Photothermal modulation of human stem cells using light-responsive 2D nanomaterials.

Two-dimensional (2D) molybdenum disulfide (MoS2) nanomaterials are an emerging class of biomaterials that are photoresponsive at near-infrared wavelengths (NIR). Here, we demonstrate the ability of 2D MoS2 to modulate cellular functions of human stem cells through photothermal mechanisms. The interaction of MoS2 and NIR stimulation of MoS2 with human stem cells is investigated using whole-transcriptome sequencing (RNA-seq). Global gene expression profile of stem cells reveals significant influence of MoS2 and NIR stimulation of MoS2 on integrins, cellular migration, and wound healing. The combination of MoS2 and NIR light may provide new approaches to regulate and direct these cellular functions for the purposes of regenerative medicine as well as cancer therapy.

Visible-Light-Driven Photocatalytic Cellulose-to-H2 Conversion by MoS2 /ZnIn2 S4 Photocatalyst with Cellulase Assistance.

Visible-light-driven photocatalytic cellulose-to-H2 conversion system was successfully designed by using MoS2 /ZnIn2 S4 as the photocatalyst and cellulase as the enzyme catalyst. At first, the cellulose was converted to glucose by cellulase. The generated glucose acted as an efficient hole trapper and electron donor, which was further converted into H2 through photocatalytic reaction over MoS2 /ZnIn2 S4 under visible light irradiation. The optimum H2 generation rate achieved under visible light irradiation (λ>420 nm) was 12.2 µmol ⋅ h-1 ⋅ g-1 in the presence of 100 mg of 3 % MoS2 /ZnIn2 S4 , 100 mg cellulase and 2 g poplar wood chip. These results open up a new possibility for the development of efficient visible-light-responding photocatalytic cellulose to H2 conversion system that combine photocatalysis and enzyme technology.

Transition-Metal Dichalcogenide Artificial Antibodies with Multivalent Polymeric Recognition Phases for Rapid Detection and Inactivation of Pathogens.

Antibodies are recognition molecules that can bind to diverse targets ranging from pathogens to small analytes with high binding affinity and specificity, making them widely employed for sensing and therapy. However, antibodies have limitations of low stability, long production time, short shelf life, and high cost. Here, we report a facile approach for the design of luminescent artificial antibodies with nonbiological polymeric recognition phases for the sensitive detection, rapid identification, and effective inactivation of pathogenic bacteria. Transition-metal dichalcogenide (TMD) nanosheets with a neutral dextran phase at the interfaces selectively recognized S. aureus, whereas the nanosheets bearing a carboxymethylated dextran phase selectively recognized E. coli O157:H7 with high binding affinity. The bacterial binding sites recognized by the artificial antibodies were thoroughly identified by experiments and molecular dynamics simulations, revealing the significance of their multivalent interactions with the bacterial membrane components for selective recognition. The luminescent WS2 artificial antibodies could rapidly detect the bacteria at a single copy from human serum without any purification and amplification. Moreover, the MoSe2 artificial antibodies selectively killed the pathogenic bacteria in the wounds of infected mice under light irradiation, leading to effective wound healing. This work demonstrates the potential of TMD artificial antibodies as an alternative to antibodies for sensing and therapy.

Prominent antibacterial effect of sub 5 nm Cu nanoparticles/MoS2composite under visible light.

Achieving an efficient and inexpensive bactericidal effect is a key point for the design of antibacterial agent. Recent advances have proved molybdenum disulfide (MoS2) as a promising platform for antimicrobial applications, while the combination of metal nanoparticle would promote the antibacterial efficiency. Nevertheless, the dispersivity, cheapness and safety of metal nanoparticle loaded on MoS2raised some concerns. In this paper, we successfully realized a uniform decoration of copper nanoparticles (CuNPs) on surface of MoS2nanosheets, and the size of CuNPs could be controlled below 5 nm. Under 5 min irradiation of 660 nm visible light, the synthesized CuNPs/MoS2composite demonstrated superior antibacterial performances (almost 100% bacterial killed) towards both Gram-negativeE. coliand Gram-positiveS. aureusover the single component (Cu or MoS2), while the bactericidal effect could last for at least 6 h. The synergism of photodynamic generated hydroxyl radical (·OH), oxidative stress without reactive oxygen species production and the release of Cu ions was considered as the mechanism for the antibacterial properties of CuNPs/MoS2. Our findings provided new insights into the development of two-dimensional antibacterial nanomaterials of high cost performance.

Octahedral Molybdenum Cluster Complexes with Optimized Properties for Photodynamic Applications.

Two new octahedral molybdenum cluster complexes act as an efficient singlet oxygen supplier in the context of the photodynamic therapy of cancer cells under blue-light irradiation. These complexes integrate the {Mo6I8}4+ core with 4'-carboxybenzo-15-crown-5 or cholate apical ligands and were characterized by 1H NMR, HR ESI-MS, and CHN elemental analysis. Both complexes display high quantum yields of luminescence and singlet oxygen formation in aqueous media associated with a suitable stability against hydrolysis. They are internalized into lysosomes of HeLa cells with no dark toxicity at pharmacologically relevant concentrations and have a strong phototoxic effect under blue-light irradiation, even in the presence of fetal bovine serum. The last feature is essential for further translation to in vivo experiments. Overall, these complexes are attractive molecular photosensitizers toward photodynamic applications.

Photoelectrochemical immunoassay platform based on MoS2 nanosheets integrated with gold nanostars for neuron-specific enolase assay.

MoS2 nanosheets were prepared by exfoliating MoS2 bulk crystals with ultrasonication in N-methylpyrrolidone and were integrated with gold nanostars (AuNS) to fabricate an AuNS/MoS2 nanocomposite. All nanomaterials were characterized by transmission electron microscope, scanning electron microscope, ultraviolet-visible spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. AuNS/MoS2 nanocomposites were coated onto a glassy carbon electrode (GCE) surface to construct a nanointerface for immobilizing neuron-specific enolase antibody (anti-NSE) thus forming a photoelectrochemical immunoassay system. AuNS can significantly promote the photoelectric conversion of MoS2 nanosheets improving the performance for a photoelectrochemical assay. Being illuminated with white light LED and controlling the potential at 0.05 V (vs. SCE), the photocurrent generated from anti-NSE(BSA)/AuNS/MoS2/GCE using 0.15 mol L-1 ascorbic acid as electron donor can be recorded with amperometry and used as an output signal for NSE quantitative assay. Under optimized experimental conditions, the photocurrent variation for the affinity-binding NSE is proportional to the logarithm of NSE concentration in the range 5.0 pg mL-1   to 1.5 ng mL-1 with a detection limit of 3.5 pg mL-1 (S/N = 3). The practicability of the PEC immunoassay system was evaluated by determining NSE in clinical serum samples. The recoveries ranged from 93.0 to 103% for the determination of NSE in serum samples with a standard addition method. The PEC immunoassay system possesses good accuracy for determining NSE in real samples. Graphical abstract.

Photoelectrochemical determination of trypsin by using an indium tin oxide electrode modified with a composite prepared from MoS2 nanosheets and TiO2 nanorods.

A photoelectrochemical (PEC) method has been developed for sensitive detection of trypsin. It is based on the use of a composite consisting of MoS2 nanosheets and TiO2 nanorods (MoS2-TiO2). The material has a high specific surface area, superior electrical conductivity, excellent biocompatibility and good band gap matching. The composite was synthesized by a one-pot method using TiO2 as a template. This results in a uniform distribution of the MoS2 nanosheets (<5 layers) in the composite. If the composite, placed on an indium tin oxide (ITO) electrode, is coupled to apoferritin, the photocurrent response decreases due to the insulating effect of the protein. Trypsin, in acting as an alkaline protease, decomposes the apoferritin. This results in the recovery of the PEC signal. Attractive features of this PEC method include (a) a superior PEC signal, (b) sensor stability, (c) simple operation, and (d) the lack of any additional modifications of the biosensor. This warrants high sensitivity, reproducibility, repeatability and practicality. The ITO sensor has a linear response in the 1 to 1000 ng·mL-1 trypsin concentration range and a 0.82 ng·mL-1 detection limit. The assay was applied to the determination of trypsin in spiked serum samples and gave satisfactory results. Graphical abstract Schematic presentation of an indium tin oxide (ITO)/MoS2-TiO2 sensor for detecting trypsin. The PEC signal was decreased after immobilization of apoferritin (APO) on the modified ITO. Trypsin catalytically hydrolyzes APO specifically and induces the PEC signal to recover.

Three-dimensional biogenic C-doped Bi2MoO6/In2O3-ZnO Z-scheme heterojunctions derived from a layered precursor.

Novel 3D biogenic C-doped Bi2MoO6/In2O3-ZnO Z-scheme heterojunctions were synthesized for the first time, using cotton fiber as template. The as-prepared samples showed excellent adsorption and photodegradation performance toward the hazardous antibiotic doxycycline under simulated sunlight irradiation. The morphology, phase composition and in situ carbon doping could be precisely controlled by adjusting processing parameters. The carbon doping in Bi2MoO6/In2O3-ZnO was derived from the cotton template, and the carbon content could be varied in the range 0.9-4.4 wt.% via controlling the heat treatment temperature. The sample with Bi2MoO6/In2O3-ZnO molar ratio of 1:2 and carbon content of 1.1 wt.% exhibited the highest photocatalytic activity toward doxycycline degradation, which was 3.6 and 4.3 times higher than those of pure Bi2MoO6 and ZnInAl-CLDH (calcined layered double hydroxides), respectively. It is believed that the Z-scheme heterojunction with C-doping, the 3D hierarchically micro-meso-macro porous structure, as well as the high adsorption capacity, contributed significantly to the enhanced photocatalytic activity.

Fluorescence immunosensor for cardiac troponin T based on Förster resonance energy transfer (FRET) between carbon dot and MoS2 nano-couple.

In this study, we demonstrated a prompt and sensitive detection technique for cardiac troponin T (cTnT) in buffer and biological fluid (serum) using an NIR-active fluorescent anti-cTnT-labelled carbon dot (CD) and molybdenum disulfide (MoS2)-based nano-couple. Exfoliated MoS2 nanosheets strongly grasp the anti-cTnT-labelled CDs over their surface, and an excited-state non-radiative energy transfer mechanism takes place from CDs to MoS2, thereby quenching the upconversion fluorescence. The nonlinear and upward Stern-Volmer relationship is observed, which indicates a combined static and dynamic quenching. Static and time-resolved fluorescence measurements predict distance-dependent Förster resonance energy transfer (FRET) dynamics, which control the detection process. In the presence of cTnT, the energy transfer process gets hindered due to strong antibody/antigen (anti-cTnT/cTnT) interaction. The cTnT molecules affect the positions of the nano-couple and cause effective detachment of CDs from the MoS2 surface. This results hindrance in the energy transfer process with consequent restoration of upconversion intensity. A linear response is observed between the cTnT concentration and the restored fluorescence intensity in the concentration range of 0.1-50 ng mL-1 with a limit of detection of 0.12 ng mL-1 and a limit of quantification of 0.38 ng mL-1. Statistical analysis shows that the present assay possesses an accuracy of 101.4 ± 3.76 with a co-relation co-efficient of 0.99. Thus, CD/MoS2 provides a promising platform for the sensitive detection of cTnT.

Investigation of Thermally Induced Cellular Ablation and Heat Response Triggered by Planar MoS2-Based Nanocomposite.

In comparison to conventional tumor treatment methods, photothermal therapy (PTT) is one of the innovative therapeutic strategies that employs light to produce localized heat for targeted ablation of cancer cells. Among the various kinds of heat generation nanomaterials, transition metal dichalcogenide nanosheets, especially molybdenum disulfide (MoS2), have recently been investigated as one of the promising PTT candidates because of their strong absorbance in the near-infrared (NIR) tissue transparency window and excellent photothermal conversion capability. In line with the great potential of MoS2-based nanomaterials in biomedical applications, their intrinsic therapeutic performance and corresponding cellular response are required to be continually investigated. In order to further improve MoS2-based PTT efficacy and dissect the molecular mechanism during heat stimuli, in this study, we successfully designed a novel and effective PTT platform by integration of MoS2 nanosheets with peptide-based inhibition molecules to block the function of heat shock proteins (Hsp90), one type of chaperone proteins that play protective roles in living systems against cellular photothermal response. Such a combined nanosystem could effectively induce cell ablation and viability assays indicated approximately 5-fold higher PTT treatment efficacy (8.8% viability) than that of MoS2 itself (48% viability) upon 808 nm light irradiation. Moreover, different from the case based on MoS2 alone that could cause tumor ablation through the process of necrosis, the detailed mechanism analysis revealed that the inhibition of Hsp90 could significantly increase the photothermally mediated apoptosis, hence resulting in remarkable enhancement of photothermal treatment. Such promising studies provide the great opportunity to better understand the cellular basis of light-triggered thermal response. Moreover, they can also facilitate the rational design of new generations of PTT platforms toward future theranostics.

Fabrication of MgFe2O4/MoS2 Heterostructure Nanowires for Photoelectrochemical Catalysis.

A novel one-dimensional MgFe2O4/MoS2 heterostructure has been successfully designed and fabricated. The bare MgFe2O4 was obtained as uniform nanowires through electrospinning, and MoS2 thin film appeared on the surface of MgFe2O4 after further chemical vapor deposition. The structure of the MgFe2O4/MoS2 heterostructure was systematic investigated by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectrometry (XPS), and Raman spectra. According to electrochemical impedance spectroscopy (EIS) results, the MgFe2O4/MoS2 heterostructure showed a lower charge-transfer resistance compared with bare MgFe2O4, which indicated that the MoS2 played an important role in the enhancement of electron/hole mobility. MgFe2O4/MoS2 heterostructure can efficiently degrade tetracycline (TC), since the superoxide free-radical can be produced by sample under illumination due to the active species trapping and electron spin resonance (ESR) measurement, and the optimal photoelectrochemical degradation rate of TC can be achieved up to 92% (radiation intensity: 47 mW/cm(2), 2 h). Taking account of its unique semiconductor band gap structure, MgFe2O4/MoS2 can also be used as an photoelectrochemical anode for hydrogen production by water splitting, and the hydrogen production rate of MgFe2O4/MoS2 was 5.8 mmol/h·m(2) (radiation intensity: 47 mW/cm(2)), which is about 1.7 times that of MgFe2O4.

Enhanced light emission from large-area monolayer MoS2 using plasmonic nanodisc arrays.

Single-layer direct band gap semiconductors such as transition metal dichalcogenides are quite attractive for a wide range of electronics, photonics, and optoelectronics applications. Their monolayer thickness provides significant advantages in many applications such as field-effect transistors for high-performance electronics, sensor/detector applications, and flexible electronics. However, for optoelectronics and photonics applications, inherent monolayer thickness poses a significant challenge for the interaction of light with the material, which therefore results in poor light emission and absorption behavior. Here, we demonstrate enhanced light emission from large-area monolayer MoS2 using plasmonic silver nanodisc arrays, where enhanced photoluminescence up to 12-times has been measured. Observed phenomena stem from the fact that plasmonic resonance couples to both excitation and emission fields and thus boosts the light-matter interaction at the nanoscale. Reported results allow us to engineer light-matter interactions in two-dimensional materials and could enable highly efficient photodetectors, sensors, and photovoltaic devices, where photon absorption and emission efficiency highly dictate the device performance.

Superlinear composition-dependent photocurrent in CVD-grown monolayer MoS2(1-x)Se2x alloy devices.

Transition metal dichalcogenides (TMDs) have emerged as a new class of two-dimensional materials that are promising for electronics and photonics. To date, optoelectronic measurements in these materials have shown the conventional behavior expected from photoconductors such as a linear or sublinear dependence of the photocurrent on light intensity. Here, we report the observation of a new regime of operation where the photocurrent depends superlinearly on light intensity. We use spatially resolved photocurrent measurements on devices consisting of CVD-grown monolayers of TMD alloys spanning MoS2 to MoSe2 to show the photoconductive nature of the photoresponse, with the photocurrent dominated by recombination and field-induced carrier separation in the channel. Time-dependent photoconductivity measurements show the presence of persistent photoconductivity for the S-rich alloys, while photocurrent measurements at fixed wavelength for devices of different alloy compositions show a systematic decrease of the responsivity with increasing Se content associated with increased linearity of the current-voltage characteristics. A model based on the presence of different types of recombination centers is presented to explain the origin of the superlinear dependence on light intensity, which emerges when the nonequilibrium occupancy of initially empty fast recombination centers becomes comparable to that of slow recombination centers.

Ion-driven photoluminescence modulation of quasi-two-dimensional MoS2 nanoflakes for applications in biological systems.

Quasi-two-dimensional (quasi-2D) molybdenum disulfide (MoS2) is a photoluminescence (PL) material with unique properties. The recent demonstration of its PL, controlled by the intercalation of positive ions, can lead to many opportunities for employing this quasi-2D material in ion-related biological applications. Here, we present two representative models of biological systems that incorporate the ion-controlled PL of quasi-2D MoS2 nanoflakes. The ion exchange behaviors of these two models are investigated to reveal enzymatic activities and cell viabilities. While the ion intercalation of MoS2 in enzymatic activities is enabled via an external applied voltage, the intercalation of ions in cell viability investigations occurs in the presence of the intrinsic cell membrane potential.

Probing timescales during back side ablation of Molybdenum thin films with optical and electrical measurement techniques.

In this study we present a new measurement technique to investigate the timescales of back side ablation of conductive films, using Molybdenum as an application example from photovoltaics. With ultrashort laser pulses at fluences below 0.6 J/cm(2), we ablate the Mo film in the shape of a fully intact Mo 'disc' from a transparent substrate. By monitoring the time-dependent current flow across a specifically developed test structure, we determine the time required for the lift-off of the disc. This value decreases with increasing laser fluence down to a minimum of 21 ± 2 ns. Furthermore, we record trajectories of the discs using a shadowgraphic setup. Ablated discs escape with a maximum velocity of 150 ± 5 m/s whereas droplets of Mo forming at the center of the disc can reach velocities up to 710 ± 11 m/s.

Laser-thinning of MoS2: on demand generation of a single-layer semiconductor.

Single-layer MoS(2) is an attractive semiconducting analogue of graphene that combines high mechanical flexibility with a large direct bandgap of 1.8 eV. On the other hand, bulk MoS(2) is an indirect bandgap semiconductor similar to silicon, with a gap of 1.2 eV, and therefore deterministic preparation of single MoS(2) layers is a crucial step toward exploiting the large direct bandgap of monolayer MoS(2) in electronic, optoelectronic, and photovoltaic applications. Although mechanical and chemical exfoliation methods can be used to obtain high quality MoS(2) single layers, the lack of control in the thickness, shape, size, and position of the flakes limits their usefulness. Here we present a technique for controllably thinning multilayered MoS(2) down to a single-layer two-dimensional crystal using a laser. We generate single layers in arbitrary shapes and patterns with feature sizes down to 200 nm and show that the resulting two-dimensional crystals have optical and electronic properties comparable to that of pristine exfoliated MoS(2) single layers.

Synergistic Photodynamic and Photothermal Antibacterial Activity of In Situ Grown Bacterial Cellulose/MoS2-Chitosan Nanocomposite Materials with Visible Light Illumination.

Owing to the rise in prevalence of multidrug-resistant pathogens attributed to the overuse of antibiotics, infectious diseases caused by the transmission of microbes from contaminated surfaces to new hosts are an ever-increasing threat to public health. Thus, novel materials that can stem this crisis, while also functioning via multiple antimicrobial mechanisms so that pathogens are unable to develop resistance to them, are in urgent need. Toward this goal, in this work, we developed in situ grown bacterial cellulose/MoS2-chitosan nanocomposite materials (termed BC/MoS2-CS) that utilize synergistic membrane disruption and photodynamic and photothermal antibacterial activities to achieve more efficient bactericidal activity. The BC/MoS2-CS nanocomposite exhibited excellent antibacterial efficacy, achieving 99.998% (4.7 log units) and 99.988% (3.9 log units) photoinactivation of Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus, respectively, under visible-light illumination (xenon lamp, 500 W, λ ≥ 420 nm, and 30 min). Mechanistic studies revealed that the use of cationic chitosan likely facilitated bacterial membrane disruption and/or permeability, with hyperthermia (photothermal) and reactive oxygen species (photodynamic) leading to synergistic pathogen inactivation upon visible-light illumination. No mammalian cell cytotoxicity was observed for the BC/MoS2-CS membrane, suggesting that such composite nanomaterials are attractive as functional materials for infection control applications.

Single shot damage mechanism of Mo/Si multilayer optics under intense pulsed XUV-exposure.

We investigated single shot damage of Mo/Si multilayer coatings exposed to the intense fs XUV radiation at the Free-electron LASer facility in Hamburg - FLASH. The interaction process was studied in situ by XUV reflectometry, time resolved optical microscopy, and "post-mortem" by interference-polarizing optical microscopy (with Nomarski contrast), atomic force microscopy, and scanning transmission electron microcopy. An ultrafast molybdenum silicide formation due to enhanced atomic diffusion in melted silicon has been determined to be the key process in the damage mechanism. The influence of the energy diffusion on the damage process was estimated. The results are of significance for the design of multilayer optics for a new generation of pulsed (from atto- to nanosecond) XUV sources.

Hot Carriers and Photothermal Effects of Monolayer MoOx for Promoting Sulfite Oxidase Mimetic Activity.

Local surface plasmon resonance (LSPR)-enhanced catalysis has brought a substantial amount of opportunities across various disciplines such as photocatalysis, photodetection, and photothermal therapeutics. Plasmon-induced photothermal and hot carriers effects have also been utilized to activate the enzyme-like reactions. Compared with natural enzymes, the relatively low catalytic performance of nanozymes severely hampered the potential applications in the field of biomedicine. For these issues mentioned above, herein, we demonstrate a highly efficient sulfite oxidase (SuOx) mimetic performance of plasmonic monolayer MoOx (ML-MoOx) upon LSPR excitation. We also established that the considerable photothermal effect and the injection of hot carriers induced by LSPR are responsible for promoting the SuOx activity of ML-MoOx. The high transient local temperature on the surface of ML-MoOx generated by the photothermal effect facilitates to impact the reaction velocity and feed the SuOx-like activity, while the generation of hot carriers which are suggested as predominant effects catalyzes the oxidation of sulfite to sulfate through significantly decreasing the activation energy for the SuOx-like reaction. These investigations present a contribution to the basic understanding of plasmon-enhanced enzyme-like reaction and provided an insight into the optimization of the SuOx mimetic performance of nanomaterials.

Visible light driven CuBi2O4/Bi2MoO6 p-n heterojunction with enhanced photocatalytic inactivation of E. coli and mechanism insight.

Here, a novel CuBi2O4/Bi2MoO6 (CBO/BMO) p-n heterojunction was fabricated and exhibited markedly improved photocatalytic inactivation capacity of E. coli cells under visible light excitation (λ > 420 nm) compared with pure CuBi2O4 and Bi2MoO6. The CBO/BMO-0.5 hybrid displayed the highest photoinactivation ability which could completely inactivate the E. coli cellswithin 4 h. The mechanism of photocatalytic disinfection towards E. coli of CBO/BMO heterojunctions was attributed to the disruption of cell-membrane, leakage and damage of cellular content including total protein and DNA as verified with SEM, fluorescence-base dead/live stain, sodium dodecyl sulfate polyacrylamide gel electropheresis (SDS-PAGE) and agarose gel electrophoresis (AGE). Additionally, the scavenge experiments showed that the reactive species h+, e- and •O2-play the predominant role in the photocatalytic system of CBO/BMO hybrids. The improved photocatalytic activity of CBO/BMO composites was mainly attributed to the promotion of spatial separation and migration rate of photoproduced electron-hole pairs, enhancement of visible light absorption and more generation of reactive species (•O2-) on the interface of catalyst and water which was demonstrated by nitroblue tetrazolium (NBT) and EPR. Our work indicated that construction of CuBi2O4/Bi2MoO6 p-n heterostructure photocatalyst is a promising environmental friendly alternative method to deal with the biohazards of pathogenic microorganisms.