Chemiluminescence‐Generating Nanoreactor Formulation for Near‐Infrared Imaging of Hydrogen Peroxide and Glucose Level in vivo

Water‐dispersed all‐in‐one nanoprobes composed of densely integrated peroxyoxalate fuel and a cyanine dye are formulated to optimize the nanoscopic chemiluminescence reaction. It is demonstrated that the chemiluminescent nanoformulation can generate bright near‐infrared signal in response to external hydrogen peroxide that is biologically implicated with cell signaling and diseases. Successful imaging of endogenously overproduces hydrogen peroxide and indirect determination of glucose level in vivo with the chemiluminescent nanoprobes offers an opportunity for early diagnosis of diseases.     

Hydrogen‐Bonded Organic Semiconductors as Stable Photoelectrocatalysts for Efficient Hydrogen Peroxide Photosynthesis

Research on semiconductor photocatalysts for the conversion of solar energy into chemical fuels has been at the forefront of renewable energy technologies. Water splitting to produce H₂ and CO₂ reduction to hydrocarbons are the two prominent approaches. A lesser‐known process, the conversion of solar energy into the versatile high‐energy product H₂O₂ via reduction of O₂ has been proposed as an alternative concept. Semiconductor photoelectrodes for the direct photosynthesis of H₂O₂ from O₂ have not been applied up to now. Photoelectrocatalytic oxygen reduction to peroxides in aqueous electrolytes by hydrogen‐bonded organic semiconductor is observed photoelectrodes. These materials have been found to be remarkably stable operating in a photoelectrochemical cell converting light into H₂O₂ under constant illumination for at least several days, functioning in a pH range from 1 to 12. This is the first report of a semiconductor photoelectrode for H₂O₂ production, with catalytic performance exceeding prior reports on photocatalysts by one to two orders of magnitude in terms of peroxide yield/catalyst amount/time. The combination of a strongly reducing conduction band energy level with stability in aqueous electrolytes opens new avenues for this widely available materials class in the field of photo(electro) catalysis.     

Catalyst Design for Electrochemical Oxygen Reduction toward Hydrogen Peroxide

Precise electrochemical synthesis under ambient conditions has provided emerging opportunities for renewable energy utilization. Among many promising systems, the production of hydrogen peroxide (H₂O₂) from the cathodic oxygen reduction reaction (ORR) has attracted considerable interest in past decades due to the increasing market demands and the vital role of ORR in the electrocatalysis field. This work describes recent advances in cathodic materials for H₂O₂ synthesis from 2e^- ORR. By using Pt as a stereotype, the tuning knobs are overviewed, including the intrinsic binding strength of oxygenated species, the intermediate diffusion path and the isolation of Pt–Pt ensembles that enable 2e^- ORR pathway from 4e^- total reduction. This knowledge is successfully applied to other transition metal systems and leads to the discovery of more efficient alloy catalysts with balanced improvement on both activity and selectivity. In addition, mesostructure engineering and heteroatoms doping strategies on carbon‐based materials, which significantly boost the H₂O₂ production efficiency as compared to intact carbon sites, are also reviewed. Finally, future directions and challenges of transferring developed catalysts from lab scale tests to pilot plant operations are briefly outlooked.     

Covalent Furan-Benzimidazole-Linked Polymer Hollow Fiber Membrane for Clean and Efficient Photosynthesis of Hydrogen Peroxide

Photocatalytic H₂O₂ production by conversion of O₂ in aqueous solution is often challenged by the use of sacrificial agents, the separation of powdery photocatalysts, solution, and contaminants, and low activity of photocatalyst. Herein, a membrane of covalent furan-benzimidazole-linked polymer (Furan-BILP) with both O- and N-containing heterocycles bonded via O C CN is reported for the first time as a photocatalyst to harvest clean H₂O₂ in pure water with high-performance. A coordination-polymer hard template strategy is developed to produce Furan-BILP hollow microfibers that can be further assembled into membranes with desired sizes. The resultant Furan-BILP membrane directly delivers clean H₂O₂ solution as the product with a high H₂O₂ production rate of 2200 µmol g⁻¹ h⁻¹ in pure water. Density functional theory calculations and experiment results indicate that the C atom from Furan ring on the linkage binds to the adsorbed OOH^*, the H atom of OOH^* forms a hydrogen bond with the N atom in the benzimidazole ring, thus the intermediate six-membered ring structure stabilizes the OOH^* and favors 2e-ORR. The strategy using both molecular engineering to tune the electronic structure and macrostructural engineering to shape the morphology may be applied to design other coordination organic polymer photocatalysts with further improved performance.     

A Melanin‐Based Natural Antioxidant Defense Nanosystem for Theranostic Application in Acute Kidney Injury

Acute kidney injury (AKI) is frequently associated with oxidative stress and causes high mortality annually in clinics. Nanotechnology‐mediated antioxidative therapy is emerging as a novel strategy for the treatment of AKI. Herein, a novel biomedical use of the endogenous biopolymer melanin as a theranostic natural antioxidant defense nanoplatform for AKI is reported. In this study, ultrasmall Mn²⁺‐chelated melanin (MMP) nanoparticles are easily prepared via a simple coordination and self‐assembly strategy, and further incorporated with polyethylene glycol (MMPP). In vitro experiments reveal the ability of MMPP nanoparticles to scavenge multiple toxic reactive oxygen species (ROS) and suppress ROS‐induced oxidative stress. Additionally, in vivo results from a murine AKI model demonstrate preferential renal uptake of MMPP nanoparticles and a subsequent robust antioxidative response with negligible side effects according to positron emission tomography/magnetic resonance (PET/MR) bimodal imaging and treatment assessment. These results indicate that the effectiveness of MMPP nanoparticles for treating AKI suggests the potential efficacy of melanin as a natural theranostic antioxidant nanoplatform for AKI, as well as other ROS‐related diseases.     

Photoacoustic Imaging Guided Near‐Infrared Photothermal Therapy Using Highly Water‐Dispersible Single‐Walled Carbon Nanohorns as Theranostic Agents

The poly(maleic anhydride‐alt‐1‐octadecene‐poly(ethylene glycol)) (C₁₈PMH‐PEG) modified single‐walled carbon nanohorns (SWNHs) are designed with high stability and biocompatibility. The as‐prepared SWNHs/C₁₈PMH‐PEG not only can serve as an excellent photothermal agent but also can be used as a promising photoacoustic imaging (PAI) agent both in vitro and in vivo due to its strong absorption in the near infrared (NIR) region. The PAI result reveals that the SWNHs/C₁₈PMH‐PEG possesses ultra long blood circulation time and can significantly be accumulated at the tumor site through the enhanced penetration and retention (EPR) effect. The maximum accumulation of SWNHs/C₁₈PMH‐PEG at tumor site could be achieved at the time point of 24 h after intravenous injection, which is considered to be the optimal time for the 808 nm laser treatment. The subsequent photothermal ablation of tumors can be achieved without triggering any side effects. Therefore, a PAI guided PTT platform based on SWNHs is proposed and highlights the potential theranostic application for biomedical uses.     

Stimuli‐Responsive Materials for Controlled Release of Theranostic Agents

Stimuli‐responsive materials are so named because they can alter their physicochemical properties and/or structural conformations in response to specific stimuli. The stimuli can be internal, such as physiological or pathological variations in the target cells/tissues, or external, such as optical and ultrasound radiations. In recent years, these materials have gained increasing interest in biomedical applications due to their potential for spatially and temporally controlled release of theranostic agents in response to the specific stimuli. This article highlights several recent advances in the development of such materials, with a focus on their molecular designs and formulations. The future of stimuli‐responsive materials will also be explored, including combination with molecular imaging probes and targeting moieties, which could enable simultaneous diagnosis and treatment of a specific disease, as well as multi‐functionality and responsiveness to multiple stimuli, all important in overcoming intrinsic biological barriers and increasing clinical viability.     

Dendritic Platinum–Copper Alloy Nanoparticles as Theranostic Agents for Multimodal Imaging and Combined Chemophotothermal Therapy

Theranostic nanoparticles that possess multiple diagnostic modalities and allow spatiotemporally controlled therapies can significantly improve therapeutic outcomes and reduce adverse effects. Here, an intelligent and biocompatible theranostic formulation is developed based on dendritic platinum–copper alloy nanoparticles (DPCN) for cancer therapy. DPCN have excellent photothermal effect, and can load anticancer drugs such as doxorubicin in their porous structure and release the loaded drugs in response to near infrared light or moderate acidic stimulus. They also inherently have multimodal imaging modalities. Upon the guidance of photoacoustic imaging, DPCN‐mediated photothermal treatment efficiently inhibits tumor growth in vivo. Furthermore, doxorubicin‐loaded DPCN completely suppress the tumor growth even under a low treatment temperature, which avoids hypothermia‐induced damage to normal tissues. Our study develops an excellent theranostic nanoparticle with inherent multimodal imaging and therapeutic modalities for chemophotothermal cancer therapy.     

Quantitative Photoacoustic Diagnosis and Precise Treatment of Inflammation In Vivo Using Activatable Theranostic Nanoprobe

Excessive production of reactive oxygen species such as H₂O₂ is the pathological basis of chronic inflammatory diseases, as well as bacterial infection‐induced inflammation. Therefore, the in situ H₂O₂ level is a reliable biomarker of inflammatory responses, and its real‐time measurement can monitor disease progression and improve therapeutic outcomes in inflammation‐linked diseases. However, the currently used strategies for the diagnosis of inflammation is mainly through routine blood test, which are limited in determining the inflammation status and cannot provide comprehensive quantitative information. In this work, a novel H₂O₂‐responsive theranostic nanoplatform comprising Ag shell coated Pd‐tipped gold nanorods (Au–Pd@Ag NR) is developed. The etching and oxidation of the Ag shell by H₂O₂ release the Ag ions, which effectively kill bacteria in vivo and trigger their absorption variation at 700 and 1260 nm. The ratiometric photoacoustic (PA) imaging at 1260 and 700 nm (PA₁₂₆₀/PA₇₀₀) accurately quantifies H₂O₂ in a mice model of bacterial infection and abdomen inflammation, even in a rabbit model of osteoarthritis. The H₂O₂ activated second near‐infrared (NIR‐II) PA images of the probe can further precisely differentiate the inflammation region and normal tissue. This nanoplatform not only can quantify H₂O₂ during inflammation but also act as a potent antibacterial agent.     

Tantalum Sulfide Nanosheets as a Theranostic Nanoplatform for Computed Tomography Imaging‐Guided Combinatorial Chemo‐Photothermal Therapy

Near‐infrared (NIR)‐absorbing metal‐based nanomaterials have shown tremendous potential for cancer therapy, given their facile and controllable synthesis, efficient photothermal conversion, capability of spatiotemporal‐controlled drug delivery, and intrinsic imaging function. Tantalum (Ta) is among the most biocompatible metals and arouses negligible adverse biological responses in either oxidized or reduced forms, and thus Ta‐derived nanomaterials represent promising candidates for biomedical applications. However, Ta‐based nanomaterials by themselves have not been explored for NIR‐mediated photothermal ablation therapy. In this work, an innovative Ta‐based multifunctional nanoplatform composed of biocompatible tantalum sulfide (TaS₂) nanosheets (NSs) is reported for simultaneous NIR hyperthermia, drug delivery, and computed tomography (CT) imaging. The TaS₂ NSs exhibit multiple unique features including (i) efficient NIR light‐to‐heat conversion with a high photothermal conversion efficiency of 39%, (ii) high drug loading (177% by weight), (iii) controlled drug release triggered by NIR light and moderate acidic pH, (iv) high tumor accumulation via heat‐enhanced tumor vascular permeability, (v) complete tumor ablation and negligible side effects, and (vi) comparable CT imaging contrast efficiency to the widely clinically used agent iobitridol. It is expected that this multifunctional NS platform can serve as a promising candidate for imaging‐guided cancer therapy and selection of cancer patients with high tumor accumulation.     

Cisplatin‐Prodrug‐Constructed Liposomes as a Versatile Theranostic Nanoplatform for Bimodal Imaging Guided Combination Cancer Therapy

Up to date, a large variety of liposomal nanodrugs have been explored for cancer nanomedicine, showing encouraging results in both preclinical animal experiments and clinical treatment of cancer patients. Herein, a phospholipid conjugated with a cisplatin prodrug is used as the major structure component of liposomes together with other commercial lipids via self‐assembling. By doping with 1,1′‐dioctadecyl‐3,3,3′,3′‐tetramethylindotricarbocyanine iodide (DiR), a lipophilic dye with strong near infrared (NIR) absorbance and fluorescence, the obtained DiR‐Pt(IV)‐liposome is found to be an effective probe for in vivo NIR fluorescence and photoacoustic bimodal imaging. Attributing to its intrinsically doped cis‐Pt(IV) prodrug, efficient photothermal conversion ability, and excellent tumor homing ability, DiR‐Pt(IV)‐liposome confers greatly enhanced therapeutic outcomes in the combined photothermal‐chemotherapy. Moreover, Pt(IV)‐liposome is also demonstrated to be an efficient carrier for both small hydrophilic molecules and proteins, which are encapsulated inside the water‐cavity of liposomes, further demonstrating the versatile functions of this nanoplatform. This study develops a unique type of liposomal nanomedicine with a prodrug conjugated phospholipid as the major structure component. Such Pt(IV)‐liposome is featured with advantages including precisely defined/easily tunable drug compositions, stealth‐like pharmacokinetics, efficient tumor passive uptake, and the capabilities to simultaneously load with various types of imaging or therapeutic agents.     

Ultrafast Synthesis of Ultrasmall Poly(Vinylpyrrolidone)‐Protected Bismuth Nanodots as a Multifunctional Theranostic Agent for In Vivo Dual‐Modal CT/Photothermal‐Imaging‐Guided Photothermal Therapy

To elaborately fabricate real‐time monitoring and therapeutic function into a biocompatible nanoplatform is a promising route in the cancer therapy field. However, the package of diagnosis and treatment into a single‐“element” nanoparticle remains challenge. Herein, ultrasmall poly(vinylpyrrolidone)‐protected bismuth nanodots (PVP‐Bi nanodots) are successfully synthesized through an ultrafacile strategy (1 min only under ambient conditions). The nanodots are easy to synthesize in both laboratory and large scale using low‐cost bismuth ingredients. PVP‐Bi nanodots with ultrasmall size show good biocompatibility. Due to the high X‐ray attenuation ability of Bi element, PVP‐Bi nanodots have prominent performance on X‐ray computed tomography (CT) imaging. Moreover, PVP‐Bi nanodots exhibit a high photothermal conversion efficiency (η = 30%) because of the strong near‐infrared absorbance, which can serve as nanotheranostic agent for photothermal imaging and cancer therapy. The subsequent PVP‐Bi‐nanodot‐mediated photothermal therapy (PTT) result shows highly efficient ablation of cancer cells both in vitro and in vivo. PVP‐Bi nanodots can be almost completely excreted from mice after 7 d. Blood biochemistry and histology analysis suggests that PVP‐Bi nanodots have negligible toxicity. All the positive results reveal that PVP‐Bi nanodots produced through the ultrafacile method are promising single‐“element” nanotheranostic platform for dual‐modal CT/photothermal‐imaging‐guided PTT.     

Amyloid‐β Oligomer‐Targeted Gadolinium‐Based NIR/MR Dual‐Modal Theranostic Nanoprobe for Alzheimer's Disease

While the deposition of amyloid‐β (Aβ) plaques is one of the main pathological hallmarks of incurable Alzheimer's disease (AD), Aβ oligomers have been identified as a more appealing AD biomarker due to their being more pathogenic and neurotoxic. Therefore, the development of a sensitive and effective technique for oligomeric Aβ detection and imaging is beneficial for the early detection of AD, monitoring disease progression, and assessing the efficacy of potential AD drugs. Herein, the development and investigation of the first Aβ oligomer‐specific Gd³⁺‐based nanoparticles (NPs), NP@SiO₂@F‐SLOH as a multimodal near‐infrared imaging (NIRI)/T₁‐weighted magnetic resonance imaging (MRI) contrast agent for real‐time visualization of Aβ contents in an AD mouse model is reported. Remarkably, the NP@SiO₂@F‐SLOH is successfully applied for in vivo and ex vivo NIRI with high sensitivity and selectivity for Aβ oligomers and for MRI with good spatial resolution in different age groups in an AD mouse model. Furthermore, the NP probe exhibits a noticeable inhibitory effect on Aβ fibrillation and neuroprotection against Aβ‐induced toxicity indicating its desirable therapeutic potential for AD. All these results illustrate the tremendous potential of this versatile and sensitive nanomaterial as an effective theranostic MRI nanoprobe for practical use.     

Engineering Gold Nanotubes with Controlled Length and Near‐Infrared Absorption for Theranostic Applications

Important aspects in engineering gold nanoparticles for theranostic applications include the control of size, optical properties, cytotoxicity, biodistribution, and clearance. In this study, gold nanotubes with controlled length and tunable absorption in the near‐infrared (NIR) region have been exploited for applications as photothermal conversion agents and in vivo photoacoustic imaging contrast agents. A length‐controlled synthesis has been developed to fabricate gold nanotubes (NTs) with well‐defined shape (i.e., inner void and open ends), high crystallinity, and tunable NIR surface plasmon resonance. A coating of poly(sodium 4‐styrenesulfonate) (PSS) endows the nanotubes with colloidal stability and low cytotoxicity. The PSS‐coated Au NTs have the following characteristics: i) cellular uptake by colorectal cancer cells and macrophage cells, ii) photothermal ablation of cancer cells using single wavelength pulse laser irradiation, iii) excellent in vivo photoacoustic signal generation capability and accumulation at the tumor site, iv) hepatobiliary clearance within 72 h postintravenous injection. These results demonstrate that these PSS‐coated Au NTs have the ideal attributes to develop their potential as effective and safe in vivo imaging nanoprobes, photothermal conversion agents, and drug delivery vehicles. To the best of knowledge, this is the first in vitro and in vivo study of gold nanotubes.     

High‐Surface‐Area Nanoporous Boron Carbon Nitrides for Hydrogen Storage

Nano‐ and mesoporous boron carbon nitrides with very high surface areas up to 1560 m² g^?1 are obtained by pyrolysis of a graphitic carbon nitride mpg‐C₃N₄ infiltrated with a borane complex. This reactive hard‐templating approach provides easy composition and texture tuning by temperature adjustment between 800 and 1400 °C. The process yields B_xC_yN_zO_vH_w materials as direct copies of the initial template with controlled compositions of 0.15 ≤ x ≤ 0.36, 0.10 ≤ y ≤ 0.12, 0.14 ≤ z ≤ 0.32, and 0.11 ≤ v ≤ 0.28. The nano and mesoporosities can also be tuned in order to provide hierarchical materials with specific surface areas ranging from 610 to 1560 m² g^?1. Such high values, coupled with resistance against air oxidation up to 700 °C, suggest potential materials for gas storage and as catalyst supports. Indeed, it is demonstrated that these compounds exhibit high and tunable H₂ uptakes from 0.55 to 1.07 wt.% at 77 K and 1 bar, thus guiding further search of materials for hydrogen storage.     

Self‐Assembled Dual Dye‐Doped Nanosized Micelles for High‐Contrast Up‐Conversion Bioimaging

Sensitized triplet–triplet annihilation based photon up‐conversion (TTA‐UC) greatly improves the scope and applicability of fluorescence bioimaging by enabling anti‐Stokes detection at low powers, thus eliminating the background autofluorescence and limiting the potential damage of the living tissues. Here the authors present a facile, one‐step protocol to prepare dual dye‐doped, TTA‐UC active nanomicelles starting from the commercially available surfactant Kolliphor EL, a component of several FDA approved preparations. These nanosized micelles show an unprecedented up‐conversion yield of 6.5% under 0.1 W cm^?2 excitation intensity in an aqueous, nondeaerated dispersion. The supramolecular architecture obtained preserves the embedded dyes from oxygen quenching, allowing satisfactory anti‐Stokes fluorescence imaging of 3T3 cells. This is the first example of efficient multicomponent up‐converters prepared using highly biocompatible materials approved by the international authority, paving the way for the development of new complex and multifunctional materials for advanced theranostics.     

Spin‐Torque Manipulation for Hydrogen Sensing

External manipulation of spin‐orbit torques (SOTs) promises not only energy‐efficient spin‐orbitronic devices but also versatile applications of spin‐based technologies in diverse fields. However, the external electric‐field control, widely used in semiconductor spintronics, is known to be ineffective in conventional metallic spin‐orbitronic devices due to the very short screening length. Here, an alternative approach to control the SOTs by using gases is shown. It is demonstrated that the spin‐torque generation efficiency of a Pd/Ni₈₁Fe₁₉ bilayer can be reversibly manipulated by the absorption and desorption of H₂ gas, which appears concomitantly with the change of the electrical resistance. It is found that compared with the change of the Pd resistance induced by the H₂ absorption, the change of the spin‐torque generation efficiency is almost an order of magnitude larger. This result provides a new method to externally manipulate the SOTs and paves a way for developing more sensitive hydrogen sensors based on the spin‐orbitronic technology.     

1D/2D Cobalt‐Based Nanohybrids as Electrocatalysts for Hydrogen Generation

The synergistic effects derived from optimizing the chemical and structural features of electrocatalysts permit them to attain remarkable activity and stability. Herein, 1D/2D cobalt‐based nanohybrid (CoNH) electrodes are developed; the structural design consists of Co₃O₄ electrospun nanoribbons (NRs) deposited onto a carbon fiber paper substrate where Co₃O₄ nanosheets are subsequently grown via an electrodeposition step and UV/ozone treatment. The content of noncovalently functionalized carbon nanotubes within the Co₃O₄ NRs is first tuned to enhance their charge transfer properties and mechanical stability. The electrocatalytic activity of the electrodes is further improved by a phosphorus modification of the 1D NRs, resulting in the formation of NaCoPO₄. The optimized 1D/2D CoNH electrode, i.e., ED‐0.09 wt% fCNTs/P‐CoNHs, displays a similar performance to that of platinum in 0.25 m Na₂S/0.35 m Na₂SO₃ (Tafel slope ≈102 mV dec^?1 for the former and ≈96 mV dec^?1 for the latter) and outstanding stability for up to 48 h. The versatility and high activity of this electrode is also demonstrated according to tests in a conventional water splitting system (cell voltage 1.55V, to produce 10 mA cm^?2) and a solar‐driven electrolyzer (1 m KOH).