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Abstract Photoactive agents based on natural products have attracted substantial attention in clinical applications because of their distinct biological activity, molecular structure multiformity, and low biotoxicity. Herein, we initially modify hypocrellin B (HB) with 1,2-diamino-2-methyl propane to form near-infrared (NIR) light (>700 nm)-responsive amino-substituted HB derivative (DPAHB). The DPAHB exhibit broad absorption (400–800 nm), NIR emission (maximum emission peak at 710 nm), and high singlet oxygen (1O 2) quantum yield (∼0.33) under NIR light (721 nm) irradiation. After self-assembly by using DPAHB with PEG-PLGA, the as-prepared nanovesicles (DPAHB NVs) retain efficient 1O 2 generation, more interestingly, show high photothermal conversion efficiency (∼0.24) under NIR light (721 nm) irradiation for synergistic photodynamic therapy (PDT) and photothermal therapy toward hypoxic tumor. The DPAHB NVs can not only be as a fluorescence/photoacoustic imaging agent but also exhibit an even stronger PDT efficiency than that of chlorin e6 (a widely used classic photosensitizer). In vitro and in vivo studies demonstrate that DPAHB NVs possess high photothermal stability, enhanced tumor accumulation, and suitable biodegradation rate, thus, show a highly promising clinical potential as a new photoactive agent for cancer therapy. [ABSTRACT FROM AUTHOR]

Abstract: Conjugated polymer dots (Pdots, also named polymer nanoparticles, PNPs), which consist of π‐conjugated organic polymers, are novel organic nanomaterials with size in the range of 1–100 nm. Compared with traditional organic small molecules, semiconductor quantum dots and inorganic nanomaterials, the Pdots exhibit significant potential applications in biological imaging, sensing and detection, drug delivery and theranostics, due to their advantages of special optical properties, diverse structure, easy surface modification and good biocompatibility. In this short review, we present a brief summary of the current development in Pdots as phototheranostic agents, including fluorescence imaging, photoacoustic imaging, photodynamic therapy and photothermal therapy. Current challenges in Pdot research and future directions in the field are proposed. [ABSTRACT FROM AUTHOR]

A novel phototheranostic platform based on tri -malonate derivative of fullerene C 70 (TFC 70 )/photosensitizer (Chlorin e6, Ce6) nanovesicles (FCNVs) has been developed for effective tumor imaging and treatment. The FCNVs were prepared from amphiphilic TFC 70 -oligo ethylene glycol -Ce6 molecules. The developed FCNVs possessed the following advantages: (i) high loading efficiency of Ce6 (up to ∼57 wt%); (ii) efficient absorption in near-infrared light region; (iii) enhanced cellular uptake efficiency of Ce6 in vitro and in vivo ; (iv) good biocompatibility and total clearance out from the body. These unique properties suggest that the as-prepared FCNVs could be applied as an ideal theranostic agent for simultaneous imaging and photodynamic therapy of tumor. This finding may provide a good solution to highly efficient phototheranostic applications based on fullerene derivatives fabricated nanostructures. [ABSTRACT FROM AUTHOR]

Abstract: A facile hydrothermal approach based on n-nonyl alcohol mediated process has been developed to synthesize self-assembled Fe3O4 hierarchical nanostructures. The as-synthesized hierarchical nanostructured Fe3O4 could be easily transformed to γ-Fe2O3 and α-Fe2O3 without changing its original morphology by calcination in air. X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were performed to investigate the evolution process of Fe3O4 hierarchical nanostructures. The growth mechanism of the as-prepared Fe3O4 nanostructure and the subsequently hierarchical nanostructures are suggested. The as-obtained iron oxide nanomaterials were used as adsorbent in water treatment, and were found an excellent ability to remove organic pollutants such as Orange II in waste water. [Copyright &y& Elsevier]

La(OH)3 nanospheres have been synthesized with La(NO3)3 and KOH as the starting materials and citric acid as a protective agent through a facile controllable hydrothermal method. The obtained products were analysed with x-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The formation mechanism of the La(OH)3 nanospheres was investigated in detail. [ABSTRACT FROM AUTHOR]

Hollow silica spheres have been widely studied for drug delivery because of their excellent biosecurity and high porosity. However, difficulties with degradation in the tumor microenvironment (TME) and premature leaking during drug delivery limit their clinical applications. To alleviate these problems, herein, hollow organosilica spheres (HOS) were initially prepared using a "selective etching strategy" and loaded with a photothermal drug: new indocyanine green (IR820). Then, the Cu2+–tannic acid complex (Cu-TA) was deposited on the surface of the HOS, and a new nanoplatform named HOS@IR820@Cu-TA (HICT) was finally obtained. The deposition of Cu-TA can gate the pores of HOS completely to prevent the leakage of IR820 and significantly enhance the loading capacity of HOS. Once in the mildly acidic TME, the HOS and outer Cu-TA decompose quickly in response, resulting in the release of Cu2+ and IR820. The released Cu2+ can react with the endogenous glutathione (GSH) to consume it and produce Cu+, leading to the enhanced production of highly toxic ·OH through a Fenton-like reaction due to the overexpressed H2O2 in the TME. Meanwhile, the ·OH generation was remarkably enhanced by the NIR light-responsive photothermal effect of IR820. These collective properties of HICT enable it to be a smart nanomedicine for dually enhanced chemodynamic therapy through GSH depletions and NIR light-triggered photothermal effects. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Currently, solid‐state fluorescent carbonized polymer dots (CPDs) have attracted attention increasingly due to their applications for optoelectronic display. However, designing CPDs possessing solid‐state fluorescence and clarifying the fluorescence mechanism remain challenging. Herein, we initially synthesized a novel type of polythiophene derivatives CPDs, poly‐4,4'‐(thiophene‐3,4‐diyl)dibenzoic acid carbonized polymer dots (PDBA‐CPDs) with solid‐state fluorescence. Subsequently, the structural and optical characterization revealed that the solid‐state fluorescence originated from the aggregation induced emission of the CPDs. In brief, in aggregation state, the remaining polymer structure groups on the surface of the CPDs overlapped and weakened the non‐radiative transition, enhancing solid‐state fluorescence emission. Thirdly, three polythiophene‐derived CPDs were designed to further demonstrate the aggregation induced solid‐state fluorescence mechanism. Finally, owing to their unique properties of solid‐state fluorescence, the white LEDs (light emitting diodes) were fabricated with high color rendering index (CRI) of 82.7 and CIE coordinates of (0.37, 0.39) using commercial 460 nm chip. This work facilitates the development of CPDs' solid‐state fluorescence mechanisms and advances the application of CPDs in the field of optoelectronics. [ABSTRACT FROM AUTHOR]

As phototheranostic agents, carbon dots (CDs), have recently drawn considerable attention due to their excellent physicochemical properties. However, the complex synthetic route and high-cost of CDs greatly limit their practical application. To address this issue, given their nearly infinite supply from nature, Hypocrella bambusae is used as the precursor for the preparation of CDs in this study. The obtained Hypocrella bambusae CDs (HBCDs) possess good water solubility, broad absorption (350–800 nm), red-light emission (maximum peak at 610 nm), and low biotoxicity. Moreover, HBCDs can highly generate 1 O 2 (0.38) and heat (27.6%) under 635 nm laser irradiation. These excellent properties of HBCDs capacitate them to be utilized for bimodal fluorescence/photoacoustic imaging-guided synergistic photodynamic therapy (PDT)/photothermal therapy (PTT). This work provides a new candidate for tumor treatment with the combination of PDT and PTT, and explores a novel approach for the preparation of CD-based phototheranostic agents with natural biomass as raw carbon sources. [ABSTRACT FROM AUTHOR]

Organic molecules that are active in the near-infrared (NIR) bio-window for photo-to-heat energy-converting theranostics have attracted much attention in cancer therapy. However, current organic NIR-absorbing molecules are still suffering from the inefficient non-radiative decay or serious photobleaching under light irradiation. Herein, we design a convenient strategy to load a new kind of NIR-absorbing nonlinear optical (NLO) chromophore FTC-3f with the biocompatible polymer, methoxy poly(ethylene glycol)-poly(lactideco-glycolide) (mPEG-PLGA). The resulted FTC-3f/PLGA nanoparticles showed excellent stability, high photothermal conversion efficiency (∼51.11%) and good photoacoustic performance. Moreover, in vitro anticancer experiments demonstrated that the FTC-3f/PLGA nanoparticles possess a high PTT (photothermal therapy) efficiency under NIR laser irradiation. This work thus provides an insight into the exploration of versatile organic NIR-absorbing nanoparticles toward future practical PTT application. [Display omitted] • A new kind of FTC-3f chromophores were synthesized with a strong absorption in the spectral region of 600–1100 nm. • FTC-3f/PLGA nanoparticles possess high stability when dispersed in water, PBS solution and DMEM solution. • FTC-3f/PLGA shows a high photothermal conversion efficiency and excellent photoacoustic/photostability performance. • In vitro antitumor result revealed a high photothermal therapy efficiency under 750 nm NIR light irradiation. [ABSTRACT FROM AUTHOR]

During the past decade, fluorescent chemosensors have become an important research field of supramolecular chemistry and have attracted great attention because of their simplicity, high selectivity and sensitivity in fluorescent assays. In the design of new fluorescent chemosensors, exploration of new sensing mechanisms between recognition and signal reporting units is of continuing interest. Based on different photophysical processes, conventional sensing mechanisms including photo-induced electron transfer (PET), intramolecular charge transfer (ICT), metal–ligand charge transfer (MLCT), twisted intramolecular charge transfer (TICT), electronic energy transfer (EET), fluorescence resonance energy transfer (FRET), and excimer/exciplex formation have been investigated and reviewed extensively in the literature. This tutorial reviewwill mainly focus on new fluorescent sensing mechanisms that have emerged in the past five years, such as aggregation-induced emission (AIE) and CN isomerization, which can be ascribed to fluorescence changes viaconformational restriction. In addition, excited-state intramolecular proton transfer (ESIPT) has not been well reviewed yet, although a number of chemosensors based on the ESIPT mechanism have been reported. Thus, ESIPT-based chemosensors have been also summarized in this review. [ABSTRACT FROM AUTHOR]

Peroxalate CL as an energy source to excite photosensitizers has attracted tremendous attention in photodynamic therapy (PDT). In this work, peroxyoxalate CPPO and hypocrellin B (HB)‐based nanoparticles (CBNPs) for ultrasound (US)‐enhanced self‐exciting PDT were designed and prepared. CBNPs showed an excellent therapeutic effect against cancer cells with the assistance of US. This US‐enhanced‐chemiluminescence system avoids the dependence on external light and provides an example for inspiring more effective and precise strategies for cancer treatment. [ABSTRACT FROM AUTHOR]

Hypocrellin B (HB) derived from naturally produced hypocrellins has attracted considerable attention in photodynamic therapy (PDT) because of its excellent photosensitive properties. However, the weak absorption within a "phototherapy window" (600–900 nm) and poor water solubility of HB have limited its clinical application. In this study, two HB derivatives (i. e., HE and HF) were designed and synthesized for the first time by introducing two different substituent groups into the HB structure. The obtained derivatives showed a broad absorption band covering the near‐infrared (NIR) region, NIR emission (peaked at 805 nm), and singlet oxygen quantum yields of 0.27/0.31. HE‐PEG‐NPs were also prepared using 2‐distearoyl‐sn‐glycero‐3‐phosphoethanolamine‐N‐[methoxy(polyethyleneglycol)‐2000] (DSPE‐mPEG2000) to achieve excellent dispersion in water and further explored their practical applications. HE‐PEG‐NPs not only retained their 1O2‐generating ability, but also exhibited a photothermal conversion efficiency of 25.9%. In vitro and in vivo therapeutic results revealed that the synergetic effect of HE‐PEG‐NPs on PDT and photothermal therapy (PTT) could achieve a good performance. Therefore, HE‐PEG‐NPs could be regarded as a promising phototheranostic agent. [ABSTRACT FROM AUTHOR]

Carbon dots (CDs), a kind of phototheranostic agent with the capability of simultaneous bioimaging and phototherapy [i.e. photodynamic therapy (PDT) or photothermal therapy (PTT)], have received considerable attention because of their remarkable properties, including flexibility for surface modification, high biocompatibility, low toxicity and photo‐induced activity for malignant tumor cells. Among numerous carbon sources, it has been found that natural biomass are good candidates for the preparation of CD phototheranostic agents. In this study, pheophytin, a type of Mg‐free chlorophyll derivative and also a natural product with low toxicity, was used as a raw carbon source for the synthesis of CDs by using a microwave method. The obtained hydrophobic CDs exhibited a maximum near‐infrared (NIR) emission peak at approximately 680 nm, and high singlet oxygen (1O2) generation with a quantum yield of 0.62. The self‐assembled CDs from the as‐prepared CDs with DSPE‐mPEG2000 retained efficient 1O2 generation. The obtained carbon dot assembly was not only an efficient fluorescence (FL) imaging agent but also a smart PDT agent. Our studies indicated that the obtained hydrophilic CD assembly holds great potential as a new phototheranostic agent for cancer therapy. This work provides a new route for synthesis of CDs and proposes a readily available candidate for tumor treatment. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Multifunctional liposomes with tumor targeted drug delivery and imaging. • Enhanced photoluminescence emission of carbon dots. • Enhanced anti-cancer efficacy of cinobufagin after loading into liposomes. Abstract Integrating the optical properties of near-infrared fluorescent carbon dots into liposomes may construct a multifunctional nano-system with the potential as a drug carrier, tracer and efficacy intensifier of the anticancer agent. In this study, the liposomes loaded with hydrophilic near-infrared carbon dots as a nano-carrier and tracer of lipophilic anticancer agent cinobufagin were developed. Prepared liposomes were characterized by particle size, morphology and entrapment efficiency. The drug release behavior, the tracer function, the anticancer effect and the side effect were investigated in vitro and in vivo. It was observed that the photoluminescence emission of carbon dots could be strongly enhanced up to 5 times by nano-liposomes. Due to this property, the bio-imaging of CDs + CB liposomes in vitro and in vivo could be clearly obtained. Our results also showed that the CDs + CB liposomes could be uptaken by cells (the lysosomes targeted) and delivered to the tumor site, and undoubtedly, the CDs + CB liposomes demonstrated sustained drug release, enhanced anticancer efficacy and low side effects in vivo. With the assistance of imaging function of CDs, the CDs + CB liposomes can easily display the distribution of drugs, which is very helpful for drug development and may open a novel avenue for drug delivery. [ABSTRACT FROM AUTHOR]

The distance-dependent based sensing mechanism, such as fluorescence resonance energy transfer (FRET) and surface plasmon resonance (SPR) absorption of gold nanoparticles, has been used widely in visual detection. In this work, we report another distance-dependent detection method for nucleoside triphosphates (NTPs) based on carbon dots (CDs) ( 1 O 2 donor) and 9, 10-diphenylanthracene-2-boronic acid (DABA, 1 O 2 acceptor). The CDs can generate singlet oxygen ( 1 O 2 ) which allows diffusion within 200 nm. Thus, the distance between CDs and DABA decreased through binding of NTPs (<200 nm), leading to absorption changes of DABA under light irradiation due to 1 O 2 trapping. This sensing system (CDs@DABA) has high selectivity for the detection of NTPs due to the double molecular recognition and a linear response in the 0–80 μM concentration range was accomplished with the detection limit as low as 4.35 μM. [ABSTRACT FROM AUTHOR]

On base of the good optical properties of coumarin and fluorescein, we designed and synthesized two coumarin/fluorescein-fused fluorescent dyes ( CF dyes), which enlarged the emission wavelength and increased the Stokes shift of fluorescein moiety. The corresponding optical properties of CF dyes were investigated in detail. CF dyes could easily introduce other groups to design different functional molecules. CF dyes also exhibited rapid and sensitive responses to pH values in the range of 4.0–7.4 through the characterization of absorption and fluorescence spectra in buffer solution. More importantly, CF ethyl ester dye ( CFE dye) not only showed good cell membrane permeability and low cytotoxicity, but also had the ability to rapidly monitor mitochondrial pH changes in living cells. [ABSTRACT FROM AUTHOR]

During the past decade, increasing attention has been paid to fluorescent carbon dots (CDs) due to their unique photoluminescence (PL) properties. As synthetic methods gradually develop, many post‐functionalization strategies have been developed to enhance the PL of CDs. However, in most cases, the PL enhancement was less than 10‐fold with multistep modification processes. In this work, a facile and efficient post‐functionalization strategy was successfully applied to enhance the PL intensity of CDs dramatically up to 69 times by surfactants at room temperature for the first time. Furthermore, the mechanism of surfactant‐induced PL enhancement of CDs was investigated and in vivo bioimaging was performed. The results demonstrated that electrostatic/non‐electrostatic interactions between CDs and surfactants could effectively lower the vibration and rotation of CDs, increase radiative decay processes and, thus, enhance the PL of CDs. This finding may provide new insights into the strategies for enhancing the PL of CDs, further broadening their potential applications. Brighter Carbon Dots: The effect of different types of surfactants on the photoluminescence of carbon dots (CDs) was investigated. The results show that interactions between carbon dots and surfactants enhance the photoluminescence of CDs. [ABSTRACT FROM AUTHOR]

A new water-soluble fluorescent probe 1 based on hemicyanine dye is designed for selective detection of glutathione (GSH). Probe 1 shows a tremendous colorimetric and ratiometric fluorescence response toward GSH with high selectivity over cysteine/homocysteine. After nucleophilic aromatic substitution reaction with GSH, probe 1 undergoes an intramolecular aldimine condensation that leads to forming a ring, which is accompanied by 107 and 41 nm red-shifts in the absorption and fluorescence spectra, respectively. Subsequent experiments in living cells indicate that probe 1 has a good photostability and response to mitochondrial GSH level in a ratiometric manner. [ABSTRACT FROM AUTHOR]

A novel fluorescent probe O-hNRSel based on tetralin-xanthene fused dye O-hNR was designed and synthesized by introducing 2,4-dinitrobenzenesulfonate functionality. This probe is able to detect selenocysteine (Sec) with rapid response time (2 min) and a large fluorescence enhancement at 624 nm (124-fold). O-hNRSel exhibited selective response to Sec over many other analy and high sensitivity with the detection limit as low as 17 nM. Furthermore, O-hNRSel has been used for fluorescent imaging of Sec in living cells with good biocompatibility. [ABSTRACT FROM AUTHOR]

The highly sensitive and rapid detection and distinction of gram-negative bacteria are essential for the early diagnosis and accurate medical treatment of bacterial infection. In this work, we investigated a new selective and sensitive method of detecting gram-negative bacteria based on a small molecule modified sensor chip by a laser scanning confocal imaging-surface plasmon resonance (LSCI-SPR) system. The small molecule (polymyxin B) strongly interacted with bacteria cell membrane. SPR signals changed with SYTO 9 stained bacteria concentrations, and fluorescence images were recorded at the same time. Results showed that Escherichia coli were distinguished clearly with a limit of detection (LOD) of 1.0 × 10 2 CFU/mL for Escherichia coli . Moreover, a good linear relationship was observed between bacteria concentrations and SPR signals from 1.0 × 10 2 CFU/mL to 1.0 × 10 6 CFU/mL with a linear coefficient R 2 of 0.99146. All these results indicated that this small-molecule modified sensor can be used for quantitative detection of known gram-negative bacteria and qualitative distinction of unknown gram-negative bacteria within 10 min each sample in real-time. [ABSTRACT FROM AUTHOR]

Abstract: Constructing complex nanoarchitectures via self‐assembly with nanoparticle building blocks is a practical strategy that produces nanostructures with properties that are absent in the individual unit. In this work, we used hydrophilic carbon dots (C‐dots) as building blocks to form C‐dot assemblies. Compared to the individual C‐dot, the self‐assembled C‐dots showed about 30 nm red‐shift of absorption, resulting in the 5.1% increasing of photothermal conversion efficiency upon a 671 nm laser irradiation. More importantly, the C‐dot assemblies enable them can be efficiently uptaken by cancer cells. Meanwhile, in vitro study demonstrated the C‐dot assemblies can efficiently kill cancer cells than that of individual C‐dot upon irradiation for 5 min at equivalent C‐dot concentration. Our study may provide a new strategy for the efficient photothermal therapy of cancer based on C‐dots. [ABSTRACT FROM AUTHOR]

The development of a fluorescent probe to distinguish between cysteine (Cys) and homocysteine (Hcy) is always a challenge owing to their structural similarity, and the simultaneous detection of Cys and Hcy by utilizing different emission channels is especially difficult. In this work, we designed and synthesized a new fluorescent probe to differentiate between Cys and Hcy on the basis of a coumarin derivative with a chlorine atom and an α,β-unsaturated aldehyde. Cys and Hcy induced different cascade reactions with the probe, which led to different products with distinct photophysical properties. The nonfluorescent probe responded to Cys and emitted strong blue fluorescence, whereas it reacted with Hcy and generated yellow fluorescence without interference from glutathione. In addition, the probe was successfully applied to distinguish between Cys and Hcy in living cells. [ABSTRACT FROM AUTHOR]

Carbon dots (CDs) have emerged as promising nanomaterials for bioimaging-guided photodynamic therapy (PDT). However, designing red-emissive CDs (RCDs) with tunable type I and type II reactive oxygen species (ROS) generation to simultaneously meet PDT applications in aerobic and hypoxic scenarios still remain major challenges. Herein, three types of RCDs with maximum emission at approximately 680 nm are successfully prepared. It is noteworthy that they exhibit the adjustable ROS production with equal superoxide anion (via type I PDT) and incremental singlet oxygen (via type II PDT). Detailed structural and optical characterizations along with theoretical calculation reveal that the unique type I/II ROS formation mainly depends on the core sizes and surface states of RCDs, which determine their identical redox potentials and tapering energy gaps between singlet- and triplet states, respectively. Additionally, due to the inherent mitochondria targeting capability, RCDs enable themselves to induce cell programmed death via activating mitochondrion-mediated apoptotic pathways. This work exploits the unprecedented RCDs with tunable type I and type II ROS generation that could ensure highly efficient tumor eradication both in vitro and in vivo, even under the harsh tumor microenvironment, providing a new prospect for CDs as nanophotosensitizers to conquer the limitations of single type PDT. Red emissive carbon dots with tunable reactive oxygen species generation are prepared to achieve highly efficient fluorescence imaging-guided type I/II photodynamic therapy via activating mitochondrion-mediated apoptotic pathways of cancer cells, providing a new prospect for carbon dots as nanophotosensitizers to conquer the limitations of single type PDT. [Display omitted] [ABSTRACT FROM AUTHOR]

A simple and general procedure is designed for in situ growth of gold nanoparticles (AuNPs) on hydrogen-bond supramolecular structures. The resulting nanocomposites are obtained via a one-pot synthetic method using chloroauric acid (HAuCl 4 ), sodium citrate, melamine (M) and cyanuric acid (CA) as precursors. At room temperature, melamine cyanurate (MCA) is formed immediately by M and CA through hydrogen bond self-assembly, possesses rich nitrogen content (49.4 wt%), and provides evenly dispersed and active sites to anchor and stabilize gold nanoparticles (AuNPs) as an ideal scaffold. The nanocomposites (AuNPs/MCA) exhibit high peroxidase-like activity that can catalyze the oxidation-reduction reaction of H 2 O 2 and peroxidase substrates over a broad pH range, including nearly neutral conditions (pH 5.0–7.4), as well as excellent stability. Combined with glucose oxidase (GO x ), AuNPs/MCA are successfully used for the quantitative determination of blood glucose via one-pot colorimetric assay. This study develops an economic approach for preparation of peroxidase mimetics with high catalytic activity at neutral pH, and well stability, expected to provide guidelines for other types of inorganic/supramolecule nanocomposites, and to broaden their applications in analytical chemistry and environmental science. [ABSTRACT FROM AUTHOR]

A fluorescent probe ( 1 ) for distinguishing amongst biothiols, including cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), is developed based on different cascade reactions. The key design feature of fluorescent probe 1 is the integration of two potential reaction groups for the thiol and amino groups of biothiols in one molecule. By reacting with the halogen atom and α, β-unsaturated malonitrile in probe 1 , Cys, Hcy and GSH can generate a total of three main products with distinct photophysical properties. Probe 1 shows a strong fluorescence turn-on response to Cys with blue–green emission by using an excitation wavelength of 390 nm. At an excitation wavelength of 500 nm, probe 1 responds to GSH over Cys and Hcy and emits strong orange fluorescence. The discrimination of biothiols can be demonstrated by cell imaging experiments, indicating that probe 1 can be a useful tool for the selective imaging of Cys and GSH in living cells. [ABSTRACT FROM AUTHOR]

Two coumarin-based boron complexes (HBN and MBN) with aggregation-induced emission were designed and synthesized. The photophysical properties of the complexes were investigated in different solvents and in the solid state. Results showed that the inhibited CN isomerization by N,O-chelated BF2 caused the significant enhancement of fluorescence in THF. In particular, the complexes displayed red-shifted emissions (>60 nm) in mixed solvents of CH3CN and water because of the aggregation-induced charge-transfer enhancement. In the solid state, the bright red emission appeared at 650 nm (620 nm), with a Stokes shift of 170 nm. Cell-imaging experiments indicated that the complexes have good membrane permeability and can be used as lysosome trackers. [ABSTRACT FROM AUTHOR]

More and more attention has been paid to the design of new fluorescent imaging agents with good photostability and water solubility, especially those with emissions in the deep-red and near-infrared regions. In this work, we designed and synthesized four novel fluorescent dyes with deep-red or NIR fluorescence by hybridizing coumarin and pyronin moieties based on our previous work. Introduction of carboxylic acid in the dyes not only imparted the dyes with water solubility but also provided a versatile sensing platform for designing the fluorescent probes and sensors of biomolecules. The photophysical properties of these new dyes were investigated through absorption and fluorescence spectroscopy. Cell imaging experiments showed that esterification products could selectively stain lysosomes with good photostability, thereby indicating that they could be useful in the development of fluorescent probes for bioimaging. [ABSTRACT FROM AUTHOR]

Fluorescence imaging is a promising tool for the visualization of biomolecules in living systems and there is great demand for new fluorescent dyes that absorb and emit in the near-infrared (NIR) region. Herein, we constructed three new fluorescent dyes ( NBC dyes) based on keto-benzo[ h]coumarin ( k-BC) and benzopyrilium salts. These dyes showed large Stokes shifts (>100 nm) and NIR emission (>800 nm). The relationship between the structures and optical properties of these dyes was further investigated by using density functional theory calculations at the B3LYP/6-3G level of theory. Fluorescence images indicated that the fabricated dyes exhibited good photostability and low cytotoxicity and, thus, have potential applications as imaging agents in living cells and animals. [ABSTRACT FROM AUTHOR]

Nanozymes are artificial enzymes that mimic natural enzyme-like activities and show great promise for tumor catalytic therapy. However, new nanozymes with multiple catalytic activities for multifunctional nanotheranostic use remain challenging to design. Herein, for the first time, iron phthalocyanine (Fe(II)Pc) was assembled with poly(l -lactide-co-glycolide)-block-poly(ethylene glycol) to prepare an Fe(II)Pc assembly (denoted as Fe(II)Pc-A). The obtained Fe(II)Pc-A could be applied as a smart near-infrared (NIR) light-responsive nanotheranostic for simultaneous photoacoustic imaging-guided photothermal therapy. Notably, Fe(II)Pc-A possessed peroxidase, catalase, and oxidase mimicking activities, which could not only catalyze the conversion of intratumoral H 2 O 2 to •OH, but also degrade H 2 O 2 to generate O 2 and continuously catalyze the conversion of O 2 to cytotoxic O 2 •-. Impressively, the dual reactive oxygen species (ROS) generation of Fe(II)Pc-A was further remarkably enhanced by the endogenous acidity of the tumor microenvironment and the exogenous NIR light-responsive photothermal effect. Moreover, the O 2 self-supplying ability of Fe(II)Pc-A led to increased generation of O 2 •- for enhancing catalytic therapy in hypoxic tumor. These collective properties of Fe(II)Pc-A nanozyme enabled it to be a dual ROS generation accelerator for photothermally enhanced tumor catalytic therapy. Thus, a new type of high-performance nanozyme for multifunctional nanotheranostic use toward cancer was presented. Fe(II)Pc-derived nanozyme with three enzyme-mimicking activities as dual reactive oxygen species generation accelerator for photothermally enhanced tumor catalytic therapy was designed and prepared, thereby providing a new type of high-performance nanozyme for multifunctional nanotheranostic use toward cancer. [Display omitted] [ABSTRACT FROM AUTHOR]

Two asymmetrical benzoxanthene dyes (BP-1 and BP-2) were designed and synthesized by a convenient one-step procedure from naphthaldehyde and m -aminophenol precursors. These dyes showed long-wavelength absorption, near-infrared emission (>650 nm), and large Stokes shifts (>90 nm) because of the asymmetrical introduction of the benzene ring into the xanthene structure. BP-1 exhibited high fluorescence quantum yield in organic solvents, whereas BP-2 showed very weak fluorescence due to the photoinduced electron transfer of 9-substituted groups. Cell experiments indicated that BP-1 with crescent-shape structure showed lower cytotoxicity and higher photostability than BP-2 and could rapidly stain RNA in nucleoli at low concentration. [Display omitted] • Two asymmetrical benzoxanthene dyes were synthesized by a convenient one-step procedure. • The dyes showed long-wavelength absorption, near-infrared emission and large Stokes shifts. • BP-1 could stained RNA in nucleoli rapidly with low cytotoxicity and good photostability. • BP-2 showed a very weak fluorescence and cytotoxicity due to 9-substituted groups. [ABSTRACT FROM AUTHOR]

Direct selective determination of free heme in the cerebral system is of great significance due to the crucial roles of free heme in physiological and pathological processes. In this work, a G-quadruplex DNAzymes-induced highly sensitive and selective colorimetric sensing of free heme in rat brain is established. Initially, the conformation of an 18-base G-rich DNA sequence, PS2.M (5′-GTGGGTAGGGCGGGTTGG-3′), in the presence of K+, changes from a random coil to a “parallel” G-quadruplex structure, which can bind free heme in the cerebral system with high affinity through π–π stacking. The resulted heme/G-quadruplex complex exhibits high peroxidase-like activity, which can be used to catalyze the oxidation of colorless ABTS2− to green ABTSṖ− by H2O2. The concentration of heme can be evaluated by the naked eye and determined by UV-vis spectroscopy. The signal output showed a linear relationship for heme within the concentration range from 1 to 120 nM with a detection limit of 0.637 nM. The assay demonstrated here was highly selective and free from the interference of physiologically important species such as dopamine (DA), 3,4-dihydroxyphenylacetic acid (DOPAC), ascorbate acid (AA), cysteine, uric acid (UA), glucose and lactate in the cerebral system. The basal dialysate level of free heme in the microdialysate from the striatum of adult male Sprague-Dawley rats was determined to be 32.8 ± 19.5 nM (n = 3). The analytic protocol possesses many advantages, including theoretical simplicity, low-cost technical and instrumental demands, and responsible detection of heme in rat brain microdialysate. [ABSTRACT FROM AUTHOR]

Volvox-like Cd xZn1− xS solid solutions with a cubic zinc blend structure were synthesized through a template-free ethylene glycol process. Cd(Ac)2 ⋅2 H2O, Zn(Ac)2 ⋅2 H2O, and thiourea are used as the starting materials and dissolved in ethylene glycol. These reaction precursors and solvent not only contributed to control over the formation of the volvox-like spherical geometry, but also exerted vigorous domination for existence of cubic-phase Cd xZn1− xS nanostructures. As-prepared volvox-like Cd xZn1− xS nanospheres have a diameter of around 100 nm with extensional shells. These samples show excellent photocatalytic H2 evolution activity from water splitting under visible-light irradiation without any cocatalyst or scaffolding, owing to their tunable band gap, cubic zinc blend structure, and unique hierarchical porous structure with a high surface area (as high as 95.2 m2 g−1). [ABSTRACT FROM AUTHOR]

Abstract: C60-carboxyfullerene, C60[C(COOH)2]2, has been proven to function as peroxidase mimetics that can catalyze the reaction of peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2 to produce a blue color reaction. Kinetic studies further indicate that C60[C(COOH)2]2 has an even higher affinity to TMB than that of the natural enzyme, horseradish peroxidase (HRP). C60[C(COOH)2]2/glucose oxidase (GO x )/TMB system provides a novel colorimetric sensor for glucose and shows good response toward glucose detection over a range of 1.0–40μM with a limit of detection 0.5μM (3σ/slope). Moreover, this sensitive and selective sensor can be successfully applied for the quantitative determination of glucose in human serum. The results indicate that it is a simple, cheap, convenient, highly selective, sensitive, and easy handling colorimetric assay. [Copyright &y& Elsevier]

Abstract: An ultrasensitive and selective detection of mercury (II) was investigated using a laser scanning confocal imaging-surface plasmon resonance system (LSCI-SPR). The detection limit was as low as 0.01ng/ml for Hg2+ ions in ultrapure and tap water based on a T-rich, single-stranded DNA (ssDNA)-modified gold film, which can be individually manipulated using specific T–Hg2+–T complex formation. The quenching intensity of the fluorescence images for rhodamine-labeled ssDNA fitted well with the changes in SPR. The changes varied with the Hg2+ ion concentration, which is unaffected by the presence of other metal ions. The coefficients obtained for ultrapure and tap water were 0.99902 and 0.99512, respectively, for the linear part over a range of 0.01–100ng/ml. The results show that the double-effect sensor has potential for practical applications with ultra sensitivity and selectivity, especially in online or real-time monitoring of Hg2+ ions pollution in tap water with the further improvement of portable LSCI-SPR instrument. [Copyright &y& Elsevier]

The dimetallic endohedral heterofullerene (EHF), Gd2@C79N, was prepared and isolated in a relatively high yield when compared with the earlier reported heterofullerene, Y2@C79N. Computational (DFT), chemical reactivity, Raman, and electrochemical studies all suggest that the purified Gd2@C79N, with the heterofullerene cage, (C79N)5- has compar- able stability with other better known isoelectronic metallofullerene (C80)6- cage species (e.g., Gd3N@C80). These results describe an exceptionally stable paramagnetic molecule with low chemical reactivity with the unpaired electron spin density localized on the internal diatomic gadolinium cluster and not on the heterofullerene cage. EPR studies confirm that the spin state of Gd2@C79N is characterized bya half-integer spin quantum number of S = 13/2. The spin (S = ½) on the N atom of the fullerene cage and two octet spins (S = 7/2) of two encapsulated gadoliniums are coupled with each other in a ferromagnetic manner with a small zero-field splitting ~arameter D. Because the central line of Gd2@C79N is due to the Kramer's doublet with a half-integer spin quantum number of S = 15/2, this relatively sharp line is prominent and the anisotropic nature of the line is weak. Interestingly, in contrast with most Gd3+ ion environments, the central EPR line (g = 1.978) is observable even at room temperature in a toluene solution. Finally, we report the first EHF derivative, a diethyl bromomalonate monoadduct of Gd2@C79N, which was prepared and isolated via a modified Bingel-Hirsch reaction. [ABSTRACT FROM AUTHOR]

A highly water-soluble [60]fullerene inclusion complex bicapped with ethylenediamino-β-cyclodextrin was prepared, which was further used to construct uniform cubical microstructure with poly (acrylic acid). The formation of the inclusion complex was confirmed by NMR studies. The analysis of X-ray photoelectron spectroscopy and thermogravimetric analysis data revealed that the fullerene molecule was bicapped with β-cyclodextrin. The self-assembly of [60]fullerene inclusion complex with poly (acrylic acid) was investigated by UV-Vis spectroscopic titrations, supporting a 1:1 monomeric units binding model and yielding a complex stability constant of 9.8 × 103 M- 1. The cubical microstructure formed was proved to be a crystalline structure by transmission electron spectroscopy measurements. [ABSTRACT FROM AUTHOR]

Efficient treatment of primary tumor and preventing cancer metastasis present intriguing alternatives to cancer therapy. Herein, for the first time, we reported the photo-triggered nano-gadofullerene (Gd@C 82 -Ala, abbreviated Gd-Ala) induced malignant tumor vascular disruption by shortening the light interval between Gd-Ala administration and light illumination, where oxygen in blood vessels was employed efficiently to produce cytotoxic reactive oxygen species (ROS). The produced ROS could not only destroy the tumor cells but also devastate the vascular endothelial cells corresponding to the loss of intercellular junctions and vessels disruption. Notably, the irradiated Gd-Ala could enhance dendritic cells (DCs) maturation, which further secreted tumor necrosis factor-α (TNF-α) and interleukin-12 (IL)-12, and then activated T lymphocytes by up-regulation of cluster of differentiation CD4+ and CD8+ T lymphocytes. Furthermore, the down-regulation of matrix metalloprotein 2 (MMP2) and MMP9 also reduce the rate of tumor metastasis. This work explored a new biomedical application of gadofullerene, thereby providing a smart carbon nanomaterial candidate for tumor ablation and inhibition of cancer metastasis. [ABSTRACT FROM AUTHOR]