ACS Earth and Space Chemistry最新文献

The atomic substitution in two-dimensional (2D) materials is propitious to achieving compositionally engineered semiconductor heterostructures. However, elucidating the mechanism and developing methods to synthesize 2D heterostructures with atomic-scale precision are crucial. Here, we demonstrate the synthesis of monolayer WSe₂–WS₂ heterostructures with a relatively sharp interface from monolayer WSe₂ using a chalcogen atom-exchange synthesis route at high temperatures for short periods. The substitution was initiated at the edges of monolayer WSe₂ and the lateral diffuse along the heterointerface, and the reaction can be controlled by the precise reaction time and temperature. The lateral heterostructure and substitution process are studied by Raman and photoluminescence (PL) spectroscopies, electron microscopy, and device characterization, revealing a possible mechanism of strain-induced transformation. Our findings demonstrate a highly controllable synthesis of 2D layered materials through atom substitutional chemistry and provide a simple route to control the atomic structure.

Emergent phenomena in traditional ferroelectrics are frequently observed at heterointerfaces. Accessing such functionalities in van der Waals ferroelectrics requires the formation of layered heterostructures, either vertically stacked (similar to oxide ferroelectrics) or laterally stitched (without equivalent in 3D-crystals). Here, we investigate lateral heterostructures of the ferroelectric van der Waals semiconductors SnSe and SnS. A two-step process produces ultrathin crystals comprising an SnSe core laterally joined to an SnS edge-band, as confirmed by Raman spectroscopy, transmission electron microscopy (TEM) imaging, and electron diffraction. TEM shows a moiré pattern across the SnSe core due to coverage by an ultrathin SnS layer. The ability of the lateral interface (IF) to direct excited carriers, probed by cathodoluminescence, shows electron transfer over 560 nm diffusion length from the SnS edge-band. Large, thin flakes supporting ferroelectricity allow investigating domains and domain wall interactions in uniform crystals and lateral heterostructures. Polarized optical microscopy of sub-20 nm flakes consistently shows ⟨110⟩ oriented stripe domains with mirror-twin domain walls. Heterostructures adopt two domain configurations, with domains either constrained to the SnSe core or propagating across the entire SnSe–SnS flakes. The combined results demonstrate multifunctional van der Waals heterostructures with high-quality IFs presenting extraordinary opportunities for manipulating carrier flows and ferroelectric domain patterns.

Nanoparticles (NPs) offer significant promise as drug delivery vehicles; however, their in vivo efficacy is often hindered by the formation of a protein corona (PC), which influences key physiological responses such as blood circulation time, biodistribution, cellular uptake, and intracellular localization. Understanding NP-PC interactions is crucial for optimizing NP design for biomedical applications. Traditional approaches have utilized hydrophilic polymer coatings like polyethylene glycol (PEG) to resist protein adsorption, but glycopolymer-coated nanoparticles have emerged as potential alternatives due to their biocompatibility and ability to reduce the adsorption of highly immunogenic proteins. In this study, we synthesized and characterized glycopolymer-based poly[2-(diisopropylamino)ethyl methacrylate-b-poly(methacrylamidoglucopyranose) (PDPA-b-PMAG) NPs as an alternative to PEGylated NPs. We characterized the polymers using a range of techniques to establish their molecular weight and chemical composition. PMAG and PEG-based NPs showed equivalent physicochemical properties with sizes of ∼100 nm, spherical morphology, and neutral surface charges. We next assessed the magnitude of protein adsorption on both NPs and catalogued the identity of the adsorbed proteins using mass spectrometry-based techniques. The PMAG NPs were found to adsorb fewer proteins in vitro as well as fewer immunogenic proteins such as Immunoglobulins and Complement proteins. Flow cytometry and confocal microscopy were employed to examine cellular uptake in RAW 264.7 macrophages and MDA-MB-231 tumor cells, where PMAG NPs showed higher uptake into tumor cells over macrophages. In vivo studies in BALB/c mice with orthotopic 4T1 breast cancer xenografts showed that PMAG NPs exhibited prolonged circulation times and enhanced tumor accumulation compared to PEGylated NPs. The biodistribution analysis also revealed greater selectivity for tumor tissue over the liver for PMAG NPs. These findings highlight the potential of glycopolymeric NPs to improve tumor targeting and reduce macrophage uptake compared to PEGylated NPs, offering significant advancements in cancer nanomedicine and immunotherapy.

Infertility is an important issue for human reproductive health, with over half of all cases of infertility associated with female factors. Dysfunction of the complex female reproductive system may cause infertility. In clinical practice, female infertility is often treated with oral medications and/or surgical procedures, and ultimately with assisted reproductive technologies. Owing to their excellent biocompatibility, low immunogenicity, and adjustable mechanical properties, hydrogels are emerging as valuable tools in the reconstruction of organ function, supplemented by tissue engineering techniques to increase their structure and functionality. Hydrogel-based female reproductive reconstruction strategies targeting the pathological mechanisms of female infertility may provide alternatives for the treatment of ovarian, endometrium/uterine, and fallopian tube dysfunction. In this review, we provide a general introduction to the basic physiology and pathology of the female reproductive system, the limitations of current infertility treatments, and the lack of translation from animal models to human reproductive physiology. We further provide an overview of the current and future potential applications of hydrogels in the treatment of female reproductive system dysfunction, highlighting the great prospects of hydrogel-based strategies in the field of translational medicine, along with the significant challenges to be overcome.

Directly assembling drugs into mesoporous nanoformulations will be greatly favored due to the combination of enhanced drug delivery efficiency and mesostructure-enabled nanobio interactions. However, such an approach is hindered due to the lack of understanding of polymer nanoparticles’ formation mechanism, especially the relationship between polymerization, self-assembly, and the nucleation process. Here, by investigating the levodopa and dopamine polymerization process, we identify π-cation interaction as pivotal in the self-assembly and nucleation control of dopa molecules. Thus, through manipulation of the π-cation interaction, we present the direct assembly of a commercial drug, levodopa, into mesoporous nanoformulations. The synthesized nanospheres, approximately 200 nm in diameter, exhibit uniform mesopores of around 8 nm. These nanoformulations, abundant in mesopores, enhance chiral phenylalanine interaction with α-synuclein (Syn), curbing aggregation, safeguarding neurons, and alleviating Parkinson’s pathology. When combating α-synuclein, the nanoformulation achieved ∼100% inhibition of protein aggregation and sustained neuron viability up to 300%. We believe that this study may advance mesoscale self-assembly knowledge, guiding future nanopharmaceutical developments.

Excitons are key to the optoelectronic applications of van der Waals semiconductors, with the potential for versatile on-demand tuning of properties. Yet, their electrical manipulation remains challenging due to inherent charge neutrality and the additional loss channels induced by electrical doping. We demonstrate the dynamic electrical control of valley polarization in charged excitonic states of monolayer tungsten disulfide, achieving up to a 6-fold increase in the degree of circular polarization under off-resonant excitation. In contrast to the weak direct tuning of excitons typically observed using electrical gating, the charged exciton photoluminescence remains stable, even with increased scattering from electron doping. By exciting at the exciton resonances, we observed the reproducible nonmonotonic switching of the charged state population as the electron doping is varied under gate bias, indicating a resonant interplay between neutral and charged exciton states.

Counterfeit products are a problem known across many industries. Chemical products such as pharmaceuticals belong to the most targeted markets, with harmful consequences for consumer health and safety. However, many of the currently used anticounterfeit measures are associated with the packaging, with the readout method and level of security varying between different solutions. Identifiers that can be directly and safely mixed into the product to securely authenticate a batch would be desirable. For this purpose, we propose the use of chemical unclonable functions based on pools of short random DNA oligos, which allow the integration of a cryptographic authentication system into chemical products. We demonstrate and characterize a simplified workflow for readout, showing that results are robust and clearly differentiate between the correct tag and a counterfeit. As a proof of concept, we demonstrate the labeling of an acetaminophen formulation with a chemical unclonable function. The acetaminophen was successfully authenticated from a subsample of the product at a DNA admixing concentration of below 50 ng/g. Stability tests revealed that the readout is stable at room temperature for several years, exceeding the shelf life of most drug products. Our work thus shows that chemical unclonable functions are a valid alternative to state-of-the-art anticounterfeit methods, enabling a secure authentication scheme that is physically linked to the product and safe for consumption. The method is widely applicable beyond pharmaceuticals, allowing for more secure product tracing across industries.

Ultrawide bandgap semiconductors such as AlGaN, AlN, diamond, and β-Ga₂O₃ have significantly enhanced the functionality of electronic and optoelectronic devices, particularly in harsh environment conditions. However, some of these materials face challenges such as low thermal conductivity, limited P-type conductivity, and scalability issues, which can hinder device performance under extreme conditions like high temperature and irradiation. In this review paper, we explore the integration of various two-dimensional materials (2DMs) to address these challenges. These materials offer excellent properties such as high thermal conductivity, mechanical strength, and electrical properties. Notably, graphene, hexagonal boron nitride, transition metal dichalcogenides, 2D and quasi-2D Ga₂O₃, TeO₂, and others are investigated for their potential in improving ultrawide bandgap semiconductor-based devices. We highlight the significant improvement observed in the device performance after the incorporation of 2D materials. By leveraging the properties of these materials, ultrawide bandgap semiconductor devices demonstrate enhanced functionality and resilience in harsh environmental conditions. This review provides valuable insights into the role of 2D materials in advancing the field of ultrawide bandgap semiconductors and highlights opportunities for further research and development in this area.

Neuromorphic computing can simulate brain function and is a pivotal element in next-generation computing, providing a potential solution to the limitations brought by the von Neumann bottleneck. Optoelectronic synaptic devices are highly promising tools for simulating biomimetic nervous systems. In this study, we developed an optoelectronic neuromorphic device with a transistor structure constructed using ferroelectric CuInP₂S₆. Essential synaptic behaviors in this device are observed in response to light and electrical stimuli. The optoferroelectric coupling is revealed, and the highly tunable gate modulation of the charge carrier is realized in a single device. On this basis, the light adaptation of the biological eyes and smarter Pavlovian dogs was implemented successfully and enhanced by ferroelectric polarization. The gate voltage application promotes the migration of additional Cu⁺ ions in the in-plane direction, thus enhancing the synaptic performance of electrical stimulation. Meanwhile, the processing ability of convolutional kernel noise images in ferroelectric devices has been achieved. Our results offer the important observation and application of ferroelectric polarization-enhanced synaptic properties of a transistor structure and have great potential in promoting the development of two-dimensional van der Waals materials and devices.

Ultrafast charge transfer in van der Waals heterostructures can effectively engineer the optical and electrical properties of two-dimensional semiconductors for designing photonic and optoelectronic devices. However, the nonlinear absorption conversion dynamics with the pump intensity and the underlying physical mechanisms in a type-II heterostructure remain largely unexplored, yet hold considerable potential for all-optical logic gates. Herein, two-dimensional ReSe₂/ReS₂ heterostructure is designed to realize an unusual transition from reverse saturable absorption to saturable absorption (SA) with a conversion pump intensity threshold of approximately 170 GW/cm². Such an intriguing phenomenon is attributed to the decrease of two-photon absorption (TPA) of ReS₂ and the increase of SA of ReSe₂ with the pump intensity. Based on the characterization results of X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, femtosecond transient absorption spectrum, Kelvin probe force microscopy, and density functional theory calculation, a type-II charge-transfer-energy level model is proposed combined with the TPA of ReS₂ and SA of ReSe₂ processes. The results reveal the critical role of ultrafast interfacial charge transfer in tuning the unusual nonlinear absorption and improving the SA of ReSe₂/ReS₂ under different excitation wavelengths. Our finding deepens the understanding of nonlinear absorption physical mechanisms in two-dimensional heterostructure materials, which may further diversify the nonlinear optical materials and photonic devices.