Significant Enhancement of Photothermal and Photoacoustic Efficiencies for Semiconducting Polymer Nanoparticles through Simply Molecular Engineering

Semiconducting polymer nanoparticles (SP NPs) are employed as efficient nanoagents for “all‐in‐one” theranostic nanoplatforms with dual photoacoustic imaging (PAI) and photothermal therapy (PTT) functions based on their photothermal conversion effect. However, the mechanisms of tuning the PTT efficiency are still elusive, though several SP NPs with high photothermal efficiency are reported. Herein, two donor–acceptor (D–A) SP NPs PTIGSVS and PIIGSVS with the same donor unit but different acceptor units are designed and synthesized. Through tuning the acceptor unit, PTIGSVS shows more planar backbone structure, stronger D–A strength, redshifted absorption, enhanced extinction efficient, weakened emission properties, and more efficient nonradiative decay in comparison to the polymeric analogue PIIGSVS . Thus, PTIGSVS NPs present much higher photothermal conversion efficiencies (74%) than PIIGSVS NPs (11%), resulting in significantly enhanced in vitro and in vivo PAI and PTT performance. This contribution demonstrates that PTIGSVS NPs are superior PA/PTT agents for effective cancer theranostic and shed light on understanding the relationship between molecular structures and photothermal effect of CPs.     

PEGylated Polypyrrole Nanoparticles Conjugating Gadolinium Chelates for Dual‐Modal MRI/Photoacoustic Imaging Guided Photothermal Therapy of Cancer

Polypyrrole nanoparticles conjugating gadolinium chelates were successfully fabricated for dual‐modal magnetic resonance imaging (MRI) and photoacoustic imaging guided photothermal therapy of cancer, from a mixture of pyrrole and pyrrole‐1‐propanoic acid through a facile one‐step aqueous dispersion polymerization, followed by covalent attachment of gadolinium chelate, using polyethylene glycol as a linker. The obtained PEGylated poly­pyrrole nanoparticles conjugating gadolinium chelates (Gd‐PEG‐PPy NPs), sized around around 70 nm, exhibited a high T₁ relaxivity coefficient of 10.61 L mm ^?1 s^?1, more than twice as high as that of the relating free Gd³⁺ complex (4.2 L mm ^–1 s^?1). After 24 h intravenous injection of Gd‐PEG‐PPy NPs, the tumor sites exhibited obvious enhancement in both T₁‐weighted MRI intensity and photoacoustic signal compared with that before injection, indicating the efficient accumulation of Gd‐PEG‐PPy NPs due to the introduction of the PEG layer onto the particle surface. In addition, tumor growth could be effectively inhibited after treatment with Gd‐PEG‐PPy NPs in combination with near‐infrared laser irradiation. The passive targeting and high MRI/photo­acoustic contrast capability of Gd‐PEG‐PPy NPs are quite favorable for precise cancer diagnosing and locating the tumor site to guide the external laser irradiation for photothermal ablation of tumors without damaging the surrounding healthy tissues. Therefore, Gd‐PEG‐PPy NPs may assist in better monitoring the therapeutic process, and contribute to developing more effective “personalized medicine,” showing great potential for cancer diagnosis and therapy.     

An Acceptor–Donor–Acceptor Structured Small Molecule for Effective NIR Triggered Dual Phototherapy of Cancer

Dual phototherapy, including photodynamic therapy (PDT) and photothermal therapy (PTT), is regarded as a more effective method for cancer treatment than single PDT or PTT. However, development of single component and near‐infrared (NIR) triggered agents for efficient dual phototherapy remains a challenge. Herein, a simple strategy to develop dual‐functional small‐molecules‐based photosensitizers for combined PDT and PTT treatment is proposed through: 1) finely modulating HOMO–LUMO energy levels to regulate the intersystem crossing (ISC) process for effective singlet oxygen (¹O₂) generation for PDT; 2) effectively inhibiting fluorescence via strong intramolecular charge transfer (ICT) to maximize the conversion of photo energy to heat for PTT or ISC process for PDT. An acceptor–donor–acceptor (A‐D‐A) structured small molecule (CPDT) is designed and synthesized. The biocompatible nanoparticles, FA‐CNPs, prepared by encapsulating CPDT directly with a folate functionalized amphipathic copolymer, present strong NIR absorption, robust photostability, cancer cell targeting, high photothermal conversion efficiency as well as efficient ¹O₂ generation under single 808 nm laser irradiation. Furthermore, synergistic PDT and PTT effects of FA‐CNPs in vivo are demonstrated by significant inhibition of tumor growth. The proposed strategy may provide a new approach to reasonably design and develop safe and efficient photosensitizers for dual phototherapy against cancer.     

An Iridium (III) Complex Bearing a Donor–Acceptor–Donor Type Ligand for NIR-Triggered Dual Phototherapy

Iridium(III) complexes are an important group of photosensitizers for photodynamic therapy (PDT). This work constructs a donor–acceptor–donor structure-based iridium(III) complex (IrDAD) with high reactive oxygen species (ROS) generation efficiency, negligible dark toxicity, and synergistic PDT and photothermal therapy (PTT) effect under near-infrared (NIR) stimulation. This complex self-assembles into metallosupramolecular aggregates with a unique aggregation-induced PDT behavior. Compared with conventional iridium(III) photosensitizers, IrDAD not only achieves NIR light deep tissue penetration but also shows highly efficient ROS and heat generation with ROS quantum yield of 14.6% and photothermal conversion efficiency of 27.5%. After conjugation with polyethylene glycol (PEG), IrDAD is formulated to a nanoparticulate system (IrDAD-NPs) with good solubility. In cancer phototherapy, IrDAD-NPs preferentially accumulate in tumor area and display a significant tumor inhibition in vivo, with 96% reduction in tumor volume, and even tumor elimination.     

Rationally Designed Donor–Acceptor Random Copolymers with Optimized Complementary Light Absorption for Highly Efficient All‐Polymer Solar Cells

Most of the high‐performance all‐polymer solar cells (all‐PSCs) reported to date are based on polymer donor and polymer acceptor pairs with largely overlapped light absorption properties, which seriously limits the efficiency of all‐PSCs. This study reports the development of a series of random copolymer donors possessing complementary light absorption with the naphthalenediimide‐based polymer acceptor P(NDI2HD‐T2) for highly efficient all‐PSCs. By controlling the molar ratio of the electron‐rich benzodithiophene (BDTT) and electron‐deficient fluorinated‐thienothiophene (TT‐F) units, a series of polymer donors with BDTT:TT‐F ratios of 1:1 (P1), 3:1 (P2), 5:1 (P3), and 7:1 (P4) are prepared. The synthetic control of polymer composition allows for precise tuning of the light absorption properties of these new polymer donors, enabling optimization of light absorption properties to complement those of the P(NDI2HD‐T2) acceptor. Copolymer P1 is found to be the optimal polymer donor for the fullerene‐based solar cells due to its high light absorption, whereas the highest power conversion efficiency of 6.81% is achieved for the all‐PSCs with P3, which has the most complementary light absorption with P(NDI2HD‐T2).     

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.     

BSA‐Mediated Synthesis of Bismuth Sulfide Nanotheranostic Agents for Tumor Multimodal Imaging and Thermoradiotherapy

Fabrication of ultrasmall single‐component omnipotent nanotheranostic agents integrated with multimodal imaging and multiple therapeutic functions becomes more and more practically relevant but challenging. In this article, sub 10 nm Bi₂S₃ biocompatible particles are prepared through a bovine serum albumin (BSA)‐mediated biomineralization process under ambient aqueous conditions. Owing to the ultrasmall size and colloidal stability, the resulting nanoparticles (NPs) present outstanding blood circulation behavior and excellent tumor targeting ability. Toward theranostic applications, the biosafety profile is carefully investigated. In addition, photothermal conversion is characterized for both photoacoustic imaging and photothermal treatment of cancers. Upon radiolabeling, the performance of the resulting particles for SPECT/CT imaging in vivo is also carried out. Additionally, different combinations of treatments are applied for evaluating the performance of the as‐prepared Bi₂S₃ NPs in photothermal‐ and radiotherapy of tumors. Due to the remarkable photothermal conversion efficiency and large X‐ray attenuation coefficient, the implanted tumors are completely eradicated through combined therapies, which highlights the potential of BSA‐capped Bi₂S₃ NPs as a novel multifunctional nanotheranostic agent.     

Tunable Förster Resonance Energy Transfer in Colloidal Nanoparticles Composed of Polycaprolactone‐Tethered Donors and Acceptors: Enhanced Near‐Infrared Emission and Compatibility for In Vitro and In Vivo Bioimaging

A near‐infrared (NIR) fluorescent donor/acceptor (D/A) nanoplatform based on Förster resonance energy transfer is important for applications such as deep‐tissue bioimaging and sensing. However, previously reported D/A nanoparticles (NPs) often show limitations such as aggregation‐induced fluorescence quenching and poor interfacial compatibility that reduces the efficiency of the energy transfer and also leads to leaching of the small molecular fluorophores from the NP matrix. Here highly NIR‐fluorescent D/A NPs with a fluorescence quantum yield as high as 46% in the NIR region (700–850 nm) and robust optical stability are reported. The hydrophobic core of each NP is composed of donor and acceptor moieties both of which are tethered with polycaprolactone (PCL), while the hydrophilic corona is composed of poly[oligo(ethylene glycol) methyl ether methacrylate] to offer colloidal stability and “stealthy” effect in aqueous media. The PCL matrix in each colloidal NP not only offers biocompatibility and biodegradability but also minimizes the aggregation‐caused fluorescence quenching of D/A chromophores and prevents the leakage of the NIR fluorophores from the NPs. In vivo imaging using these NIR NPs in live mice shows contrast‐enhanced imaging capability and efficient tumor‐targeting through enhanced permeability and retention effect.     

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.     

Ultra‐Small Iron Oxide Doped Polypyrrole Nanoparticles for In Vivo Multimodal Imaging Guided Photothermal Therapy

Recently, near‐infrared (NIR) absorbing conjugated polymeric nanoparticles have received significant attention in photothermal therapy of cancer. Herein, polypyrrole (PPy), a NIR‐absorbing conjugate polymer, is used to coat ultra‐small iron oxide nanoparticles (IONPs), obtaining multifunctional IONP@PPy nanocomposite which is further modified by the biocompatible polyethylene glycol (PEG) through a layer‐by‐layer method to acquire high stability in physiological solutions. Utilizing the optical and magnetic properties of the yielded IONP@PPy‐PEG nanoparticles, in vivo magnetic resonance (MR) and photoacoustic imaging of tumor‐bearing mice are conducted, revealing strong tumor uptake of those nanoparticles after intravenous injection. In vivo photothermal therapy is then designed and carried out, achieving excellent tumor ablation therapeutic effect in mice experiments. These results promise the use of multifunctional NIR‐absorbing organic‐inorganic hybrid nanomaterials, such as IONP@PPy‐PEG presented here, for potential applications in cancer theranostics.     

Organic Small Molecule Based Photothermal Agents with Molecular Rotors for Malignant Breast Cancer Therapy

Organic photothermal nanoagents are promising candidates for treating primary tumors and inhibiting metastasis. However, they often exhibit poor photostability, low absorptivity, or limited photothermal conversion efficiency (PCE). Herein, a facile molecular engineering approach to produce efficient organic photothermal molecules is demonstrated. By integrating donor–acceptor structure and molecular motors, a small molecule ( TA1 ) is synthesized with large absorptivity (22.4 L g^?1 cm^?1), negligible reactive oxygen species generation, high PCE (84.8%), excellent photothermal stability, and good biocompatibility. Furthermore, microfluidics is used to thoroughly study the relationship between the size and process conditions, yielding small uniform nanoparticles (NPs) with a diameter of 44 nm. Importantly, TA1 NPs under near‐infrared laser irradiation significantly suppressed primary breast tumor growth and metastasis, both in vitro and in vivo. This study shows that small organic molecule nanoparticles are promising candidates for future cancer nanomedicine.     

Enhanced Photocurrent Spectral Response in Low‐Bandgap Polyfluorene and C70‐Derivative‐Based Solar Cells

Plastic solar cells have been fabricated using a low‐bandgap alternating copolymer of fluorene and a donor–acceptor–donor moiety (APFO‐Green1), blended with 3′‐(3,5‐bis‐trifluoromethylphenyl)‐1′‐(4‐nitrophenyl)pyrazolino[70]fullerene (BTPF70) as electron acceptor. The polymer shows optical absorption in two wavelength ranges, λ < 500 nm and 600 < λ < 1000 nm. The BTPF70 absorbs light at λ < 700 nm. A broad photocurrent spectral response in the wavelength range 300 < λ < 1000 nm is obtained in solar cells. A photocurrent density of 3.4 mA cm^–2, open‐circuit voltage of 0.58 V, and power‐conversion efficiency of 0.7 % are achieved under illumination of AM1.5 (1000 W m^–2) from a solar simulator. Synthesis of BTPF70 is presented. Photoluminescence quenching and electrochemical studies are used to discuss photoinduced charge transfer.     

Ultrasmall Semiconducting Polymer Dots with Rapid Clearance for Second Near‐Infrared Photoacoustic Imaging and Photothermal Cancer Therapy

Phototheranostic agents in the second near‐infrared (NIR‐II) window (1000–1700 nm) are emerging as a promising theranostic platform for precision medicine due to enhanced penetration depth and minimized tissue exposure. The development of metabolizable NIR‐II nanoagents for imaging‐guided therapy are essential for noninvasive disease diagnosis and precise ablation of tumors. Herein, metabolizable highly absorbing NIR‐II conjugated polymer dots (Pdots) are reported for the first time for photoacoustic imaging guided photothermal therapy (PTT). The unique design of low‐bandgap D‐A π‐conjugated polymer (DPP‐BTzTD) together with modified nanoreprecipitation conditions allows to fabricate NIR‐II absorbing Pdots with ultrasmall (4 nm) particle size. Extensive experimental tests demonstrate that the constructed Pdots exhibit good biocompatibility, excellent photostability, bright photoacoustic signals, and high photothermal conversion efficiency (53%). In addition, upon tail‐vein intravenous injection of tumor‐bearing mice, Pdots also show high‐efficient tumor ablation capability with rapid excretion from the body. In particular, both in vitro and in vivo assays indicate that the Pdots possess remarkable PTT performance under irradiation with a 1064 nm laser with 0.5 W cm^?2, which is much lower than its maximum permissible exposure limit of 1 W cm^?2. This pilot study thus paves a novel avenue for the development of organic semiconducting nanoagents for future clinical translation.     

Engineering Versatile Nanoparticles for Near‐Infrared Light‐Tunable Drug Release and Photothermal Degradation of Amyloid β

Nanomedicines that inhibit/disassemble amyloid β (Aβ) aggregates in Alzheimer's disease (AD) are highly desirable yet remain challenging. Therapeutic efficacy and systemic delivery of reported molecules and nanoparticles (NPs) are hampered by various challenges, including low biocompatibility, off‐target toxicity, and lack of specificity. Herein, a versatile NP is designed by integrating high Aβ‐binding affinity, stimuli‐responsive drug release, and photothermal degradation properties for efficient disassembly of Aβ. Near‐infrared (NIR)‐absorbing conjugated polymer PDPP3T‐O14 serves as a photothermal core while thermal‐responsive polymer 1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphocholine at the outer layer as the NIR‐stimuli gatekeeper. Curcumin, an inhibitor of Aβ aggregation, is loaded into the NP with high encapsulation efficiency. The 5‐mer β‐sheet breaker peptides LPFFD (Leu‐Pro‐Phe‐Phe‐Asp) having high binding affinity toward Aβ are further anchored onto the surface of polyethylene glycol‐lipid shell for active Aβ‐targeting. The resultant NPs exhibit good Aβ‐targeting ability and obvious photothermal dissociation effect together with Aβ aggregation‐dependent fluorescence detection capability. Upon NIR laser irradiation, entrapped curcumin can be effectively released from the unconsolidated NPs to enhance the anti‐amyloid activity. In vitro studies demonstrate that the NPs dramatically lower Aβ‐induced cytotoxicity of PC12 cells, and therefore show great potential for the application in AD treatment.     

Improved All‐Polymer Solar Cell Performance by Using Matched Polymer Acceptor

By the introduction of different building blocks and side‐chains, a series of donor–acceptor type polymer acceptors containing naphthalene diimide have been successfully prepared. The theoretical and experimental results show that the molecular design effectively tunes the energy levels, solubility, and coplanarity of the acceptor polymers. The intermolecular packing, which has been considered as a key factor in the bulk heterojunction morphology, has been adjusted by changing the coplanarity. As a result of improved morphology and fine‐tuned energy levels, a power conversion efficiency of 6.0% has been demonstrated for the optimized devices, which is among the highest‐efficiencies for reported all‐polymer solar cells. The improved device performance may be attributed to the resemble crystallinity of the donor/acceptor polymers, which can lead to the optimal phase separation morphology balancing both charge transfer and transport.     

Calcination‐ and Etching‐Free Photolithography of Inorganic Phosphor Films Consisting of Rare Earth Ion Doped Nanoparticles on Plastic Sheets

It is demonstrated that patterned inorganic phosphor films consisting of rare earth ion doped nanoparticles (RE‐NPs) can be fabricated on plastic sheets using calcination‐ and etching‐free photolithography. Green up‐conversion luminescence and near‐infrared (NIR) fluorescence appears from the RE‐NPs that are prepared from Y₂O₃ doped with 1 mol% Er³⁺ and 0.85 mol% Yb³⁺. The diameter of the RE‐NPs is estimated to be about 300 nm using dynamic light scattering. Visible transmittance of the RE‐NP film fabricated by dip‐coating is more than 90%. Patterned RE‐NP films are obtained by dip‐coating the RE‐NPs on patterned photoresist films fabricated by UV exposure through a photomask, followed by selective removal of the photoresist. Optical, fluorescence, scanning electron, atomic force, and Kelvin probe force microscopies are used for the characterization of the patterned RE‐NP films. The present methodology enables fabrication of patterned RE‐NP films, not only on inorganic substrates but also on plastic sheets, with low cost and material consumption.     

Solar Cells with Enhanced Photocurrent Efficiencies Using Oligoaniline‐Crosslinked Au/CdS Nanoparticles Arrays on Electrodes

Different configurations of CdS nanoparticles (NPs) are linked to Au electrodes by electropolymerization of thioaniline‐functionalized CdS NPs onto thioaniline‐functionalized Au‐electrodes. In one configuration, thioaniline‐functionalized CdS NPs are electropolymerized in the presence of thioanline‐modified Au NPs to yield an oligoaniline‐crosslinked CdS/Au NPs array. The NP‐functionalized electrode generates a photocurrent with a quantum yield that corresponds to ca. 9%. The photocurrent intensities are controlled by the potential applied on the electrode, and the redox‐state of the oligoaniline bridge. In the oxidized quinoide state of the oligoaniline units, the bridges act as electron acceptors that trap the conduction‐band electrons that are transported to the electrode and lead to high quantum yield photocurrents. The reduced π‐donor oligoaniline bridges act as π‐donor sites that associate N,N′‐dimethyl‐4,4′‐bipyridinium, MV²⁺, by donor/acceptor interactions, K_a = 5270 M^?1. The associated MV²⁺ acts as an effective trap of the conduction‐band electrons, and in the presence of triethanolamine (TEOA) as an electron donor, high photocurrent values are measured (ca. 12% quantum yield). The electropolymerization of thioaniline‐functionalized Au NPs and thioaniline‐modified CdS NPs in the presence of MV²⁺ yields a MV²⁺‐imprinted NP array. The imprinted array exhibits enhanced affinities toward the association of MV²⁺ to the oligoaniline π‐donor sites, K_a = 2.29 × 10⁴ M^?1. This results in the effective trapping of the conduction‐band electrons and an enhanced quantum yield of the photocurrent, ca. 34%. The sacrificial electron donor, TEOA, was substituted with the reversible donor I₃^?. A solar cell consisting of the imprinted CdS/Au NPs array, with MV²⁺ and I₃^?, was constructed. The cell generated a photocurrent with a quantum yield of 4.7%.     

Supramolecular Photothermal Nanomaterials as an Emerging Paradigm toward Precision Cancer Therapy

The concept of the “supramolecular photothermal effects” refers to the collection property and photothermal conversion efficiency resulting from the supramolecular assembly of molecular photothermal sensitizers. This review considers organic supramolecular photothermal materials assembled at the nanoscale via various molecular self‐assembly strategies and associated with the organization of multiple noncovalent interactions. In these materials, the individual photosensitizer molecules are typically aggregated through self‐assembly in a certain form that exhibits enhanced biostability, increased photothermal conversion efficiency with photoluminescence quenching, and improved photothermal therapeutic effects in comparison with those of the monomeric photosensitizer molecules. These supramolecular photothermal effects are controlled or influenced by intermolecular noncovalent interactions, especially the hydrophobic effects, which are distinct from the mechanisms of conventional sensitizer molecules and polymers and inorganic photothermal agents. A focus lies on how self‐assembly strategies give rise to supramolecular photothermal effects, including polymer and protein fabrication, small molecule self‐assembly, and the construction of donor–acceptor binary systems. Emphases are placed on the rational design of supramolecular photothermal nanomaterials, drug delivery, and in vivo photothermal therapeutic effects. Finally, the key challenges and promising prospects of these supramolecular photothermal nanomaterials in terms of both technical advances and clinical translation are discussed.     

A Versatile Nanotheranostic Agent for Efficient Dual‐Mode Imaging Guided Synergistic Chemo‐Thermal Tumor Therapy

The integration of efficient imaging for diagnosis and synergistic tumor therapy into a single‐component nanoplatform is much promising for high efficacy tumor treatment but still in a great challenge. Herein, a smart and versatile nanotheranostic platform based on hollow mesoporous Prussian blue nanoparticles (HMPBs) with perfluoropentane (PFP) and doxorubicin (DOX) inside, has been designed, for the first time, to achieve the distinct in vivo synergistic chemo‐thermal tumor therapy and synchronous diagnosis and monitoring by ultrasound (US)/photoacoustic (PA) dual mode imaging. The prepared HMPBs show excellent photothermal conversion properties with large molar extinction coefficient (≈1.2 × 10¹¹m ^?1 cm^?1) and extremely high photothermal conversion efficiency (41.4%). Such a novel theranostic nanoplatform is expected to overcome the inevitable tumor recurrence and metastasis resulting from the inhomogeneous ablation of single thermal therapy, which will find a promising prospect in the application of noninvasive cancer therapy.