Nongenetic Precise Neuromodulation and Spatiotemporal Neuroprotection for Epilepsy Therapy via Rationally Designed Multifunctional Nanotransducer.

The precise modulation of electrical activity in specific neuronal populations is paramount for rectifying abnormal neurological functions and is a critical element in the therapeutic arsenal for neurological disorders. However, achieving a balance between minimal invasiveness and robust neuroprotection poses a considerable challenge. Herein, we present a nanoneuromodulation strategy integrating neuroprotective features to effectively address epilepsy with minimal invasiveness and enable wireless functionality. Strategically engineered nanotransducer, adorned with platinum (Pt) decoration with titanium disulfide (TiS2) (TiS2/Pt), enables precise modulation of neuronal electrical activity in vitro and in vivo, ensuring exceptional temporal fidelity under millisecond-precision near-infrared (NIR) light pulses irradiation. Concurrently, TiS2/Pt showcase a pronounced enhancement in enzyme-mimicking activity, offering a robust defense against oxidative neurological injury in vitro. Nanotransducer-enabled wireless neuromodulation with biocatalytic neuroprotective capacity is highly effective in alleviating epileptic high-frequency neural activity and diminishing oxidative stress levels, thereby restoring redox equilibrium. This integrated therapeutic approach reduces the severity of epilepsy, demonstrating minimal invasiveness and obviating the requirements for genetic manipulation and optical fiber implantation, while providing an alternative avenue for neurological disorder treatment.

Ultrathin TiS2@N,S-Doped Carbon Hybrid Nanosheets as Highly Efficient Photoresponsive Antibacterial Agents.

Nanobactericides are employed as a promising class of nanomaterials for eradicating microbial infections, considering the rapid resistance risks of conventional antibiotics. Herein, we present a pioneering approach, reporting the synthesis of two-dimensional titanium disulfide nanosheets coated by nitrogen/sulfur-codoped carbon nanosheets (2D-TiS2@NSCLAA hybrid NSs) using a rapid l-ascorbic acid-assisted sulfurization of Ti3C2Tx-MXene to achieve efficient alternative bactericides. The as-developed materials were systematically characterized using a suite of different spectroscopy and microscopy techniques, in which the X-ray diffraction/Raman spectroscopy/X-ray photoelectron spectroscopy data confirm the existence of TiS2 and C, while the morphological investigation reveals single- to few-layered TiS2 NSs confined by N,S-doped C, suggesting the successful synthesis of the ultrathin hybrid NSs. From in vitro evaluation, the resultant product demonstrates impressive bactericidal potential against both Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacteria, achieving a substantial decrease in the bacterial viability under a 1.2 J dose of visible-light irradiation at the lowest concentration of 5 µg·mL-1 compared to Ti3C2Tx (15 µg·mL-1), TiS2-C (10 µg·mL-1), and standard antibiotic ciprofloxacin (15 µg·mL-1), respectively. The enhanced degradation efficiency is attributed to the ultrathin TiS2 NSs encapsulated within heteroatom N,S-doped C, facilitating effective photogenerated charge-carrier separation that generates multiple reactive oxygen species (ROS) and induced physical stress as well as piercing action due to its ultrathin structure, resulting in multimechanistic cytotoxicity and damage to bacterial cells. Furthermore, the obtained results from molecular docking studies conducted via computational simulation (in silico) of the as-synthesized materials against selected proteins (ß-lactamasE. coli/DNA-GyrasE. coli) are well-consistent with the in vitro antibacterial results, providing strong and consistent validation. Thus, this sophisticated study presents a simple and effective synthesis technique for the structural engineering of metal sulfide-based hybrids as functionalized synthetic bactericides.

Investigation on Contact Properties of 2D van der Waals Semimetallic 1T-TiS2/MoS2 Heterojunctions.

Two-dimensional transition metal dichalcogenides (2D TMDCs) are considered promising alternatives to Si as channel materials because of the possibility of retaining their superior electronic transport properties even at atomic body thicknesses. However, the realization of high-performance 2D TMDC field-effect transistors remains a challenge owing to Fermi-level pinning (FLP) caused by gap states and the inherent high Schottky barrier height (SBH) within the metal contact and channel layer. This study demonstrates that high-quality van der Waals (vdW) heterojunction-based contacts can be formed by depositing semimetallic TiS2 onto monolayer (ML) MoS2. After confirming the successful formation of a TiS2/ML MoS2 heterojunction, the contact properties of vdW semimetal TiS2 were thoroughly investigated. With clean interfaces of the TiS2/ML MoS2 heterojunctions, atomic-layer-deposited TiS2 can induce gap-state saturation and suppress FLP. Consequently, compared with conventional evaporated metal electrodes, the TiS2/ML MoS2 heterojunctions exhibit a lower SBH of 8.54 meV and better contact properties. This, in turn, substantially improves the overall performance of the device, including its on-current, subthreshold swing, and threshold voltage. Furthermore, we believe that our proposed strategy for vdW-based contact formation will contribute to the development of 2D materials used in next-generation electronics.

Encapsulation of Titanium Disulfide into MOF-Derived N,S-Doped Carbon Nanotablets Toward Suppressed Shuttle Effect and Enhanced Sodium Storage Performance.

Titanium disulfide (TiS2) is a promising anode material for sodium-ion batteries due to its high theoretical capacity, but it suffers from severe volume variation and shuttle effect of the intermediate polysulfides. To overcome the drawbacks, herein the successful fabrication of TiS2@N,S-codoped C (denoted as TiS2@NSC) through a chemical vapor reaction between Ti-based metal-organic framework (NH2-MIL-125) and carbon disulfide (CS2) is demonstrated. The C─N bonds enhance the electronic/ionic conductivity of the TiS2@NSC electrode, while the C─S bonds provide extra sodium storage capacity, and both polar bonds synergistically suppress the shuttle effect of polysulfides. Consequently, the TiS2@NSC electrode demonstrates outstanding cycling stability and rate performance, delivering reversible capacities of 418/392 mAh g-1 after 1000 cycles at 2/5 A g-1. Ex situ X-ray photoelectron spectroscopy and transmission electron microscope analyses reveal that TiS2 undergoes an intercalation-conversion ion storage mechanism with the generation of metallic Ti in a deeper sodiation state, and the pristine hexagonal TiS2 is electrochemically transformed into cubic rock-salt TiS2 as a reversible phase with enhanced reaction kinetics upon sodiation/desodiation cycling. The strategy to encapsulate TiS2 in N,S-codoped porous carbon matrices efficiently realizes superior conductivity and physical/chemical confinement of the soluble polysulfides, which can be generally applied for the rational design of advanced electrodes.

Physisorption-Mediated Charge Transfer in TiS2 Nanodiscs: A Room Temperature Sensor for Highly Sensitive and Reversible Carbon Dioxide Detection.

Real-time and high-performance monitoring of trace carbon dioxide (CO2) has become a necessity due to its substantial impact on the global climate, human health, indoor occupancy, and crop productivity. Two-dimensional materials such as transition metal dichalcogenides (TMDs) have gained significant interest in gas sensing applications owing to their intrinsically high surface-to-volume ratio. However, the research has been limited to prominent TMDs such as WS2 and MoS2. Specifically, the chemiresistive sensing performance of titanium disulfide (TiS2) has rarely been investigated. We present an electric-field-assisted TiS2 nanodisc assembly for the fabrication of a low-cost, low-power CO2 gas sensor based on charge transfer between physisorbed CO2 analyte molecules and TiS2 nanodiscs operating at room temperature. The physiochemical properties of the synthesized TiS2 nanodiscs were investigated via scanning electron microscopy (SEM), electron diffraction spectroscopy (EDS), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy. The fabricated sensor demonstrated an ultra-high sensor response of 60%, a fast response time of 37 s toward 500 ppm CO2 gas, and the lowest detection limit of 5 ppm under ambient conditions. The low adsorption energies and vdW interaction between CO2 molecules and TiS2 resulted in easy desorption, allowing the sensor to self-recover without the need for external stimuli, which is hardly been witnessed in other 2D material analogues. Furthermore, the sensor has excellent reproducibility and stability for successive analyte exposures, as well as excellent selectivity for CO2 over other interfering gases. This reported sensor based on 2D TMDs is the first of its type to integrate such a broad range of sensor characteristics (such as high sensor response and sensitivity, rapid response and recovery times, a high signal-to-noise ratio, and excellent selectivity at room temperature) into a single, revolutionary device for CO2 detection.

Enhanced Photocatalytic Hydrolysis Performance of Chiral Molecule Loaded Titanium Disulfide Nanosheets.

The photoelectrochemical (PEC) water decomposition is a promising method to produce hydrogen from water. To improve the water decomposition efficiency of the PEC process, it is necessary to inhibit the generation of H2 O2 byproducts and reduce the overpotential required by cheap catalysts and a high current density. Studies have shown that coating the electrode with chiral molecules or chiral films can increase the hydrogen production and reduce the generation of H2 O2 byproducts. This is interpreted as the result of a chiral induced spin selectivity (CISS) effect, which induces a spin correlation between the electrons that are transferred to the anode. Here, we report the adsorption of chiral molecules onto titanium disulfide nanosheets. Firstly, titanium disulfide nanosheets were synthesized via thermal injection and then dispersed through ultrasonic crushing. This strategy combines the CISS with the plasma effect caused by the narrow bandgap of two-dimensional sulfur compounds to promote the PEC water decomposition with a high current density.

Titanium Disulfide Based Saturable Absorber for Generating Passively Mode-Locked and Q-Switched Ultra-Fast Fiber Lasers.

In our work, passively mode-locked and Q-switched Er-doped fiber lasers (EDFLs) based on titanium disulfide (TiS2) as a saturable absorber (SA) were generated successfully. Stable mode-locked pulses centred at 1531.69 nm with the minimum pulse width of 2.36 ps were obtained. By reducing the length of the laser cavity and optimizing the cavity loss, Q-switched operation with a maximum pulse energy of 67.2 nJ and a minimum pulse duration of 2.34 µs was also obtained. Its repetition rate monotonically increased from 13.17 kHz to 48.45 kHz with about a 35 kHz tuning range. Our experiment results fully indicate that TiS2 exhibits excellent nonlinear absorption performance and significant potential in acting as ultra-fast photonics devices.

Albumin exfoliated titanium disulfide nanosheet: a multifunctional nanoplatform for synergistic photothermal/radiation colon cancer therapy.

PURPOSE: TiS2-HSA-FA, a nanoagent based on titanium disulfide (TiS2), human serum albumin (HSA), and folic acid (FA), was synthesized for potential use in synergistic photothermal/radiation therapy for colon cancer. METHODS: TiS2 nanosheets were synthesized through a HSA-assisted exfoliation method and then modified with PEGylated FA. The morphology, size, zeta potential, stability, cellular uptake, cytotoxicity, biodistribution, and in vitro and in vivo biocompatibility of the nanoparticles as well as their suitability for synergistic photothermal/radiation colon cancer therapy were investigated. RESULTS: The as-synthesized TiS2-HSA-FA nanoparticles showed excellent physiological stability, as well as high absorption values in the near-infrared (NIR) and X-ray regions, giving them superb activity as a photothermal and radiation sensitizer. In vitro and in vivo experiments indicated that TiS2-HSA-FA showed high tumor targeting selectivity, blood circulation time, biocompatibility, and suitability for synergistic tumor photothermal radiotherapy. CONCLUSION: A multifunctional nanoplatform based on TiS2 was developed and found to be potentially suitable for synergistic photothermal/radiation therapy for colon cancer.

In Situ Electron Microscopy Investigation of Sodiation of Titanium Disulfide Nanoflakes.

Two-dimensional (2D) metal sulfides show great promise for their potential applications as electrode materials of sodium ion-batteries because of the weak interlayer van der Waals interactions, which allow the reversible accommodation and extraction of sodium ions. The sodiation of metal sulfides can undergo a distinct process compared to that of lithiation, which is determined by their metal and structural types. However, the structural and morphological evolution during their electrochemical sodiation is still unclear. Here, we studied the sodiation reaction dynamics of TiS2 by employing in situ transmission electron microscopy and first-principles calculations. During the sodium-ion intercalation process, we observed multiple intermediate phases (phase II, phase Ib, and phase Ia), different from its lithiation counterpart, with varied sodium occupation sites and interlayer stacking sequences. Further insertion of Na ions prompted a multistep extrusion reaction, which led to the phase separation of Ti metal from the Na2S matrix, with its 2D morphology expanded to a 3D morphology. In contrast to regular conversion electrodes, TiS2 still maintained a compact structure after a full sodiation. First-principles calculations reveal that the as-identified phases are thermodynamically preferred at corresponding intercalation/extrusion stages compared to other possible phases. The present work provides the fundamental mechanistic understanding of the sodiation process of 2D transition metal sulfides.

Mitochondria-Targeted and Resveratrol-Loaded Dual-Function Titanium Disulfide Nanosheets for Photothermal-Triggered Tumor Chemotherapy.

A subcellular organelle-targeted delivery of anti-cancer drugs is a promising strategy to maximize the anti-cancer effects and minimize the adverse effects. Herein, we prepared a mitochondria-targeted drug delivery nanoplatform based on IR780 iodide (IR780) and titanium disulfide (TiS2) nanosheets. Due to the large specific surface area of TiS2 nanosheets, the nanoplatform could highly load anti-cancer drug resveratrol (RV). The as-prepared nanocomposite (IR780-TiS2/RV) was used for an efficacious photothermal-triggered tumor chemotherapy. IR780-TiS2/RV showed satisfactory stability and biocompatibility, and the loading ratio of RV and IR780 was about 112% and 56%, respectively. Upon the near-infrared (NIR) irradiation, the heat generated by IR780-TiS2/RV could trigger the RV release. Due to the conjugation with the mitochondria-specific IR780, IR780-TiS2/RV could target and accumulate in mitochondria and release RV when triggered by NIR to decrease the mitochondrial membrane potential, rapidly induce the upregulation of key intrinsic apoptotic factors such as cytochrome c, and initiate the caspase cascade, thereby achieving the chemotherapeutic effect. The IR780-TiS2/RV nanocomposite was demonstrated to have a high anti-tumor efficacy in vitro and in vivo as well as no remarkable tissue toxicity. We believe our study demonstrates that the NIR-triggered IR780-TiS2/RV nanoplatform could be a promising chemotherapeutic agent in clinical practice.

In Situ-Generated Volatile Precursor for CVD Growth of a Semimetallic 2D Dichalcogenide.

Semimetallic-layered transition-metal dichalcogenides, such as TiS2, can serve as a platform material for exploring novel physics modulated by dimensionality, as well as for developing versatile applications in electronics and thermoelectrics. However, controlled synthesis of ultrathin TiS2 in a dry-chemistry way has yet to be realized because of the high oxophilicity of active Ti precursors. Here, we report the ambient pressure chemical vapor deposition (CVD) method to grow large-size, highly crystalline two-dimensional (2D) TiS2 nanosheets through in situ generating titanium chloride as the gaseous precursor. The addition of NH4Cl promoter can react with Ti powders and switch the solid-phase sulfurization reaction into a CVD process, thus enabling the controllability over the size, shape, and thickness of the TiS2 nanosheets via tuning the synthesis conditions. Interestingly, this semimetallic 2D material exhibits near-infrared surface plasmon resonance absorption and a memristor-like electrical behavior, both holding promise for further application developments. Our method hence opens a new avenue for the CVD growth of 2D metal dichalcogenides directly from metal powders and pave the way for exploring their intriguing properties and applications.

Potential-Dependent, Switchable Ion Selectivity in Aqueous Media Using Titanium Disulfide.

The selective removal of ions by an electrochemical process is a promising approach to enable various water-treatment applications such as water softening or heavy-metal removal. Ion intercalation materials have been investigated for their intrinsic ability to prefer one specific ion over others, showing a preference for (small) monovalent ions over multivalent species. In this work, we present a fundamentally different approach: tunable ion selectivity not by modifying the electrode material, but by changing the operational voltage. We used titanium disulfide, which shows distinctly different potentials for the intercalation of different cations and formed binder-free composite electrodes with carbon nanotubes. Capitalizing on this potential difference, we demonstrated controllable cation selectivity by online monitoring the effluent stream during electrochemical operation by inductively coupled plasma optical emission spectrometry of aqueous 50 mm CsCl and MgCl2 . We obtained a molar selectivity of Mg2+ over Cs+ of 31 (strong Mg preference) in the potential range between -396 mV and -220 mV versus Ag/AgCl. By adjusting the operational potential window from -219 mV to +26 mV versus Ag/AgCl, Cs+ was preferred over Mg2+ by 1.7 times (Cs preference).

Highly Conductive Porous Transition Metal Dichalcogenides via Water Steam Etching for High-Performance Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries show significant advantages for next-generation energy storage systems owing to their high energy density and cost effectiveness. The main challenge in the development of long-life and high-performance Li-S batteries is to simultaneously facilitate the redox kinetics of sulfur species and suppress the shuttle effect of polysulfides. In this contribution, we present a general and green water-steam-etched approach for the fabrication of H- and O-incorporated porous TiS2 (HOPT). The conductivity, porosity, chemisorptive capability, and electrocatalytic activity of HOPT are enhanced significantly when compared with those of raw TiS2. The synthetic method can be expanded to the fabrication of other highly conductive transition metal dichalcogenides such as porous NbS2 and CoS2. The as-obtained HOPT can serve as both a substitute of conductive agents and an additive of interlayer materials. The optimal electrode delivers discharge capacities of 950 mA h g-1 after 300 cycles at 0.5 C and 374 mA h g-1 after 1000 cycles at 10 C. Impressively, an unprecedented reversible capacity of 172 mA h g-1 is achieved after 2500 cycles at 30 C, and the average capacity fading rate per cycle is as low as 0.015%. Importantly, four half-cells based on this electrode in series could drive 60 light-emitting diode indicator modules (the nominal power 3 W) after 20 s of charging. The instantaneous current and power of this device on reaching 275 A g-1 and 2611 W g-1, respectively, indicate outstanding high-power discharge performance and potential applications in electric vehicles and other large-scale energy storage systems.

Dielectric Mismatch Mediates Carrier Mobility in Organic-Intercalated Layered TiS2.

The dielectric constant is a key parameter that determines both optical and electronic properties of materials. It is desirable to tune electronic properties though dielectric engineering approach. Here, we present a systematic approach to tune carrier mobilities of hybrid inorganic/organic materials where layered two-dimensional transition-metal dichalcogenide TiS2 is electrochemically intercalated with polar organic molecules. By manipulating the dielectric mismatch using polar organic molecules with different dielectric constants, ranging from 10 to 41, the electron mobility of the TiS2 layers was changed three times due to the dielectric screening of the Coulomb-impurity scattering processes. Both the overall thermal conductivity and the lattice thermal conductivity were also found to decrease with an increasing dielectric mismatch. The enhanced electrical mobility along with the decreased thermal conductivity together gave rise to a significantly improved thermoelectric figure of merit of the hybrid inorganic/organic materials at room temperature, which might find applications in wearable electronics.

Evolution of chemical bonding and electron density rearrangements during D(3h) → D(3d) reaction in monolayered TiS2: a QTAIM and ELF study.

Monolayered titanium disulfide TiS2, a prospective nanoelectronic material, was previously shown to be subject to an exothermic solid-state D3h -D3d reaction that proceeds via a newly discovered transition state. Here, we study the reaction in detail using topological methods of quantum chemistry (quantum theory of atoms in molecules and electron localization function analysis) and show how electron density and chemical bonding between the atoms change in the course of the reaction. The reaction is shown to undergo a series of topological catastrophes, associated with elementary chemical events such as break and formation of bonds (including the unexpected formation of S-S bonding between sulfur layers), and rearrangement of electron density of outer valence and core shells.

Synthetic Strategy and Structural and Optical Characterization of Thin Highly Crystalline Titanium Disulfide Nanosheets.

Two-dimensional (2D) nanomaterials have recently received significant attention because of their attractiveness for use in many nanostructured devices. Layered transition-metal dichalcogenides are of particular interest because reducing their dimensionality causes changes in their already anisotropic physical and chemical properties. The present study describes the first bottom-up solution-phase synthesis of thin highly crystalline titanium disulfide (TiS2) nanosheets (NSs) using abundant low-cost molecular precursors. The obtained TiS2 NSs have average dimensions of ∼500 nm × 500 nm in the basal plane and have thicknesses of ∼5 nm. They exhibit broad absorption in the visible that tails out into the near-infrared. The obtained results demonstrate new opportunities in synthesizing low-dimensional 2D nanomaterials with potential use in various photochemical energy applications.