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Human cellular retinol binding protein II (hCRBPII) was used as a protein engineering platform to rationally regulate absorptive and emissive properties of a covalently bound fluorogenic dye. We demonstrate the binding of a thio-dapoxyl analog via formation of a protonated imine between an active site lysine residue and the chromophore's aldehyde. Rational manipulation of the electrostatics of the binding pocket results in a 204 nm shift in absorption and a 131 nm shift in emission. The protein is readily expressed in mammalian systems and binds with exogenously delivered fluorophore as demonstrated by live-cell imaging experiments.

Butterflies constitute approximately 10% of lepidopteran insects, and along with silkworms, they can produce silk; however, this feature is often ignored. In the present study, we observed two primary methods used by butterflies to hang pupae on trees using silk: pupa adheraena ( Danaus chrysippus ) and pupa contigua ( Papilio polytes ). Anchoring the abdominal ends of pupae with a silk pad was the most common method used in both cases, whereas wrapping silk around the body using a silk girdle was a method unique to pupa contigua. The connection between the cremaster and silk pad was observed to be similar to that between the hook and loop of a Velcro fastener, except that the cremaster hook is anchor-shaped rather than being a single hook. Such a connection will remain secure, ensuring the safety of the pupae during exposure to wind and rain. Through determining the mechanical properties of silk, the performance of butterfly silk was found to be weaker than that of silkworm silk. Therefore, the P. polytes silk girdle adopts the strategy of merging a dozen silk threads to improve its strength and toughness, thereby making it difficult to break. In addition, we explained how the protein sequence and structure of butterfly silk impact its performance. In conclusion, we discovered that butterfly pupae develop unique body features to establish secure bonds with silk. This enables them to effectively undergo metamorphosis and endure harsh weather conditions and surroundings.

Iron is an essential element in the composition of living organisms and plays a crucial role in a wide range of biological activities. The human body primarily obtains essential iron through the consumption of food. Therefore, it is vital for the health of human body to maintain iron homeostasis. The reducing character of the cellular microenvironment enables Fe 2+ to occupy a dominant position within the cell. Hence, there is an urgent need for a simple and sensitive tool that can detect a large amount of Fe 2+ in organisms. In this work, a highly specific fluorescent chemodosimeter NPCO ("NP" represents the naphthalimide fluorophore, and "CO" represents the carbamoyl oxime structure) for the detection of Fe 2+ with excellent sensitivity (LOD = 82 nM) was constructed by incorporating a novel carbamoyl oxime structure as the recognition group. NPCO can be effectively employed for the detection of Fe 2+ in food samples, living cells, and zebrafish. Furthermore, by using soybean sprouts as a model plant, the application of NPCO was expanded to detect Fe 2+ in plants. Therefore, NPCO could be used as an excellent assay tool for detecting Fe 2+ in organisms and is expected to be an important aid in exploring the mechanism of iron regulation.

Research on metal-metal bonds involving f-block actinides, such as thorium, lags far behind the well-studied metal-metal bonds of d-block transition metals. The complexes with Th-TM bonds are extremely rare; all previously identified examples have only a single Th-TM bond with the Th center at an invariably +IV oxidation state. Herein, we report a series of Th 2 Pd n ( n = 2, 3, and 6) clusters (complexes 3 , 4 , and 7 ) with multiple Th(III)-Pd bonds. Theoretical studies reveal that the Th 2 Pd n unit allows electronic delocalization and σ aromaticity, leading to unexpected closed-shell singlet structures for these Th(III) species. This electronic delocalization is evident in the highest occupied molecular orbital of Th(III) complexes and facilitates a 2e reduction of alkyne by complex 7 , resulting in the formation of 8 . Complexes 7 and 8 are distinctive in featuring a Th 2 Pd 6 core with six and eight Th-Pd bonds, respectively, making them the largest known d-f heterometallic clusters exhibiting metal-metal bonding.

Polymer brushes have received great attention in recent years due to their distinctive properties and wide range of applications. The synthesis of polymer brushes typically employs surface-initiated atom transfer radical polymerization (SI-ATRP) techniques. To realize the control of the polymerization process in different environments, various SI-ATRP techniques triggered by different stimuli have been developed. This review focuses on the latest developments in different stimuli-triggered SI-ATRP methods, such as electrochemically mediated, photoinduced, enzyme-assisted, mechanically controlled, and organocatalyzed ATRP. Additionally, SI-ATRP technology triggered by a combination of multiple stimuli sources is also discussed. Furthermore, the applications of polymer brushes in lubrication, biological applications, antifouling, and catalysis are also systematically summarized and discussed. Despite the advancements in the synthesis of various types of 1D, 2D, and 3D polymer brushes via controlled radical polymerization, contemporary challenges remain in the quest for more efficient and straightforward synthetic protocols that allow for precise control over the composition, structure, and functionality of polymer brushes. We anticipate the readers could promote the understanding of surface functionalization based on ATRP-mediated polymer brushes and envision future directions for their application in surface coating technologies.

The accurate quantification of cancer-derived exosomes, which are emerging as promising noninvasive biomarkers for liquid biopsies in the early diagnosis of cancer, is becoming increasingly imperative. In our work, we developed a magnetically controlled photothermal, colorimetric, and fluorescence trimode aptasensor for human gastric cancer cell (SGC-7901)-derived exosomes. This sensor relied on CP/Mn-PBA DSNBs nanocomposites, created by decorating copper peroxide (CP) nanodots on polyethyleneimine-modified manganese-containing Prussian blue analogues double-shelled nanoboxes (PEI-Mn-PBA DSNBs). Through self-assembly, we attached CD63 aptamer-labeled CP/Mn-PBA DSNBs (Apt-CP/Mn-PBA DSNBs) to complementary DNA-labeled magnetic beads (cDNA-MB). During exosome incubation, these aptamers preferentially formed complexes with exosomes, and we efficiently removed the released CP/Mn-PBA DSNBs by using magnetic separation. The CP/Mn-PBA DSNBs exhibited high photoreactivity and photothermal conversion efficiency under near-infrared (NIR) light, leading to temperature variations under 808 nm irradiation, correlating with different exosome concentrations. Additionally, colorimetric detection was achieved by monitoring the color change in a 3,3',5,5'-tetramethylbenzidine (TMB) system, facilitated by PEI modification, NIR-enhanced peroxidase-like activity of CP/Mn-PBA DSNBs and their capacity to generate Cu 2+ and H 2 O 2 under acidic conditions. Moreover, in the presence of Cu 2+ and ascorbic acid (AA), DNA sequences could form dsDNA-templated copper nanoparticles (CuNPs), which emitted strong fluorescence at around 575 nm. Increasing exosome concentrations correlated with decreases in temperature, absorbance, and fluorescence intensity. This trimode biosensor demonstrated satisfactory ability in differentiating gastric cancer patients from healthy individuals using human serum samples.

Conductive hydrogels have shown promising application prospects in the field of flexible sensors, but they often suffer from poor mechanical properties, low sensitivity, and lack of frost resistance. Herein, we report a tough, highly sensitive, and antifreeze strain sensor assembled from a conductive organohydrogel composed of a dual-cross-linked polyacrylamide and poly(vinyl alcohol) (PVA) network, as well as MXene nanosheets as nanofillers and poly(3,4-ethylenedioxythiophene)-doped poly(styrenesulfonate) (PEDOT/PSS) as the main conducting component (PPMP-OH organohydrogel). The tensile strength and toughness of PPMP-OH had been greatly enhanced by MXene nanosheets due to the mechanical reinforcement of MXene nanosheets, as well as various strong noncovalent interactions formed in the organohydrogels. The PPM 1 P-OH organohydrogels showed a tensile strength of 1.48 MPa at 772% and a toughness of 5.59 MJ/m 3 . Moreover, the conductivity and strain-sensing performance of PPMP-OH were significantly improved by PEDOT/PSS, which can form hydrogen bonds with PVA and electrostatic interactions with MXene. This was greatly beneficial for constructing a uniformly distributed and stable 3D conductive network and helped to obtain strain-dependent resistance of PPMP-OH. The strain sensors assembled from PPMP 1 -OH exhibited a high sensitivity of 5.16, a wide range of detectable strains up to 500%, and a short response time of 122 ms, which can effectively detect various physiological activities of the human body with high stability. In addition, the corresponding pressure sensor array also showed high sensitivity in identifying pressure magnitude and position.

Atom transfer radical polymerization (ATRP) is one of the most widely used methods for modifying surfaces with functional polymer films and has received considerable attention in recent years. Here, we report an electrochemically mediated surface-initiated ATRP to graft polymer brushes onto solid substrates catalyzed by ppm amounts of Cu II /TPMA in water/MeOH solution. We systematically investigated the type and concentrations of copper/ligand and applied potentials correlated to the polymerization kinetics and polymer brush thickness. Gradient polymer brushes and various types of polymer brushes are prepared. Block copolymerization of 2-hydroxyethyl methacrylate (HEMA) and 3-sulfopropyl methacrylate potassium salt (PSPMA) (poly(HEMA- b -SPMA)) with ultralow ppm eATRP indicates the remarkable preservation of chain end functionality and a pronounced "living" characteristic feature of ppm-level eATRP in aqueous solution for surface polymerization.

The operation of aerospace equipment is often affected by icing and frosting. In order to reduce the loss caused by icing in the industrial field, it is an effective method to prepare superhydrophobic coatings by modifying nanoparticles with low surface energy materials. In order to explore a method of preparing a superhydrophobic surface that can be popularized, a two-step spraying method was employed to create a superhydrophobic coating. The surface was characterized by Fourier transform infrared spectroscopy (FTIR) and field emission scanning electron microscopy (SEM). The optimal preparation process was obtained by analyzing the surface contact angle data. The results showed that stearic acid was grafted onto the surface of TiO 2 by esterification reaction. The existence of long methyl and methylene hydrophobic groups in the tail of the stearic acid molecule made the modified TiO 2 hydrophobic. It is verified that water molecules have strong adsorption on the surface of unmodified TiO 2 . Stearic acid molecules can reduce the interfacial energy in the system., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The direct construction of 1,3-hydroxyfunctionalized molecules is still a significant challenge, as they can currently be obtained through multiple synthetic steps. Herein, we report a general and efficient 1,3-hydroxyfunctionalization of arylcyclopropanes by electrochemical oxidation with a strategic choice of nucleophiles and H 2 O. 1,3-Amino alcohols, 1,3-alkynyl alcohols, 1,3-hydroxyesters, and 1,3-halo alcohols are achieved with high levels of chemo- and regio-selectivity, opening a new dimension for 1,3-difunctionalization reaction.

Here, we report an oxygen-tolerant photografting technique to grow polymer brushes employing microliter volumes of monomer solution under ambient conditions. With the key advantages that include spatial control, initiator/catalyst-free nature, and high oxygen tolerance, a series of homo-, multiblock, and arbitrary patterned polymer brushes were successfully obtained by photografting. Moreover, a dual-functional surface with hydrophilic and hydrophobic properties could easily be realized by one-pot photografting. These results illustrated the practicality and versatility of this strategy, which will allow nonexperts access to polymer brush architectures and broaden the potential applications of polymer brushes.

Currently, kinase inhibitors have been applied in the diagnosis or treatment of cancer with their unique advantages. It is of great significance to develop some comprehensive theranostic reagents based on kinase inhibitors to improve the performance of reagents for biomedical applications. Besides, tracking changes in the intracellular environment (e.g., pH) during cancer development and drug delivery is also critical for cancer research and treatment. Therefore, it is an urgent desire to design some novel multifunctional reagents based on kinase inhibitor strategies that can trace changes in the microenvironment of cancer cells. In this paper, a multifunctional theranostic reagent based on Pim-1 kinase inhibitor 5-bromobenzofuran-2-carboxylic acid is proposed. The theranostic probe binds to tumor-specific Pim-1 kinase, releases strong fluorescence, and produces cytotoxicity, thus achieving cell screening and killing effects. Furthermore, the probe can specifically target lysosomes and sensitively respond to pH. It can be used to track the pH changes in the intracellular environment under conditions of autophagy and external stimulation, as a visual tool to monitor pH fluctuations during cancer treatment. In conclusion, this simple but multifunctional theranostic reagent proposed in this work is expected to provide a promising method for cancer diagnosis and therapy.

Chirality has risen as an attractive topic in materials research in recent years, but the attainment of enantiopure materials remains a major challenge. Herein, we obtained homochiral nanoclusters by a recrystallization strategy, without any chiral factors (i.e., chiral ligands, counterions, etc.). Through the rapid flipping of configuration of silver nanoclusters in solution, the initial racemic Ag 40 (triclinic) nanoclusters are converted to homochiral (orthorhombic) as revealed by X-ray crystallography. In the seeded crystallization, one homochiral Ag 40 crystal is used as a seed to direct the growth of crystals with specific chirality. Furthermore, enantiopure Ag 40 nanoclusters can be used as amplifiers for the detection of chiral carboxylic drugs. This work not only provides chiral conversion and amplification strategies to obtain homochiral nanoclusters but also explains the chirality origin of nanoclusters at the molecular level.

Intensive efforts have been conducted to realize the reliable interfacial joining of thermoelectric materials and electrode materials with low interfacial contact resistance, which is an essential step to make thermoelectric materials into thermoelectric devices for industrial application. In this review, the roles of structural integrity, interdiffusion, and contact resistance in long-term reliabilities of thermoelectric modules are outlined first. Then interfacial reactions of near-room-temperature Bi 2 Te 3 -based thermoelectric materials and various electrode materials are reviewed comprehensively. We also summarized the joining behavior of the mid-temperature PbTe-based thermoelectric materials and commonly used electrode materials. Subsequently, for other thermoelectric materials systems, i.e., SiGe, CoSb 3 , and Mg 3 Sb 2 , previous attempts to join with some electrode materials are also recapitulated. Finally, some future prospects to further improve the joint reliability in thermoelectric device manufacturing are proposed. We believe that this review will provide guidance for preparing thermoelectric devices and optimizing thermoelectric device design.

Herein, we report a versatile solvent-mediated polymerization-induced self-assembly (PISA) strategy to directly synthesize highly N-doped hierarchically porous structured carbon spheres with a tunable meso-macroporous configuration. The introduction of intermolecular hydrogen bonds is verified to enhance the interfacial interactions between block copolymers, oil droplets, and polyphenols. Moreover, the dominant hydrogen-bond-driven interactions can be systematically manipulated by selecting different cosolvent systems to generate diverse porous structures from the transformation of micellar and precursor co-assembly. Impressively, hierarchically structured meso-macroporous N-doped carbon spheres present simultaneously tunable sphere sizes and mesopores and macropores, ranging from 1.2 μm, 9/50 and 227 nm to 1.0 μm, 40, and 183 nm and 480, 24, and 95 nm. As a demonstration, dendritic-like N-doped hierarchically meso-macroporous carbon spheres manifest excellent enzyme-like activity, which is attributed to the continuous mass transport from the multiordered porosity. The current study provides a new platform for the synthesis of novel well-defined porous materials.

Defect passivation is a key strategy to prepare high-performance perovskite solar cells (PVSCs). Even though abundant passivation molecules have been applied, the absence of detailed researches with regard to different functional groups in polymer additives may inevitably impede the establishment of passivation molecules selection rules. In this work, three passivation molecules including poly(vinyl alcohol) (PVA), polymethyl acrylate (PMA), and poly(acrylic acid) (PAA) are employed to systematically analyze the passivation effect from hydroxyl, carbonyl, and carboxyl groups. In general, PVA (-OH) can form hydrogen bonds with perovskite and PMA (-C═O) can complex with uncoordinated Pb 2+ . Specifically, PAA (-COOH) can interact selectively with MA + and I - ions via hydrogen bonding and complex with uncoordinated Pb 2+ to passivate defects more effectively. Hence, the PAA-incorporated PVSCs based on MAPbI 3 achieve the champion power conversion efficiency (PCE) of 20.29% with open-circuit voltage up to 1.13 V. In addition, PAA cross-linking perovskite grains can relieve mechanical stress, as well as occupy the major channels to suppress ion migration and water/oxygen erosion. The corresponding unencapsulated devices demonstrate a superior light soaking stability, retaining more than 80% of the original PCE under one sun illumination for 1000 h.

Cancer, as a malignant tumor, seriously endangers human health. The study of cancer diagnosis and therapy has great practical significance. The development of theranostic agents has become a very important research topic. Nevertheless, some existing agents still have imperfections, such as complex structures and difficult syntheses. Therefore, it is urgent for researchers to develop simple novel theranostic agents. In this study, the precipitated fluorophore HAPQ was used as a simple drug molecule for the first time and combined with NBD-Cl to construct a simple and efficient theranostic probe ( HAPQ-NBD ). The theranostic probe can distinguish between tumor cells and normal cells based on the higher levels of biothiol in tumor cells. In addition, the probe can use biothiol as a control switch to release higher levels of precipitated fluorophore HAPQ in tumor cells, leading to selective high toxicity to tumor cells, thus achieving the goal of selectively killing tumor cells. The construction of probe HAPQ-NBD provides a practical tool for the diagnosis and therapy of cancer. It is expected that the development and utilization of precipitated fluorophore will provide a new method and strategy for cancer diagnosis and therapy.

The systematicness, flexibility, and complexity of natural biological organisms are a constant stream of inspiration for researchers. Therefore, mimicking the natural intelligence system to develop microrobotics has attracted broad interests. However, developing a multifunctional device for various application scenarios has great challenges. Herein, we present a bionic multifunctional actuation device─a light-driven mudskipper-like actuator that is composed of a porous silicone elastomer and graphene oxide. The actuator exhibits a reversible and well-integrated response to near-infrared (NIR) light due to the photothermal-induced contractile stress in the actuation film, which promotes generation of cyclical and rapid locomotion upon NIR light being switched on and off, such as bending in air and crawling in liquid. Furthermore, through rational device design and modulation of light, the mechanically versatile device can float and swim controllably following a predesigned route at the liquid/air interface. More interestingly, the actuator can jump from liquid medium to air with an extremely short response time (400 ms), a maximum speed of 2 m s -1 , and a height of 14.3 cm under the stimulation of near-infrared light. The present work possesses great potential in the applications of bioinspired actuators in various fields, such as microrobots, sensors, and locomotion.

Upconversion nanoparticle based ratiometric nanothermometry has shown many advantages including high relative sensitivity, fast temperature response, and high spatial resolution. However, most of the existing designs are on the basis of thermally coupled upconversion emissions, and it remains a challenge to improve the thermo-sensitivity. Here, we report a new nanoplatform of NaYF 4 :Yb/Er/Ce@NaYF 4 @NaYF 4 :Yb/Tm core-shell-shell nanostructure to improve the thermal sensitivity through the nonthermally coupled upconversion emissions. With the increase of temperature, the green upconversion of Er 3+ shows a decline while the blue upconversion of Tm 3+ exhibits a rapid increase, leading to a huge contrast in both intensity ratio and emission colors. The maximum relative sensitivity can reach up to 9.86% K -1 at 303 K. It is further found that introducing Ce 3+ is able to improve the sensitivity and expand the thermochromic green-to-blue gamut greatly. These results show great potential in ultrasensitive lanthanide-based nanothermometry and anticounterfeiting.

Natural polysaccharide (NPH)-based injectable hydrogels have shown great potential for critical-sized bone defect repair. However, their osteogenic, angiogenic, and mechanical properties are insufficient. Here, MgO nanoparticles (NPs) were incorporated into a newly synthesized water-soluble phosphocreatine-functionalized chitosan (CSMP) water solution to form an injectable hydrogel (CSMP-MgO) via supramolecular combination between phosphate groups in CSMP and magnesium in MgO NPs to circumvent these drawbacks of chitosan-based injectable hydrogels. Water-soluble chitosan deviate CSMP was first synthesized by grafting methacrylic anhydride and phosphocreatine into a chitosan chain in a one-step lyophilization process. The phosphocreatine in this hydrogel not only provides sites to combine with MgO NPs to form supramolecular binding but also serves as the reservoir to control Mg 2+ release. As a result, the lyophilized CSMP-MgO hydrogels presented a porous structure with some small holes in the pore wall, and the pore diameters ranged from 50 to 100 μm. The CSMP-MgO injectable hydrogels were restricted from swelling in DI water (lowest swelling ratio was 16.0 ± 1.1 g/g) and presented no brittle failure during compression even at a strain above 85% (maximum compressive strength was 195.0 kPa) versus the control groups (28.0 and 41.3 kPa for CSMP and CSMP-MgO (0.5) hydrogels), with regulated Mg 2+ release in a stable and sustained manner. The CSMP-MgO injectable hydrogels promoted in vitro calcium phosphate (hydroxyapatite (HA) and tetracalcium phosphate (TTCP)) deposition in supersaturated calcium phosphate solution and presented no cytotoxicity to MC3T3-E1 cells; the CSMP-MgO hydrogel promoted MC3T3-E1 cell osteogenic differentiation with upregulation of BSP, OPN, and Osterix osteogenic gene expression and mineralization and HUVEC tube formation. Among them, CSMP-MgO (5) presented most of these properties. Moreover, this hydrogel (CSMP-MgO (5)) showed an excellent ability to promote new bone formation in critical-sized calvarial defects in rats. Thus, the CSMP-MgO injectable hydrogel shows great promise for bone regeneration.

Garbage and biomass contain more chlorine, which reacts with H 2 to form HCl gas during combustion or gasification, resulting in corrosion of metal walls. In this paper, based on the chlorine mechanism in Ansys Chemkin-Pro, the laminar combustion characteristics of H 2 /Cl 2 are simulated with different diluents CO 2 /N 2 under an initial temperature of 298 K, equivalence ratio range of 0.6-1.4, and initial pressure of 0.1-0.5 MPa. The results show that the laminar burning velocity of H 2 /Cl 2 decreases significantly with the increase of dilution gas ratio, and the effect of diluent CO 2 is more significant than that of N 2 . Due to the dilution effect, the fuel and oxidation components are reduced. Through sensitivity analysis, reaction R2: Cl + H 2 = HCl + H is the main reaction of HCl formation. On improving the initial pressure, the laminar burning velocity is slightly lowered, and the thermal diffusivity of the fuel mixture increases with the increase of the initial pressure. According to the sensitivity analysis of the velocity, reactions R2, R9, and R10 are the main reactions that affect the laminar burning velocity, and the product HCl will be generated with a delay with the increase of the initial pressure., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Engineered small extracellular vesicles (sEVs) are used as tools to enhance therapeutic efficacy. However, such application of sEVs is associated with several issues, including high costs and a high risk of tumorigenesis. Nanotopography has a greater influence on bone-related cell behaviors. However, whether nanotopography specifically mediate sEV content to perform particular biological functions remains unclear. Here, we demonstrate that selective nanotopography may be used to sequentially mediate human bone mesenchymal stem cell (hBMSC) sEVs to enhance the therapeutic efficacy of hBMSCs-EVs for osteogenesis. We subjected sEVs harvested from hBMSCs cultured on polished titanium plates (Ti) or nanotopographical titanium plates (Ti4) after 7, 14, and 21 d for RNA sequencing, and we found that there was no significant difference in sEV-miRNA expression after 7 d. Differentially expressed osteogenic-related microRNAs were founded after 14 days, and KEGG analysis indicated that the main microRNAs were associated with osteogenesis-related pathways, such as TGF-beta, AMPK, and FoxO. A significant difference was found in sEV-miRNAs expression after 21 d. We loaded sEV secreted from hBMSCs cultured on Ti4 after 21 d on 3D-printed porous PEEK scaffolds with poly dopamine (PDA) and found that such scaffolds showed superior osteogenic ability after 6- and 12-weeks. Here, we demonstrate the alkali- and heat-treated nanotopography with the ability of stimulating osteogenic differentiation of hBMSC can induce the secretion of pro-osteogenesis sEV, and we also found that sEVs meditate osteogenesis through miRNA. Thus, whether nanotopography has the ability to regulate other contents of sEVs such as proteins for enhancing osteogenesis needs further research. These findings may help us use nanotopography to extract sEVs for other biomedical applications, including cancer therapy.

A facile and general strategy for preparing uniform and multifunctional polyphenol-based colloidal particles through amine-catalyzed polymerization-induced self-assembly is described. The size and interfacial adhesion of polyphenol spheres can be easily controlled over a wide range via adjusting the concentration of the cosolvent and monomer. Moreover, the polyphenol spheres showed excellent thermal and chemical stability and highly active properties and could efficiently deplete the reactive oxygen species (ROS), which are helpful for in vivo ROS regulation for inflammatory therapeutic. The accessible and versatile method provides a feasible way for the rational engineering of multifunctional polyphenol spheres, which have great potential in many fields.

Cancer is a serious threat to human health, and there is an urgent need to develop new treatment methods to overcome it. Organelle targeting therapy, as a highly effective and less toxic side effect treatment strategy, has great research significance and development prospects. Being an essential organelle, the Golgi apparatus plays a particularly major role in the growth of cancer cells. Acting as an indispensable and highly expressed antioxidant in cancer cells, glutathione (GSH) also contributes greatly during the Golgi oxidative stress. Therefore, it counts for much to track the changes of GSH concentration in Golgi for monitoring the occurrence and development of tumor cells, and exploring Golgi-targeted therapy is also extremely important for effective treatment of cancer. In this work, we designed and synthesized a simple Golgi-targeting fluorescent probe GT-GSH for accurately detecting GSH. The probe GT-GSH reacting with GSH decomposes toxic substances to Golgi, thereby killing cancer cells. At the same time, the ratiometric fluorescent probe can detect the concentration changes of GSH in Golgi stress with high sensitivity and selectivity in living cells. Therefore, such a GSH-responsive fluorescent probe with a Golgi-targeted therapy effect gives a new method for accurate treatment of cancer.

The incredible potential for fluorescent proteins to revolutionize biology has inspired the development of a variety of design strategies to address an equally broad range of photophysical characteristics, depending on potential applications. Of these, fluorescent proteins that simultaneously exhibit high quantum yield, red-shifted emission, and wide separation between excitation and emission wavelengths (Large Stokes Shift, LSS) are rare. The pursuit of LSS systems has led to the formation of a complex, obtained from the marriage of a rationally engineered protein (human cellular retinol binding protein II, hCRBPII) and different fluorogenic molecules, capable of supporting photobase activity. The large increase in basicity upon photoexcitation leads to protonation of the fluorophore in the excited state, dramatically red-shifting its emission, leading to an LSS protein/fluorophore complex. Essential for selective photobase activity is the intimate involvement of the target protein structure and sequence that enables Excited State Proton Transfer (ESPT). The potential power and usefulness of the strategy was demonstrated in live cell imaging of human cell lines.

Oxazole is an important pharmacophore and exists in the backbone of many bioactive peptide natural products and peptidomimetics. Efficient methods for the synthesis and direct functionalization of complex oxazole-containing peptides are in high demand. Herein, we report the late-stage site-selective functionalization of oxazole-containing peptides via palladium-catalyzed δ-C(sp 2 )-H olefination of phenylalanine, tryptophan, and tyrosine residues. This strategy utilizes oxazole motifs as internal directing groups and provides access to oxazole-containing peptide macrocycles with bioactivities.

Tin-based perovskite solar cells (PVSCs) are regarded as the most promising alternative among lead-free PVSCs. However, the rapid crystallization for tin-based perovskite tends to cause inferior film morphology and abundant defect states, which make poor photovoltaic performance. Here, 1-butyl-3-methylimidazolium bromide (BMIBr) ionic liquids (ILs) with strong polarity and a low melting point are first employed to produce the Ostwald ripening effect and obtain high-quality tin-based perovskite films with a large grain size. Meanwhile, the non-radiative recombination ascribed from defect states can also be effectively reduced for BMIBr-treated perovskite films. Consequently, a photoelectric conversion efficiency (PCE) of 10.09% for inverted tin-based PVSCs is attained by the Ostwald ripening effect. Moreover, the unencapsulated devices with BMIBr retain near 85% of the original PCE in a N 2 glovebox beyond 1200 h and about 40% of the original PCE after exposure to air for 48 h.

Calix[4]pyrrole 1 can form host-guest complexes with certain thallium salts, for example, TlF, not only in the gas phase but also in solution and in the solid state. The complexation of TlF by calix[4]pyrrole 1 was found to promote self-assembly and the formation of well-defined and highly ordered fibrous supramolecular morphologies, as revealed by polarizing microscopy and scanning electron microscopy. The findings reported here serve to broaden the scope of cationic substrates that may be complexed as ion pairs by calix[4]pyrrole receptors while setting the stage for the development of new hosts for thallium(I) salts.

The composition of low calorific value synthesis gas varies greatly depending on the raw material and processing technology, which makes the combustion extremely complicated. The three mechanisms of the GRI-Mech 3.0, Li-Model, and FFCM-Mech are used to numerically simulate CH 4 /CO/H 2 /N 2 air premixed combustion by using ANSYS CHEMKIN-PRO. The numerical simulation is the calculation of laminar flame velocity and adiabatic flame temperature at an initial temperature of 298 K, an equivalence ratio of 0.6-1.4, and an initial pressure of 0.1-0.5 MPa, discussing through thermodynamics and chemical kinetics. The formation of NO X , H, and OH radicals by fuel composition was analyzed. The result shows that the concentrations of H, O, and OH radicals have a positive effect on laminar flame velocity. The combustion reaction of H 2 is higher than that of CH 4 and CO; with the increase of N 2 content, the priority is higher. The thermal diffusivity of flame under different equivalence ratios is affected by inert gas, which affects adiabatic combustion temperature and laminar combustion velocity. In thermal kinetics and chemical kinetics, CH 4 has more influence on combustion temperature than CO, while laminar flame velocity is relatively low. Under the change of initial pressure, the laminar combustion flux increases to the initial pressure and the laminar combustion velocity decreases to the increase in pressure. Reactions H + O 2 = O + OH, HO 2 + H = 2OH, and CH 3 + HO 2 = OH + CH 3 O are mainly due to change in the concentration of O, H, and OH radicals., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Heterocyclic aromatic amines (HAAs) are potential human mutagens and carcinogens mainly generated in heat-treated meat. In this work, a broad-spectrum HAAs antibody was prepared and used to develop an indirect competitive ELISA (ic-ELISA) for simultaneous determination of eight HAAs, including 2-amino-3-methylimidazo[4,5- f ]quinoline (IQ), 2-amino-3,4-dimethylimidazo[4,5- f ] quinoline (MeIQ), 2-amino-3-methylimidazo[4,5- f ]quinoxaline (IQx), 2-amino-3,8-dimethylimidazo[4,5- f ]quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5- f ]quinoxaline (4,8-DiMeIQx), 2-amino-3,7,8-trimethylimidazo[4,5- f ]quinoxaline (7,8-DiMeIQx), 2-amino-3,4,7,8-tetramethylimidazo[4,5- f ]quinoxaline (4,7,8-TriMeIQx), and 2-amino-1-methyl-6-phenylimidazo[4,5- b ]pyridine (PhIP) in grilled and fried meat samples. The limit of detection (LOD, calculated as IC 10 ) and 50% inhibition concentration (IC 50 ) of ic-ELISA were 5.29 μg/L and 99.08 μg/L, respectively. The detection results of this ic-ELISA were in good agreement with the detection results of UPLC-MS/MS in real samples, which indicated that this ic-ELISA can be applied to detect the total content of eight HAAs in heat processed meat. Use of a broad-spectrum antibody is an efficient strategy in developing immunoassay for simultaneous measuring food risk factors with similar structure.

Perovskite polycrystalline films contain numerous intrinsic and interfacial defects ascribed to the solution preparation process, which are harmful to both the photovoltaic performance and the stability of perovskite solar cells (PVSCs). Although various passivators have been proved to be promising materials for passivating perovskite films, there is still a lack of deeper understanding of the effectiveness of the different passivation methods. Here, the mechanism between antisolvent dripping and additive doping strategies on the passivation effects in PVSCs is systematically investigated with a nonfullerene small molecule (F8IC). Such a passivated effect of F8IC is realized via coordination interactions between the carbonyl (C═O) and nitrile (C-N) groups of F8IC with Pb 2+ ion of MAPbI 3 . Interestingly, F8IC antisolvent dripping can effectively passivate the surface defects and thus inhibit the nonradiative charge recombination on the upper part of the perovskite layer, whereas F8IC additive doping significantly reduces the surface and bulk defects and produces a compact perovskite film with denser crystal grains, thus facilitating charge transmission and extraction. Therefore, these benefits are translated into significant improvements in the short-circuit current density ( J sc ) to 21.86 mA cm -2 and a champion power conversion efficiency of 18.40%. The selection of an optimal passivation strategy should also be considered according to the energy level matching between the passivators and the perovskite. The large energetic disparity is unsuitable for additive doping, whereas it is expected in antisolvent dripping.

A facile and universal oxygen-tolerant, capillary microfluidic-derived, controlled radical polymerization for surface structuring (gradient and patterned polymer brushes) is reported. A syringe pump and a filter paper sheet are used as capillary microfluidic to supply the reaction solution (monomer, solvent, and ligand) to a sandwich-shaped setup by placing a flat copper plate onto an ATRP initiator-modified substrate and resulting in gradient polymer brush formation with controlled thickness, steepness, and grafting area, polymers are showing the high chain-end fidelity. Two different polymer brushes (binary polymer brushes) can be simultaneously grown from both ends of the initiator modified substrate by using this method, which can be used to study the interfacial properties of different polymer brushes.

Graphitic carbon nitride (gCN) has a broad range of promising applications, from energy harvesting and storage to sensing. However, most of the applications are still restricted due to gCN poor dispersibility and limited functional groups. Herein, a direct photografting of gCN using various polymer brushes with tailorable functionalities via UV photopolymerization at ambient conditions is demonstrated. The systematic study of polymer brush-functionalized gCN reveals that the polymerization did not alter the inherent structure of gCN. Compared to the pristine gCN, the gCN-polymer composites show good dispersibility in various solvents such as water, ethanol, and tetrahydrofuran (THF). Patterned polymer brushes on gCN can be realized by employing photomask and microcontact printing technology. The polymer brushes with incorporated silver nanoparticles (AgNPs) on gCN can act as a multifunctional recyclable active sensing layer for surface-enhanced Raman spectroscopy (SERS) detection and photocatalysis. This multifunctionality is shown in consecutive cycles of SERS and photocatalytic degradation processes that can be applied to in situ monitor pollutants, such as dyes or pharmaceutical waste, with high chemical sensitivity as well as to water remediation. This dual functionality provides a significant advantage to our AgNPs/polymer-gCN with regard to state-of-the-art systems reported so far that only allow SERS pollutant detection but not their decomposition. These results may provide a new methodology for the covalent functionalization of gCN and may enable new applications in the field of catalysis, biosensors, and, most interestingly, environmental remediation.

As a eukaryotic organelle, the Golgi apparatus plays an essential role in various physiological activities such as stress response. The Golgi stress response is an important physiological process of conferring cytoprotection by regulating the synthesis and metabolism of bioactive molecules. Therefore, the development of new suitable in situ analytical techniques for monitoring related small molecular substances in the stress reaction of the Golgi apparatus is very helpful for further study of the regulatory mechanism of the Golgi apparatus. Recent studies have shown that endogenous hydrogen sulfide (H 2 S) also possesses crucial bioregulatory and protective performances in the stress response. Therefore, the high-fidelity in situ mapping of H 2 S production under the Golgi stress response plays an important role not only in revealing cytoprotection functions of H 2 S in the stress response but also in further understanding the regulatory mechanism of the Golgi stress response. In this work, we designed a simple Golgi-targetable H 2 S fluorescent probe ( Gol-H 2 S ) that responds accurately and sensitively to H 2 S in the Golgi apparatus of living cells and zebrafish. On the basis of its superior bioimaging performances, probe Gol-H 2 S was successfully applied to the in situ visualization of H 2 S production under the Golgi stress response elicited by monensin, a specific-Golgi stressor. The related process of the Golgi stress response was validated by stimulation and inhibition experiments. These findings fully demonstrate that H 2 S is an alternative biomarker of the Golgi stress response. Moreover, probe Gol-H 2 S can also be used as a potential tool for disclosing the detailed H 2 S-cytoprotection mechanisms under the regulation of the Golgi stress response in related diseases.

A novel type of dibenzothiophene [ b ]-fused core-expanded azaBODIPYs were obtained through an efficient post-functionalization of tetrabrominated azadipyrromethenes, using CuI-catalyzed cyclization, followed by BF 2 complexation. These dyes show nearly planar skeletons, strong NIR absorption with maximum peaks up to 733 nm, and remarkable low-lying LUMO level of -4.15 eV. The field-effect transistor based on 1b exhibits bipolar transport properties, with the highest electron and hole mobilities up to 0.012 and 0.046 cm 2 V -1 s -1 , respectively.

Hypochlorous acid (HOCl) has received special attention by virtue of its pivotal antimicrobial nature, and the appropriate amount of HOCl is beneficial to innate immunity of host to cope with microbial invasion. However, the uncontrollable accumulation of HOCl is implicated in many human diseases and even cancers. Thus, to determine its deeper biological functions, it is significantly important to specifically monitor intracellular HOCl in biosystems. Herein, we rationally designed a simple fluorescent probe FH - HA on the basis of the formylhydrazine recognition receptor and rhodamine B fluorophore. It is worth noting that the formylhydrazine moiety for the first time is adopted as the recognition receptor for specifically recognizing HOCl. Additionally, probe FH - HA also exhibited excellent performance in many areas including satisfactory water-solubility, high specificity, and excellent sensitivity. Notably, probe FH - HA could quickly respond to HOCl (within 3 s), which facilitates the tracing of transient HOCl. More importantly, probe FH - HA was capable of specifically tracing the fluctuations of endogenous HOCl in living cells and zebrafish, and it could monitor basal HOCl in cancer cells to distinguish cancer cells from normal ones.

A new synthetic method to build phenanthrene-fused boron dipyrromethenes (BODIPYs) through tandem Suzuki couplings on readily available 2,3,5,6-tetrabromoBODIPYs, followed by an intramolecular oxidative aromatic coupling mediated by iron(III) chloride is reported. This efficient synthesis allows a very straightforward approach for tuning the absorption and emission of BODIPYs in the red/near-infrared (NIR) range. These resulting phenanthrene-fused BODIPYs exhibit strong absorption (extinction coefficients up to 2.2 × 10 5 M -1 cm -1 ) and emission in the near-infrared (NIR) range (688-754 nm). Substituents on the resulting phenanthrene rings have a significant impact on the photophysical properties of these phenanthrene-fused BODIPYs.

5-Hydroxymethylcytosine (5hmC) arises from the oxidation of 5-methylcytosine (5mC) by Fe 2+ and 2-oxoglutarate-dependent 10-11 translocation (TET) family proteins. Substantial levels of 5hmC accumulate in many mammalian tissues, especially in neurons and embryonic stem cells, suggesting a potential active role for 5hmC in epigenetic regulation beyond being simply an intermediate of active DNA demethylation. 5mC and 5hmC undergo dynamic changes during embryogenesis, neurogenesis, hematopoietic development, and oncogenesis. While methods have been developed to map 5hmC, more efficient approaches to detect 5hmC at base resolution are still highly desirable. Herein, we present a new method, Jump-seq, to capture and amplify 5hmC in genomic DNA. The principle of this method is to label 5hmC by the 6- N3-glucose moiety and connect a hairpin DNA oligonucleotide carrying an alkyne group to the azide-modified 5hmC via Huisgen cycloaddition (click) chemistry. Primer extension starts from the hairpin motif to the modified 5hmC site and then continues to "land" on genomic DNA. 5hmC sites are inferred from genomic DNA sequences immediately spanning the 5-prime junction. This technology was validated, and its utility in 5hmC identification was confirmed.

The precise cellular function of peroxynitrite (ONOO - ) in biosystems remains elusive, primarily owing to being short of ultrasensitive techniques for monitoring its intracellular distribution. In this work, a novel rhodamine B cyclic 1,2-dimethylhydrazine fluorescent chemodosimeter RDMH-PN for highly specific and ultrasensitive monitoring of basal ONOO - in biosystems was rationally designed. The fluorescence titration experiments demonstrated that RDMH-PN was capable of quantitatively detecting 0-100 nM ONOO - (limit of detection = 0.68 nM). In addition, RDMH-PN has outstanding performances of ultrafast measurement, naked-eye detection, and preeminent selectivity toward ONOO - to accurately detect intracellular basal ONOO - . Finally, it has been confirmed that RDMH-PN could not only map the intracellular basal ONOO - level by inhibition tests but also trace the fluctuations of endogenous and exogenous ONOO - levels with diverse stimulations in live cells and zebrafish.

The modulation of threshold voltage ( V TH ) of organic thin-film transistors (OTFTs) was investigated by embedding a thin CuO layer between the two semiconductor layers. The results showed that the V TH of OTFTs with a CuO layer can be effectively tuned by controlling the positive gate-to-source voltage ( V GS0 ) under stress of gate-to-source voltages. The V TH shifts from -3.67 to -0.82 V when the positive V GS0 varies from 30 to 50 V. This can be explained by the mechanism of trapping electrons at the interface between the CuO charge-separation layer and the active layer. To confirm the role of the CuO layer acting as the charge-separation source, two organic thin-film diodes, indium-tin oxide(ITO)/tris (8-quinolinolato) aluminum(III) (Alq 3 )/pentacene/Al (inverted-stack diode) and ITO/Alq 3 /CuO/pentacene/Al (inverted-stack diode with a CuO layer), were fabricated and their diode current characteristics were measured. For the second device, a large current flow was observed at positive bias on the ITO electrodes, which is ascribed to the internal bipolar charge separation within the added CuO zone., Competing Interests: The authors declare no competing financial interest.

Liver cancer is a kind of high mortality cancer due to the difficulty of early diagnosis. And according to the reports, the concentration of reactive oxygen species (ROS) was higher in cancer cells than normal cells. Therefore, developing an effective fluorescent probe for hepatoma-selective imaging of hypochlorous acid (HOCl) which is one of the vital ROS is of great importance for understanding the role of HOCl in liver cancer pathogenesis. However, the cell-selective fluorescent probe still remains a difficult task among current reports. Herein, a galactose-appended naphthalimide (Gal-NPA) with p-aminophenylether as a new receptor and galactose moiety as hepatoma targeting unit was synthesized and employed to detect endogenous HOCl in living HepG2 cells. This probe was proved to possess good water solubility and could respond specifically to HOCl. In addition, probe Gal-NPA could completely react to HOCl within 3 s meanwhile accompanied by tremendous fluorescence enhancement. The quantitative linear range between fluorescence intensities and the HOCl concentrations was 0 to 1 μM (detection limit = 0.46 nM). More importantly, fluorescence confocal imaging experiments showed that probe Gal-NPA could discriminate hepatoma cells over other cancer cells and simultaneously trace endogenous HOCl levels in living HepG2 cells. And we thus anticipate that probe Gal-NPA has the potential application for revealing the functions of HOCl in hepatoma cells.

In the past decades, enormous efforts have been made to synthesize photocatalysts for N 2 conversion driven by visible light. However, it is still a major challenge to develop an efficient photocatalyst. In this paper, monodoped and codoped TiO 2 nanofibers were fabricated by vapor-phase growth. Vapor-phase implantation of the guest atoms into TiO 2 nanofibers may greatly prolong the lifetime of electron-hole pairs. The doped TiO 2 nanofibers were demonstrated to be an excellent photocatalyst for nitrogen photofixation under a 300 W Xe-lamp irradiation. The amount of ammonia produced over the Fe, V codoped TiO 2 nanofibers reached 14 783 μmol/L·g-cata after irradiation for 2 h. The strategy could be easily extended to prepare other species doped TiO 2 nanofibers as high-efficiency photocatalysts.

Mesenchymal stem cells (MSCs) play an important role in cutaneous wound healing; however, the functional mechanisms involved in the healing process are poorly understood. A series of studies indicate that keratinocytes that migrate into the wound bed rely on an epithelial-mesenchymal transition (EMT)-like process to initiate re-epithelialization. We therefore examined whether bone marrow-derived MSCs (BMSCs) could affect biological behavior and induce EMT-like characteristics in the human epidermal keratinocytes (HEKs) and in the immortalized human keratinocyte cell line HaCaT cells, and we investigated the signaling pathways of BMSC-mediated phenotypic changes. By assessing the expression of EMT-related markers including E-cadherin, α-SMA, and Snail family transcription factors by β 2 -adrenergic receptor (β 2 -AR) blockage using ICI-118,551, a β 2 -AR selective antagonist, or β 2 -AR small interfering RNA (siRNA), we showed an involvement of β 2 -AR signaling in the induction of EMT-like alterations in human keratinocytes in vitro. β 2 -AR signaling also affected collective and individual cell migration in human keratinocyte cell lines, which was attenuated by administration of ICI-118,551. Treating the cells with BMSC-conditioned media (BMSC-CM) not only recapitulated the effect of isoproterenol (ISO) on cell migration but also induced the expression of β 2 -AR and a panel of proteins associated with mesenchymal phenotype in HEKs and HaCaT cells. Similarly, a blockade of the β 2 -AR by either ICI-118,551 or β 2 -AR siRNAs reversed both responses of the epidermal keratinocyte cell lines relative to BMSC-CM exposure. These results were further verified in our vivo findings and indicated that the exogenous application of MSCs promoted cutaneous wound healing and endowed the keratinocytes surrounding the wound area with an increased migratory phenotype through activation of β 2 -AR signaling. Our findings suggest a biochemical mechanism underlying the function of MSCs in wound re-epithelization, which provides a reliable theoretical basis for the wide application of MSCs in the treatment of chronic wounds.

Enhanced macropinocytosis has been found in K-Ras mutant pancreatic cancer cells, through which albumin can massively enter into the K-Ras-driven cancer cells, suggesting its role in serving as a macropinocytosis-intensifying drug delivery carrier. In the present study, a novel recombinant protein Fv-LDP-D3 and its reconstituted analogue Fv-LDP-D3-AE were designed and prepared. Fv is the fragment of an anti-EGFR antibody, D3 is the domain III of human serum albumin (HSA), LDP is the apoprotein of the antitumor antibiotic lidamycin (LDM), and AE is an extremely cytotoxic enediyne chromophore derived from LDM. As shown, the recombinant protein Fv-LDP-D3 presented intensive and selective binding capacity to pancreatic cancer cells and inhibited cell proliferation by blocking EGFR signaling. Moreover, Fv-LDP-D3 showed prominent tumor imaging in pancreatic carcinoma xenograft. The reconstituted, enediyne-integrated analogue Fv-LDP-D3-AE displayed highly potent cytotoxicity to pancreatic cancer cells through apoptosis induction and G2/M arrest. Fv-LDP-D3 and Fv-LDP-D3-AE markedly inhibited the tumor growth of the pancreatic carcinoma AsPC-1 xenograft. Study results indicated that the novel recombinant protein displays both EGFR-targeting and macropinocytosis-intensifying attributes, presenting a new format of scFv antibody that integrates with albumin domain III. It might be a feasible strategy to develop targeted drugs for K-Ras mutant pancreatic cancer.

Annularly fused azaBODIPY-based organic fluorophores (HBPs 2) containing up to 13 aromatic ring fusions were synthesized by a Suzuki coupling reaction with bromoazadipyrromethenes and a subsequent regioselective oxidative ring-fusion reaction. X-ray analysis indicates almost planar dipyrrin cores for all crystals but overall curved or "wave" conformations for those HBP dyes. These molecules exhibit unique structural and physical properties including excellent spectral selectivity (negligible absorption between 300 and 700 nm), sharp near-infrared (NIR) absorption (up to 878 nm) and emission (up to 907 nm), large extinction coefficient (up to 4.5 × 10 5 M -1 cm -1 ), and excellent photostabilities.

A set of dipyrrolyldipyrrins have been efficiently synthesized from a direct S N Ar reaction on 1,9-dihalodipyrrins with pyrroles and show intense absorption in the NIR region (650-800 nm, as HCl salts). Substituents on both 1,9-dihalodipyrrins and pyrroles greatly affected the reactivity of this S N Ar reaction and the absorption properties of the resultant dipyrrolyldipyrrins. These dipyrrolyldipyrrins show sensitive and selective "turn-on" fluorescence response toward Zn 2+ .

A new substitution pattern of BF 2 azadipyrromethene (azaBODIPY) dyes was obtained by phenanthrene fusion through a key palladium-catalyzed intramolecular C-H activation reaction. These [a]-phenanthrene-fused azaBODIPYs have a near planar structure of the phenanthrene-fused azadipyrromethene core in the crystalline state. The chromophore absorbs (log ε > 5) and fluoresces (ϕ = 0.32-0.38) strongly above 700 nm with excellent photostability and may be used as an attractive bright NIR bioimaging agent.

Postfunctionalization of azaBODIPY (the BF 2 complex of azadipyrromethene) is highly desirable due to the strong tunable absorption bands at wavelengths above 650 nm and the wide-ranging applications of this class of dyes in biomedicine and materials science. Currently available postfunctionalization methods for this class of dyes have been limited to the Pd-catalyzed coupling reactions on β-halogenated (brominated or iodinated) azaBODIPY platforms. In this work, we report a new strategy for the facile postfunctionalization of the azaBODIPY chromophore with various vinyl ketone and vinyl esters based on a Wittig reaction on our previously developed β-formylazaBODIPYs and our recently developed β-bromo-β'-formylazaBODIPYs. Our strategy uses easily accessible starting materials and mild reaction conditions. It is highly compatible with various common phosphonium ylides (aliphatic, aromatic, and ester substituted ones). These resultant bromo-containing β-vinyl ketone/ester functionalized azaBODIPYs are potential photosensitizers and can be further functionalized via coupling reactions. The ester groups on some of these resultant azaBODIPYs can be further hydrolyzed to achieve the desired water solubility and conjugate with the biomolecule and solid surface., Competing Interests: The authors declare no competing financial interest.

Three novel π-extended BF 2 complexes of β,β-bisphenanthrene-fused azadipyrromethenes containing nine fused rings have been synthesized on the basis of a tandem Suzuki coupling reaction on readily available 2,6-dibromoazaBODIPYs followed by an intramolecular oxidative aromatic coupling mediated by iron(III) chloride. These resultant BF 2 complexes exhibit strong absorption (extinction coefficients up to 2.4 × 10 5 M -1 cm -1 ) and emission in the near-infrared (NIR) range (790-816 nm) with excellent photo and thermal stabilities. The hole mobility of the thin-film field-effect transistors of these dyes fabricated by a solution process reaches up to 0.018 cm 2 V -1 s -1 .

Theranostic nanoparticles with combined imaging and therapy functions show great promise in cancer precision medicine. In this study, we constructed near-infrared (NIR) "OFF-ON" fluorescent nanohybrids (F-PNDs) for synchronous tumor imaging and microRNA (miRNA) modulation therapy against esophageal cancer. Nanodiamond clusters (NDs) were first functionalized for protamine sulfate immobilization (PNDs) on their surfaces via a noncovalent self-assembling approach and simultaneous encapsulation of NIR emitting fluorescence dye cyanine 5 (Cy-5) (F-PNDs). Tumor suppressor miRNA-203 (miR-203) was then adsorbed onto the surface of F-PNDs to form miR-203/F-PNDs via electrostatic interactions. The size, morphology, photophysical and stability properties of miR-203/F-PNDs were analyzed. We found that the NIR fluorescence of miR-203/F-PNDs could be activated to the "ON" state in intracellular environment while remaining in the "OFF" state in extracellular or blood environment. Furthermore, in vivo live imaging experiments showed that miR-203/F-PNDs could be predominantly accumulated in tumor tissues and image the tumor sites 24 h postintravenous injection. In addition, intravenous and intratumoral injection of miR-203/F-PNDs could efficiently inhibit tumor growth through down-regulation of the expressions of oncogenes Ran and Δp63. Our study indicated that miRNA/F-PNDs could serve as a promising theranostic platform for synchronous tumor imaging and miRNA-based modulation therapy against cancer.