construction strategy, nanostructure modulation, and biomedical effects. This review highlights the importance of self‐assembled peptide nanostructures for nanomedicine and can facilitate further knowledge and understanding of these nanosystems toward clinical translation.     

Stimuli‐Responsive Optical Nanomaterials

Responsive optical nanomaterials that can sense and translate various external stimuli into optical signals, in the forms of observable changes in appearance and variations in spectral line shapes, are among the most active research topics in nanooptics. They are intensively exploited within the regimes of the four classic optical phenomena—diffraction in photonic crystals, absorption of plasmonic nanostructures, as well as color‐switching systems, refraction of assembled birefringent nanostructures, and emission of photoluminescent nanomaterials and molecules. Herein, a comprehensive review of these research activities regarding the fundamental principles and practical strategies is provided. Starting with an overview of their substantial developments during the latest three decades, each subtopic discussion is led with fundamental theories that delineate the correlation between nanostructures and optical properties and the delicate research strategies are elaborated with specific attention focused on working principles and optical performances. The unique advantages and inherent limitations of each responsive optical nanoscale platform are summarized, accompanied by empirical criteria that should be met and perspectives on research opportunities where the developments of next‐generation responsive optical nanomaterials might be directed.     

One Dimensional Silver‐based Nanomaterials: Preparations and Electrochemical Applications

One dimensional (1D) silver‐based nanomaterials have a great potential in various fields because of their high specific surface area, high electric conductivity, optoelectronic properties, mechanical flexibility and high electro‐catalytic efficiency. In this Review, the preparations of 1D silver‐based nanomaterials is classified by structure composed of simple silver nanowires/rods/belts/tubes, core‐shells, and hybrids. The latest applications based on 1D silver nanomaterials and their composite materials are summarized systematically including electrochemical capacitors, lithium‐ion/lithium‐oxygen batteries, electrochemical sensors and electrochemical catalysis. The preparation process, tailored material properties and electrochemical applications are discussed.     

Mobility Deception in Nanoscale Transistors: An Untold Contact Story

Mobility is a critical parameter that is routinely used for benchmarking the performance of field‐effect transistors (FETs) based on novel nanomaterials. In fact, mobility values are often used to champion nanomaterials since high‐performance devices necessitate high mobility values. The current belief is that the contacts can only limit the FET performance and hence the extracted mobility is an underestimation of the true channel mobility. However, here, such misconception is challenged through rigorous experimental effort, backed by numerical simulations, to demonstrate that overestimation of mobility occurs in commonly used geometries and in nanomaterials for which the contact interface, contact doping, and contact geometry play a pivotal role. In particular, dual‐gated FETs based on multilayer MoS₂ and WSe₂ are used as case studies in order to elucidate and differentiate between intrinsic and extrinsic contact effects manifesting in the mobility extraction. The choice of 2D layered transition metal dichalcogenides (TMDCs) as the semiconducting channel is motivated by their potential to replace and/or coexist with Si‐based aging FET technologies. However, the results are equally applicable to nanotube‐ and nanowire‐based FETs, oxide semiconductors, and organic‐material‐based thin‐film FETs.     

Recent Advances in Managing Atherosclerosis via Nanomedicine

Atherosclerosis, driven by chronic inflammation of the arteries and lipid accumulation on the blood vessel wall, underpins many cardiovascular diseases with high mortality rates globally, such as stroke and ischemic heart disease. Engineered bio‐nanomaterials are now under active investigation as carriers of therapeutic and/or imaging agents to atherosclerotic plaques. This Review summarizes the latest bio‐nanomaterial‐based strategies for managing atherosclerosis published over the past five years, a period marked by a rapid surge in preclinical applications of bio‐nanomaterials for imaging and/or treating atherosclerosis. To start, the biomarkers exploited by emerging bio‐nanomaterials for targeting various components of atherosclerotic plaques are outlined. In addition, recent efforts to rationally design and screen for bio‐nanomaterials with the optimal physicochemical properties for targeting plaques are presented. Moreover, the latest preclinical applications of bio‐nanomaterials as carriers of imaging, therapeutic, or theranostic agents to atherosclerotic plaques are discussed. Finally, a mechanistic understanding of the interactions between bio‐nanomaterials and the plaque (“athero–nano” interactions) is suggested, the opportunities and challenges in the clinical translation of bio‐nanomaterials for managing atherosclerosis are discussed, and recent clinical trials for atherosclerotic nanomedicines are introduced.     

Gold Nanomaterials in Consumer Cosmetics Nanoproducts: Analyses,Characterization, and Dermal Safety Assessment

Establishment of analytical methods of engineered nanomaterials in consumer products for their human and environmental risk assessment becomes urgent for both academic and industrial needs. Owing to the difficulties and challenges around nanomaterials in complex media, proper chemical separation and biological assays of nanomaterials from nanoproducts needs to be firstly developed. Herein, a facile and rapid method to separate and analyze gold nanomaterials in cosmetics is reported. Gold nanomaterials are successfully separated from different facial or eye creams and their physiochemical properties are analyzed by quantitative and qualitative state‐of‐the art techniques with high sensitivity or high spatial resolution. In turn, a protocol including quantification of gold by inductively coupled plasma mass spectrometry and thorough characterization of morphology, size distribution, and surface property by electron microscopes, atomic force microscope, and X‐ray photoelectron spectroscope is developed. Subsequently, the preliminary toxicity assessment indicates that gold nanomaterials in cosmetic creams have no observable toxicity to human keratinocytes even after 24 h exposure up to a concentration of 200 μg mL^?1. The environmental scanning electron microscope reveals that gold nanomaterials are mostly attached on the cell membrane. Thus, the present study provides a full analysis protocol for toxicity assessment of gold nanomaterials in consumer products (cosmetic creams).     

A Water‐Processable and Bioactive Multivalent Graphene Nanoink for Highly Flexible Bioelectronic Films and Nanofibers

The capabilities of conductive nanomaterials to be produced in liquid form with well‐defined chemical, physical, and biological properties are highly important for the construction of next‐generation flexible bioelectronic devices. Although functional graphene nanomaterials can serve as attractive liquid nanoink platforms for the fabrication of bioelectronics, scalable synthesis of graphene nanoink with an integration of high colloidal stability, water processability, electrochemical activity, and especially bioactivity remains a major challenge. Here, a facile and scalable synthesis of supramolecular‐functionalized multivalent graphene nanoink (mGN‐ink) via [2+1] nitrene cycloaddition is reported. The mGN‐ink unambiguously displays a well‐defined and flat 2D morphology and shows good water processability and bioactivity. The uniquely chemical, physical, and biological properties of mGN‐ink endow the constructed bioelectronic films and nanofibers with high flexibility and durability, suitable conductivity and electrochemical activity, and most importantly, good cellular compatibility and a highly efficient control of stem‐cell spreading and orientation. Overall, for the first time, a water‐processable and bioactive mGN‐ink is developed for the design of flexible and electrochemically active bioelectronic composites and devices, which not only presents manifold possibilities for electronic‐cellular applications but also establishes a new pathway for adapting macroscopic usages of graphene nanomaterials in bionic, biomedical, electronic, and even energy fields.     

Functionalization of Hollow Nanomaterials for Catalytic Applications: Nanoreactor Construction

Hollow nanomaterials have attracted a broad interest in multidisciplinary research due to their unique structure and preeminent properties. Owing to the high specific surface area, well‐defined active site, delimited void space, and tunable mass transfer rate, hollow nanostructures can serve as excellent catalysts, supports, and reactors for a variety of catalytic applications, including photocatalysis, electrocatalysis, heterogeneous catalysis, homogeneous catalysis, etc. Based on state‐of‐the‐art synthetic methods and characterization techniques, researchers focus on the purposeful functionalization of hollow nanomaterials for catalytic mechanism studies and intricate catalytic reactions. Herein, an overview of current reports with respect to the catalysis of functionalized hollow nanomaterials is given, and they are classified into five types of versatile strategies with a top‐down perspective, including textual and composition modification, encapsulation, multishelled construction, anchored single atomic site, and surface molecular engineering. In the detailed case studies, the design and construction of hierarchical hollow catalysts are discussed. Moreover, since hollow structure offers more than two types of spatial‐delimited sites, complicated catalytic reactions are elaborated. In summary, functionalized hollow nanomaterials provide an ideal model for the rational design and development of efficient catalysts.     

Au NPs@MoS2 Sub‐Micrometer Sphere‐ZnO Nanorod Hybrid Structures for Efficient Photocatalytic Hydrogen Evolution with Excellent Stability

MoS₂ shows promising applications in photocatalytic water splitting, owing to its uniquely optical and electric properties. However, the insufficient light absorption and lack of performance stability are two crucial issues for efficient application of MoS₂ nanomaterials. Here, Au nanoparticles (NPs)@MoS₂ sub‐micrometer sphere‐ZnO nanorod (Au NPs@MoS₂‐ZnO) hybrid photocatalysts have been successfully synthesized by a facile process combining the hydrothermal method and seed‐growth method. Such photocatalysts exhibit high efficiency and excellent stability for hydrogen production via multiple optical‐electrical effects. The introduction of Au NPs to MoS₂ sub‐micrometer spheres forming a core–shell structure demonstrates strong plasmonic absorption enhancement and facilitates exciton separation. The incorporation of ZnO nanorods to the Au NPs@MoS₂ hybrids further extends the light absorption to a broader wavelength region and enhances the exciton dissociation. In addition, mutual contacts between Au NPs (or ZnO nanorods) and the MoS₂ spheres effectively protect the MoS₂ nanosheets from peeling off from the spheres. More importantly, efficiently multiple exciton separations help to restrain the MoS₂ nanomaterials from photocorrosion. As a result, the Au@MoS₂‐ZnO hybrid structures exhibit an excellent hydrogen gas evolution (3737.4 μmol g^?1) with improved stability (91.9% of activity remaining) after a long‐time test (32 h), which is one of the highest photocatalytic activities to date among the MoS₂ based photocatalysts.     

Nanomaterials for Neural Interfaces

This review focuses on the application of nanomaterials for neural interfacing. The junction between nanotechnology and neural tissues can be particularly worthy of scientific attention for several reasons: (i) Neural cells are electroactive, and the electronic properties of nanostructures can be tailored to match the charge transport requirements of electrical cellular interfacing. (ii) The unique mechanical and chemical properties of nanomaterials are critical for integration with neural tissue as long‐term implants. (iii) Solutions to many critical problems in neural biology/medicine are limited by the availability of specialized materials. (iv) Neuronal stimulation is needed for a variety of common and severe health problems. This confluence of need, accumulated expertise, and potential impact on the well‐being of people suggests the potential of nanomaterials to revolutionize the field of neural interfacing. In this review, we begin with foundational topics, such as the current status of neural electrode (NE) technology, the key challenges facing the practical utilization of NEs, and the potential advantages of nanostructures as components of chronic implants. After that the detailed account of toxicology and biocompatibility of nanomaterials in respect to neural tissues is given. Next, we cover a variety of specific applications of nanoengineered devices, including drug delivery, imaging, topographic patterning, electrode design, nanoscale transistors for high‐resolution neural interfacing, and photoactivated interfaces. We also critically evaluate the specific properties of particular nanomaterials—including nanoparticles, nanowires, and carbon nanotubes—that can be taken advantage of in neuroprosthetic devices. The most promising future areas of research and practical device engineering are discussed as a conclusion to the review.     

Metal‐Containing Polydopamine Nanomaterials: Catalysis,Energy, and Theranostics

Polydopamine (PDA) is a major type of artificial melanin material with many interesting properties such as antioxidant activity, free‐radical scavenging, high photothermal conversion efficiency, and strong metal‐ion chelation. The high affinity of PDA to a wide range of metals/metal ions has offered a new class of functional metal‐containing polydopamine (MPDA) nanomaterials with promising functions and extensive applications. Understanding and controlling the metal coordination environment is vital to achieve desirable functions for which such materials can be exploited. MPDA nanomaterials with metal/metal ions as the active functions are reviewed, including their synthesis and metal coordination environment and their applications in catalysis, batteries, solar cells, capacitors, medical imaging, cancer therapy, antifouling, and antibacterial coating. The current trends, limitations, and future directions of this area are also explored.