Photoactive Hybrid AuNR‐Pt@Ag2S Core–Satellite Nanostructures for Near‐Infrared Quantitive Cell Imaging

The quantitative detection of microRNA (miR) and multimode‐imaging‐induced photothermal therapy in vivo have become the focus of much attention. Platinum (Pt) decorated gold nanorods (AuNR‐Pt) and Ag₂S core–satellite (AuNR‐Pt@Ag₂S) multifunctional nanostructures are fabricated to quantify intracellular miRs (miR‐21), near‐infrared fluorescence cell quantitative imaging, and tumor ablation in vivo. When combined with miR‐21, the nanoassembly displays significant fluorescence intensity in the second window of the near‐infrared region (1000–1700 nm) after 808 nm excitation. The Ag₂S fluorescence intensity has a good linear relationship with the amount of intracellular miR in the range of 0.054–20.45 amol ng_RNA ^?1 and a limit of detection of 0.0082 amol ng_RNA ^?1. The nanoassembly is also used to develop multimodal bioimaging, including near‐infrared, X‐ray computed tomographic, and photoacoustic imaging in HeLa‐tumor‐bearing mice. Moreover, the tumors are completely eliminated by the high photothermal capacity of the AuNR‐Pt@Ag₂S assembly. This nanoassembly provides a multifunctional nanoplatform for the ultrasensitive detection of miRs and tumor diagnosis and therapy in vivo.     

金纳米微粒的光学性质及其在生物成像和光热疗法中的应用

作为生物探针,纳米微粒以其独特的光学性质,易控的表面化学能力,在基于生物成像和诊断的分子生物学和医学领域中引起越来越广泛的关注.贵金属,尤其是金纳米微粒,由于其表面等离子体共振(SPR)等强吸收和发光特性,在生物组织成像,癌症的诊断和治疗中存在着巨大的应用前景.结合配体的金纳米微粒能够特异性地标记癌症细胞上的受体,并提供特定分子的特有信息,进行生物成像和癌症检测.另外,金纳米微粒能够有效地吸收光能量进行局部加热,导致蛋白质变性,并致细胞死亡.主要回顾各种不同尺寸和形状的金纳米微粒的光学特性,以及选择性标记的金纳米微粒在生物成像,癌症诊断和光热疗法中的研究进展.     

High‐Yield Synthesis of Multifunctional Tellurium Nanorods to Achieve Simultaneous Chemo‐Photothermal Combination Cancer Therapy

Tellurium (Te) is an important semiconductor material with low band‐gap energy, which has attracted considerable attention in recent years, due to its special chemical and physical properties and wide potential in electrochemistry, optoelectronics, and biological fields. This study demonstrates a facile and high‐yield synthesis strategy of Te nanorods (PTW‐TeNRs) decorated by polysaccharide–protein complex, which can achieve simultaneous chemo‐photothermal combination therapy against cancers. PTW‐TeNRs alone possess high stability under physiological conditions, potent anticancer activities through induction of reactive oxygen species overproduction, and high selectivity among tumor and normal cells. More importantly, they exhibit strong near‐infrared (NIR) absorbance and good photothermal conversion ability from NIR light to heat energy. Furthermore, in combination with NIR laser irradiation, PTW‐TeNRs exhibit excellent chemo‐photothermal efficiency and low toxicity as evidenced by highly efficient tumor ablation ability, but show no obvious histological damage to the major organs. Taken together, this study provides a valid tactic for facile synthesis of multifunctional tellurium nanorods for efficient and combinational cancer therapy.     

Effective Eradication of Tumors by Enhancing Photoacoustic-Imaging-Guided Combined Photothermal Therapy and Ultrasonic Therapy

Exploiting a comprehensive strategy that processes diagnosis and therapeutic functions is desired for eradicating tumors. In this study, two versatile nanoparticles are introduced: one is polyethylene glycol- and polyethyleneimine-modified gold nanorods (mPEG–PEI–AuNRs), and the other is formed by electrostatic interactions between mPEG–PEI and calcium carbonate nanoparticles (mPEG–PEI/CaNPs). These two nanoparticles possess following favorable properties: 1) mPEG–PEI–AuNRs and mPEG–PEI/CaNPs show not only high cell uptake in acidic tumoral pH, but also efficient accumulation in tumors with prolonged circulation. 2) mPEG–PEI/CaNPs can generate carbon dioxide (CO₂) bubbles in acidic tumoral environment and the photoacoustic (PA) signals from mPEG–PEI–AuNRs can be enhanced with the generation of CO₂ bubbles. 3) The tumors can be eradicated by combining photothermal therapy (PTT) with ultrasonic therapy (UST) under the near-infrared (NIR) laser and ultrasonic irradiation with the presence of mPEG–PEI–AuNRs and CO₂ bubbles from mPEG–PEI/CaNPs. The detailed evaluation of cellular uptake, photothermal property of mPEG–PEI–AuNRs, CO₂ bubbles’ generation from mPEG–PEI/CaNPs, imaging, and combined PTT and UST are carried out in vitro or in vivo. This work has great potential usage for diagnosis and treatment in the future.     

Reversible and Rapid Laser Actuation of Liquid Crystalline Elastomer Micropillars with Inclusion of Gold Nanoparticles

It is highly desirable for liquid crystal elastomer (LCE) based microactuators to activate and actuate in a highly controlled fashion without perturbing the surrounding environment. To reach this goal, in this study, a novel experimental protocol is developed to successfully incorporate gold nanosphere (AuNS) and gold nanorod (AuNR) into polyacrylate based LCE elastomer to fabricate LCE/AuNR and LCE/AuNS micropillars or microactuators. The effect of gold nanoparticle inclusion has been studied by spectroscopy (UV–vis‐near‐infrared), microscopy (transmission electron microscopy), thermal analysis (differential scanning calorimetry and thermogravimetric analysis), and x‐ray scattering (wide‐angle x‐ray scattering and small‐angle x‐ray scattering). Finite element analysis is performed to examine the feasibility of utilizing the photothermal effect of AuNR/AuNS to enable photothermal actuation of LCE/AuNR and LCE/AuNS micropillars. The comparative experimental studies on the thermal and photothermal actuation behavior of the LCE, LCE/AuNS, and LCE/AuNR micropillar suggested that AuNR is an excellent candidate for developing high‐performance LCE actuators with photothermal actuation capability. With inclusion of less than 1 wt% of AuNR, the very high maximum actuation strain (30%) and rapid response (a few seconds) have been achieved in LCE/AuNR micropillar actuators under 635 nm laser irradiation.     

Pillar[5]arene-Modified Gold Nanorods as Nanocarriers for Multi-Modal Imaging-Guided Synergistic Photodynamic-Photothermal Therapy

Supramolecular approaches have opened up vast possibilities to construct versatile materials, especially those with stimuli-responsiveness and integrated functionalities of multi-modal diagnosis and synergistic therapeutics. In this study, a hybrid theranostic nanosystem named TTPY-Py⊂CP5@AuNR is constructed via facile host–guest interactions, where TTPY-Py is a photosensitizer with aggregation-induced emission and CP5@AuNR represents the carboxylatopillar[5]arene (CP5)-modified Au nanorods. TTPY-Py⊂CP5@AuNR integrates the respective advantages of TTPY-Py and CP5@AuNR such as the high performance of reactive oxygen species generation and photothermal conversion, and meanwhile shows fluorescence responses to both temperature and pH stimuli. The successful modification of CP5 macrocycles on AuNRs surfaces can eliminate the cytotoxicity of AuNRs and enable them to serve as the nanocarrier of TTPY-Py for further theranostic applications. Significantly, in vitro and in vivo evaluations demonstrate that this supramolecular nanotheranostic system possesses multiple modalities including intensive fluorescence imaging (FLI), photoacoustic imaging (PAI), efficient photodynamic therapy (PDT), and photothermal therapy (PTT), indicating its great potential for FLI-PAI imaging-guided synergistic PDT-PTT therapy. Moreover, TTPY-Py can be released upon activation by the acidic environment of lysosomes and then specifically light up mitochondria. This study demonstrates a new strategy for the design of versatile nanotheranostics for accurate tumor imaging and cancer therapies.     

Gold‐Coated Fe3O4 Nanoroses with Five Unique Functions for Cancer Cell Targeting,Imaging, and Therapy

The development of nanomaterials that combine diagnostic and therapeutic functions within a single nanoplatform is extremely important for molecular medicine. Molecular imaging with simultaneous diagnosis and therapy will provide the multimodality needed for accurate diagnosis and targeted therapy. Here, gold‐coated iron oxide (Fe₃O₄@Au) nanoroses with five distinct functions are demonstrated, integrating aptamer‐based targeting, magnetic resonance imaging (MRI), optical imaging, photothermal therapy. and chemotherapy into one single probe. The inner Fe₃O₄ core functions as an MRI agent, while the photothermal effect is achieved through near‐infrared absorption by the gold shell, causing a rapid rise in temperature and also resulting in a facilitated release of the anticancer drug doxorubicin carried by the nanoroses. Where the doxorubicin is released, it is monitored by its fluorescence. Aptamers immobilized on the surfaces of the nanoroses enable efficient and selective drug delivery, imaging, and photothermal effect with high specificity. The five‐function‐embedded nanoroses show great advantages in multimodality.     

Folic‐Acid‐Mediated Functionalized Gold Nanocages for Targeted Delivery of Anti‐miR‐181b in Combination of Gene Therapy and Photothermal Therapy against Hepatocellular Carcinoma

Therapeutic strategies based on modulation of microRNAs (miRNAs) activity hold much promise for cancer therapy, but for clinical applications, the efficient delivery of miRNAs to tumor cells or tumor tissues remains a great challenge. In this work, microRNA‐181b inhibitor (anti‐miR‐181b) is successfully condensed into polyethyleneimine (PEI)‐modified and folate receptor (FR)‐targeted PEGylated gold nanocages (AuNCs). This delivery system is designated as anti‐miR‐181b/PTPAuNCs nanocomplexes (PTPAuNC‐NPs), which begin with chemical modification of AuNCs with SH‐PEG₅₀₀₀‐folic acid (SH‐PEG₅₀₀₀‐FA) and SH‐PEG₅₀₀₀ through a gold–sulfur bond, followed by conjugating PEI using lipoic acid as a linker. Finally anti‐miR‐181b is condensed via electrostatic interactions. In vitro and in vivo experiments show that PTPAuNC‐NPs can efficiently deliver anti‐miR‐181b into target sites to suppress tumor growth, and considerably decrease tumor volumes in SMMC‐7721 tumor‐bearing nude mice under near‐infrared radiation. All these results suggest that PTPAuNC‐NP gene delivery system with combination of gene therapy and photothermal therapy will be of great potential use in future cancer therapy.     

SnTe@MnO2‐SP Nanosheet–Based Intelligent Nanoplatform for Second Near‐Infrared Light–Mediated Cancer Theranostics

Near infrared light, especially the second near‐infrared light (NIR II) biowindows with deep penetration and high sensitivity are widely used for optical diagnosis and phototherapy. Here, a novel kind of 2D SnTe@MnO₂‐SP nanosheet (NS)‐based nanoplatform is developed for cancer theranostics with NIR II‐mediated precise optical imaging and effective photothermal ablation of mouse xenografted tumors. The 2D SnTe@MnO₂‐SP NSs are fabricated via a facile method combining ball‐milling and liquid exfoliation for synthesis of SnTe NSs, and surface coating MnO₂ shell and soybean phospholipid (SP). The ultrathin SnTe@MnO₂‐SP NSs reveal notably high photothermal conversion efficiency (38.2% in NIR I and 43.9% in NIR II). The SnTe@MnO₂‐SP NSs inherently feature tumor microenvironment (TME)‐responsive biodegradability, and the main metabolite TeO₃^2? shows great antitumor effect, coupling synergetic chemotherapy for cancer. Moreover, the SnTe@MnO₂‐SP NSs also exhibit great potential for fluorescence, photoacoustic (PA), and photothermal imaging agents in the NIR II biowindow with much higher resolution and sensitivity. This is the first report, as far as is known, with such an inorganic nanoagent setting fluorescence/PA/photothermal imaging and photothermal therapy in NIR II biowindow and TME‐responsive biodegradability rolled into one, which provide insight into the clinical potential for cancer theranostics.     

Fabricating Aptamer‐Conjugated PEGylated‐MoS2/Cu1.8S Theranostic Nanoplatform for Multiplexed Imaging Diagnosis and Chemo‐Photothermal Therapy of Cancer

Fabricating theranostic nanoparticles combining multimode disease diagnosis and therapeutic has become an emerging approach for personal nanomedicine. However, the diagnostic capability, biocompatibility, and therapeutic efficiency of theranostic nanoplatforms limit their clinic widespread applications. Targeting to the theme of accurate diagnosis and effective therapy of cancer cells, a multifunctional nanoplatform of aptamer and polyethylene glycol (PEG) conjugated MoS₂ nanosheets decorated with Cu_1.8S nanoparticles (ATPMC) is developed. The ATPMC nanoplatform accomplishes photoluminescence imaging, photoacoustic imaging, and photothermal imaging for in vitro and in vivo tumor cells imaging diagnosis. Meanwhile, the ATPMC nanoplatform facilitates selective delivery of gene probe to detect intracellular microRNA aberrantly expressed in cancer cells and anticancer drug doxorubicin (DOX) for chemotherapy. Moreover, the synergistic interaction of MoS₂ and Cu_1.8S renders the ATPMC nanoplatform with superb photothermal conversion efficiency. The ATPMC nanoplatform loaded with DOX displays near‐infrared laser‐induced programmed chemotherapy and advanced photothermal therapy, and the targeted chemo‐photothermal therapy presents excellent antitumor efficiency.     

Multifunctional Carbon–Silica Nanocapsules with Gold Core for Synergistic Photothermal and Chemo‐Cancer Therapy under the Guidance of Bimodal Imaging

Carbon‐based nanomaterials have been developed for photothermal cancer therapy, but it is still a great challenge to fabricate their multifunctional counterparts with facile methods, good biocompatibility and dispersity, and high efficiency for cancer theranostics. In this work, an alternative multifunctional nanoplatform is developed based on carbon–silica nanocapsules with gold nanoparticle in the cavity (Au@CSN) for cancer theranostics. The encapsulated chemodrug doxorubicin can be released from the Au@CSN with mesoporous and hollow structure in a near‐infrared light and pH stimuli‐responsive manner, facilitating spatiotemporal therapy to decrease off‐target toxicity. The nanocapsules with efficient photothermal conversion and excellent biocompatibility achieve a synergistic effect of photothermal and chemotherapy. Furthermore, the nanocapsules can act as a multimodal imaging agent of computed tomography and photoacoustic tomography imaging for guiding the therapy. This new design platform can provide a promising strategy for precise cancer theranostics.     

PEI–PEG–Chitosan‐Copolymer‐Coated Iron Oxide Nanoparticles for Safe Gene Delivery: Synthesis,Complexation, and Transfection

Gene therapy offers the potential of mediating disease through modification of specific cellular functions of target cells. However, effective transport of nucleic acids to target cells with minimal side effects remains a challenge despite the use of unique viral and non‐viral delivery approaches. Here, a non‐viral nanoparticle gene carrier that demonstrates effective gene delivery and transfection both in vitro and in vivo is presented. The nanoparticle system (NP–CP–PEI) is made of a superparamagnetic iron oxide nanoparticle (NP), which enables magnetic resonance imaging, coated with a novel copolymer (CP–PEI) comprised of short chain polyethylenimine (PEI) and poly(ethylene glycol) (PEG) grafted to the natural polysaccharide, chitosan (CP), which allows efficient loading and protection of the nucleic acids. The function of each component material in this nanoparticle system is illustrated by comparative studies of three nanoparticle systems of different surface chemistries, through material property characterization, DNA loading and transfection analyses, and toxicity assessment. Significantly, NP–CP–PEI demonstrates an innocuous toxic profile and a high level of expression of the delivered plasmid DNA in a C6 xenograft mouse model, making it a potential candidate for safe in vivo delivery of DNA for gene therapy.     

Hierarchical Nanohybrids of Gold Nanorods and PGMA‐Based Polycations for Multifunctional Theranostics

Organic/inorganic nanohybrids hold great importance in fabricating multifunctional theranostics to integrate therapeutic functions with real‐time imaging. Although Au nanorods (NRs) have been employed for theranostics, complicated design of materials limits their practical applications. In this work, new multifunctional theranostic agents are designed and synthesized employing Au NRs with desirable near‐infrared absorbance as the cores. A facile “grafting‐onto” approach is put forward to prepare the series of hierarchical nanohybrids (Au‐PGEA and Au‐PGED) of Au NRs and poly(glycidyl methacrylate)‐based polycations. The resultant nanohybrids can be utilized as gene carriers with high gene transfection performances. The structural effect of polycations on gene transfection is investigated in detail, and Au‐PGEA with abundant hydroxyl groups on the surface exhibits superior performance. Au‐PGEA nanohybrids are further validated to possess remarkable capability of combined photothermal therapy (PTT) and gene therapy (GT) for complementary tumor treatment. Moreover, significantly enhanced computed tomography (CT)/photoacoustic (PA) signals are detected both in vitro and in vivo, verifying the potential of Au‐PGEA for dual‐modal imaging with precise and accurate information. Therefore, these multifunctional nanohybrids fabricated from a simple and straightforward strategy are promising for in vivo dual‐modal CT/PA imaging guided GT/PTT therapy with high antitumor efficacy.     

Semiconducting Nanocomposite with AIEgen‐Triggered Enhanced Photoluminescence and Photodegradation for Dual‐Modality Tumor Imaging and Therapy

Semiconducting polymer nanoparticles (SPNs) have potential in biological applications. While some SPNs have significant photothermal conversion efficiencies (PCEs) as photothermal and photoacoustic agents, other SPNs offer high fluorescence yields as photoluminescent agents. However, the energy balance distribution in SPNs inhibits their successful applications in photoluminescence/photoacoustic (PL/PA) dual‐modality imaging. Additionally, the ultrastability of SPNs in vivo may cause damage to organisms. This work reports nanocomposite semiconducting polymer and tetraphenylethene nanoparticles (STNPs) constructed by semiconducting polymers (SPs) and tetraphenylethene aggregation‐induced emission luminogens (TPE AIEgens). The SP SPC10 endows good photothermal conversion ability, and the AIEgen TPBM supports enhanced photoluminescence of the STNPs. The results show that the STNPs can act as PL/PA dual‐modality imaging agents. The signal‐to‐noise (S/N) ratio in the PL modality reaches 8.7, and the imaging depth in the PA modality is 5.8 mm. The SPC10 in the STNPs can be decomposed under 90 mW cm^?2 white light irradiation in 6 h without any other additional agents. Furthermore, the STNPs are sufficient for the treatment of xenograft 4T1 tumor‐bearing mice based on photothermal therapy. The nanocomposite STNPs achieve optimized dual‐modality PL/PA imaging and the AIEgen‐triggered in situ photodegradation of SPNs. These properties indicate the significant potential of STNPs in clinical diagnosis and noninvasive therapy.     

Precise Modulation of Gold Nanorods for Protecting against Malignant Ventricular Arrhythmias via Near‐Infrared Neuromodulation

Hyperactivity of the left stellate ganglion (LSG) contributes to the occurrence of ventricular arrhythmias (VAs). Recently, advances in neuromodulation have been achieved with near‐infrared (NIR)‐sensitive gold nanorods (AuNRs). Here, AuNRs are precisely regulated and applied to inhibit LSG function as well as neural activity, thus ameliorating myocardial ischemia‐induced VAs in a canine model. Specifically, the optimized AuNRs are synthesized and microinjected into the LSG of anesthetized dogs, and then followed by 5 min of NIR laser irradiation at a wavelength of 808 nm. The results demonstrate that 5 min NIR laser irradiation on the PEG‐AuNR‐treated LSG can reversely inhibit LSG function and neural activity, thereby ameliorating myocardial ischemia‐induced VAs. With the tissue‐penetrating NIR and excellent photothermal effect of AuNRs, this method may become a promising and noninvasive therapeutic strategy for suppressing hyperactivity of the cardiac sympathetic nerves, therefore benefiting patients with VAs in the future.     

High‐Security Nanocluster for Switching Photodynamic Combining Photothermal and Acid‐Induced Drug Compliance Therapy Guided by Multimodal Active‐Targeting Imaging

High‐security nanoplatform with enhanced therapy compliance is extremely promising for tumor. Herein, using a simple and high‐efficient self‐assembly method, a novel active‐targeting nanocluster probe, namely, Ag₂S/chlorin e6 (Ce6)/DOX@DSPE‐mPEG₂₀₀₀‐folate (ACD‐FA) is synthesized. Experiments indicate that ACD‐FA is capable of specifically labeling tumor and guiding targeting ablation of the tumor via precise positioning from fluorescence and photoacoustic imaging. Importantly, the probe is endowed with a photodynamic “on‐off” effect, that is, Ag₂S could effectively quench the fluorescence of chlorin e6 (89.5%) and inhibit release of ¹O₂ (92.7%), which is conducive to avoid unwanted phototoxicity during transhipment in the body, and only after nanocluster endocytosed by tumor cells could release Ce6 to produce ¹O₂. Moreover, ACD‐FA also achieves excellent acid‐responsive drug release, and exhibits eminent chemo‐photothermal and photodynamic effects upon laser irradiation. Compared with single or two treatment combining modalities, ACD‐FA could provide the best cancer therapeutic effect with a relatively low dose, because it made the most of combined effect from chemo‐photothermal and controlled photodynamic therapy, and significantly improves the drug compliance. Besides, the active‐targeting nanocluster notably reduces nonspecific toxicity of both doxorubicin and chlorin e6. Together, this study demonstrates the potency of a newly designed nanocluster for nonradioactive concomitant therapy with precise tumor‐targeting capability.     

A Robust Design for Cellular Vehicles of Gold Nanorods for Multimodal Imaging

The pursuit of more selectivity in the delivery of plasmonic particles to tumors is critical before their penetration into clinical applications as the photoacoustic imaging and the photothermal ablation of cancer. As their direct infusion into the bloodstream remains problematic, due to a multitude of biological barriers, the development of alternative approaches is emerging as a new challenge. In this context, the recruitment of homologous tumor‐tropic cells that may serve as Trojan horses stands out as a fascinating possibility. Here, a novel model of gold nanorods is presented that feature a composite shell and undergo efficient and reproducible endocytic uptake from murine macrophages, which is fine‐tunable over a broad range of conditions. These cells preserve their viability and more than 90% of their innate chemotactic behavior in vitro, even with a cargo exceeding 200 000 particles per cell. In addition, we show that these vehicles are detectible by photoacoustic imaging down to concentrations in the order of 1% in whole blood and by clinical X‐ray computed tomography below 10%, which is within the typical fraction of a leukocytic infiltrate in a tumor microenvironment, and may even work as contrast agents for the photothermal ablation of cancer.     

Porphyrinic Metal–Organic Frameworks Coated Gold Nanorods as a Versatile Nanoplatform for Combined Photodynamic/Photothermal/Chemotherapy of Tumor

In this paper, a simple, but effective method is reported to construct the core?shell gold nanorod@metal–organic frameworks (AuNR@MOFs) as a multifunctional theranostic platform by using functionalized AuNRs as seed crystal for the growth of porphyrinic MOFs on the surface of AuNR. Such a delicate tunable core?shell composite not only possesses the improved drug loading efficiency, near‐infrared light‐trigger drug release, and fluorescence imaging, but also can produce reactive oxygen species as well as photothermal activity to achieve combined cancer therapy. It is further demonstrated that the camptothecin loaded AuNR@MOFs show distinctively synergistic efficiency for damaging the cancer cell in vitro and inhibiting the tumor growth and metastasis in vivo. The development of this high‐performance incorporated nanostructure will provide more perspectives in the design of versatile nanomaterials for biomedical applications.     

Hollow Nanostars with Photothermal Gold Caps and Their Controlled Surface Functionalization for Complementary Therapies

Gold nanoparticles exhibiting absorption in the desirable near‐infrared region are attractive candidates for photothermal therapy (PTT). Furthermore, the construction of one nanoplatform employing gold nanoparticles for complementary therapy is still a great challenge. Here, well‐defined unique hollow silica nanostars with encapsulated gold caps (starlike Au@SiO₂) are readily synthesized using a sacrificial template method. Ethanolamine‐functionalized poly(glycidyl methacrylate) (denoted as BUCT‐PGEA) brushes are then grafted controllably from the surface of starlike Au@SiO₂ nanoparticles via surface‐initiated atom transfer radical polymerization to produce starlike Au@SiO₂‐PGEA. The photothermal effect of gold caps with a cross cavity can be utilized for PTT. The interior hollow feature of starlike Au@SiO₂ nanoparticles endows them with excellent drug loading capability for chemotherapy, while the polycationic BUCT‐PGEA brushes on the surface provide good transfection performances for gene therapy, which will overcome the penetration depth limitation of PTT for tumor therapy. Compared with ordinary spherical Au@SiO₂‐PGEA counterparts, the starlike Au@SiO₂‐PGEA hybrids with sharp horns favor endocytosis, which can contribute to enhanced antitumor effectiveness. The rational integration of photothermal gold caps, hollow nanostars, and polycations through the facile strategy might offer a promising avenue for complementary cancer therapy.     

Plasmon‐Enhanced Fluorescence‐Based Core–Shell Gold Nanorods as a Near‐IR Fluorescent Turn‐On Sensor for the Highly Sensitive Detection of Pyrophosphate in Aqueous Solution

Developing plasmon‐enhanced fluorescence (PEF) technology for identifying important biological molecules has a profound impact on biosensing and bioimaging. However, exploration of PEF for biological application is still at a very early stage. Herein, novel PEF‐based core–shell nanostructures as a near‐infrared fluorescent turn‐on sensor for highly sensitive and selective detection of pyrophosphate (PPi) in aqueous solution are proposed. This nanostructure gold nanorod (AuNR)@SiO₂@meso‐tetra(4‐carboxyphenyl) porphyrin (TCPP) contains a gold nanorod core with an aspect ratio of 2.3, a silica shell, and TCPP molecules covalently immobilized onto the shell surface. The silica shell is employed a rigid spacer for precisely tuning the distance between AuNR and TCPP and an optimum fluorescence enhancement is obtained. Due to the quenching effect of Cu²⁺, the copper porphyrin (TCPP‐Cu²⁺) results in a weak fluorescence. In the presence of PPi, the strong affinity between Cu²⁺ and PPi can promote the disassembly of the turn‐off state of TCPP‐Cu²⁺ complexes, and therefore the fluorescence can be readily restored. By virtue of the amplified fluorescence signal imparted by PEF, this nanosensor obtains a detection limit of 820 × 10^?9m of PPi with a good selectivity over several anions, including phosphate. Additionally, the potential applicability of this sensor in cell imaging is successfully demonstrated.