Carbonization of quercetin into nanogels: a leap in anticoagulant development.

Quercetin, a flavonoid abundantly found in onions, fruits, and vegetables, is recognized for its pharmacological potential, especially for its anticoagulant properties that work by inhibiting thrombin and coagulation factor Xa. However, its clinical application is limited due to poor water solubility and bioavailability. To address these limitations, we engineered carbonized nanogels derived from quercetin (CNGsQur) using controlled pyrolysis and polymerization techniques. This led to substantial improvements in its anticoagulation efficacy, water solubility, and biocompatibility. We generated a range of CNGsQur by subjecting quercetin to varying pyrolytic temperatures and then assessed their anticoagulation capacities both in vitro and in vivo. Coagulation metrics, including thrombin clotting time (TCT), activated partial thromboplastin time (aPTT), and prothrombin time (PT), along with a rat tail bleeding assay, were utilized to gauge the efficacy. CNGsQur showed a pronounced extension of coagulation time compared to uncarbonized quercetin. Specifically, CNGsQur synthesized at 270 °C (CNGsQur270) exhibited the most significant enhancement in TCT, with a binding affinity to thrombin exceeding 400 times that of quercetin. Moreover, variants synthesized at 310 °C (CNGsQur310) and 290 °C (CNGsQur290) showed the most substantial delays in PT and aPTT, respectively. Our findings indicate that the degree of carbonization significantly influences the transformation of quercetin into various CNGsQur forms, each affecting distinct coagulation pathways. Additionally, both intravenous and oral administrations of CNGsQur were found to extend rat tail bleeding times by up to fivefold. Our studies also demonstrate that CNGsQur270 effectively delays and even prevents FeCl3-induced vascular occlusion in a dose-dependent manner in mice. Thus, controlled pyrolysis offers an innovative approach for generating quercetin-derived CNGs with enhanced anticoagulation properties and water solubility, revealing the potential for synthesizing self-functional carbonized nanomaterials from other flavonoids for diverse biomedical applications.

Fluorescent carbon dots for labeling of bacteria: mechanism and prospects-a review.

The search for bacteria-labeling agents that are more efficient and less toxic compared to existing staining dyes is ongoing. Fluorescent quantum dots and carbon dots (CDs) have been extensively researched for various bioimaging applications. Priority is given to CDs due to several advantages, including lower toxicity, versatility in tuning their properties, and better photostability compared to metal-based quantum dots. Although significant progress is still needed to replace existing dyes with CDs for bacteria labeling, they offer promising potential for further improvement in efficiency. Surface charges and functional groups have been reported as decisive factors for bacterial discrimination and live/dead assays; however, a complete guideline for preparing CDs with optimum properties for efficient staining and predicting their labeling performance is lacking. In this review, we discuss the application of fluorescent CDs for bacterial labeling and the underlying mechanisms and principles. We primarily focus on the application and mechanism of CDs for Gram differentiation, live imaging, live/dead bacteria differentiation, bacterial viability testing, biofilm imaging, and the challenges associated with application of CDs. Based on proposed mechanisms of bacterial labeling and ambiguous results reported, we provide our view and guidelines for the researchers in this field to overcome the challenges associated with bacteria labeling using fluorescent CDs.

Augmenting Neutrophil Extracellular Traps with Carbonized Polymer Dots: A Potential Treatment for Bacterial Sepsis.

Sepsis is a life-threatening condition that can progress to septic shock as the body's extreme response to pathogenesis damages its own vital organs. Staphylococcus aureus (S. aureus) accounts for 50% of nosocomial infections, which are clinically treated with antibiotics. However, methicillin-resistant strains (MRSA) have emerged and can withstand harsh antibiotic treatment. To address this problem, curcumin (CCM) is employed to prepare carbonized polymer dots (CPDs) through mild pyrolysis. Contrary to curcumin, the as-formed CCM-CPDs are highly biocompatible and soluble in aqueous solution. Most importantly, the CCM-CPDs induce the release of neutrophil extracellular traps (NETs) from the neutrophils, which entrap and eliminate microbes. In an MRSA-induced septic mouse model, it is observed that CCM-CPDs efficiently suppress bacterial colonization. Moreover, the intrinsic antioxidative, anti-inflammatory, and anticoagulation activities resulting from the preserved functional groups of the precursor molecule on the CCM-CPDs prevent progression to severe sepsis. As a result, infected mice treated with CCM-CPDs show a significant decrease in mortality even through oral administration. Histological staining indicates negligible organ damage in the MRSA-infected mice treated with CCM-CPDs. It is believed that the in vivo studies presented herein demonstrate that multifunctional therapeutic CPDs hold great potential against life-threatening infectious diseases.

Hepatotoxicity evaluations of different surface charged carbon quantum dots in vivo and in vitro.

Recently, carbon quantum dots (CQDs) have become popular because of their simple synthesis and potential applications. Although CQDs have high biocompatibility, their biotoxicity must be verified to reduce the possible risks associated with large-scale application. In this study, the hepatotoxicity of three CQD types, namely diammonium citrate (AC)-based (CQDs-AC), spermidine trihydrochloride (Spd)-based (CQDs-Spd), and AC- and Spd-based CQDs (CQDs-AC/Spd), were evaluated in vivo and in vitro. It was observed in vivo that CQDs-Spd and CQDs-AC/Spd, but not CQDs-AC, caused histopathological damage, including liver steatosis and mild mixed inflammatory cell infiltration; however, reduced liver function was only observed in CQD-Spd-treated mice. The in vitro results revealed that only CQDs-Spd significantly decreased the number of viable HepG2 cells (NADH depletion) and induced oxidative stress (heme oxygenase-1 activation) after 24 h of exposure, which promoted inflammatory factor secretion (NF-κB activation). Additionally, decreasing zonula occludens-2 and α1-antitrypsin protein expression in HepG2 cells suggested that CQD-Spd exposure increases the risk of liver diseases. Our results revealed that CQDs-Spd had greater hepatotoxic potential than CQDs-AC and CQDs-AC/Spd, which might be attributable to their high positive surface charge. Overall, the risk of CQD-induced hepatotoxic risk must be considered when applying positively charged CQDs.

Curcumin-derived carbon quantum dots: Dual actions in mitigating tau hyperphosphorylation and amyloid beta aggregation.

The amyloid cascade and tau hypotheses both hold significant implications for the pathogenesis of Alzheimer's disease (AD). Curcumin shows potential by inhibiting the aggregation of amyloid beta (Aß) and reducing tau hyperphosphorylation, however, its use is limited due to issues with solubility and bioavailability. Carbon dots, recognized for their high biocompatibility and optimal water solubility, have demonstrated the capability to inhibit either Aß or tau aggregation. Nonetheless, their effects on tau hyperphosphorylation are yet to be extensively explored. This study aims to evaluate the water-soluble curcumin-derived carbon quantum dots (Cur-CQDs) synthesized via an eco-friendly method, designed to preserve the beneficial effects of curcumin while overcoming solubility challenges. The synthesis of Cur-CQDs involves a single-step dry heating process using curcumin, resulting in dots that exhibit negligible cytotoxicity to SH-SY5Y cells at the examined concentrations. Notably, Cur-CQDs have shown the ability to simultaneously mitigate Aß aggregation and tau hyperphosphorylation. Therefore, it is suggested that Cur-CQDs may hold potential for AD treatment, a hypothesis deserving of further research.

Ultrahigh-Efficacy VEGF Neutralization Using Carbonized Nanodonuts: Implications for Intraocular Anti-Angiogenic Therapy.

Ocular angiogenesis, associated with diseases such as retinopathy of prematurity and diabetic retinopathy, is a leading cause of irreversible vision loss. Herein, carbon nanodonuts (CNDs) with a donut-shaped structure are synthesized using sodium alginate (SA) and 1,8-diaminooctane (DAO) through a one-step thermal process. The formation of SA/DAO-CNDs occurs through a crosslinking reaction between SA and DAO, creating amide bonds followed by partial carbonization. In human retinal pigment epithelial cells exposed to H2 O2 or lipopolysaccharide, the SA/DAO-CNDs display a more than fivefold reduction in reactive oxygen species and proinflammatory cytokines, such as IL-6 and IL-1ß, when compared to carbonized nanomaterials produced exclusively from SA. Furthermore, the CNDs effectively inhibit vascular endothelial growth factor A-165 (VEGF-A165 )-induced cell migration and tube formation in human umbilical vein endothelial cells due to their strong affinity for VEGF-A165 , with a dissociation constant of 2.2 × 10-14  M, over 1600 times stronger than the commercial drug bevacizumab (Avastin). Trypsin digestion coupled with LC-MS/MS analysis reveals that VEGF-A165 interacts with SA/DAO-CNDs through its heparin-binding domain, leading to activity loss. The SA/DAO-CNDs demonstrate excellent biocompatibility and potent anti-angiogenic effects in chicken embryos and rabbit eyes. These findings suggest that SA/DAO-CNDs hold promise as a therapeutic agent for treating various angiogenesis-related ocular diseases.

Unveiling the Power of Gabapentin-Loaded Nanoceria with Multiple Therapeutic Capabilities for the Treatment of Dry Eye Disease.

Dry eye (DE) disease, which is primarily linked to aqueous deficiency, is an escalating health issue worldwide, mainly due to the widespread use of electronic devices. The major obstacles in DE pharmacotherapy include insufficient therapeutic efficacy and low ocular bioavailability. This study presents the development of a ceria-based nanosystem to carry gabapentin (GBT), aiming to offer comprehensive relief from DE symptoms. We prepared multifunctional nanoceria capped with thiolated gelatin followed by cross-linking with glutaraldehyde, yielding a nanocarrier with desirable biocompatibility and antioxidant, anti-inflammatory, antiangiogenic, antiapoptotic, and neuronal protective activities. Specifically, the highly abundant thiol groups on gelatin increased the cellular uptake of the nanocarrier by 2.3-fold and its mucin-binding efficiency by 10-fold, thereby extending ocular retention and amplifying therapeutic activity. Moderate cross-linking of the thiolated gelatin not only enhanced the ocular bioavailability of the nanoceria but also provided slow, degradation-controlled release of GBT to promote the lacrimal stimulation to restore the tear film. In a rabbit model of DE, topical administration of our GBT/nanoceria nanoformulation resulted in comprehensive alleviation of symptoms, including repairing corneal epithelial damage, preserving corneal nerve density, and stimulating tear secretion, demonstrating superior performance in comparison to the free drug. These results underscore the safety and potential of this innovative nanoformulation for DE pharmacotherapy.

NIR-activated quercetin-based nanogels embedded with CuS nanoclusters for the treatment of drug-resistant biofilms and accelerated chronic wound healing.

We have developed multifunctional nanogels with antimicrobial, antioxidant, and anti-inflammatory properties, facilitating rapid wound healing. To prepare the multifunctional nanogels, we utilized quercetin (Qu) and a mild carbonization process to form carbonized nanogels (CNGs). These CNGs possess excellent antioxidative and bacterial targeting properties. Subsequently, we utilized the Qu-CNGs as templates to prepare nanogels incorporating copper sulfide (CuS) nanoclusters, further enhancing their functionality. Notably, the CuS/Qu-CNGs nanocomposites demonstrated an exceptional minimum inhibitory concentration against tested bacteria, approximately 125-fold lower than monomeric Qu or Qu-CNGs. This enhanced antimicrobial effect was achieved by leveraging near-infrared II (NIR-II) light irradiation. Additionally, the CuS/Qu-CNGs exhibited efficient penetration into the extracellular biofilm matrix, eradicating methicillin-resistant Staphylococcus aureus-associated biofilms in diabetic mice wounds. Furthermore, the nanocomposites were found to suppress proinflammatory cytokines, such as IL-1ß, at the wound sites while regulating the expression of anti-inflammatory factors, including IL-10 and TGF-ß1, throughout the recovery process. The presence of CuS/Qu-CNGs promoted angiogenesis, epithelialization, and collagen synthesis, thereby accelerating wound healing. Our developed CuS/Qu-CNGs nanocomposites have great potential in addressing the challenges associated with delayed wound healing caused by microbial pathogenesis.

In Situ Hybridization of Polymeric Curcumin to Arginine-Derived Carbon Quantum Dots for Synergistic Treatment of Bacterial Infections.

Effective infectious keratitis treatment must eliminate the pathogen, reduce the inflammatory response, and prevent persistent damage to the cornea. Infectious keratitis is generally treated with broad-spectrum antibiotics; however, they have the risk of causing corneal epithelial cell damage and drug resistance. In this study, we prepared a nanocomposite (Arg-CQDs/pCur) from arginine (Arg)-derived carbon quantum dots (Arg-CQDs) and polymeric curcumin (pCur). Partial carbonization of arginine hydrochloride in the solid state by mild pyrolysis resulted in the formation of CQDs, which exhibited enhanced antibacterial activity. pCur was formed by the polymerization of curcumin, and further crosslinking reduced its cytotoxicity and improved antioxidative, anti-inflammatory, and pro-proliferative activities. The pCur in situ conjugated with Arg-CQDs to form the Arg-CQDs/pCur nanocomposite, which showed a minimum inhibitory concentration of ca. 10 µg mL-1, which was >100-fold and >15-fold lower than that of the precursor arginine and curcumin, respectively, against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The Arg-CQDs/pCur nanocomposite with combined antibacterial, antioxidative, anti-inflammatory, pro-proliferative properties, and long-term retention on cornea enabled synergistic treatment of bacterial keratitis. In a rat model, it can effectively treat P. aeruginosa-induced bacterial keratitis at a concentration 4000-fold lower than the commercially used drug, Sulmezole eye drops. Arg-CQDs/pCur nanocomposites have great potential for application in antibacterial and anti-inflammatory nanoformulations for clinical use to treat infectious diseases.

Carbon Nanomaterials: Emerging Roles in Immuno-Oncology.

Cancer immunotherapy has made breakthrough progress in cancer treatment. However, only a subset of patients benefits from immunotherapy. Given their unique structure, composition, and interactions with the immune system, carbon nanomaterials have recently attracted tremendous interest in their roles as modulators of antitumor immunity. Here, we focused on the latest advances in the immunological effects of carbon nanomaterials. We also reviewed the current preclinical applications of these materials in cancer therapy. Finally, we discussed the challenges to be overcome before the full potential of carbon nanomaterials can be utilized in cancer therapies to ultimately improve patient outcomes.

Post-administration labeling with Palladium(II) ions enables ICP-MS-based determination of the biodistribution of carbonized nanogels.

Carbonized nanogels (CNGs) are carbon-based nanomaterials possessing excellent antibacterial and antiviral activities for treating infectious diseases. Thus, investigations of the biodistribution of CNGs are crucial in ensuring their biosafety for in vivo applications. In this study, we combined a labeling scheme, employing tetrachloropalladate (PdCl42-) ions to selectively label the administered CNGs in solubilized tissue samples, and an automatic sample pretreatment scheme, using a knotted reactor to effectively separate the PdCl42--labeled CNGs from the free PdCl42- ions and the tissue matrices, to enable reliable and interference-free quantification of CNGs through measuring the signal intensities of Pd using inductively coupled plasma mass spectrometry (ICP-MS). After optimizing the labeling conditions and the separation scheme, we observed that the PdCl42- ions bound strongly to the CNGs (dissociation constant: 23.0 nM), with the method's detection limits reaching 1.6 fg L-1 and 0.9 µg L-1 within working ranges from 10-4 to 1 µg L-1 and from 1 to 1000 µg L-1, respectively. We verified the reliability and applicability of this analytical method through spike analyses of solubilized rat liver, spleen, kidney, lung, brain, and blood samples (recoveries ranging from 96 to 102%) and through analyses of these rat organ and tissue samples after giving rats an intravenous dose of CNGs (2.5 mg kg-1 body weight). The biodistribution data indicated that these administered CNGs deposited mainly in the liver, lung, and spleen at 10 min and 1 h post-administration. Our study revealed that this post-administration labeling scheme coupled with ICP-MS allows accurate determination of the biodistribution of carbonized nanomaterials.

Synthesis of novel Type-II MnNb2O6/g-C3N4 Mott-Schottky heterojunction photocatalyst: Excellent photocatalytic performance and degradation mechanism of fluoroquinolone-based antibiotics.

Fluoroquinolone antibiotics have been encountered in aquatic environments in quantities giving rise to significant concern recently. To cope with this problem, it is necessary to design a semiconductor photocatalyst having excellent photocatalytic efficiency to eliminate the antibiotics. The heterojunction is a likely situate where the efficiency of relevant photocatalyst can be strengthened. In this study, the performance of MnNb2O6/g-C3N4 (MNO/g-CN) composites in the photocatalytic degradation of ciprofloxacin (CIP) and tetracycline-HCl (TCH) antibiotics was explored. Enhanced photocatalytic activity of MNO/g-CN was found to be owing to electron's shifting between the MNO, and g-CN sheets, which promotes the formation of photo-generated e⁻/h⁺ pairs. This shows a low-waste, high-performance material exists to eradicate CIP and TCH from wastewater. Further, the structural, photochemical and light interacted properties of the MNO/g-CN photocatalyst, prepared by solvothermal method and sonication, were described using photochemical, physiochemical and electrochemical approaches. The synthesized photocatalyst owes its particular efficiency to its methodical photo-degradation of CIP and TC using visible light. The optimum composite 15% MNO/g-CN evinced the greatest photocatalytic efficiency with CIP and TCH photo-degradation of 94.10%, and 98.50%, respectively, and degradation mechanism were investigated using LC-MS spectroscopy. The suitable photocatalytic activity is ascribed to lower the recombination's rate of e⁻/h⁺ pairs. The scavenging evaluations proved that the h+ and •O2- were two major photoactive species accomplishing the CIP and TCH photodegradation over MNO/g-CN under visible region. Our findings pave the way for the construction of efficient binary photocatalysts for antibiotic restitution.

A self-powered multifunctional dressing for active infection prevention and accelerated wound healing.

Interruption of the wound healing process due to pathogenic infection remains a major health care challenge. The existing methods for wound management require power sources that hinder their utilization outside of clinical settings. Here, a next generation of wearable self-powered wound dressing is developed, which can be activated by diverse stimuli from the patient's body and provide on-demand treatment for both normal and infected wounds. The highly tunable dressing is composed of thermocatalytic bismuth telluride nanoplates (Bi2Te3 NPs) functionalized onto carbon fiber fabric electrodes and triggered by the surrounding temperature difference to controllably generate hydrogen peroxide to effectively inhibit bacterial growth at the wound site. The integrated electrodes are connected to a wearable triboelectric nanogenerator (TENG) to provide electrical stimulation for accelerated wound closure by enhancing cellular proliferation, migration, and angiogenesis. The reported self-powered dressing holds great potential in facilitating personalized and user-friendly wound care with improved healing outcomes.

Dual-emissive carbonized polymer dots for the ratiometric fluorescence imaging of singlet oxygen in living cells.

Singlet oxygen (1O2) is a type of reactive oxygen species (ROS), playing a vital role in the physiological and pathophysiological processes. Specific probes for monitoring intracellular 1O2 still remain challenging. In this study, we develop a ratiometric fluorescent probe for the real-time intracellular detection of 1O2 using o-phenylenediamine-derived carbonized polymer dots (o-PD CPDs). The o-PD CPDs possessing dual-excitation-emission properties (blue and yellow fluorescence) were successfully synthesized in a two-phase system (water/acetonitrile) using an ionic liquid tetrabutylammonium hexafluorophosphate as a supporting electrolyte through the electrolysis of o-PD. The o-PD CPDs can act as a photosensitizer to produce 1O2 upon white LED irradiation, in turn, the generated 1O2 selectively quenches the yellow emission of the o-PD CPDs. This quenching behavior is ascribed to the specific cycloaddition reaction between 1O2 and alkene groups in the polymer scaffolds on o-PD CPDs. The interior carbon core can be a reliable internal standard since its blue fluorescence intensity remains unchanged in the presence of 1O2. The ratiometric response of o-PD CPDs is selective toward 1O2 against other ROS species. The developed o-PD CPDs have been successfully applied to monitor the 1O2 level in the intracellular environment. Furthermore, in the inflammatory neutrophil cell model, o-PD CPDs can also detect the 1O2 and other ROS species such as hypochlorous acid after phorbol 12-myristate 13-acetate (PMA)-induced inflammation. Through the dual-channel fluorescence imaging, the ratiometric response of o-PD CPDs shows great potential for detecting endogenous and stimulating 1O2in vivo.

High performance carbon dots based prodrug Platform: Image-Guided photodynamic and chemotherapy with On-Demand drug release upon laser irradiation.

The design of therapeutic nanoplatforms based on fluorescent carbon dots (CDs) has become a viable strategy because of their aqueous solubility, biocompatibility, and ease of further functionalization. By doping various heteroatoms into pristine CDs structures, we synthesized N-, Cl-, and S-doped CDs (NClS/CDs), as well as Se-, N-, and Cl-doped CDs (NClSe/CDs) with superior optoelectronic properties using rapid and straightforward microwave heating. The quantum efficiencies of these NClS/CDs and NClSe/CDs were enhanced to 30.7 % and 42.9 %, respectively, compared to those of undoped CDs (0.66 %). Owing to their better light absorption properties, NClS/CDs efficiently produced reactive oxygen species (ROS) under 532 nm laser irradiation for photodynamic therapy (PDT). Considering the ROS generation and surface carrier abilities of NClS/CDs, we designed the loading of camptothecin (CPT) drug via a thioketal linker (TL), resulting in h/CDs@CPT nanovesicles (NVs) with a drug-loading efficiency of 46.5 %. Under laser irradiation in an acidic environment, ROS-triggered CPT release was observed, with 50.2 % of CPT released following the breakdown of the ROS-sensitive TL. In vitro cellular studies revealed that h/CDs@CPT NVs possessed minimal cytotoxicity toward HeLa and 4 T1 cancer cells, despite the high clinical efficacy of PDT and ROS-induced chemotherapeutic response under laser treatment. Confocal microscopy of HeLa and 4 T1 cells revealed that h/CDs@CPT NVs produced red-emissive photographs for potential cancer cell detection. Therefore, our study presents an image-guided PDT and chemotherapeutic platform based on h/CDs@CPT NVs, which will be an attractive candidate for future cancer treatment.

Photoswitchable carbon-dot liposomes mediate catalytic cascade reactions for amplified dynamic treatment of tumor cells.

Most biochemical reactions that occur in living organisms are catalyzed by a series of enzymes and proceed in a tightly controlled manner. The development of artificial enzyme cascades that resemble multienzyme complexes in nature is of current interest due to their potential in various applications. In this study, a nanozyme based on photoswitchable carbon-dot liposomes (CDsomes) was developed for use in programmable catalytic cascade reactions. These CDsomes prepared from triolein are amphiphilic and self-assemble into liposome-like structures in an aqueous environment. CDsomes feature excitation-dependent photoluminescence and, notably, can undergo reversible switching between a fluorescent on-state and nonfluorescent off-state under different wavelengths of light irradiation. This switching ability enables the CDsomes to exert photocatalytic oxidase- and peroxidase-like activities in their on- (bright) and off- (dark) states, respectively, resulting in the conversion of oxygen molecules into hydrogen peroxide (H2O2), followed by the generation of active hydroxyl radicals (OH). The two steps of oxygen activation can be precisely controlled in a sequential manner by photoirradiation at different wavelengths. Catalytic reversibility also enables the CDsomes to produce sufficient reactive oxygen species (ROS) to effectively kill tumor cells. Our results reveal that CDsomes is a promising photo-cycling nanozyme for precise tumor phototherapy through regulated programmable cascade reactions.

Pulsed laser irradiation induces the generation of alloy cluster ions for the screening of protease activity.

Pulsed laser irradiation can cause the fragmentation of nanoparticles, which generates cluster ions. This allows nanoparticles to be adopted as mass tag/signal amplifiers in laser desorption/ionization mass spectrometry (LDI-MS) bioassays. Herein, we demonstrate the potential of using the signal from alloy cluster ions in bioassays through a fibrin clot model to determine the activity of thrombin. A mixed solution of silver and gold nanoparticles functionalized with fibrinogen (Fg‒Ag NPs/Fg‒Au NPs) treated with thrombin can form clots composed of aggregated fibrin-Au NPs/Ag NPs. These clots analyzed with LDI-MS are noted to form intense Ag-Au alloy cluster ions, especially [Ag2Au]+, which were used to detect thrombin concentration with a dynamic range of 2.5-50 pM in human plasma. This sensing platform was further employed for the screening of direct thrombin inhibitors. This work developed a novel bioassay utilizing metallic gas-phase reactions generated from pulsed laser irradiation of aggregated nanoparticles to monitor enzymatic activity and to screen inhibitors. We believe that LDS-MS can serve as a new platform for gas-phase reaction-based bioassays.

Synthesis and in situ sulfidation of molybdenum carbide MXene using fluorine-free etchant for electrocatalytic hydrogen evolution reactions.

Synthesizing MXenes from Mn+1AXn (MAX) phases using hazardous hydrogen fluoride is a common and effective method. However, fluorine termination on the basal planes and edges of the resulting MXenes is undesirable for the electrocatalytic hydrogen evolution reaction (HER), while oxygen (O), hydroxyl (OH), and sulfur (S) termination favors this reaction. Herein, we unveil a simple fluorine-free exfoliation and two-step vulcanization method for synthesizing molybdenum sulfide-modified molybdenum carbide (MoS2/Mo2CTx MXene, T = OH, O, S) for the HER in alkaline medium. Microwave-assisted hydrothermal treatment of the MAX phase (Mo3AlC2) with sodium hydroxide-sodium sulfide as an etching solution and thioacetamide as a source of sulfide ions enabled the selective dissolution of the aluminum (Al) layer and sulfidation of the surface Mo atoms to form amorphous MoS2. Thus, the vulcanization of Mo2CTx MXene resulted in the formation of MoS2/Mo2CTx MXene. The MoS2 formed on the surface of Mo2CTx provided enhanced stability by preventing oxidation. MoS2/Mo2CTx exhibited enhanced electrocatalytic activity toward the HER, mainly due to the O, OH, and amorphous MoS2 functionalities. The MoS2 sites on the surface exhibited an overpotential of 110 ± 7 mV at a current density of 10 mA cm-2 as a result of enhanced charge transfer and mass transfer. Thus, the sulfidation method demonstrated herein is capable of producing amorphous MoS2 structures on Mo2CTx MXene, which could be applied for the surface modification of other molybdenum-based nanomaterials or electrocatalysts to improve stability and enhance electrocatalytic activity.

Aminoglycoside-mimicking carbonized polymer dots for bacteremia treatment.

Bacteremia and associated bacterial sepsis are potentially fatal and occur when the host response to microbial invasion is impaired or compromised. This motivated us to develop carbonized polymer dots (CPDsMan/AA) from a mixture of mannose (Man) and positively charged amino acids [AAs; lysine, arginine (Arg), or histidine] through a one-step mild pyrolysis procedure, which effectively inhibited drug-resistant bacterial strains isolated from septic patients. The as-prepared CPDsMan/AA showed broad-spectrum antibacterial activity, including multidrug-resistant bacteria, even in human plasma. The minimal inhibitory concentration of CPDsMan/Arg is ca. 1.0 µg mL-1, which is comparable to or lower than those of other tested antibiotics (e.g., ampicillin, gentamicin, and vancomycin). In addition to directly disrupting bacterial membranes, the CPDsMan/Arg feature a structure similar to aminoglycoside antibiotics that could bind to 16S rRNA, thereby blocking bacterial protein synthesis. In vitro cytotoxic and hemolytic assays demonstrated the high biocompatibility of the CPDsMan/AA. In addition, in vivo studies on methicillin-resistant Staphylococcus aureus-infected mice treated with the CPDsMan/Arg showed a significant decrease in mortality-even better than that of antibiotics. Overall, the synthesis of the CPDsMan/AA is cost-efficient, straightforward, and effective for treating bacteremia. The polymeric features of the CPDsMan/Arg, including cationic charges and specific groups, can be recognized as a safe and broad-spectrum biocide to lessen our reliance on antibiotics to treat systemic bacterial infections in the future.