Direct Observation of Photon Induced Giant Band Renormalization in 2D PdSe2 Dichalcogenide by Transient Absorption Spectroscopy.

Insight into fundamental light-matter interaction as well as underlying photo-physical processes is crucial for the development of novel optoelectronic devices. Palladium diselenide (PdSe2 ), an important representative of emerging 2D noble metal dichalcogenides, has gain considerable attention owing to its unique optical, physical, and chemical properties. In this study, 2D PdSe2 nanosheets (NSs) are prepared using the liquid-phase exfoliation method. A broadband carrier relaxation dynamics from visible to near-infrared bands are revealed using a time-resolved transient absorption spectrometer, giving results that indicate band filling and bandgap renormalization (BGR) effects in the 2D PdSe2 NSs. The observed blue-shift of the transient absorption spectra at the primary stage and the subsequent red-shift can be ascribed to this BGR effect. These findings reveal the many-body character of the 2D TMDs material and may hold keys for applications in the field of optoelectronics and ultrafast photonics.

CRISPR-Cas13a-powered electrochemical biosensor for the detection of the L452R mutation in clinical samples of SARS-CoV-2 variants.

Since the end of 2019, a highly contagious disease caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has deprived numerous lives worldwide, called COVID-19. Up to date, omicron is the latest variant of concern, and BA.5 is replacing the BA.2 variant to become the main subtype rampaging worldwide. These subtypes harbor an L452R mutation, which increases their transmissibility among vaccinated people. Current methods for identifying SARS-CoV-2 variants are mainly based on polymerase chain reaction (PCR) followed by gene sequencing, making time-consuming processes and expensive instrumentation indispensable. In this study, we developed a rapid and ultrasensitive electrochemical biosensor to achieve the goals of high sensitivity, the ability of distinguishing the variants, and the direct detection of RNAs from viruses simultaneously. We used electrodes made of MXene-AuNP (gold nanoparticle) composites for improved sensitivity and the CRISPR/Cas13a system for high specificity in detecting the single-base L452R mutation in RNAs and clinical samples. Our biosensor will be an excellent supplement to the RT-qPCR method enabling the early diagnosis and quick distinguishment of SARS-CoV-2 Omicron BA.5 and BA.2 variants and more potential variants that might arise in the future.

Chemiresistive gas sensor based on Mo0.5W0.5S2 alloy nanoparticles with good selectivity and ppb-level limit of detection to ammonia.

Transition metal dichalcogenides (TMDs) are promising materials for chemiresistive gas sensor, while TMD alloys (two chalcogenide or/and metal elements) with tunable electronic structures have drawn little attention in gas sensing. Herein, Mo0.5W0.5S2 alloy nanoparticles (NPs) were prepared by a facile sonication exfoliation method and then tested for ammonia sensing. The crystal structure, geometric morphology, and elemental composition of Mo0.5W0.5S2 NPs were investigated. The gas sensing measurements demonstrated Mo0.5W0.5S2 NPs with good response to ammonia at 80 °C with a limit of detection down to 500 part per billion (ppb). The sensor also displayed good stability as well as superb selectivity to ammonia in the presence of interferences, such as methanol, acetone, benzene, and cyclohexane. The theoretical calculations revealed Mo and W atoms at edges (such as Mo0.5W0.5S2 (010)) of sheet-like NPs as the active sites for ammonia adsorption. Electrons donated by the adsorbed ammonia were combined with holes in p-type Mo0.5W0.5S2 NPs, and the concentration of the main charge carrier was reduced, resulting in resistance enhancement.

CdS@CdSe Core/Shell Quantum Dots for Highly Improved Self-Powered Photodetection Performance.

Uniform, well-defined cadmium sulfide@cadmium selenide core/shell quantum dots (CdS@CdSe QDs) were, for the first time, successfully synthesized by a solvothermal method and chemical bath growth for photoelectrochemical activities. The as-synthesized CdS@CdSe QDs not only exhibit superior self-powered photoresponse behavior and excellent stability under ambient conditions but also display significantly improved current densities and photoresponsivity compared to those of individual CdS QDs or CdSe QDs, mainly due to the built-in electric field, and thus have great potential in the fields of renewable energy and renewable energy consumption for carbon neutrality target achievement.

Defects in lead halide perovskite light-emitting diodes under electric field: from behavior to passivation strategies.

Lead halide perovskites (LHPs) are emerging semiconductor materials for light-emitting diodes (LEDs) owing to their unique structure and superior optoelectronic properties. However, defects that initiate degradation of LHPs through external stimuli and prompt internal ion migration at the interfaces remain a significant challenge. The electric field (EF), which is a fundamental driving force in LED operation, complicates the role of these defects in the physical and chemical properties of LHPs. A deeper understanding of EF-induced defect behavior is crucial for optimizing the LED performance. In this review, the origins and characterization of defects are explored, indicating the influence of EF-induced defect dynamics on LED performance and stability. A comprehensive overview of recent defect passivation approaches for LHP bulk films and nanocrystals (NCs) is also provided. Given the ubiquity of EF, a summary of the EF-induced defect behavior can enhance the performance of perovskite LEDs and related optoelectronic devices.

Ultrasensitive and Specific Clustered Regularly Interspaced Short Palindromic Repeats Empowered a Plasmonic Fiber Tip System for Amplification-Free Monkeypox Virus Detection and Genotyping.

The urgent necessity for highly sensitive diagnostic tools has been accentuated by the ongoing mpox (monkeypox) virus pandemic due to the complexity in identifying asymptomatic and presymptomatic carriers. Traditional polymerase chain reaction-based tests, despite their effectiveness, are hampered by limited specificity, expensive and bulky equipment, labor-intensive operations, and time-consuming procedures. In this study, we present a clustered regularly interspaced short palindromic repeats (CRISPR)/Cas12a-based diagnostic platform with a surface plasmon resonance-based fiber tip (CRISPR-SPR-FT) biosensor. The compact CRISPR-SPR-FT biosensor, with a 125 µm diameter, offers high stability and portability, enabling exceptional specificity for mpox diagnosis and precise identification of samples with a fatal mutation site (L108F) in the F8L gene. The CRISPR-SPR-FT system can analyze viral double-stranded DNA from mpox virus without amplification in under 1.5 h with a limit of detection below 5 aM in plasmids and about 59.5 copies/µL when in pseudovirus-spiked blood samples. Our CRISPR-SPR-FT biosensor thus offers fast, sensitive, portable, and accurate target nucleic acid sequence detection.

Early and Sensitive Detection of Pathogens for Public Health and Biosafety: An Example of Surveillance and Genotyping of SARS-CoV-2 in Sewage Water by Cas12a-Facilitated Portable Plasmonic Biosensor.

Infectious diseases severely threaten public health and global biosafety. In addition to transmission through the air, pathogenic microorganisms have also been detected in environmental liquid samples, such as sewage water. Conventional biochemical detection methodologies are time-consuming and cost-ineffective, and their detection limits hinder early diagnosis. In the present study, ultrafine plasmonic fiber probes with a diameter of 125 µm are fabricated for clustered regularly interspaced short palindromic repeats/CRISPR-associated protein (CRISPR/Cas)-12a-mediated sensing of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Single-stranded DNA exposed on the fiber surface is trans-cleaved by the Cas12a enzyme to release gold nanoparticles that are immobilized onto the fiber surface, causing a sharp reduction in the surface plasmon resonance (SPR) wavelength. The proposed fiber probe is virus-specific with the limit of detection of ~2,300 copies/ml, and genomic copy numbers can be reflected as shifts in wavelengths. A total of 21 sewage water samples have been examined, and the data obtained are consistent with those of quantitative polymerase chain reaction (qPCR). In addition, the Omicron variant and its mutation sites have been fast detected using S gene-specific Cas12a. This study provides an accurate and convenient approach for the real-time surveillance of microbial contamination in sewage water.

Dynamics of Photogenerated Charge Carriers in Inorganic/Organic S-Scheme Heterojunctions.

Step-scheme heterojunctions formed between two firmly bound photocatalysts facilitate charge separation due to interfacial charge transfer, which is usually illustrated by the gain or loss of electrons in the constituent photocatalysts characterized by in situ irradiated X-ray photoelectron spectroscopy. This technique provides a steady-state view of charge distribution but overlooks the transient and complex dynamics of charge transfer, trapping, and recombination. To provide a molecular-level and dynamic view of these processes, we investigated the behaviors of photogenerated charge carriers within an inorganic/organic TiO2/polydopamine S-scheme heterojunction using ultrafast transient absorption spectroscopy and time-resolved photoluminescence spectroscopy. We found the interfacial charge transfer within the step-scheme heterojunction occurred at a smaller shorter time scale than recombination, leading to efficient charge separation. Moreover, the charge-discharge property of polydopamine induces electron backflow, which should be avoided in practical photocatalytic applications. The composite showed higher photocatalytic H2O2-production activities due to faster H2O2 formation and suppressed H2O2 decomposition.

Optical Properties of Few-Layer Ti3CN MXene: From Experimental Observations to Theoretical Calculations.

Despite the emerging interest in research and development of Ti3CN MXene nanosheet (NS)-based optoelectronic devices, there is still a lack of in-depth studies of the underlying photophysical processes, like carrier relaxation dynamics and nonlinear photon absorption, operating in such devices, hindering their further and precise design. In this paper, we attempt to remedy the situation by fabricating few-layer Ti3CN NSs via combining selective etching and molecular intercalation and by investigating the carrier relaxation possesses and broadband nonlinear optical responses via transient absorption and Z-scan techniques. These results are complemented by first-principle theoretical analyses of the optical properties. Both saturable absorption and reverse saturable absorption phenomena are observed due to multiphoton absorption effects. The analysis of these results adds to the understanding of the basic photophysical processes, which is anticipated to be beneficial for the further design of MXene-based devices.

Mid-Infrared Optoelectronic Devices Based on Two-Dimensional Materials beyond Graphene: Status and Trends.

Since atomically thin two-dimensional (2D) graphene was successfully synthesized in 2004, it has garnered considerable interest due to its advanced properties. However, the weak optical absorption and zero bandgap strictly limit its further development in optoelectronic applications. In this regard, other 2D materials, including black phosphorus (BP), transition metal dichalcogenides (TMDCs), 2D Te nanoflakes, and so forth, possess advantage properties, such as tunable bandgap, high carrier mobility, ultra-broadband optical absorption, and response, enable 2D materials to hold great potential for next-generation optoelectronic devices, in particular, mid-infrared (MIR) band, which has attracted much attention due to its intensive applications, such as target acquisition, remote sensing, optical communication, and night vision. Motivated by this, this article will focus on the recent progress of semiconducting 2D materials in MIR optoelectronic devices that present a suitable category of 2D materials for light emission devices, modulators, and photodetectors in the MIR band. The challenges encountered and prospects are summarized at the end. We believe that milestone investigations of 2D materials beyond graphene-based MIR optoelectronic devices will emerge soon, and their positive contribution to the nano device commercialization is highly expected.

Density Functional Investigation on α-MoO3 (100): Amines Adsorption and Surface Chemistry.

The (100) surface of α-MoO3 should possess overwhelmingly more exposed Mo atoms than the (010), and the exposed Mo has been extensively considered as an active site for amine adsorption. However, α-MoO3 (100) has drawn little attention concerning the amine sensing mechanism. In this research, adsorption of ammonia (NH3), monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA) is systematically investigated by density functional theory (DFT). All four of these molecules have high affinity to α-MoO3 (100) through interaction between the N and the exposed Mo, and the affinity is mainly influenced by both the characteristics of the molecules and the geometric environment of the surface active site. Adsorption and dissociation of water and oxygen molecule on stoichiometric and defective α-MoO3 (100) surfaces are then simulated to fully understand the surface chemistry of α-MoO3 (100) in practical conditions. At low temperature, α-MoO3 (100) must be covered with a large number of water molecules; the water can desorb or dissociate into hydroxyl groups at high temperature. Oxygen vacancy (VO) can be generated through the annealing process during sensor device fabrication; VO must be filled with an O2 molecule, which can further interact with adsorbed water nearby to form hydroxyl groups. According to this research, α-MoO3 (100) must be the active surface for amine sensing and its surface chemistry is well understood. In the near future, further reaction and interaction will be simulated at α-MoO3 (100), and much more attention should be paid to α-MoO3 (100) not only theoretically but also experimentally.

Modification of DSSC Based on Polymer Composite Gel Electrolyte with Copper Oxide Nanochain by Shape Effect.

Solvent evaporation and leakage of liquid electrolytes that restrict the practicality of dye-sensitized solar cells (DSSCs) motivate the quest for the development of stable and ionic conductive electrolyte. Gel polymer electrolyte (GPE) fits the criteria, but it still suffers from low efficiency due to insufficient segmental motion within the electrolytes. Therefore, incorporating metal oxide nanofiller is one of the approaches to enhance the performance of electrolytes due to the presence of cross-linking centers that can be coordinated with the polymer segments. In this research, polymer composite gel electrolytes (PCGEs) employing poly (vinyl butyral-co-vinyl alcohol-co-vinyl acetate) (P(VB-co-VA-co-VAc)) terpolymer as host polymer, tetrapropylammonium iodide (TPAI) as dopant salt, and copper oxide (CuO) nanoparticles as the nanofillers were produced. The CuO nanofillers were synthesized by sonochemical method and subsequently calcined at different temperatures (i.e., 200, 350, and 500 °C), denoted as CuO-200, CuO-350, and CuO-500, respectively. All CuO nanoparticles have different shapes and sizes that are connected in a chain which impact the amorphous phase and the roughness of the surface, proven by the structural and the morphological analyses. It was found that the PCGE consisting of CuO-350 exhibited the highest ionic conductivity of 2.54 mS cm-1 and apparent diffusion coefficient of triiodide of 1.537 × 10-4 cm2 s-1. The enhancement in the electrochemical performance of the PCGEs is correlated with the change in shape (rod to sphere) and size of CuO particles which disrupted the structural order of the polymer chain, facilitating the redox couple transportation. Additionally, a DSSC was fabricated and achieved the highest power conversion efficiency of 7.05% with JSC of 22.1 mA cm-2, VOC of 0.61 V, and FF of 52.4%.

2D-ultrathin MXene/DOXjade platform for iron chelation chemo-photothermal therapy.

An increased demand for iron is a hallmark of cancer cells and is thought necessary to promote high cell proliferation, tumor progression and metastasis. This makes iron metabolism an attractive therapeutic target. Unfortunately, current iron-based therapeutic strategies often lack effectiveness and can elicit off-target toxicities. We report here a dual-therapeutic prodrug, DOXjade, that allows for iron chelation chemo-photothermal cancer therapy. This prodrug takes advantage of the clinically approved iron chelator deferasirox (ExJade®) and the topoisomerase 2 inhibitor, doxorubicin (DOX). Loading DOXjade onto ultrathin 2D Ti3C2 MXene nanosheets produces a construct, Ti 3 C 2 -PVP@DOXjade, that allows the iron chelation and chemotherapeutic functions of DOXjade to be photo-activated at the tumor sites, while potentiating a robust photothermal effect with photothermal conversion efficiencies of up to 40%. Antitumor mechanistic investigations reveal that upon activation, Ti 3 C 2 -PVP@DOXjade serves to promote apoptotic cell death and downregulate the iron depletion-induced iron transferrin receptor (TfR). A tumor pH-responsive iron chelation/photothermal/chemotherapy antitumor effect was achieved both in vitro and in vivo. The results of this study highlight what may constitute a promising iron chelation-based phototherapeutic approach to cancer therapy.

A CRISPR/Cas12a-empowered surface plasmon resonance platform for rapid and specific diagnosis of the Omicron variant of SARS-CoV-2.

The outbreak of the COVID-19 pandemic was partially due to the challenge of identifying asymptomatic and presymptomatic carriers of the virus, and thus highlights a strong motivation for diagnostics with high sensitivity that can be rapidly deployed. On the other hand, several concerning SARS-CoV-2 variants, including Omicron, are required to be identified as soon as the samples are identified as 'positive'. Unfortunately, a traditional PCR test does not allow their specific identification. Herein, for the first time, we have developed MOPCS (Methodologies of Photonic CRISPR Sensing), which combines an optical sensing technology-surface plasmon resonance (SPR) with the 'gene scissors' clustered regularly interspaced short palindromic repeat (CRISPR) technique to achieve both high sensitivity and specificity when it comes to measurement of viral variants. MOPCS is a low-cost, CRISPR/Cas12a-system-empowered SPR gene-detecting platform that can analyze viral RNA, without the need for amplification, within 38 min from sample input to results output, and achieve a limit of detection of 15 fM. MOPCS achieves a highly sensitive analysis of SARS-CoV-2, and mutations appear in variants B.1.617.2 (Delta), B.1.1.529 (Omicron) and BA.1 (a subtype of Omicron). This platform was also used to analyze some recently collected patient samples from a local outbreak in China, identified by the Centers for Disease Control and Prevention. This innovative CRISPR-empowered SPR platform will further contribute to the fast, sensitive and accurate detection of target nucleic acid sequences with single-base mutations.

Tailoring the ultrafast and nonlinear photonics of MXenes through elemental replacement.

Due to the outstanding electronic properties, unique chemical surface termination units and rich elemental compositions, MXenes have become promising candidates for the development of new generation optoelectronic devices. However, there is still a gap between advanced photonics applications and fundamental understanding of ultrafast carrier photo-physics dynamics and a nonlinear optical response in layered MXenes. Here, we present insight into the excited state relaxation processes and nonlinear optical response of few-layer Ti3CN and Ti3C2 nanosheets (NSs) via transient absorption spectroscopy and Z-scan measurements. Owing to similar structural compositions, the transient absorption and nonlinear absorption characteristics behave totally opposite. In addition, photo-induced bandgap renormalization and Pauli blocking phenomena exist in Ti3C2 and Ti3CN NSs, respectively. The element replacement may be a new strategy for tunable carrier kinetics and nonlinear optical response of MXenes. These research studies may provide insight into ultrafast carrier photo-physics dynamics as well as promote MXene-based advanced photonics and their applications in optoelectronic devices.

Strategic Design of Intelligent-Responsive Nanogel Carriers for Cancer Therapy.

Owing to the distinctive constituents of tumor tissue from those healthy organs, nanomedicine strategies show significant potentials in smart drug delivery. Nowadays, stimuli-responsive nanogels are playing increasingly important roles in the application of cancer therapy because of their sensitivity to various internal or external physicochemical stimuli, which exhibit site-specific and markedly enhanced drug release. Besides, nanogels are promising as drug carriers because of their porous structures, good biocompatibility, large surface area, and excellent capability with drugs. Taking advantage of multiresponsiveness, recent years have witnessed the rapid evolution of stimulus-responsive nanogels from monoresponsive to multiresponsive systems; however, there lacks a comprehensive review summarizing these reports. In this Review, we discuss the properties, synthesis, and characterization of nanogels. Moreover, tumor microenvironment and corresponding designing strategies for stimuli-response nanogels, both exogenous (temperature, magnetic field, light) and endogenous (pH, biomolecular, redox, ROS, pressure, hypoxia) are summarized on the basis of the recent advances in multistimuli-responsive nanogel systems. Nanogel and two-dimensional material composites show excellent performance in the field of constructing multistimulus-responsive nanoparticles and precise intelligent drug release integrated system for multimodal cancer diagnosis and therapy. Finally, potential progresses and suggestions are provided for the further design of hybrid nanogels based on emerging two-dimensional materials.

2D materials for bone therapy.

Due to their prominent physicochemical properties, 2D materials are broadly applied in biomedicine. Currently, 2D materials have achieved great success in treating many diseases such as cancer and tissue engineering as well as bone therapy. Based on their different characteristics, 2D materials could function in various ways in different bone diseases. Herein, the application of 2D materials in bone tissue engineering, joint lubrication, infection of orthopedic implants, bone tumors, and osteoarthritis are firstly reviewed comprehensively together. Meanwhile, different mechanisms by which 2D materials function in each disease reviewed below are also reviewed in detail, which in turn reveals the versatile functions and application of 2D materials. At last, the outlook on how to further broaden applications of 2D materials in bone therapies based on their excellent properties is also discussed.

Modifying the Crystal Field of CsPbCl3:Mn2+ Nanocrystals by Co-doping to Enhance Its Red Emission by a Hundredfold.

CsPbCl3:Mn2+ is a practical solution for obtaining red-orange light inorganic perovskite nanocrystals since CsPbI3 is unstable. Increasing the concentration of Mn2+ is an effective way to enhance the orange-red emission of CsPbCl3:Mn2+. However, the relationship between emission intensity of the Mn2+ dopant and the concentration of Mn2+ is very chaotic in different studies. As a transition metal ion, the electronic states of Mn2+ are very sensitive to the crystal field environment. Here, the crystal field of the CsPbCl3:Mn2+ nanocrystals was adjusted by co-doping other cations, and the concentration of Mn2+ remained unchanged. Additionally, the crystal field strength of different samples was calculated. Compared with the CsPbCl3:Mn2+ nanocrystals, the red-orange peak in the fluorescence spectrum of CsPbCl3:Mn2+, Er3+ nanocrystals was redshifted from 580 to 600 nm and enhanced by 100 times successfully. The same experiment was carried out on CsPbCl3:Mn2+ nanoplatelets at the same time to confirm the changed crystal field around Mn2+. The effect of co-doping cations on the luminescence properties of Mn2+ is similar to that in nanocubes, and the mechanism was analyzed in detail.

Heterojunction Photocatalysts.

Semiconductor-based photocatalysis attracts wide attention because of its ability to directly utilize solar energy for production of solar fuels, such as hydrogen and hydrocarbon fuels and for degradation of various pollutants. However, the efficiency of photocatalytic reactions remains low due to the fast electron-hole recombination and low light utilization. Therefore, enormous efforts have been undertaken to solve these problems. Particularly, properly engineered heterojunction photocatalysts are shown to be able to possess higher photocatalytic activity because of spatial separation of photogenerated electron-hole pairs. Here, the basic principles of various heterojunction photocatalysts are systematically discussed. Recent efforts toward the development of heterojunction photocatalysts for various photocatalytic applications are also presented and appraised. Finally, a brief summary and perspectives on the challenges and future directions in the area of heterojunction photocatalysts are also provided.

Two-dimensional layered composite photocatalysts.

Two-dimensional (2D) layered nanostructure composites are promising candidates for conducting high-performance energy conversion and environmental remediation. The construction of 2D layered composite photocatalysts can generate many unique properties that do not exist in other kinds of semiconductor composite photocatalyst, which are beneficial for photocatalytic performance enhancement, band gap tuning, heterojunction formation, etc. Recently, these advantages have greatly stimulated the study of 2D layered composite photocatalysts in the field of photocatalysis. This feature article summarizes the recent developments of 2D layered composite photocatalysts for photocatalytic applications, such as photocatalytic hydrogen production, bacterial disinfection, and pollutant degradation. Finally, perspectives on the challenges and opportunities for the future exploration of 2D layered composite photocatalysts are put forward.