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Dual-labeled single fluorescent probes are powerful tools for studying autophagy on the molecular scale, yet their development has been hampered by design complexity and a lack of valid strategies. Herein, for the first time, we introduce a combinatorial regulation strategy to fabricate dual-labeled probes for studying autophagy by integrating the specific organelle-targeting group and the functional fluorescence switch into a pentacyclic pyrylium scaffold (latent dual-target scaffold). For proof of concept, we prepared a range of dual-labeled probes (TMOs) that display different emission colors in duple organelles. In these probes, TMO1and TMO2enabled the simultaneous two-color visualization of the lysosomes and mitochondria. The other probes (TMO3and TMO4) discriminatively targeted lysosomes/nucleolus and lysosomes/lipid droplets (LDs) with dual-color emission characteristics, respectively. Intriguingly, by simply connecting the endoplasmic reticulum (ER) targeting group to the pentacyclic pyrylium scaffold, we created the first dual-labeled probe TMO5for simultaneously labeling lysosomes/ER in distinctive fluorescent colors. Subsequently, using the dual-labeled probe TMO2, drug-induced mitophagy was successfully recorded by evaluating the alterations of multiple mitophagy-related parameters, and the mitophagy defects in a cellular model of Parkinson’s disease (PD) were also revealed by simultaneous dual-color/dual-organelle imaging. Further, the probe TMO4can track the movement of lysosomes and LDs in real time and monitor the dynamic process of lipophagy. Therefore, this work not only presents attractive dual-labeled probes to promote the study of organelle interactions during autophagy but also provides a promising combinatorial regulation strategy that may be generalized for designing other dual-labeled probes with multiple organelle combinations.

Porphyrins and their derivatives are widely used as photosensitizers and sonosensitizers in tumor treatment. Nevertheless, their poor water solubility and low chemical stability reduce their singlet oxygen (1O2) yield and, consequently, their photodynamic therapy (PDT) and sonodynamic therapy (SDT) efficiency. Although strategies for porphyrin molecule assembly have been developed to augment 1O2generation, there is scope for further improving PDT and SDT efficiencies. Herein, we synthesized ordered manganese porphyrin (SM) nanoparticles with well-defined self-assembled metalloporphyrin networks that enabled efficient energy transfer for enhanced photocatalytic and sonocatalytic activity in 1O2production. Subsequently, Au nanoparticles were grown in situon the SM surface by anchoring the terminal alkynyl of porphyrin to form plasmonic SMA heterostructures, which showed the excellent near-infrared-II (NIR-II) region absorption and photothermal properties, and facilitated electron–hole pair separation and transfer. With the modification of hyaluronic acid (HA), SMAH heterostructure nanocomposites exhibited good water solubility and were actively targeted to cancer cells. Under NIR-II light and ultrasound (US) irradiation, the SMAH generates hyperthermia, and a large amount of 1O2, inducing cancer cell damage. Both in vitroand in vivostudies confirmed that the SMAH nanocomposites effectively suppressed tumor growth by decreasing GSH levels in SDT-augmented PDT/PTT. Moreover, by utilizing the strong absorption in the NIR-II window, SMAH nanocomposites can achieve NIR-II photoacoustic imaging-guided combined cancer treatment. This work provides a paradigm for enhancing the 1O2yield of metalloporphyrins to improve the synergistic therapeutic effect of SDT/PDT/PTT.

The tumor immunosuppressive microenvironment (TIME) and uncontrollable release of antigens can lower the efficacy of nanovaccine-based immunotherapy (NBI). Therefore, it is necessary to develop a new strategy for TIME reshaping and controllable release of antigens to improve the NBI efficacy. Herein, an acidity-responsive Schiff base-conjugated polyphenol-coordinated nanovaccine was constructed for the first time to realize bidirectional TIME reshaping and controllable release of antigens for activating T cells. In particular, an acidity-responsive tannic acid-ovalbumin (TA-OVA) nanoconjugate was prepared viaa Schiff base reaction. FeIIIwas coordinated with TA-OVA to produce a FeIII-TA-OVA nanosystem, and 1-methyltryptophan (1-MT) as an indoleamine 2,3-dioxygenase inhibitor was loaded to form a polyphenol-coordinated nanovaccine. The coordination between FeIIIand TA could cause photothermal ablation of primary tumors, and the acidity-triggered Schiff base dissociation of TA-OVA could controllably release OVA to realize lysosome escape, initiating the body's immune response. More importantly, oxidative stress generated by a tumor-specific Fenton reaction of Fe ions could promote the polarization of tumor-associated macrophages from the M2 to M1 phenotype, resulting in the upregulation of cytotoxic T cells and helper T cells. Meanwhile, 1-MT could downregulate immunosuppressive regulatory T cells. Overall, such skillful combination of bidirectional TIME reshaping and controllable antigen release into one coordination nanosystem could effectively enhance the NBI efficacy of tumors.

Natural biopolymers can be controllably in situsynthesized in organisms and play important roles in biological activities. Inspired by this, the manipulation of in situbiosynthesis of functional polymers in vivowill be an important way to obtain materials for meeting biological requirements. Herein, in situbiosynthesis of functional conjugated polymer at the tumor site was achieved via the utilization of specific tumor microenvironment (TME) characteristics for the first time. Specially, a water-soluble aniline dimer derivative (N-(3-sulfopropyl) p-aminodiphenylamine, SPA) was artfully in situpolymerized into polySPA (PSPA) nanoparticles at the tumor site, which was activated via the catalysis of hydrogen peroxide (H2O2) overexpressed in TME to produce hydroxyl radical (•OH) by coinjected horseradish peroxidase (HRP). Benefiting from outstanding near-infrared (NIR)-II absorption of PSPA, the in situpolymerization process can be validly monitored by photoacoustic (PA) signal at the NIR-II region. Meanwhile, in situpolymerization would induce the size of polymeric materials from small to large, improving the distribution and retention of PSPA at the tumor site. On the combination of NIR-II absorption of PSPA and the size variation induced by polymerization, such polymerization can be applied for tumor-specific NIR-II light mediated PA image and photothermal inhibition of tumors, enhancing the precision and efficacy of tumor phototheranostics. Therefore, the present work opens the way to manipulate TME-activated in situbiosynthesis of functional conjugated polymer at the tumor site for overcoming formidable challenges in tumor theranostics.

Phototheranostics has attracted considerable attention in the fields of cancer diagnosis and treatment. However, the complete eradication of solid tumors using traditional phototheranostics is difficult because of the limited depth and range of laser irradiation. New phototheranostics enabling precise phototherapy and post-treatment imaging-guided programmed therapy for residual tumors is urgently required. Accordingly, this study developed a novel transformable phototheranostics by assembling hyaluronic acid (HA) with copper-nitrogen-coordinated carbon dots (CDs). In this transformable nanoplatform, named copper-nitrogen-CDs@HA, the HA component enables the specific targeting of cluster determinant (CD) 44-overexpressing tumor cells. In the tumor cells, redox glutathione converts Cu(II) (cupric ions) into Cu(I) (cuprous ions), which confers the novel transformable functionality to phototheranostics. Both in vitroand in vivoresults reveal that the near-infrared-light-photoactivated CuII-N-CDs@HA could target CD44-overexpressing tumor cells for precise synergistic photothermal therapy and photodynamic therapy. This study is the first to observe that CuII-N-CDs@HA could escape from lysosomes and be transformed in situinto CuI-N-CDs@HA in tumor cells, with the d9electronic configuration of Cu(II) changing to the d10electronic configuration of Cu(I), which turns on their fluorescence and turns off their photothermal properties. This transformable phototheranostics could be used for post-treatment imaging-guided photodynamic therapy on residual tumor cells. Thus, the rationally designed copper-nitrogen-coordinated CDs offer a simple in situtransformation strategy for using multiple-stimulus-responsive precise phototheranostics in post-treatment monitoring of residual tumor cells and imaging-guided programmed therapy.

The therapeutic effect of photothermal therapy (PTT) and photodynamic therapy (PDT) is severely limited because of the shallow tissue penetration depth of the first near-infrared (NIR-I) light. Multifunctional nanotheranostics irradiated by the second near-infrared (NIR-II) light have received wide interest with respect to deeper tissue penetration, and sonodynamic therapy (SDT) synergistic phototherapy can achieve the complete elimination of tumors. Herein, we successfully constructed a single NIR-II light-induced nanotheranostic using cerium oxide (CeO2–x) with abundant oxygen vacancies for photoacoustic imaging-guided SDT-enhanced phototherapy for the first time. CeO2–xwith surface crystalline disorder showed extensive NIR-II region absorption and an outstanding photothermal conversion ability. In addition, the CeO2–xlayer with numerous oxygen defects can promote the separation of holes and electrons by ultrasound irradiation, which can remarkably enhance the efficacy of phototherapy to achieve high-efficiency tumor ablation. CeO2–xwas surface modified with hyaluronic acid (HA) to prepare CeO2–x@HA to allow active tumor targeting efficiency. Both cell and animal experiments confirmed that all-in-one CeO2–x@HA exhibited a high therapeutic efficacy of SDT-enhanced PDT/PTT under 1064 nm laser irradiation, which achieved complete tumor eradication without systemic toxicity. This study significantly broadened the application of NIR-II-responsive CeO2–xfor photoacoustic imaging-mediated SDT-enhanced phototherapy to the highly efficient and precise elimination of tumors.

Phototheranostic offers a regional-focused tumor treatment upon photoirradiation. However, it is difficult to completely eradicate solid tumors using a conventional phototheranostic owing to the residual tumor cells outside the laser irradiation range. Herein, we fabricated a metallopolysaccharide-based smart nanotheranostic (Fe–dHA) via a nanoassembly-driven method, in which Fe3+ions were coordinated to dopamine-modified biopolysaccharide hyaluronic acid (dHA). Taking advantage of the structural backbone and intrinsic dual-information-related functions of HA as well as the bi-functional Fe(III)-coordination centers, Fe–dHA can efficiently target tumor cells for phototheranostic. Additionally, it can be activated by endogenous overexpressed hyaluronidase to achieve sequential ferroptosis in tumor cells. The precise imaging and effective tumor inhibition using this metallopolysaccharide-based nanotheranostic were significantly demonstrated in vivo and in vitro. Thus, this rationally designed Fe–dHA provided a simple metallopolysaccharide strategy to develop an “all-in-one” smart nanotheranostic to synergize different therapeutic modalities for improving cancer therapy.

Computer simulations are widely applied to study surface-initiated polymerization (SIP), but in many studies, the chains are assumed to grow at the same speed, implying a homogeneous reaction environment. It has been ignored that SIP is a heterogeneous reaction. A simple stochastic reaction model is proposed in which the heterogeneity of the reaction environment is inherently considered by calculating the reaction probability of each active end individually. It was confirmed that SIP is a heterogeneous reaction, in which the inner chains grow in a monomer-poor region while the outer chains grow in a monomer-rich region. The different chain growths lead to a larger dispersity and a broader molecular weight distribution compared with the counterparts of an even chain growth system, which further affects properties like the density profile and the brush height. The results suggest that the heterogeneous reaction environment should be considered, especially when the grafting density is high.

The integration of surface-enhanced Raman spectrum (SERS) and fluorescence-photoacoustic multimodal imaging in near-infrared photothermal therapy is highly desirable for cancer theranostic. However, typically, gold nanotheranostics usually require an additional modification of fluorophores and complex design refinements. In this work, by integrating surface-modified cysteine-hydroxyl merocyanine (CyHMC) molecules onto AuNRs, a novel lysosome-targeted gold-based nanotheranostics AuNRs-CyHMC that combines the specificity of Raman spectrum, the speed of fluorescence imaging, and deep penetration of photoacoustic imaging was successfully fabricated. Interestingly, fluorescence and Raman signals in this AuNRs-CyHMC system do not interfere, but it has pH-sensitive Raman signals and self-fluorescence localization ability under different excitation wavelengths. Fluorescence co-localization experiments further confirmed the lysosome-targeting ability of AuNRs-CyHMC. Typically, the proposed nanotheranostics were capable of SERS monitoring pH changes in both phosphate-buffered saline and living cells. Meanwhile, in vitroand in vivoexperiments revealed that AuNRs-CyHMC possessed excellent fluorescence-photoacoustic performance and could be used for multimodal imaging-guided photothermal therapy. Furthermore, our work implied that gold nanotheranostics can provide great potential for cancer diagnosis and treatment.

The development of efficient and stable photocatalysts to solve environmental issues is essential and remains a big challenge. In this work, flower-like CoNiFe-LDH is deposited in situon g-C3N4nanosheets, successfully constructing a Z-scheme heterojunction CoNiFe-LDH/g-C3N4photocatalyst for the photoreduction of CO2and photodegradation of MB dye. The synthesized nanohybrid shows superior photocatalytic CO2performance (42.04 μmol g−1h−1) and fast photodegradation MB performance (0.1057 min−1). The improved photocatalytic performance was attributed to the formation of the Z-scheme heterojunction with matched energy bands, and the intimate heterojunction contact interface, which significantly enhanced the interfacial charge transfer rate and improved the separation efficiency of electron–hole pairs. Moreover, the photocatalytic mechanism was proposed based on PL, photocurrent responses, EIS, and EPR experiments. This work can shed light on further application for environmental problems of Z-scheme heterojunction photocatalysts.

In this study, sorted nitrogen-doped graphene quantum dots were prepared and subsequently conjugated with polymers. The synthesized materials exhibited excitation-wavelength-independent photoluminescence emissions ranging from ultraviolet to near-infrared and were 0.9–8.4 nm in size. The materials also exhibited high-photoluminescence quantum yields and excellent two-photon properties. Therefore, in two-photon bioimaging the materials with different emission spectra can be effective two-photon contrast agents. Specific antibodies were used to label organelles in cancer cells and identify nuclear antigens, thereby enabling the simultaneous detection of four targets in cells at a single two-photon excitation wavelength. The sorted nitrogen-doped graphene quantum dot materials were determined to be considerably more advantageous than organic dyes in identifying multiplexed targets, and they can be effective probes in cellular imaging.

Second near-infrared (NIR-II) window responsive phototheranostic agents have a precise spatiotemporal potential for the diagnosis and treatment of cancer. In this study, a full-spectrum responsive ZrO2-based phototheranostic agent was found to achieve NIR-II photoacoustic (PA) imaging-guided tumour-targeting phototherapy. Initially, the ZrO2-based phototheranostic agent was fabricated through NaBH4reduction to form boron-doped oxygen-deficient zirconia (ZrO2−x-B), an amino-functionalised SiO2shell and a further covalent connection with hyaluronic acid (HA), namely, ZrO2−x-B@SiO2-HA. In the ZrO2−x-B@SiO2-HA system, the oxygen vacancy and boron doping resulted in full-spectrum absorption, enabling a high NIR-II photothermal conversion, high-resolution PA imaging ability and a remarkable production of reactive oxygen species (ROS). The surface modification of HA provided ZrO2−x-B@SiO2-HA with water dispersibility and a targeting capability for CD44 overexpressed cancer cells. Furthermore, in vitroand in vivoexperiments showed that NIR-II activated ZrO2−x-B@SiO2-HA had a targeted photothermal/photodynamic effect for cancer elimination under the real-time guidance of NIR-II PAs. Hence, ZrO2−x-B@SiO2-HA displays a precise NIR-II radiation-activated phototheranostic potential for PA imaging-guided cancer-targeting photothermal/photodynamic therapy.

Copper-mediated programmed cell death, which influences the regulation of tumor progression, is an effective approach for antitumor molecular therapy. Unlike apoptosis, copper complex-induced cuproptosis by lipid-acylated protein aggregation triggers the mitochondrial proteotoxic stress response, which could be associated with immunomodulation. However, it remains a great challenge to understand the distinctive molecular mechanisms that presumably activate immunity by cuproptosis. Here, the new nonlabeling fluorescent molecular tools of Cu-DPPZ-Py+and Cu-DPPZ-Ph are synthesized and used to investigate the differential immune signaling mechanisms induced by copper-mediated cuproptosis or apoptosis. With Cu-DPPZ-Py+and Cu-Elesclomol, there is strong evidence that the triggering cuproptosis significantly drives mitochondrial DNA (mtDNA) release to activate innate immunity via cyclic GMP-AMP synthase-stimulation of interferon genes (cGAS-STING), which can improve T cell antitumor immunity in vivo. By contrast, it is observed that Cu-DPPZ-Ph treated tumor cells could release intracellular caspase-3, resulting in apoptosis-associated immunosuppression. This study supports insights into how cuproptosis bridges cGAS-STING immune pathways, contributing to the development of cuproptosis-based antitumor immunotherapy.

Photodynamic therapy (PDT) of hypericin (Hyp) is hampered by poor water solubility and photostability. Incorporation of photosensitizers into nanocarriers has been designed to solve these issues. Herein, SWNH-Hyps nanohybrids were first fabricated by loading hypericin on the surface of single-walled carbon nanohorns (SWNHs) through ??? interaction and exhibited high solubility and stability in aqueous water. SWNH-Hyps could be utilized for a single platform for cancer therapy because it could simultaneously generate enough reactive oxygen species and hyperthermia using light irradiation. Moreover, the SWNHs not only improved water solubility, photostability, and therapy effects of Hyp but also protected it from light degradation. SWNH-Hyps could effectively ablate 4T1 cells by photodynamic/photothermal synergistic therapy upon 590 and 808 nm light irradiations compared with PDT. Furthermore, remarkable tumor cell death as well as tumor growth inhibition was proved via photothermal therapy and PDT of SWNH-Hyps under 590 and 808 nm light irradiations, which demonstrated that synergistic anticancer ability of SWNH-Hyps was better than that of free Hyp in vivo. Such a simple and facile adsorption method improved water solubility of Hyp and then enhanced its therapy effect, which displays that SWNHs can be hopefully used in medicines in the future.

Although phototherapy has been considered as an emerging and promising technology for cancer therapy, its therapeutic specificity and efficacy are severely limited by nonspecific uptake by normal tissues, tumor hypoxia, and so on. Herein, combination-responsive strategy (CRS) is applied to develop one kind of hyaluronic acid-hybridized Ru nanoaggregates (HA-Ru NAs) for enhanced cancer phototherapy via the reasonable integration of receptor-mediated targeting (RMT) and tumor-microenvironment responsiveness (TMR). In this nanosystem, the HA component endows HA-Ru NAs with RMT characteristic to selectively recognize CD44-overexpressing cancer cells, whereas the Ru nanocomponent makes HA-Ru NAs have TMR therapy activity. Specially, the Ru nanocomponent not only has near-infrared-mediated photothermal and photodynamic functions but also can catalyze H2O2in tumor tissue to produce O2for the alleviation of tumor hypoxia and toxic •OH for chemodynamic therapy. Benefitting from these, HA-Ru NAs can be considered as a promising kind of CRS nanoplatforms for synergistic photothermal/photodynamic/chemodynamic therapies of cancer, which will not only effectively improve the phototherapeutic specificity and efficacy but also simplify the therapeutic nanosystems. Meanwhile, HA-Ru NAs can serve as a photoacoustic and computed tomography imaging contrast agent to monitor tumors. Such CRS nanoplatforms hold significant potential in improving therapeutic specificity and efficacy for enhanced cancer phototheranostics.

Indocyanine green (ICG), a multifunctional near-infrared (NIR) imaging agent approved by the FDA, has been extensively used in clinical cancer theranosis, but limited by its inherent instability, short plasma half-life and lack of targeting ability. Herein, an in situformed photothermal network based thermosensitive hydrogel (PNT-gel) constructed by using supramolecular cross-linking conjugated polymers was developed for the stabilization of ICG and efficient combinatorial photothermal/photodynamic antitumor therapy. While the conjugated polymeric backbone in PNT-gel anchored the aromatic phototherapeutic agent ICG viaπ–π stacking interactions to avoid premature leakage, it also directly converted low-dose NIR light to induce localized hyperthermia to enhance the photothermal effect. The PNT-gel shows a reversible gel-to-sol upper critical solution temperature (UCST) that is slightly above body temperature. Therefore, the controlled release of ICG was switched on or off by NIR viaphotothermal-induced gel–sol transition. In vitroand in vivoantitumor experiments demonstrated that ICG loaded PNT-gel not only efficiently induced the killing of 4T1 cancer cells, but also achieved almost complete eradication of 4T1 cells by one-dose intratumoral injection in combinatorial photothermal/photodynamic therapy under irradiation of a low-dose 808 nm laser (0.14 W cm−2). Additionally, the combinational therapy proved to enhance the effectiveness of photodestruction without tumor recurrence compared with photothermal therapy (PTT) or photodynamic therapy (PDT) treatment alone.

Specific targeting capabilities and effective phototherapeutic functions are the key demands for precise cancer phototherapeutic agents. Herein, a bioinspired nanoplatform composed of Cu(ii)-chlorophyll–hyaluronic acid nanoparticles (Cu(ii)Chl–HA NPs) was developed for targeting cancer and synergistic photodynamic/photothermal therapy. Inspired by the photonic biosystem of the chloroplast, Cu(ii) chlorophyll was used as a photosensitive substituent to covalently connect with a hydrophilic HA tail rather than a natural phytol tail, and this conjugate further assembled into a nanoparticle-like morphology under non-covalent interaction. Time-dependent density functional theory calculations reveal that the Cu(ii) chlorophyll has a much smaller energy gap between an excited singlet and excited triplet, and theoretically leads to rapid electron intersystem crossing that would benefit the PDT effect. In addition, a series of experiments have proven that, under 650 nm laser irradiation, the nanoplatform of Cu(ii)Chl–HA can produce a high amount of singlet oxygen and exhibit an outstanding photothermal conversion capability. More interestingly, owing to the specific interactions between the HA component and the CD44 receptor on the cell membrane, the HA tails impart Cu(ii)Chl–HA NPs an excellent receptor-mediated targeting performance toward CD44-overexpressing cancer cells. Based on these features, the nanoplatform of Cu(ii)Chl–HA NPs presents active targeting and outstanding dual modality synergistic PDT/PTT performance of cancer both in vitroand in vivo. Thus, this work opens up a new strategy to fabricate a bioinspired multifunctional cancer phototherapy nanoplatform.

It is of extreme importance to reduce side effects resulting from the nonspecific uptake of phototherapeutic agents by normal tissues. Currently, the single responsive strategy still cannot entirely satisfy the requirements of practical applications. In this study, we developed one kind of combination-responsive phototherapeutic nanoplatforms, where oxygen-deficient molybdenum oxide (MoO3–x) hybridized hyaluronic acid (HA) hollow nanospheres, namely, MoO3–x@HA HNSs, were constructed via a facile one-step method. In MoO3–x@HA HNSs, the reasonable combination of actively targeted specificity endowed by the HA component and tumor microenvironment-responsive phototherapy activity induced by the MoO3–xcomponent can effectively improve the precision of phototherapy. The in vitroand in vivoexperimental results confirm that MoO3–x@HA HNSs can selectively kill CD44-overexpressing cancer cells and inhibit tumor growth under an 808 nm laser irradiation, revealing their remarkable synergistic photothermal therapy/photodynamic therapy effect with CD44 receptor-targeted specificity and pH responsiveness in treating cancer. We also prove that MoO3–x@HA HNSs can serve as one kind of contrast agent to achieve the computed tomography/photoacoustic imaging. Encouraged by these results, it is anticipated that the reasonable combination of active targeting and tumor microenvironment responsiveness can be a promising strategy to develop phototherapeutic nanoplatforms for precise multimodality cancer theranostics.

Hybrid Nanoenzymes In article 2300385by Xing‐Can Shen and co‐workers, a bioinspired metalloprotein‐like hybrid nanozyme (FeS@GOx) is designed by incorporating the FeS nanozyme as brand‐new cofactors within natural GOx protein scaffolds, providing a feasible H2S gas amplified ROS cascade strategy for precise and efficient tumor chemodynamic immunotherapy.

Chemodynamic immunotherapy that utilizes catalysts to produce reactive oxygen species (ROS) for killing tumor cells and arousing antitumor immunity has received considerable attention. However, it is still restricted by low ROS production efficiency and insufficient immune activation, due to intricate redox homeostasis in the tumor microenvironment (TME). Herein, a metalloprotein‐like hybrid nanozyme (FeS@GOx) is designed by in situ growth of nanozyme (ferrous sulfide, FeS) in a natural enzyme (glucose oxidase, GOx) to amplify ROS cascade for boosting chemodynamic immunotherapy. In FeS@GOx, GOx allows the conversion of endogenous glucose to gluconic acid and hydrogen peroxide, which provides favorable increasing hydrogen peroxide for subsequent Fenton reaction of FeS nanozymes, thus reinforcing ROS production. Notably, hydrogen sulfide (H2S) release is activated by the gluconic acid generation‐related pH decrease, which can suppress the activity of endogenous thioredoxin reductase and catalase to further inhibit ROS elimination. Thus, FeS@GOx can sustainably amplify ROS accumulation and perturb intracellular redox homeostasis to improve chemodynamic therapy and trigger robust immunogenic cell death for effective immunotherapy combined with immune checkpoint blockade. This work proposes a feasible H2S amplified ROS cascade strategy employing a bioinspired hybrid nanozyme, providing a novel pathway to multi‐enzyme‐mediated TME modulation for precise and efficient chemodynamic immunotherapy. A bioinspired metalloprotein‐like hybrid nanozyme (FeS@GOx) is designed by incorporating the ferrous sulfide (FeS) nanozyme as brand‐new cofactors within natural glucose oxidase (GOx) protein scaffolds. Due to the novel multi‐enzyme‐mediated pathway to modulate the tumor microenvironment, the FeS@GOx hybrid nanozyme provides a feasible hydrogen sulfide gas amplified reactive oxygen species cascade strategy for precise and efficient tumor chemodynamic immunotherapy.

Design and development of photosensitizers that can efficiently convert energy of near-infrared (NIR) laser irradiation are of major importance for cancer photoassisted therapeutics. Herein, for the first time, it is demonstrated that Prussian blue (PB), a classic coordination compound, can act as a novel photosensitizer with efficient generation of singlet oxygen and excellent photothermal conversion via NIR photoirradiation-induced energy transfer. After modification with hyaluronic acid (HA), the as-prepared HA-modified PB nanocubes (HA@PB) are highly dispersible in aqueous and physiological solutions, as well as show excellent photothermal/photodynamic activities under NIR (808 nm) photoexcitation. On the basis of these features, HA@PB is used to study their in vitro and in vivo combined therapeutic effect. Owing to the CD44 ligand of HA, HA@PB have specific uptake by CD44-positive cells in vitro and can be precisely in vivo delivered to the tumor site. HA@PB as one of the synergistically photodynamic/photothermal combination nanoplatforms could achieve excellent therapeutic efficacy with targeted specificity under the guidance of dual-modality photoacoustic/infrared thermal imaging. Hence, this work is expected to pave the way for using PB-based nanomaterials as a promising multifunctional theranostic nanoplatform in biomedical fields.

Effectively eliminating mercury pollution in aqueous solutions remains an onerous task and important environmental challenge for protecting the public health and environment. Herein, we report a facile one-step hydrothermal approach to synthesis widened molybdenum disulfide (W-MoS2) nanosheets/natural cellulose fiber composite (W-MoS2/NCF) for highly efficient elimination of Hg(II) from aquatic systems. Benefiting from the synergistic advantages of the intrinsically sulfur-rich characteristic of W-MoS2combined with its enlarged interlayer spacing (0.94 nm) that fully exposes the sulfur atoms as binding sites, as well as the vertical immobilization of W-MoS2nanosheets on the cellulose fibers that enables the easy accessibility of all the S binding sites, the maximum adsorption capacity of W-MoS2/NCF towards Hg(II) was 1206 mg g−1, implying that almost all the S binding sites were fully utilized for mercury uptake. Moreover, the 3D structure characteristics can not only avoid the self-aggregation of 2D nanosheets, but also benefit the removal, regeneration, and reuse of this composite in practical application by offering convenient operations. In consequence, the W-MoS2/NCF outperformed the most of MoS2-based composites in terms of mercury removal capacity, utilization efficiency of S, operation convenience, and recyclability. Taken together, the combination of the advantages of its excellent Hg(II) capture performance, facile and scalable synthesis process, the easy availability of raw materials, easy recyclability and reusability endowed the as-prepared W-MoS2/NCF with promising potential for being used as a highly effective scavenger to decontaminate Hg(II) contaminated wastewater.

The biomedical applications of carbon nanomaterials, especially integrating noninvasive photothermal therapy (PTT) and photodynamic therapy (PDT), into a single system have enormous potential in cancer therapy. Herein, we present a novel and facile one-step method for the preparation of water-soluble single-walled carbon nanohorns (SWNHs) and metal phthalocyanines (MPc) hybrid for PTT and PDT. The hydrophilic MPc, tetrasulfonic acid tetrasodium salt copper phthalocyanine (TSCuPc), is coated on the surface of SWNHs via noncovalent π–π interaction using the sonication method. In this PTT/PDT nanosystem, SWNHs acts as a photosensitizer carrier and PTT agent, while TSCuPc acts as a hydrophilic and PDT agent. The EPR results demonstrated that the generated reactive oxygen species (ROS) not only from the photoinduced electron transfer process from TSCuPc to SWNHs but also from SWNHs without exciting TSCuPc to its excited state. The test of photothermal conversion proved that not only do SWNHs contribute to the photothermal therapy (PTT) effect, TSCuPc probably also contributes to that when it coats on the surface of SWNHs upon exposure to a 650-nm laser. More importantly, the results of in vitrocell viability revealed a significantly enhanced anticancer efficacy of combined noninvasive PTT/PDT, indicating that the SWNHs–TSCuPc nanohybrid is a hopeful candidate material for developing an efficient and biocompatible nanoplatform for biomedical application.

Hexavalent chromium Cr(VI) is one of the most toxic heavy metal pollutants in water due to its high water solubility, high toxicity, strong mutagenicity and carcinogenicity. To enable efficient Cr(VI) removal from wastewater, it remains difficult to fabricate advanced adsorbents with good selectivity and high adsorption capacity in large scale. Herein, a poly(hexamethylenediamine-tannic acid)-bacterial cellulose (denoted as HTA-BC) composite was prepared by using natural raw materials with abundance, low cost and nontoxicity in a facile one-step method and applied for the decontamination of highly toxic Cr(VI). The as-synthesized HTA-BC functionalized with abundant amino and phenolic hydroxyl groups had demonstrated high capacity (534.8 mg g−1) and good selectivity for Cr(VI) scavenging. Notably, the treatment of real water samples with the HTA-BC composite could efficiently reduce the concentration of the spiked Cr(VI) below the acceptable levels for drinking water. Moreover, high-purity Cr2O3was obtained by calcination of the Cr species-laden HTA-BC to ensure that the toxic Cr(VI) residing in the spent adsorbents can’t leak out into the surroundings, thus avoiding the secondary pollution. The natural abundance, low cost, easy availability, and sustainability of the raw materials, combined with the facile and green synthesis endowed the HTA-BC composite with great potential for not only decontaminating Cr(VI) wastewater, but also recycling Cr by calcination of the Cr-laden HTA-BC. Moreover, no secondary pollution would be brought during the synthesis and the post-treatment after the Cr(VI) removal, thus it is expected to be a green and sustainable approach for the purification of Cr(VI) containing wastewater.

Silk fibroin (SF) from the Bombyx morisilkworm exhibits attractive potential applications as biomechanical materials, due to its unique mechanical and biological properties. This review outlines the structure and properties of SF, including of its biocompatibility and biodegradability. It highlights recent researches on the fabrication of various SF-based composites scaffolds that are promising for tissue engineering applications, and discusses synthetic methods of various SF-based composites scaffolds and valuable approaches for controlling cell behaviors to promote the tissue repair. The function of extracellular matrices and their interaction with cells are also reviewed here.

Various functional groups have been suggested to play essential roles on biomineralization of calcium carbonate (CaCO3) in natural system. 2D and 3D models of regularly arranged functional groups have been established to investigate their effect on CaCO3crystallization. This mini-review summarizes the recent progress and the future development is prospected.

Four families of magic-sized ZnSe quantum dots (ZnSe MSQDs) with the first exciton absorption peaks at 280 nm (F280), 291 nm (F291), about 319 nm (F319), and 347 nm (F347) were synthesized using fatty amine−H2Se complex as selenium precursor via noninjection one-pot or hot-injection approaches. The formation, growth, and transformation of these families of ZnSe MSQDs were monitored mainly by ultraviolet−visible absorption spectroscopy. Relatively pure F291 and F347 were obtained via the combination of hot-injection technology with purification treatment and were further characterized using mass spectroscopy, infrared spectroscopy, fluorescence spectroscopy, transmission electron microscopy, and X-ray powder diffraction. F291 and F347 are speculated to be [(Zn7Se7)(OLA)2(OA)] (OLA = oleylamine, OA = octylamine) and [(Zn16Se15)(OLA)7], respectively, by analyzing the corresponding mass and the infrared and absorption spectra; both emit narrow exciton fluorescence with relatively small stokes shift of 9 and 2 nm, respectively. Ultrafine ZnSe nanorods with a diameter of about 1.7 nm formed via oriented attachment of F347 were observed using transmission electron microscopy. Fatty amine−H2Se complex has been demonstrated to be a simple, phosphine-free, low-cost, and effective selenium precursor for the synthesis of ZnSe MSQDs or regular quantum dots (RQDs).

The aminosilane-modified magnetite nanoparticles were synthesized by the coprecipitation and surface modification with 3-aminopropyltriethoxysilane (APTTS). The superparamagnetic APTTS/Fe3O4nanospheres with an average diameter of 10 nm were characterized significantly with functional group, well dispersion and stabilization in aqueous fluids, as well as a maximized saturation magnetization of 63.54 emu/g.