Mechanism underlying the effect of MnO2 nanosheets for A549 cell chemodynamic therapy.

MnO2 nanosheets (MnO2NSs) were synthesized by one-step method, and MnO2NSs were applied to A549 cell chemodynamic Therapy (CDT). The cytotoxicity, redox ability, and reactive oxygen species production of MnO2NSs have been investigated, and differences in cell metabolism during CDT were determined using liquid chromatography-mass spectrometry (LC-MS/MS). In addition, the metabolites of A549 lung cancer cells affected by MnO2NSs treatment are identified; metabolite differences were identified by PCA, PLS-DA, orthogonal PLS-DA, and other methods; and these differences were analyzed using non-targeted metabolomics. We found that A549 cells which were treated by MnO2NSs have 17 different metabolites and 9 metabolic pathways that varied markedly. Owing to their unique composition, structure, and physicochemical properties, MnO2NSs and their composites have become a favored type of nanomaterial used for CDT in cancer therapy. This work provides insights into the mechanism underlying the effects of MnO2NSs on the tumor microenvironment of A549 lung cancer cells, effectively making up for the deficiency of the study on cellular mechanism of CDT-induced apoptosis of cancer cells. It could aid the development of cancer CDT treatment strategies and help improve the use of nanomaterials in the clinical field.

Metabolomics analysis of MnO2 nanosheets CDT for breast cancer cells and mechanism of cytotoxic action.

Chemodynamic therapy (CDT) has received more and more attention as an emerging therapeutic strategy, especially transition metals with Fenton or Fenton-like activity have good effects in CDT research, manganese dioxide nanosheets (MnO2 NSs) and their complexes have become one of the most favored nanomaterials in CDT of tumors. CDT is mainly based on the role of reactive oxygen species (ROS) in tumor treatment, which have clear chemical properties and produce clear chemical reactions. However, their mechanism of interaction with cells has not been fully elucidated. Here, we performed CDT on mouse breast cancer cells (4T1) based on MnO2 NSs, extracted the metabolites from the 4T1 cells during the treatment, and analyzed the differences in metabolites by using high-resolution liquid chromatography-mass spectrometry (LC-MS). Untargeted metabolomics studies were conducted using the relevant data. This study mainly explored the changes in MnO2 NSs on the metabolite profile of 4T1 cells and their potential impact on tumor therapy, in order to determine the mechanism of action of MnO2 NSs in the treatment of breast cancer. The results of the study showed the presence of 11 different metabolites in MnO2 NSs CDT for 4T1 tumor cells, including phosphoserine, sphingine, phosphocholine, and stearoylcarnitine. These findings provide a deeper understanding of breast cancer treatment, and are beneficial for the further research and clinical application of CDT.

CeO2@CuS@PDA-FA as targeted near-infrared PTT/CDT therapeutic agents for cancer cells.

Single tumor treatment method usually has some defects, which makes it difficult to achieve good therapeutic effect. The ingenious combination of multiple tumor treatment methods on a single nanoplatform to achieve multifunctional treatment can effectively improve the efficiency of treatment. The targeted modification of nanomaterials can augment the precision of nanotherapeutic drugs in tumor treatment. Herein, a multifunctional nanoplatform (CeO2@CuS@PDA-FA) based on cerium dioxide nanoparticles engineered with copper sulfide (CeO2@CuS) has been constructed for synergistic photothermal therapy (PTT) and chemodynamic therapy (CDT). The CeO2@CuS were coated using polydopamine (PDA), and the modification of PDA surface by folic acid, in order to achieve the targeted effect for tumors. The localized hyperthermia induced by PTT can further improve the CDT efficiency of the nanoplatform, leading to a PTT/CDT synergistic effect. The nanoplatform possessed the capability of cancer cell-targeted and achieved better therapeutic efficacyin vitro. This work provided a new strategy for combined multifunctional theranostic platform and shows strong potential in practical applications.

N-Octadecane Encapsulated by Assembled BN/GO Aerogels for Highly Improved Thermal Conductivity and Energy Storage Capacity.

The rapid development of industry has emphasized the importance of phase change materials (PCMs) with a high latent-heat storage capacity and good thermal stability in promoting sustainable energy solutions. However, the inherent low thermal conductivity and poor thermal-cycling stability of PCMs limit their application. In this study, we constructed three-dimensional (3D) hybrid graphene aerogels (GBA) based on synergistic assembly and cross-linking between GO and modified hexagonal boron nitride (h-BN). Highly thermally conductive GBA was utilized as the supporting optimal matrix for encapsulating OD, and further implied that composite matrix n-octadecane (OD)/GBA composite PCMs were further prepared by encapsulating OD within the GBA structure. Due to the highly thermally conductive network of GBA, the latent heat of the composite PCMs improved to 208.3 J/g, with negligible changes after 100 thermal cycles. In addition, the thermal conductivity of the composite PCMs was significantly enhanced to 1.444 W/(m·k), increasing by 738% compared to OD. These results sufficiently confirmed that the novel GBA with a well-defined porous structure served as PCMs with excellent comprehensive performance offer great potential for thermal energy storage applications.

Mechanism of Cytotoxic Action of Gold Nanorods Photothermal Therapy for A549 Cell.

Photothermal therapy has developed into an important field of tumor treatment research, and numerous studies have focused on the preparation of photothermal therapeutic agents, tumor targeting, diagnosis, and treatment integration. However, there are few studies on the mechanism of photothermal therapy acting on cancer cells. Here we investigated the metabolomics of lung cancer cell A549 during gold nanorod (GNR) photothermal treatment by high-resolution LC/MS, and several differential metabolites and corresponding metabolic pathways during photothermal therapy were found. The main differential metabolites contained 18-hydroxyoleate, beta-alanopine and cis-9,10-epoxystearic acid, and phosphorylcholine. Pathway analysis also showed metabolic changes involving cutin, suberine, and wax biosynthesis, pyruvate and glutamic acid synthesis, and choline metabolism. Analysis also showed that the photothermal process of GNRs may induce cytotoxicity by affecting pyruvate and glutamate synthesis, normal choline metabolism, and ultimately apoptosis.

One-Step Synthesis of a Non-Precious-Metal Tris (Fe/N/F)-Doped Carbon Catalyst for Oxygen Reduction Reactions.

Advancements in inexpensive, efficient, and durable oxygen reduction catalysts is important for maintaining the sustainable development of fuel cells. Although doping carbon materials with transition metals or heteroatomic doping is inexpensive and enhances the electrocatalytic performance of the catalyst, because the charge distribution on its surface is adjusted, the development of a simple method for the synthesis of doped carbon materials remains challenging. Here, a non-precious-metal tris (Fe/N/F)-doped particulate porous carbon material (21P2-Fe1-850) was synthesized by employing a one-step process, using 2-methylimidazole, polytetrafluoroethylene, and FeCl3 as raw materials. The synthesized catalyst exhibited a good oxygen reduction reaction performance with a half-wave potential of 0.85 V in an alkaline medium (compared with 0.84 V of commercial Pt/C). Moreover, it had better stability and methanol resistance than Pt/C. This was mainly attributed to the effect of the tris (Fe/N/F)-doped carbon material on the morphology and chemical composition of the catalyst, thereby enhancing the catalyst's oxygen reduction reaction properties. This work provides a versatile method for the gentle and rapid synthesis of highly electronegative heteroatoms and transition metal co-doped carbon materials.

Annealing-Insensitive, Alcohol-Processed MoOx Hole Transport Layer for Universally Enabling High-Performance Conventional and Inverted Organic Solar Cells.

At present, most solution-processed molybdenum oxide (s-MoOx) hole transport layers (HTLs) are still mainly used in conventional organic solar cells (OSCs) but unsuitable for inverted OSCs. Herein, we demonstrate for the first time an annealing-insensitive, alcohol-processed MoOx HTL that can universally enable high-performance conventional and inverted OSCs. The s-MoOx HTL is spin-coated from the MoOx nanoparticle dispersion in alcohol, where the MoOx nanoparticles are synthesized by simple nonaqueous pyrolysis conversion of MoO2(acac)2. The MoOx nanoparticles possess uniform and very small sizes of less than 5 nm and can be well dispersed in alcohol, so the s-MoOx HTLs on ITO and active layer both show an overall uniform and smooth surface, suitable for conventional and inverted OSCs. In addition, the s-MoOx HTL possesses decent optical transmittance and appropriate work function. Utilizing the s-MoOx HTL annealed between room temperature and 110 °C and PM6:Y6 active layer, the conventional OSCs show an excellent power conversion efficiency (PCE) of 16.64-17.09% and the inverted OSCs also show an excellent PCE of 15.74-16.28%, which indicate that the s-MoOx HTL could be annealing-insensitive and universal for conventional and inverted OSCs. Moreover, conventional and inverted OSCs with the s-MoOx HTLs annealed at 80 °C both exhibit optimal PCEs of 17.09 and 16.28%, respectively, which are separately superior than that of the PEDOT:PSS-based conventional OSCs (16.94%) and the thermally evaporated MoO3 (e-MoO3)-based inverted OSCs (16.03%). Under light soaking and storage aging in air, the unencapsulated inverted OSCs based on the s-MoOx HTL show similarly excellent ambient stability compared to the e-MoOx-based devices. In addition, the s-MoOx HTL also shows a universal function in conventional and inverted OSCs with PBDB-T:ITIC and PM6:L8-BO active layers. Notably, the s-MoOx-based conventional and inverted OSCs with the PM6:L8-BO active layer exhibit very excellent PCEs of 18.21 and 17.12%, respectively, which are slightly higher than those of the corresponding PEDOT:PSS-based device (18.17%) and e-MoO3-based device (17.00%). The annealing-insensitive, alcohol-processed MoOx HTL may be very promising for flexible and large-scale processing conventional/inverted OSCs.

Single Molecule-Level Detection via Liposome-Based Signal Amplification Mass Spectrometry Counting Assay.

Because of the low atomization and/or ionization efficiencies of many biological macromolecules, the application of mass spectrometry to the direct quantitative detection of low-abundance proteins and nucleic acids remains a significant challenge. Herein, we report mass spectrum tags (MS-tags) based upon gold nanoparticle (AuNP)-templated phosphatidylcholine phospholipid (DSPC) liposomes, which exhibit high and reliable signals via electrospray ionization (ESI). Using these MS-tags, we constructed a liposome signal amplification-based mass spectrometric (LSAMS) "digital" counting assay to enable ultrasensitive detection of target nucleic acids. The LSAMS system consists of liposomes modified with a gold nanoparticle core and surface-anchored photocleavable DNA. In the presence of target nucleic acids, the modified liposome and a magnetic bead simultaneously hybridize with the target nucleic acid. After magnetic separation and photolysis, the MS-tag is released and can be analyzed by ESI-MS. At very low target concentrations, one liposome particle corresponds to one target molecule; thus, the concentration of the target can be estimated by counting the number of liposomes. With this assay, hepatitis C (HCV) virus RNA was successfully analyzed in clinical samples.

Single-Molecule Detection of Nucleic Acids via Liposome Signal Amplification in Mass Spectrometry.

A single-molecule detection method was developed for nucleic acids based on mass spectrometry counting single liposome particles. Before the appearance of symptoms, a negligible amount of nucleic acids and biomarkers for the clinical diagnosis of the disease were already present. However, it is difficult to detect extremely low concentrations of nucleic acids using the current methods. Hence, the establishment of an ultra-sensitive nucleic acid detection technique is urgently needed. Herein, magnetic beads were used to capture target nucleic acids, and liposome particles were employed as mass tags for single-particle measurements. Liposomes were released from magnetic beads via photocatalytic cleavage. Hence, one DNA molecule corresponded to one liposome particle, which could be counted using mass spectrometric measurement. The ultrasensitive detection of DNA (10-18 M) was achieved using this method.

Cadmium Sulfide-Reinforced Double-Shell Microencapsulated Phase Change Materials for Advanced Thermal Energy Storage.

Phase change materials (PCMs) are widely used to improve energy utilization efficiency due to their high energy storage capacity. In this study, double-shell microencapsulated PCMs were constructed to resolve the liquid leakage issue and low thermal conductivity of organic PCMs, which also possess high thermal stability and multifunctionality. We used assembly to construct an inorganic-organic double shell for microencapsulate PCMs, which possessed the unprecedented synergetic properties of a cadmium sulfide (CdS) shell and melamine-formaldehyde polymeric shell. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images confirmed the well-designed double-shell structure of the microcapsules, and the CdS was successfully assembled as the second shell on the surface of the polymer shell. The differential scanning calorimeter (DSC) showed that the double-shell microcapsules had a high enthalpy of 114.58 J/g, which indicated almost no changes after experiencing 100 thermal cycles, indicating good thermal reliability. The microcapsules also showed good shape stability and antileakage performance, which displayed no shape change and leakage after heating at 60 °C for 30 min. In addition, the photothermal conversion efficiency of the double-shell microcapsules reached 91.3%. Thus, this study may promote the development of microencapsulated PCMs with multifunctionality, offering considerable application prospects in intelligent temperature management for smart textiles and wearable electronic devices in combination with their solar thermal energy conversion and storage performance.

The diversity of alkane-degrading bacterial communities in seagrass ecosystem of the South China Sea.

Seagrass meadows are one of the most important marine ecosystems. Alkanes are the common hydrocarbon contaminants that can affect seagrass growth. In this study, a large spatial-scale investigation has been carried out on the alkane-degrading bacterial community structure in the rhizosphere and non-rhizosphere sediments of two seagrass species (Thalassia hemprichii and Halophila ovalis). AlkB gene was employed as a biomarker gene to study the alkane-degrading bacterial community structure. The results showed that the alpha diversity of the alkane-degrading bacterial community in T. hemprichii non-rhizosphere sediments was higher than that of its rhizosphere sediments. However, the alpha diversity of the alkane-degrading bacterial community in H. ovalis rhizosphere sediments was higher than that of its non-rhizosphere sediments in the open sea, but the result was contrast in the coast area. In addition, the alpha diversity of alkane-degrading bacterial communities in the coast area was higher than that of far away from the coast in the T. hemprichii rhizosphere and non-rhizosphere sediments. The phylogenetic analysis result revealed that the alkB sequences from the seagrass ecosystem were mainly affiliated with the class Alphaproteobacteria, and had the two novel lineages. Genus Agrobacterium was the most predominant alkane-degrading bacteria. These results contributed to disclose the geographical distribution pattern of alkane-degrading bacteria in the seagrass ecosystem of the South China Sea.

Multielement Synergetic Effect of Boron Nitride and Multiwalled Carbon Nanotubes for the Fabrication of Novel Shape-Stabilized Phase-Change Composites with Enhanced Thermal Conductivity.

Shape-stabilized phase-change composites (SSPCCs) have been widely applied for thermal energy storage and thermal management because of their excellent properties. To further improve their thermal conductivity and thermal cycling stability, we successfully designed and synthesized a series of SSPCCs with three-dimensional (3D) thermally conductive networks by exploiting the synergistic effect between one-dimensional (1D) carbon nanotubes (CNTs) and two-dimensional (2D) hexagonal boron nitride (h-BN). The interconnected thermally conductive network composed of h-BN and multiwalled carbon nanotubes (MWCNTs) enhanced the SSPCC performance. The micromorphologies of the prepared SSPCCs revealed that well-dispersed MWCNTs, hydroxylated h-BN, and polyethylene glycol (PEG) molecular chains effectively bonded into a 3D cross-linking structure of the SSPCCs. Moreover, the chemical and crystalline structural and thermal properties and thermal cycling stability of the novel SSPCCs were systematically investigated by various characterization techniques. The presence of a 3D thermally conductive network in the as-synthesized SSPCCs evidently improved the shape stability, phase-change behavior, and thermal stability. Benefiting from the 3D nanostructural uniqueness of SSPCCs, the thermal conductivity of SSPCC-2 was up to 1.15 W m-1 K-1, which represented a significant enhancement of 239.7% compared with that of pure PEG. Meanwhile, the efficient synergistic effect of h-BN and MWCNTs remarkably enhanced the heat-transfer rate of the SSPCCs. These results demonstrate that the prepared SSPCCs have potential for applications in thermal energy storage and thermal management systems. This study opens a new avenue toward the development of SSPCCs with good comprehensive properties.

Atomic Plane-Vacancy Engineering of Transition-Metal Dichalcogenides with Enhanced Hydrogen Evolution Capability.

Introducing anion vacancies on two-dimensional transition-metal dichalcogenides (TMDs) would significantly improve their catalytic activity. In this work, we proposed a solid-phase reduction (SPR) strategy to simultaneously achieve efficient exfoliation and controlled generation of chalcogen vacancies on TMDs. Consecutive sulfur vacancies were successfully created on the basal plane of the bulk MoS2 and WS2, and their interlamellar distances were distinctly expanded after the SPR treatment (about 16%), which can be conveniently exfoliated by only gentle shaking. The S-vacancy significantly increases the hydrogen-evolution reaction activity of the MoS2 and WS2 nanosheets, with overpotential of -238 and -241 mV at 10 mA cm-2, respectively. We anticipate that our SPR strategy will supply a general platform for the development of TMD-based electrocatalysts for industrial water splitting and hydrogen production in the near future.

Controlled Assembly of Porphyrin-MoS2 Composite Nanosheets for Enhanced Photoelectrochemical Performance.

As a promising non-precious metal photoelectrochemical (PEC) catalyst, MoS2 exhibits high electrocatalytic activity and stability, while the weak light absorption efficiency and low photoresponse current limit its practical application. Herein, a facile co-assembly approach is proposed to construct porphyrin-MoS2 composite photoelectrocatalysts. The as-prepared photoelectrocatalysts show a significantly enhanced photocurrent response as high as 16 µA cm-2 , which is about 2 times higher than that of bare MoS2 . Furthermore, the obtained porphyrin-MoS2 catalysts exhibit excellent durability when tested for 23000 s, thus providing a useful strategy for the design of highly efficient dye-sensitized PEC catalysts.

Surface Enhanced Laser Desorption Ionization of Phospholipids on Gold Nanoparticles for Mass Spectrometric Immunoassay.

High-throughput and sensitive detection of proteins are essential for clinical diagnostics and biomarker discovery. We develop a novel high-throughput, multiplexed, sensitive mass spectrometric (MS) immunoassay method, which utilizes antibody-modified phospholipid bilayer coated gold nanoparticles (PBL-AuNPs) as the detection label and antibody-immobilized magnetic beads as the capture reagent. This method enables magnetic enrichment of the PBL-AuNPs label specific to target protein, allowing sensitive surface enhanced laser desorption ionization (SELDI)-TOF MS detection of the protein via its specific label. AuNPs act as not only the support but also the matrix for the phospholipids in SELDI TOF MS detection. Moreover, with phospholipids with varying molecular weights as the encoded MS reporters, this method allows multiplexed detection of multiple proteins. With the use of a predefined phospholipids internal standard, this method also affords excellent reproducibility in protein quantification. We have demonstrated this method using the assays of two tumor biomarkers, and the results reveal that it provides a sensitive platform for multiplexed protein detection with detection limits in the picomolar ranges. This method may provide a useful platform for high-throughput and sensitive detection of protein biomarkers for clinical diagnostics.

Mass Spectrometry Based Ultrasensitive DNA Methylation Profiling Using Target Fragmentation Assay.

Efficient tools for profiling DNA methylation in specific genes are essential for epigenetics and clinical diagnostics. Current DNA methylation profiling techniques have been limited by inconvenient implementation, requirements of specific reagents, and inferior accuracy in quantifying methylation degree. We develop a novel mass spectrometry method, target fragmentation assay (TFA), which enable to profile methylation in specific sequences. This method combines selective capture of DNA target from restricted cleavage of genomic DNA using magnetic separation with MS detection of the nonenzymatic hydrolysates of target DNA. This method is shown to be highly sensitive with a detection limit as low as 0.056 amol, allowing direct profiling of methylation using genome DNA without preamplification. Moreover, this method offers a unique advantage in accurately determining DNA methylation level. The clinical applicability was demonstrated by DNA methylation analysis using prostate tissue samples, implying the potential of this method as a useful tool for DNA methylation profiling in early detection of related diseases.