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S-scheme heterojunction photocatalyst MAPbI 3 @PCN-222 with light absorption extending to the NIR region is constructed by embedding organic-inorganic hybrid perovskite (MAPbI 3 ) into porphyrinic Zr-MOF (PCN-222). Both in situ X-ray photoelectron spectroscopy, ultraviolet photoelectron spectral characterization, and photocatalytic polymerization experiment prove the formation of S-scheme heterojunction. MAPbI 3 @PCN-222 with a low dosage (90 ppm) displays an impressive photocatalytic ability for 980 nm light-mediated photoinduced electron/energy-transfer-reversible addition-fragmentation chain-transfer (PET-RAFT) polymerization in air. The well-defined controllable-molecular weight polymers including block copolymers and ultrahigh-molecular weight polymers can be achieved with narrow distributions ( M w < 1.20) via rapid photopolymerization. The industrial application potential of the photocatalyst also has been proved by scale-up synthesis of polymers with low polydispersity under NIR light-induced photopolymerization in a large-volume reaction system (200 mL) with high monomer conversion up to 99%. The penetration photopolymerization through the 5 mm polytetrafluoroethylene plate and excellent photocontrollable behavior illustrate the existence of long-term photogenerated electron transfer of heterojunction and abundant free radicals in photopolymerization. The photocatalyst still retains high catalytic activity after 10 cycles of photopolymerization in air. It is revealed for the first time that the special PET-RAFT polymerization pathway is initiated by the aldehyde-bearing α-aminoalkyl radical derived from the oxidization of triethanolamine (TEOA) by the heterojunction photocatalyst. This research offers a new insight into understanding the NIR-light-activated PET-RAFT polymerization mechanism in the presence of TEOA.M n < 1.20) via rapid photopolymerization. The industrial application potential of the photocatalyst also has been proved by scale-up synthesis of polymers with low polydispersity under NIR light-induced photopolymerization in a large-volume reaction system (200 mL) with high monomer conversion up to 99%. The penetration photopolymerization through the 5 mm polytetrafluoroethylene plate and excellent photocontrollable behavior illustrate the existence of long-term photogenerated electron transfer of heterojunction and abundant free radicals in photopolymerization. The photocatalyst still retains high catalytic activity after 10 cycles of photopolymerization in air. It is revealed for the first time that the special PET-RAFT polymerization pathway is initiated by the aldehyde-bearing α-aminoalkyl radical derived from the oxidization of triethanolamine (TEOA) by the heterojunction photocatalyst. This research offers a new insight into understanding the NIR-light-activated PET-RAFT polymerization mechanism in the presence of TEOA.

Soft actuators with photo-response can be selectively driven by the light source, but it is challenging to achieve a selective response of multiple components under a uniform light field, which is actually of great importance for the development of soft robots. In this work, a series of near-infrared light (NIR)-responsive vitrimers (CR-vitrimers) are synthesized by carboxylate transesterification using carboxyl-bearing croconaine dye (CR-800) as a photothermal agent (PTA). NIR-responsive liquid crystalline elastomers (CR-vitrimer-LCEs) under NIR laser (λ max = 808 nm) without the template can be further prepared. More importantly, the dynamic covalent bonding properties of vitrimer allow for the fabrication of a hand-shaped actuator by hot pressing, consisting of "fingers" with different NIR-response threshold values. After programming as needed, the hand-shaped actuator successfully achieves local and sequential control under a uniform NIR light field.

Here, we report the first PbS quantum dot (QD)-based micromotors with NIR-I light-driven photocatalytic propulsion and NIR-II fluorescence. Under the irradiation of NIR-I light (808 nm), PbS QD-doped cuprous oxide (Cu 2 O@PbS) micromotors can display efficient propulsion in a variety of biocompatible fuels such as malic acid, glucose, and urea. Among them, the Cu 2 O@PbS micromotors exhibit the best propulsion performance in a very low concentration of malic acid, with an average speed as high as 11.86 μm/s. The enhanced NIR-I photocatalytic activity of Cu 2 O@PbS micromotors benefits from the doping of NIR-I PbS QDs that can be excited by NIR-I light and exhibit high electron transport efficiency. The doped PbS QDs can effectively increase the absorption efficiency of the micromotors in the NIR-I region while also inhibiting the recombination of photogenerated electron-hole pairs. Interestingly, due to the presence of NIR PbS QDs, the Cu 2 O@PbS micromotors demonstrate prominent and stable NIR-II fluorescence (emission wavelength: 1100 nm), which offer promising potential for visualization of their position in vivo. In comparison to other photocatalytic micromotors, the simple fabrication strategy, excellent NIR-II fluorescence, together with the NIR-I light-dependent propulsion behavior of the current Cu 2 O@PbS micromotors, thus pave the way for further development of advanced smart "robots" for intelligent biomedical applications.

As a micro-/nano-sized hydrogel, polymeric microgel not only has three-dimensional (3D) molecular networks but also displays the small-size effect, which has been widely used in various fields, such as drug nanocarrier, photonic crystal, functional coating, and aqueous lubrication. In this work, a photothermal lubricating coating was prepared using polymeric/inorganic hybrid microgels and its surficial friction was deliberately modulated by the remote irradiation of near-infrared (NIR) light. Specifically, a photothermal hybrid microgel, Fe 3 O 4 @poly( N -isopropylacrylamide- co -polyacrylic acid) (Fe 3 O 4 @PNA), was first fabricated and then sprayed onto poly(ethyleneimine) (PEI)-modified substrate to form a lubricating microgel coating. At room temperature, this microgel coating was hydrophilic and achieved good hydration lubrication with relatively low friction. After the introduction of NIR light, the photothermal microgel coating converted light energy into heat energy for increasing its own temperature rapidly. Due to the thermosensitive PNA shell, the wettability of the coating was transformed to hydrophobicity above the lower critical solution temperature (LCST), resulting in a remarkable increase in friction. In other words, the surficial friction of this microgel coating could be reversibly modulated using NIR light. This work expands the application scope of microgels in the field of aqueous lubrication and introduces the functional microgels into making the smart lubricating coating for the first time. This basic research in the field of friction control may provide an efficient strategy for the design of interfacial sensing, controlled transmission, and intelligent manipulator.

Conversion of light energy and chemical energy in a wide spectrum region, especially in the near-infrared (NIR) light region, is still a challenge in the field of photocatalysis. In this work, a layered Bi-WN photocatalyst with a heterojunction was prepared by reducing flake-shaped WN and flower-shaped Bi 2 O 3 in an ammonia atmosphere. Under the process of NIR light (λ > 700 nm)-driven water splitting, the optimal hydrogen (H 2 ) generation rates based on the Bi-WN photocatalyst can reach to 7.49 μmol g -1 h -1 , which is 2.47 times higher than that of WN of 3.03 μmol g -1 h -1 . The result indicates that the Bi-WN photocatalyst can be effective under NIR light. Through ultraviolet-visible-NIR diffuse reflectance spectrum analysis, it can be seen that the light absorption edge of Bi-WN is obviously redshifted. Combining the results of electrochemical characterizations, we have found that the addition of the Bi metal plays an important role in NIR light-driven water splitting. Under irradiation of NIR light, the electrons on the Bi-WN substrate are stronger due to local surface plasmon resonance, which reduces the possibility of recombination of photogenerated electrons and holes on WN. In addition, after the Bi metal absorbs the photon energy, the electron-hole pairs are separated, and the H 2 production rate increases significantly under the combined action of the charge transfer mechanism and the local electric field enhancement mechanism.

Synthetic polymersomes have structure similarity to bio-vesicles and could disassemble in response to stimuli for "on-demand" release of encapsulated cargos. Though widely applied as a drug delivery carrier, the burst release mode with structure complete destruction is usually taken for most responsive polymersomes, which would shorten the effective drug reaction time and impair the therapeutic effect. Inspired by the cell organelles' communication mode via regulating membrane permeability for transportation control, we highlight here a biomimetic polymersome with sustained drug release over a specific period of time via near-infrared (NIR) pre-activation. The polymersome is prepared by the self-assembling amphiphilic diblock copolymer P (OEGMA- co -EoS)- b -PNBOC and encapsulates the hypoxia-activated prodrug AQ4N and upconversion nanoparticle (PEG-UCNP) in its hydrophilic centric cavity. Thirty minutes of NIR pre-activation triggers cross-linking of NBOC and converts the permeability of the polymersome with sustained AQ4N release until 24 h after the NIR pre-activation. The photosensitizer EoS is activated and aggravates environmental hypoxic conditions during a sustained drug release period to boost the AQ4N therapeutic effect. The combination of sustained drug release with concurrent hypoxia intensification results in a highly efficient tumor therapeutic effect both intracellularly and in vivo . This biomimetic polymersome will provide an effective and universal tumor therapeutic approach.

DNA methylation is a kind of a crucial epigenetic marker orchestrating gene expression, molecular function, and cellular phenotype. However, manipulating the methylation status of specific genes remains challenging. Here, a clustered regularly interspaced palindromic repeats-Cas9-based near-infrared upconversion-activated DNA methylation editing system (CNAMS) was designed for the optogenetic editing of DNA methylation. The fusion proteins of photosensitive CRY2PHR, the catalytic domain of DNMT3A or TET1, and the fusion proteins for CIBN and catalytically inactive Cas9 (dCas9) were engineered. The CNAMS could control DNA methylation editing in response to blue light, thus allowing methylation editing in a spatiotemporal manner. Furthermore, after combination with upconversion nanoparticles, the spectral sensitivity of DNA methylation editing was extended from the blue light to near-infrared (NIR) light, providing the possibility for remote DNA methylation editing. These results demonstrated a meaningful step forward toward realizing the specific editing of DNA methylation, suggesting the wide utility of our CNAMS for functional studies on epigenetic regulation and potential therapeutic strategies for related diseases.

A precisely controlled drug release is a great challenge in exploring methodologies of drug administration and fighting drug resistance for successful cancer chemotherapy. Herein, we developed a dual-mode nanocarrier to specifically deliver doxorubicin (Dox) and precisely control the drug release in target tumor cells. This hierarchical nanocarrier consisted of a gold nanorod as the heating core, biodegradable mesoporous silica as the storage chamber, and graphene quantum dot (GQD) as a drug carrier. The Arg-Gly-Asp peptides on the nanocarrier surface facilitated the specific interaction with integrin-overexpressed tumor cells and subsequent uptake via receptor-mediated endocytosis. Once exposed under the near-infrared (NIR) laser, the internalized nanocarrier rapidly heated the surrounding environment, which led to an instantaneous drug release by collapsing the π-π interaction between Dox and GQDs at high temperature and thereby intensified therapeutic efficacy. On the other hand, the silica shells underwent gradual degradation in the cellular matrix environment, along with stepwise liberation of the embedded GQD-Dox composites from the confined porous structure for the Dox release, exerting a long-term lethality to the tumor cells. By virtue of the physicochemical properties and synergistic behavior of the multiple components in this hierarchical nanocarrier, the NIR-triggered prompt release mode and the biodegradation-mediated slow release mode functioned in a precise and collaborative fashion, providing a promising way to manipulate the pharmacokinetics for precise cancer treatment.

Cost-efficient nanoparticle carbocatalysts composed of fluorescent carbon dots (CDs) embedded in carbon matrix were synthesized via one-step acid-assisted hydrothermal treatment (200 °C) of glucose. These as-synthesized CD-based carbocatalysts have excellent photoluminescence (PL) properties over a broad range of wavelengths and the external visible or NIR irradiation on the carbocatalysts could produce electrons to form electron-hole (e(-)-h(+)) pairs on the surface of carbocatalysts. These restant electron-hole pairs will react with the adsorbed oxidants/reducers on the surface of the CD-based carbocatalysts to produce active radicals for reduction of 4-nitrophenol and degradation of dye molecules. Moreover, the local temperature increase over CD-based carbocatalyst under NIR irradiation can enhance the electron transfer rate between the organic molecules and CD-based carbocatalysts, thus obviously increase the catalytic activity of the CD-based carbocatalyst for the reduction of 4-nitrophenol and the degradation of dye molecules. Such a type of CD-based carbocatalysts with excellent properties and highly efficient metal-free photocatalytic activities is an ideal candidate as photocatalysts for the reduction of organic pollutants under visible light and NIR radiation.

Near-infrared light is an attractive stimulus due to its noninvasive and deep tissue penetration. Particularly, NIR light is utilized for cancer thermotherapy and on-demand release of drugs by the disruption of the delivery carriers. Here we have prepared a novel NIR-responsive DNA-hybrid-gated nanocarrier based on mesoporous silica-coated Cu1.8S nanoparticles. Cu1.8S nanoparticles, possessing high photothermal conversion efficiency under a 980 nm laser, were chosen as photothermal agents. The mesoporous silica structure could be used for drug storage/delivery and modified with aptamer-modified GC-rich DNA-helix as gatekeepers, drug vectors, and targeting ligand. Simultaneously, the as-produced photothermal effect caused denaturation of DNA double strands, which triggered the drug release of the DNA-helix-loaded hydrophilic drug doxorubicin and mesopore-loaded hydrophobic drug curcumin, resulting in a synergistic therapeutic effect. The Cu1.8S@mSiO2 nanocomposites endocytosed by cancer cells through the aptamer-mediated mode are able to generate rational release of doxorubicin/curcumin under NIR irradiation, strongly enhancing the synergistic growth-inhibitory effect of curcumin against doxorubicin in MCF-7 cells, which is associated with a strong mitochondrial-mediated cell apoptosis progression. The underlying mechanism of apoptosis showed a strong synergistic inhibitory effect both on the expression of Bcl-2, Bcl-xL, Mcl-1, and upregulated caspase 3/9 activity and on the expression level of Bak and Bax. Therefore, Cu1.8S@mSiO2 with efficient synergistic therapeutic efficiency is a potential multifunctional cancer therapy nanoplatform.

Herein, we present a phototriggered drug delivery system based on light responsive nanoparticles, which is able to release doxorubicin upon NIR light illumination. The proposed system is based on upconversion fluorescence nanoparticles of β-NaYF4:Yb,Tm@SiO2-PEG with a mean diameter of 52±2.5 nm that absorb the NIR light and emit UV light. The UV radiation causes the degradation of photodegradable ortho-nitrobenzyl alcohol derivates, which are attached on one side to the surface of the nanoparticles and on the other to doxorubicin. This degradation triggers the doxorubicin release. This drug delivery system has been tested "in vitro" with HeLa cells. The results of this study demonstrated that this system caused negligible cytotoxicity when they were not illuminated with NIR light. In contrast, under NIR light illumination, the HeLa cell viability was conspicuously reduced. These results demonstrated the suitability of the proposed system to control the release of doxorubicin via an external NIR light stimulus.