Layered Double Hydroxide-Based PdCux@LDH Alloy Nanozyme for a Singlet Oxygen-Boosted Sonodynamic Therapy.

Redox nanozymes have demonstrated tremendous promise in disrupting cellular homeostasis toward cancer therapy, but a dysfunctional competition of diverse activities makes it normally restricted by the complex tumor microenvironment (TME). As palladium nanocrystals can achieve the precise regulation of the enzyme-like activity by regulating exposed crystal planes, noble metal nanoalloys can enhance the enzyme-like activity by promoting electron transfer and enhanced active sites. Herein, bimetallic nanoalloys with optimized enzymatic activity were intelligently designed via the interaction between the Pd and layered double hydroxide, denoted as PdCux@LDH. This PdCux@LDH is able to produce long-lived singlet oxygen (1O2) with high efficiency and selectivity for ultrasound-improved cancer therapy. In addition, this PdCux@LDH nanozyme demonstrated unique surface-dependent multienzyme-mimicking activities for catalyzing cascade reactions: oxidase (OXD)- and catalase (CAT)-mimicking activities. Interestingly, ultrasound (US) stimulation can further improve the dual-enzyme-mimicking activities and impart superior reactive oxygen species (ROS) generation activity, thereby further consuming nicotinamide adenine dinucleotide (NADH) to cause mitochondrial dysfunction, resulting in a highly efficient alloy nanozyme-mediated cancer therapy. This work opens a new research avenue to apply nanozymes for effective sonodynamic therapies (SDT).

Construction of an Injectable Composite Double-Network Hydrogel as a Liquid Embolic Agent.

Conventional embolists disreputably tend to recanalization arising from the low filling ratio due to their rigidity or instability. As a result, intelligent hydrogels with a tunable modulus may meaningfully improve the therapeutic efficacy. Herein, an injectable composite double-network (CDN) hydrogel with high shear responsibility was prepared as a liquid embolic agent by cross-linking poly(vinyl alcohol) (PVA) and carboxymethyl chitosan (CMC) via dynamic covalent bonding of borate ester and benzoic-imine. A two-dimensional nanosheet, i.e., layered double hydroxide (LDH), was incorporated into the network through physical interactions which led to serious reduction of yield stress for the injection of the hydrogel and the capacity for loading therapeutic agents like indocyanine green (ICG) and doxorubicin (DOX) for the functions of photothermal therapy (PTT) and chemotherapy. The CDN hydrogel could thus be transported through a thin catheter and further in situ strengthened under physiological conditions, like in blood, by secondarily cross-linking with phosphate ions for longer degradation duration and better mechanical property. These characteristics met the requirements of arterial interventional embolization, which was demonstrated by renal embolism operation on rabbits, and meanwhile favored the inhibition of subcutaneous tumor growth on an animal model. Therefore, this work makes a breakthrough in the case of largely reducing the embolism risks, thus affording a novel generation for interventional embolization.

Polymer-Protein Assemblies with Tunable Vesicular and Hierarchical Nanostructures.

The construction of variable structured multi-protein nano-assemblies is of great interest for the development of protein-based therapeutic systems. This study showcases the synthesis of polymer-protein assemblies with tunable structure like single- and multi-layer polymer-crosslinked protein vesicles, Janus protein vesicles and other hierarchical-structured assemblies by utilizing a dynamic template-assistant intermittent-assembly approach. The generalization of the methodology helps the protein assemblies to gain notable functional complexity. And we demonstrate compelling evidence highlighting the substantial impact of the topological morphology of protein nanoaggregates on their cellular uptake capacity.

Oxygen and pH responsive theragnostic liposomes for early-stage diagnosis and photothermal therapy of solid tumours.

The development of cancer treatment is of great importance, especially in the early stage. In this work, we synthesized a pH-sensitive amphiphilic ruthenium complex containing two alkyl chains and two PEG chains, which was utilized as an oxygen sensitive fluorescent probe for co-assembly with lipids to harvest a liposomal delivery system (RuPC) for the encapsulation of a photothermal agent indocyanine green (ICG). The resultant ICG encapsulated liposome (RuPC@ICG) enabled the delivery of ICG into cells via a membrane fusion pathway, by which the ruthenium complex was localized in the cell membrane for better detection of the extracellular oxygen concentration. Such characteristics allowed ratiometric imaging to distinguish the tumour location from normal tissues just 3 days after cancer cells were implanted, by monitoring the hypoxia condition and tracing the metabolism. Moreover, the pH sensitivity of the liposomes favoured cell uptake, and improved the anti-tumour efficiency of the formulation in vivo under NIR irradiation. Assuming liposomal systems have fewer safety issues, our work not only provides a facile method for the construction of a theragnostic system by combining phototherapy with photoluminescence imaging, but hopefully paves the way for clinical translation from bench to bedside.

Constructing multifunctional Cu Single-Atom nanozyme for synergistic nanocatalytic Therapy-Mediated Multidrug-Resistant bacteria infected wound healing.

Developing an effective strategy to combat multi-drug-resistant (MDR) bacteria and promote wound healing without overuse of antibiotics remains an important and challenging goal. Herein, we established a synergistic reactive oxygen species (ROS) and reactive nitrogen species (RNS)-mediated nanocatalytic therapy, which was consisted of a multifunctional Cu single-atom nanozyme loaded with the l-arginine (l-Arg@Cu-SAzymes) and a low level of hydrogen peroxide (H2O2) as a trigger. l-Arg@Cu-SAzymes can possess excellent dual enzyme-like activities: catalase (CAT)-like activity that decompose H2O2 into O2, and subsequent oxidase (OXD)-like activity that convert O2 to cytotoxic superoxide anion radical (•O2-). Meanwhile, l-Arg@Cu-SAzymes can also be triggered by H2O2 to release nitric oxide (NO), which can continue to react with •O2- to generate more lethal peroxynitrite (ONOO-). Collectively, the synergistic ROS and RNS mediated by l-Arg@Cu-SAzymes endow the treatment system with an outstanding antibacterial ability against MDR bacteria and reduce the inflammation at the wound site. Furthermore, l-Arg@Cu-SAzymes-mediated NO and O2 release promote the cell proliferation, collagen synthesis, and the angiogenesis, as well as facilitate macrophage polarization to reparative M2 phenotype, thereby accelerating wound closure and tissue remodeling. Therefore, l-Arg@Cu-SAzymes-based synergistic nanocatalytic therapy can be regarded as a promising strategy for MDR bacterial infected wounds treatment, owing to their potent antibacterial efficacy and enhanced tissue remodeling effects.

Three-Dimensional Sulfated Bacterial Cellulose/Gelatin Composite Scaffolds for Culturing Hepatocytes.

The liver is the hub of human metabolism and involves many diseases. To better work on the mechanism and treatment of liver diseases, it is of particular interest to design 3-dimensional scaffolds suitable for culturing hepatocytes in vitro to simulate their metabolic and regenerative abilities. In this study, sulfated bacterial cellulose (SBC) was prepared as the building block of cell scaffolds, motivated by the anionic nature and 3-dimensional structure of hepatic extracellular matrix, and its reaction condition for sulfate esterification was optimized by changing the reaction time. The analysis and study of the microscopic morphology, structure, and cytocompatibility of SBCs showed that they possess good biocompatibility and meet the requirements for tissue engineering. Next, SBC was mixed with gelatin for composite scaffolds (SBC/Gel) for culturing hepatocytes by homogenization and freeze-drying methods, whose physical properties such as pore size, porosity, and compression properties were compared with gelatin (Gel) scaffolds as the control group, and the cytological activity and hemocompatibility of the composite scaffolds were investigated. The results showed that the SBC/Gel composite has better porosity and compression properties, as well as good cytocompatibility and hemocompatibility, and could be applied to 3-dimensional culture of hepatocytes for drug screening or liver tissue engineering.

Unveiling the Mechanism of Alleviating Ischemia Reperfusion Injury via a Layered Double Hydroxide-Based Nanozyme.

Oxidative stress after ischemia reperfusion can cause irreversible brain damage. Thus, it is vital to timely consume excessive reactive oxygen species (ROS) and conduct molecular imaging monitoring on the brain injury site. However, previous studies have focused on how to scavenge ROS while ignoring the mechanism of relieving the reperfusion injury. Herein, we reported a layered double hydroxide (LDH)-based nanozyme (denoted as ALDzyme), which was fabricated by the confinement of astaxanthin (AST) with LDH. This ALDzyme can mimic natural enzymes, which include superoxide dismutase (SOD) and catalase (CAT). Furthermore, the SOD-like activity of ALDzyme is 16.3 times higher than that of CeO2 (a typical ROS scavenger). Based on these enzyme-mimicking properties, this one-of-a-kind ALDzyme offers strong anti-oxidative properties as well as high biocompatibility. Importantly, this unique ALDzyme can establish an efficient magnetic resonance imaging platform, thus guiding the in vivo details. As a result, the infarct area can be reduced by 77% after reperfusion therapy, and the neurological impairment score can be lowered from 3-4 to 0-1. Density functional theory computations can reveal more about the mechanism of this ALDzyme's significant ROS consumption. These findings provide a method for unraveling the neuroprotection application process in ischemia reperfusion injury using an LDH-based nanozyme as a remedial nanoplatform.

Layered double hydroxide-based nanozyme for NO-boost multi-enzyme dynamic therapy with tumor specificity.

The development of dual chemodynamic therapy and NO therapy can significantly improve the efficiency of cancer treatment. Therefore, designing a multifunctional agent to take full advantage of them and maximize their therapeutic effect remains a challenging goal. Herein, we have developed a novel LDHzyme by the confinement of L-arginine (L-Arg) on the surface of Mn-LDH nanosheets. The LDHzyme can exhibit multiple enzyme-like catalytic activities, including peroxidase (POD), oxidase (OXD), and nitric oxide synthase (iNOS). Based on these enzyme-mimicking properties, LDHzyme possesses significant catalytic efficiency with a high maximum velocity of 1.41 × 10-6 M s-1, which is higher than the majority of other nanozymes. In addition, this LDHzyme can exhibit outstanding NO-enhanced lethality of ROS and further improve its efficacy. The therapeutic effect of LDHzyme has been verified to significantly inhibit tumor growth in HeLa xenograft Balb/c nude mice models, as demonstrated in both in vitro and in vivo models, revealing the promising prospects of NO-enhanced multi-enzyme dynamic therapy (MDT). These results open up an opportunity to enable the utilization of an LDH-based nanozyme as a curative nanosystem to inhibit tumor growth.

Targeted alleviation of ischemic stroke reperfusion via atorvastatin-ferritin Gd-layered double hydroxide.

In acute ischemic stroke therapy, potent neuroprotective agents are needed that prevent neural injuries caused by reactive oxygen species (ROS) during ischemic reperfusion. Herein, a novel 2D neuroprotective agent (AFGd-LDH) is reported, comprising Gd-containing layered double hydroxide nanosheets (Gd-LDH, as a drug nanocarrier/MRI contrast agent), atorvastatin (ATO, as a neuroprotective drug) and the ferritin heavy subunit (FTH, as a blood brain barrier transport agent). Experiments revealed AFGd-LDH to possess outstanding antioxidant activity, neuroprotective properties, blood‒brain barrier transit properties, and biocompatibility. In vitro studies demonstrated the ROS scavenging efficiency of AFGd‒LDH to be ∼90%, surpassing CeO2 (50%, a ROS scavenger) and edaravone (52%, a clinical neuroprotective drug). Ischemia‒reperfusion model studies in mice showed AFGd‒LDH could dramatically decrease apoptosis induced by reperfusion, reducing the infarct area by 67% and lowering the neurological deficit score from 3.2 to 0.9. AFGd-LDH also offered outstanding MRI performance, thus enabling simultaneous imaging and ischemia reperfusion therapy.

Bioinspired Construction of an Enzyme-Mimetic Supramolecular Nanoagent for RNS-Augmented Cascade Chemodynamic Therapy.

Inspired by natural enzymes, specific enzyme-like cascade catalytic reactions can be obtained by imitating the metal active sites of natural enzymes and assembling inorganic materials at the molecular level via supramolecular interactions, which can greatly expand their application in biology. Herein, it is reported that a bioinspired SNP/MgMnFe-LDH (denoted as S2MFL) supramolecular nanoagent has been successfully synthesized via the intercalation between nitroprusside (SNP) and MgMnFe-layered double hydroxides (denoted as 2MFL). Initially, the resulting S2MFL possesses peroxidase-, catalase-, and oxidase (OXD)-like activities under tumor microenvironment (TME) stimulation. It should be noted that this S2MFL demonstrates a high OXD-like activity rate level of 9.508 × 10-6 Ms-1 in the chemodynamic therapy (CDT) study. Furthermore, the superoxide anions (O2•-) generated via OXD-like activity can react with NO (GSH-responsive), followed by the production of reactive nitrogen species (RNS). The synergistic reactive oxygen species (ROS) and RNS generation destroys the intratumoral redox balance and extensively promotes cancer cell inhibition without additional energy introduction and has excellent T1/T2-weighted magnetic resonance imaging (MRI) ability. Overall, this RNS-enhanced CDT strategy provides a novel approach for TME-mediated therapy.

Discovery of Chemokine CXCL12 Inhibitors by Tandem Application of Virtual Screening and NMR Spectrometry.

The CXC chemokine ligand CXCL12 and its receptor CXCR4 play critical roles in stem-cell homing, infectious diseases, and cancer, which led the CXCL12/CXCR4 signaling axis to attract much attention in drug discovery. CXCR4 is regarded as the primary target while CXCL12 is considered too small to be a druggable target. In this paper, we employed virtual screening approaches and ligand-based NMR screening methods from a SPECS library and in-house natural products to discover new CXCR12 inhibitors. Four natural triterpene saponins were confirmed, and the triterpene sapogenin was identified as the main binding epitope by saturation transfer difference-nuclear magnetic resonance and molecular docking studies. The pentacyclic triterpene scaffold and its elucidated structure-activity relationships provide a new and valuable research direction for the development of novel CXCL12 inhibitors.

In vitro and in vivo low-dose exposure of simulated cooking oil fumes to assess adverse biological effects.

Cooking oil fumes (COFs) represent a major indoor environmental pollutant and exhibit potent mutagenic or carcinogenic health effects caused by containing various heterocyclic aromatic amines (HAAs) and long-chain aldehydes. Despite some evaluation of the cumulative exposure of COFs to cancer cells under high concentration were evaluated, their biological adverse effects with low-dose exposure to healthy cells had been inadequately investigated. Herein, we firstly scrutinized the three selected typically toxic compounds of heterocyclic amine 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 3,8-dimethylammidazo[4,5-f]quinoxalin-2-amine (MeIQx) and trans, trans-2,4-decadienal (TDA)) emitted from COFs. In vitro studies revealed that the PhIP, MeIQx and TDA aerosol particles were negligible toxicity to cancer cells (A549 and HepG-2) but strong cytotoxicity to normal healthy cells (HelF and L02) under 0.5-4 µg/mL low dose exposure based on the reactive oxygen species (ROS) mechanism. In vivo studies demonstrated that PhIP caused significant lung and liver damage after exposure to PhIP for 30 days with mice. These results indicated the direct proof of healthy cell damage even at low-dose exposure to HAAs and aldehydes.

Vacancy defect-promoted nanomaterials for efficient phototherapy and phototherapy-based multimodal Synergistic Therapy.

Phototherapy and multimodal synergistic phototherapy (including synergistic photothermal and photodynamic therapy as well as combined phototherapy and other therapies) are promising to achieve accurate diagnosis and efficient treatment for tumor, providing a novel opportunity to overcome cancer. Notably, various nanomaterials have made significant contributions to phototherapy through both improving therapeutic efficiency and reducing side effects. The most key factor affecting the performance of phototherapeutic nanomaterials is their microstructure which in principle determines their physicochemical properties and the resulting phototherapeutic efficiency. Vacancy defects ubiquitously existing in phototherapeutic nanomaterials have a great influence on their microstructure, and constructing and regulating vacancy defect in phototherapeutic nanomaterials is an essential and effective strategy for modulating their microstructure and improving their phototherapeutic efficacy. Thus, this inspires growing research interest in vacancy engineering strategies and vacancy-engineered nanomaterials for phototherapy. In this review, we summarize the understanding, construction, and application of vacancy defects in phototherapeutic nanomaterials. Starting from the perspective of defect chemistry and engineering, we also review the types, structural features, and properties of vacancy defects in phototherapeutic nanomaterials. Finally, we focus on the representative vacancy defective nanomaterials recently developed through vacancy engineering for phototherapy, and discuss the significant influence and role of vacancy defects on phototherapy and multimodal synergistic phototherapy. Therefore, we sincerely hope that this review can provide a profound understanding and inspiration for the design of advanced phototherapeutic nanomaterials, and significantly promote the development of the efficient therapies against tumor.

Pyranodipyran Derivatives with Tyrosyl DNA Phosphodiesterase 1 Inhibitory Activities and Fluorescent Properties from Aspergillus sp. EGF 15-0-3.

Four new benzodipyran racemates, namely (±)-aspergiletals A-D (3-6), representing a rare pyrano[4,3-h]chromene scaffold were isolated together with eurotiumide G (1) and eurotiumide F (2) from the soft-coral-derived fungus Aspergillus sp. EGF 15-0-3. All the corresponding optically pure enantiomers were successfully separated by a chiral HPLC column. The structures and configurations of all the compounds were elucidated based on the combination of NMR and HRESIMS data, chiral separation, single-crystal X-ray diffraction, quantum chemical 13C NMR, and electronic circular dichroism calculations. Meanwhile, the structure of eurotiumide G was also revised. The TDP1 inhibitor activities and photophysical properties of the obtained compounds were evaluated. In the TDP1 inhibition assay, as a result of synergy between (+)-6 and (-)-6, (±)-6 displayed strong inhibitory activity to TDP1 with IC50 values of 6.50 ± 0.73 µM. All compounds had a large Stokes shift and could be utilized for elucidating the mode of bioactivities by fluorescence imaging.

Ultrathin Nanosheet-Supported Ag@Ag2O Core-Shell Nanoparticles with Vastly Enhanced Photothermal Conversion Efficiency for NIR-II-Triggered Photothermal Therapy.

Photothermal therapy (PTT) working in the second near-infrared (NIR-II) region has aroused a huge interest due to its potential application in terms of clinical cancer treatment. However, owing to the lack of photothermal nanoagents with high photothermal conversion efficiency, NIR-II-driven PTT still suffers from poor efficiency and subsequent cancer recurrence. In this work, we show a new and highly efficient preparation approach for NIR-II photothermal nanoagents and tailor ultrathin layered double hydroxide (LDH)-supported Ag@Ag2O core-shell nanoparticles (Ag@Ag2O/LDHs-U), vastly improving NIR-II photothermal performance. A combination study (high-resolution transmission electron microscopy (HRTEM), extended X-ray absorption fine structure spectroscopy (EXAFS), and X-ray photoelectron spectroscopy (XPS)) verifies that ultrafine Ag@Ag2O core-shell nanoparticles (∼3.8 nm) are highly dispersed and firmly immobilized within ultrathin LDH nanosheets, and their Ag2O shell possesses abundant vacancy-type defects. These unique Ag@Ag2O/LDHs-U display an impressive photothermal conversion efficiency as high as 76.9% at 1064 nm. Such an excellent photothermal performance is likely attributed to the enhanced localized surface plasmon resonance (LSPR) coupling effect between Ag and Ag2O and the reduced band gap caused by vacancy-type defects in the Ag2O shell. Meanwhile, Ag@Ag2O/LDHs-U also show prominent photothermal stability, due to the unique supported core-shell nanostructure. Moreover, both in vitro and in vivo studies further confirm that Ag@Ag2O/LDHs-U possess good biocompatible properties and outstanding PTT therapeutic efficacy in the NIR-II region. This research shows a new strategy in the rational design and preparation of an efficient photothermal agent, which is helpful to achieve more accurate and effective cancer theranostics.

Nanocarbon Framework-Supported Ultrafine Mo2C@MoOx Nanoclusters for Photothermal-Enhanced Tumor-Specific Tandem Catalysis Therapy.

Recent advances in the synthesis of multifunctional nanomaterials create new opportunities for the rational design of multimodal chemodynamic therapy (CDT) agents. Precisely tailoring the nanostructure and composition of CDT nanoagents for maximum efficacy remains a challenge. Herein, we report the successful synthesis of nanocarbon framework-supported ultrafine Mo2C@MoOx nanoclusters (C/Mo2C@MoOx) via a pyrolysis of a Mo/ZIF-8 MOF precursor at 900 °C followed by mild surface oxidation. The developed C/Mo2C@MoOx composite demonstrated outstanding performance in photothermal-enhanced tumor-specific tandem catalysis therapy. Specifically, C/Mo2C@MoOx efficiently catalyzed the conversion of endogenous H2O2 to cytotoxic 1O2 via a Russell mechanism, while also converting the O2 byproduct to cytotoxic ·O2- via an oxidase-like mechanism. A high dispersion of active Mo5+ sites in the exposed MoOx shell enhanced the reactive oxygen species (ROS)-generating efficiency of C/Mo2C@MoOx. Moreover, the Mo2C core in the ultrafine Mo2C@MoOx nanoclusters allowed NIR-II (1064 nm)-driven photothermal heating, which significantly boosted the CDT process through photothermal effects. Additionally, the CDT process relied on a redox cycle involving Mo5+/Mo6+ species, which could be sustained by glutathione (GSH) consumption. Given these advantages, C/Mo2C@MoOx demonstrated remarkable synergistic therapeutic efficacy for cancer treatment (both in vitro and in vivo) through tumor microenvironment-stimulated generation of multiple ROS and NIR-II photothermal activity.

Photogenerated-hole-induced rapid elimination of solid tumors by the supramolecular porphyrin photocatalyst.

The rapid, complete, targeted and safe treatment for tumors remains a key issue in cancer therapy. A novel treatment of solid tumors by supramolecular photocatalyst Nano-SA-TCPP with the irradiation of 600-700 nm wavelength is established. Solid tumors (100 mm3) can be eliminated within 10 min. The 50-day mouse survival rate was increased from 0% to 100% after the photocatalytic therapy. The breakthrough was owing to the cell membrane rupture and the cytoplasmic loss caused by photogenerated holes inside cancer cells. The porphyrin-based photocatalysts can be internalized in a targeted manner by cancer cells due to the size selection effect, without entering the normal cells. The therapy has no toxicity or side effects for normal cells and organisms. Moreover, the photocatalytic therapy is effective for a variety of cancer cell lines. Because of its high efficiency, safety and universality, the photocatalytic therapy provides us with a new lancet to conquer the tumor.

Self-Cycling Free Radical Generator from LDH-Based Nanohybrids for Ferroptosis-Enhanced Chemodynamic Therapy.

Nonapoptotic ferroptosis has been a novel form of programmed cell death, which provides a new solution to enrich the anticancer treatment efficacy of traditional apoptotic therapeutic modality. Herein, a novel nanohybrid is designed by loading the PEG-encapsulated Artemisinin (denoted as A@P) on the ultrathin MgFe-LDH nanosheets (denoted as uLDHs) for improved chemodynamic therapy (CDT). The A@P/uLDHs cannot only realize the self-assembly between the Art and carrier but also be regarded as free radical generator. A comprehensive mechanistic study suggests that this unique A@P/uLDHs is able to in situ activate Art and self-cycling generate toxic C-centered free radical inside the cancer cells, without depending on abundant H2 O2 , accompanied with diminished cancerous antioxidation by depleting glutathione (GSH). The accumulation of ROS and depletion of GSH can further oxidize unsaturated fatty acid to generate lipid peroxide, whose overexpression can induce cell ferroptosis accompanied by cellular iron homeostasis turbulence. Both in vitro and in vivo results exhibit that A@P/uLDHs are an efficient nanoagent for highly efficient ferroptosis-enhanced CDT treatment. This work imparts the promising new visions about the ferroptosis-enhanced CDT via fine regulation of material design for improved cancer treatments.

Carbon-Defect-Driven Boron Carbide for Dual-Modal NIR-II/Photoacoustic Imaging and Photothermal Therapy.

Recently, tremendous attention has been evoked in the discovery of defect-engineered nanomaterials for near-infrared second window (NIR-II)-driven cancer therapy. Herein, we have constructed a novel type of carbon defects enriched in boron carbide nanomaterial (denoted as B4C@C) through reacting B4C and glucose by a hydrothermal method. The carbon defect concentration in B4C@C has been significantly increased after coating with glucose; thus, B4C@C exhibited a distinct photothermal response under the NIR-II window and the efficiency of photothermal conversion is determined to reach 45.4%, which is higher than the carbon-based nanomaterials in the NIR-II region. Both Raman spectra and X-ray photoelectron spectroscopy (XPS) spectra reveal that B4C@C has rich sp2-hybridized carbon defects and effectively increases the NIR-II window light absorption capacity, thus enhancing the nonradiative recombination rate and improving the NIR-II photothermal effect. Furthermore, the B4C@C nanosheets allows for tumor phototherapy and simultaneous photoacoustic imaging. This work indicates the huge potential of B4C@C as a novel photothermal agent, which might arise much attention in exploring boron-based nanomaterials for the advantage of cancer therapy.

Electron Donor-Acceptor Effect-Induced Organic/Inorganic Nanohybrids with Low Energy Gap for Highly Efficient Photothermal Therapy.

For the design and optimization of near-infrared photothermal nanohybrids, tailoring the energy gap of nanohybrids plays a crucial role in attaining a satisfactory photothermal therapeutic efficacy for cancer and remains a challenge. Herein, we report an electron donor-acceptor effect-induced organic/inorganic nanohybrid with a low energy gap (denoted as ICG/Ag/LDH) by the in situ deposition of Ag nanoparticles onto the CoAl-LDH surface, followed by the coupling of ICG. A combination study verifies that the supported Ag nanoparticles as the electron donor (D) push electrons into the conjugated system of ICG by the electronic interaction between ICG and Ag, while OH groups of LDHs as the electron acceptor (A) pull electrons from the conjugated system of ICG by hydrogen bonding (N···H-O). This induces the formation of the D-A conjugated π-system and has a strong influence on the π-conjugated system of ICG, thus leading to a prominent decrease toward the energy gap and correspondingly an ultra-long redshift (∼115 nm). The resulting ICG/Ag/LDHs show an enhanced photothermal conversion efficiency (∼45.5%) at 808 nm laser exposure, which is ∼1.6 times larger than that of ICG (∼28.4%). Such a high photothermal performance is attributed to the fact that ICG/Ag/LDHs possess a D-π-A hybrid structure and a resulting lower energy gap, thus effectively promoting nonradiative transitions and leading to enhancement of the photothermal effect. Both in vitro and in vivo results confirm the good biocompatible properties and capability of the ICG/Ag/LDHs for NIR-triggered cancer treatment. This research demonstrates a successful paradigm for the rational design and preparation of new nanohybrids through the modulation of electron donor-acceptor effect, which offers a new avenue to achieve efficient phototherapeutic agent for improving the cancer therapeutic outcomes.