A smartphone-integrated portable platform based on polychromatic ratiometric fluorescent paper sensors for visual quantitative determination of norfloxacin.

The emergence of "superbugs" due to antibiotics overuse poses a significant threat to human health and security. The development of sensitive and effective antibiotics detection is undoubtedly a prerequisite for addressing antibiotics overuse-associated issues. However, current techniques for monitoring antibiotics typically require costly equipment and well-trained professionals. Hence, we developed herein a rapid, instrument-free, and on-site detection method for antibiotic residues such as norfloxacin (NOR) based on a ratiometric sensing platform utilizing "on-off-on" response properties of polychromatic fluorescence for direct visual quantitative NOR analysis. Specifically, this platform integrated iron ions (Fe3+)-chelated blue carbon dots (BCDs) for signal sensing and red carbon dots (RCDs) as an internal reference. The sensor mechanism is selective quenching of BCDs' blue fluorescence by Fe3+ via an inner filter effect with unaffected RCDs' red fluorescence. Further NOR addition led to competitive binding with BCDs due to Fe3+ shedding from the BCDs' surface for a recovered blue fluorescence signal. Notably, the ratiometric fluorescence sensor demonstrated rapid and highly sensitive NOR detection in a concentration range of 1-70 µM with an impressive detection limit of 6.84 nM. The ratiometric fluorescence sensing platform was constructed by integrating smartphone and paper-based strategies, which exhibited exceptional sensitivity, selectivity, and rapid response for portable, instrument-free, visual quantification of NOR in real samples.

Aqueous green synthesis of organic/inorganic nanohybrids with an unprecedented synergistic mechanism for enhanced near-infrared photothermal performance.

Silver sulfide (Ag2S) nanoparticles (NPs) represent one of the most popular inorganic reagents for near-infrared (NIR) photothermal therapy (PTT). However, the extensive biomedical applications of Ag2S NPs are greatly compromised by the hydrophobicity of the NPs prepared in organic solvents, their low photothermal conversion efficiency, certain surface modification-induced damage to their intrinsic properties and short circulation time. To develop a facile yet efficient green approach to overcome these shortcomings for improved properties and performance of Ag2S NPs, we report herein the construction of Ag2S@polydopamine (PDA) nanohybrids via a "one-pot" organic-inorganic hybridization strategy, which produces uniform Ag2S@PDA nanohybrids with well-modulated sizes in the range of 100-300 nm via the self-polymerization of dopamine (DA) and subsequent synergistic assembly of PDA with Ag2S NPs in a three-phase mixed medium containing water, ethanol and trimethylbenzene (TMB). Integration of dual photothermal moieties, i.e., Ag2S and PDA at a molecular level, endows Ag2S@PDA nanohybrids with synergistically enhanced NIR photothermal properties that are much better than those of either PDA or Ag2S NPs due to calculated combination indexes (CIs) of 0.3-0.7 between Ag2S NPs and PDA based on a modified Chou-Talalay method. Therefore, this study not only developed a facile "one-pot" green approach toward producing uniform Ag2S@PDA nanohybrids with well-modulated dimensions, but also revealed an unprecedented synergistic mechanism for organic/inorganic nanohybrids that is based on dual photothermal moieties providing enhanced near-infrared photothermal performance.

A tube-like Pd@coordination polymer with enhanced solar light harvesting for boosting photocatalytic H2 production in a wide pH range and seawater.

Coordination polymers (CPs) have emerged as promising candidates for photocatalytic H2 production owing to their structural tailorability and functional diversity. However, the development of CPs with high energy transfer efficiency for highly efficient photocatalytic H2 production in a wide pH range still faces many challenges. Here we constructed a novel tube-like Pd(ii) coordination polymer with well-distributed Pd nanoparticles (denoted as Pd/Pd(ii)CPs) based on the coordination assembly of rhodamine 6G and Pd(ii) ions and further photo-reduction under visible light irradiation. Both the Br- ion and double solvent play a key role in forming the hollow superstructures. The resulting tube-like Pd/Pd(ii)CPs exhibit high stability in aqueous solution with the pH range from 3 to 14 due to the high Gibbs free energies of protonation and deprotonation, which provides the feasibility of photocatalytic hydrogen generation in a wide pH range. Electromagnetic field calculations showed that the tube-like Pd/Pd(ii)CPs have a good confinement effect on light. Therefore, the H2 evolution rate could reach 112.3 mmol h-1 g-1 at pH 13 under visible light irradiation, which is far superior to those of reported coordination polymer-based photocatalysts. Moreover, such Pd/Pd(ii)CPs could also reach a H2 production rate of 37.8 mmol h-1 g-1 in seawater under visible light with low optical density (40 mW cm-2) close to morning or cloudy sunlight. The above unique characteristics make the Pd/Pd(ii)CPs possess great potential for practical applications.

Pd(II)-based coordination polymer nanosheets for ratiometric colorimetric and photothermal dual-mode assay of serum alkaline phosphatase.

Fabrication of a multi-signal readout assay with high sensitivity and selectivity is highly desirable for clinical and biochemical analysis, but remains a challenge due to laborious procedures, large-scale instruments, and inadequate accuracy. Herein, a straightforward, rapid, and portable detection platform based on palladium(II) methylene blue (MB) coordination polymer nanosheets (PdMBCP NSs) was unveiled for the ratiometric dual-mode detection of alkaline phosphatase (ALP) with temperature and colorimetric signal readout properties. The sensing mechanism is the ALP-catalyzed generation of ascorbic acid for competitive binding and etching PdMBCP NSs to release free MB in a quantitive means for detection. Specifically, ALP addition led to the decrease of temperature signal readout from the decomposed PdMBCP NSs under 808 nm laser excitation, and simultaneous increase of the temperature from the generated MB with a 660 nm laser, together with the corresponding absorbance changes at both wavelengths. Notably, this ratiometric nanosensor exhibited a detection limit of 0.013 U/L (colorimetric) and 0.095 U/L (photothermal) within 10 min, respectively. The reliability and satisfactory sensing performance of the developed method were further confirmed by clinic serum samples. Therefore, this study provides a new insight for the development of dual-signal sensing platforms for convenient, universal, and accurate detection of ALP.

Hyaluronic acid-based injectable nanocomposite hydrogels with photo-thermal antibacterial properties for infected chronic diabetic wound healing.

A hydrogel wound dressing with a single functionality fails to meet the requirements for successful clinical treatment of chronic diabetic wounds that generally possess complicated microenvironments. A multifunctional hydrogel is thus highly desirable for improved clinical treatment. For this purpose, we reported herein construction of an injectable nanocomposite hydrogel with self-healing and photo-thermal properties as an antibacterial adhesive via dynamic Michael addition reaction and electrostatic interactions among three building moieties, i.e., catechol and thiol-modified hyaluronic acid (HA-CA and HA-SH), poly(hexamethylene guanidine) (PHMG), and black phosphorus nanosheets (BPs). An optimized hydrogel formulation eliminated over 99.99 % of bacteria (E. coli and S. aureus) and exhibited a free radical scavenging capability >70 % as well as photo-thermal properties in addition to viscoelastic characteristics, degradation properties in vitro, good adhesion and self-adaptation capacity. Wound healing experiments in vivo further confirmed the better performance of the developed hydrogels than that of a commercially available dressing (Tegaderm™) in promoting the healing of infected chronic wounds by preventing wound infection, decreasing inflammation, supporting collagen deposition, facilitating angiogenesis, and improving granulation tissues formation in the wound sites. Overall, the HA-based injectable composite hydrogels developed herein represent promising multifunctional wound dressings for infected diabetic wound repair.

Review of lipoic acid: From a clinical therapeutic agent to various emerging biomaterials.

Lipoic acid (LA), an endogenous small molecule in organisms, has been extensively used for the highly efficient clinical treatment of malignant diseases, which include diabetes, Alzheimer's disease, and cancer over the past seven decades. Tremendous progresses have been made on the use of LA in nanomedicine for the development of various biomaterials because of its unique biological properties and highly adaptable structure since the first discovery. However, there are few reviews thus far, to our knowledge, summarizing this hot subject of research of LA and its derived biomaterials. For this purpose, we present herein the first comprehensive summary on the design and development of LA and its derived materials for biomedical applications. This review first discusses the therapeutic use of LA followed by the description of synthesis and preclinical study of LA-derived-small molecules. The applications of various LA and poly (lipoic acid) (PLA)-derived-biomaterials are next summarized in detail with an emphasis on the use of LA for the design of biomaterials and the diverse properties. This review describes the development of LA from a clinical therapeutic agent to a building unit of various biomaterials field, which will promote the further discovery of new therapeutic uses of LA as therapeutic agents and facile development of LA-based derivates with greater performance for biomedical applications.

NIR-to-Vis Handheld Platforms for Detecting miRNA Level and Mutation Based on Sub-10 nm Sulfide Nanodots and HCR Amplification.

Sub-10 nm monodisperse alkaline-earth sulfide nanodots (ASNDs) with bright near-infrared (NIR)-excitation fluorescence and adjustable emission wavelength were prepared by a thermal decomposition method for the first time. The ASNDs exhibited high NIR-to-vis conversion efficiency and served as multicolor fluorescent labels in the proposed miR-224 assay. Targeted detection of the miR-224 level and single-nucleotide variation in miR-224 was carried out on a smartphone-based platform using a hybridization chain reaction (HCR) amplification strategy. In the presence of miR-224, the ASND-labeled HCR probes self-assembled on the surface of the diagnosis kits, generating strong fluorescent signals linearly proportional to miR-224 contents in the range of 10-2000 fM. Significantly, mutations in miR-224 led to the variation in the fluorescence intensity ratio in RGB channels. Simultaneously, evident changes of fluorescent brightness and color were easily visualized by the naked eye, which enabled on-site discrimination of miR-224 with different mutant loci. This work provides a novel preparation approach for ultrasmall NIR excitation sulfide nanodots and reveals the potential of the as-synthesized ASNDs in point-of-care (POC) nucleic acid testing. Further, it may provide a handheld platform for miRNA single-nucleotide polymorphism analysis.

Shuttle-Shape Carrier-Free Platinum-Coordinated Nanoreactors with O2 Self-Supply and ROS Augment for Enhanced Phototherapy of Hypoxic Tumor.

The synergistic nanotheranostics of reactive oxygen species (ROS) augment or phototherapy has been a promising method within synergistic oncotherapy. However, it is still hindered by sophisticated design and fabrication, lack of a multimodal synergistic effect, and hypoxia-associated poor photodynamic therapy (PDT) efficacy. Herein, a kind of porous shuttle-shape platinum (IV) methylene blue (Mb) coordination polymer nanotheranostics-loaded 10-hydroxycamptothecin (CPT) is fabricated to address the abovementioned limitations. Our nanoreactors possess spatiotemporally controlled O2 self-supply, self-sufficient singlet oxygen (1O2), and outstanding photothermal effect. Once they are taken up by tumor cells, nanoreactors as a cascade catalyst can efficiently catalyze degradation of the endogenous hydrogen peroxide (H2O2) into O2 to alleviate tumor hypoxia. The production of O2 can ensure enhanced PDT. Subsequently, under both stimuli of external red light irradiation and internal lysosomal acidity, nanoreactors can achieve the on-demand release of CPT to augment in situ mitochondrial ROS and highly efficient tumor ablation via phototherapy. Moreover, under the guidance of near-infrared (NIR) fluorescent imaging, our nanoreactors exhibit strongly synergistic potency for treatment of hypoxic tumors while reducing damages against normal tissues and organs. Collectively, shuttle-shape platinum-coordinated nanoreactors with augmented ROS capacity and enhanced phototherapy efficiency can be regarded as a novel tumor theranostic agent and further promote the research of synergistic oncotherapy.

Solution-phase vertical growth of aligned NiCo2O4 nanosheet arrays on Au nanosheets with weakened oxygen-hydrogen bonds for photocatalytic oxygen evolution.

Vertical heterojunctions of two-dimensional (2D) semiconducting materials have attracted more and more research interest recently due to their unique optical, electrical, and catalytic properties and potential applications. Although great progress has been made, vertical integration of the layered materials formed by 2D semiconductor nanosheets and 2D plasmatic metal nanosheets remains a huge challenge. Here, we demonstrate for the first time a solution-phase growth of vertical plasmatic metal-semiconductor heterostructures in which aligned NiCo2O4 nanosheet arrays vertically grow on a single Au nanosheet, forming vertically aligned NiCo2O4-Au-NiCo2O4 sandwich-type heterojunctions with hierarchical open channels. Such vertical NiCo2O4-Au-NiCo2O4 heterojunctions can effectively promote the separation and transfer of a photoinduced charge. Density functional theory (DFT) studies and time-resolved transient absorption spectroscopy show that electrons transfer from NiCo2O4 to Au, and the formation of the heterojunction weakens the H-O bond of H2O. Due to the unique structure and superiority of the component, the vertical NiCo2O4-Au-NiCo2O4 heterojunctions exhibit significant activity with an O2 production rate of up to 33 µmol h-1 and long-term stability for photocatalytic water oxidation. We calculated the apparent quantum efficiency (AQE) to be 21.9% for NiCo2O4-Au-NiCo2O4 heterojunctions at the wavelength λ = 450 ± 10 nm, which is higher than that of NiCo2O4 nanosheets (10.9%), Au nanosheets (0.96%) and other photocatalysts. The present study paves the way for the controlled synthesis of novel vertical heterojunctions based on 2D semiconductor nanosheets and 2D metal nanosheets for efficient photocatalysis.

Spatiotemporally controlled O2 and singlet oxygen self-sufficient nanophotosensitizers enable the in vivo high-yield synthesis of drugs and efficient hypoxic tumor therapy.

Carrying out the in vivo syntheses of drugs toxic to tumors based on the specific features of the tumor microenvironment is critical for ensuring specific antitumor efficacy. However, achieving in situ high-yield synthetic toxic drugs from non-toxic agents and reducing their drug resistance in hypoxic tumors remain challenges. Herein we created a tumor-microenvironment-responsive porous Pt/Pt(iv) methylene blue coordination polymer nanoshuttle (Pt/PtMBCPNS) photosensitizer with spatiotemporally controlled O2 and singlet oxygen (1O2) self-sufficient for the in vivo high-yield synthesis of drugs and efficient hypoxic tumor therapy. After being endocytosed, the nanophotosensitizer as a cascade catalyst was observed to effectively catalyze the conversion of endogenous H2O2 to O2, and was hence found to play a dual role in the enhanced tumor therapy. PtMBCPNSs, upon being irradiated with red light, efficiently converted O2 into 1O2. Subsequently, 1O2 oxidized non-toxic 1,5-dihydroxynaphthalene to form the anticancer agent juglone with a high yield. In addition, O2 was found to be able to improve the hypoxic microenvironment without light irradiation, thus enhancing the antitumor efficacy of the produced drugs and reducing drug resistance. As a result, by enhancing the synergistic effect of the treatment, this nanophotosensitizer significantly inhibited the growth of tumors and avoided damage to normal tissues/organs. Collectively, this work highlights a robust nanoplatform with the spatiotemporally controlled in vivo high-yield synthesis of drugs and generation of O2 to help overcome the current limitations of chemical-based therapies against hypoxic tumors.

Palladium Coordination Polymers Nanosheets: New Strategy for Sensitive Photothermal Detection of H2S.

New strategies for portable detection of highly toxic environmental pollutants are still in urgent need. Here, through Pd2+ and methylene blue (MB) coordination, photothermal two-dimensional palladium coordination polymers nanosheets (2D PdCPsNSs) have been synthesized for sensitive photothermal detection of H2S. The sensing mechanism is based on the decomposing effect of H2S to 2D PdCPsNSs, accompanied by the decrease of PdCPsNSs concentration and the increase of MB concentration. Upon H2S addition, the heat released from the 2D PdCPsNSs under 808 nm lasers irradiation decreased, and the heat released from the MB increased under 650 nm lasers irradiation, respectively. Such temperature change signals could be easily detected by a portable thermometer. The 2D PdCPsNSs showed highly sensitive ratiometric response to H2S with a detection limit of 30 nM. In addition, such probe presents an excellent selective ratiometric response to H2S relative to other anionic species and thiols because of the specific interaction between Pd2+ and H2S. Moreover, the probe was suitable for the ratiometric determination of H2S in different actual water samples, providing a promising platform for convenient, stable, and universal analysis of H2S.

Atomic-scale imaging of the ferrimagnetic/diamagnetic interface in Au-Fe3O4 nanodimers and correlated exchange-bias origin.

Exchange-biased magnetic heterostructures have become one of the research frontiers due to their significance in enriching the fundamental knowledge in nanomagnetics and promising diverse applications in the information industry. However, the physical origin of their exchange bias effect is still controversial. A key reason for this is the lack of unequivocal observations of interface growth. In this work, we fill this gap by experimentally imaging the ferrimagnetic/diamagnetic interfaces of Au-Fe3O4 nanodimers at the atomic level. A different physical mechanism from the reported mechanisms is found based on the atomic-resolution observation of their interfacial structure and electronic states, which reveals that the antiferromagnetic and ferromagnetic interactions of the formed weak/strong ferrimagnetic bilayer are responsible for the intrinsic exchange-bias origin in Au-Fe3O4 nanodimers. The theoretical quantitative analysis of the exchange bias shift based on the observed interfacial occupation model agrees well with the experimental value for the exchange bias effect, strongly verifying the proposed exchange-bias mechanism.

Photochemical strategies for the green synthesis of ultrathin Au nanosheets using photoinduced free radical generation and their catalytic properties.

Two-dimensional gold nanosheets represent a class of materials with excellent chemical and structural properties, which are often prepared using a template or toxic CO in organic solvents. Here, we report methylene blue (MB) radicals as a reducing agent to grow freestanding hexagonal ultrathin Au nanosheets with well-tuned thicknesses in water. This is the first time that carbon organic radicals have been used as a reducing agent in metal nanosheet synthesis. Notably, no template is used throughout the synthesis process, and the yield of Au nanosheets is very high. It is found that MB is decisive in the growth of Au nanosheets because no Au nanosheets are obtained in the absence of MB with the same reaction parameters. The resulting nanosheets exhibit excellent catalytic activity during H2O2 decomposition to generate nontoxic O2. Thus, folic acid-conjugated oxygen generating nanosheets could detect cancer cells in serum samples with high sensitivity through pressure signals. Furthermore, the nanosheets exhibit highly efficient activity and selectivity toward the hydrogenation of α,ß-unsaturated aldehydes. We anticipate that using MB radicals for the high-yield synthesis of 2D materials in this unique system has demonstrated their effectiveness and provides a green alternative route for producing other 2D nanomaterials.

Constructing two-dimensional CuFeSe2@Au heterostructured nanosheets with an amorphous core and a crystalline shell for enhanced near-infrared light water oxidation.

Although substantial efforts have been made toward the synthesis of noble metal-semiconductor heteronanostructures, direct in situ synthesis of two-dimensional (2D) core-shell semiconductor@noble metal heterostructured nanosheets remains largely unexplored. Herein, we report the synthesis of a novel 2D core-shell CuFeSe2@Au heterostructured nanosheet with an amorphous core and a crystalline shell based on the reversed growth of Au nanosheets on the CuFeSe2 frameworks under near-infrared (NIR) illumination. The nanosheet exhibits strong absorbance in the NIR region, and the valence band top of CuFeSe2@Au nanosheets is higher than the oxidation potential of O2/H2O. Owing to the unique structural features, the resulting nanosheets show excellent photocatalytic activity and high stability toward water oxidation with an O2 generation rate up to 3.48 mmol h-1 g-1 compared to those of the constituent materials under NIR light irradiation (λ > 850 nm). This work brings new opportunities to prepare 2D core-shell semiconductor@noble metal heterostructured nanosheets, which can be applied as photocatalysts toward water splitting and solar energy conversion at long wavelengths.