Reticular Ratchets for Directing Electrochemiluminescence.

Electrochemiluminescence (ECL) involves charge transfer between electrochemical redox intermediates to produce an excited state for light emission. Ensuring precise control of charge transfer is essential for decoding ECL fundamentals, yet guidelines on how to achieve this for conventional emitters remain unexplored. Molecular ratchets offer a potential solution, as they enable the directional transfer of energy or chemicals while impeding the reverse movement. Herein, we designed 10 pairs of imine-based covalent organic frameworks as reticular ratchets to delicately manipulate the intrareticular charge transfer for directing ECL transduction from electric and chemical energies. Aligning the donor and acceptor (D-A) directions with the imine dipole effectively facilitates charge migration, whereas reversing the D-A direction impedes it. Notably, the ratchet effect of charge transfer directionality intensified with increasing D-A contrast, resulting in a remarkable 680-fold improvement in the ECL efficiency. Furthermore, dipole-controlled exciton binding energy, electron/hole decay kinetics, and femtosecond transient absorption spectra identified the electron transfer tendency from the N-end toward the C-end of reticular ratchets during ECL transduction. An exponential correlation between the ECL efficiency and the dipole difference was discovered. Our work provides a general approach to manipulate charge transfer and design next-generation electrochemical devices.

Mitigation Measures Could Aggravate Unbalanced Nitrogen and Phosphorus Emissions from Land-Use Activities.

Socioeconomic factors and mitigation potentials are essential drivers of the dynamics of nutrient emissions, yet these drivers are rarely examined at broad spatiotemporal scales. Here, we combine material flow analysis and geospatial analysis to examine the past and future changes of nitrogen and phosphorus emissions in China. Results show that anthropogenic nitrogen and phosphorus emissions increased by 17% and 32% during 2000-2019, respectively. Meanwhile, many regions witnessed decreasing nitrogen emissions but rising phosphorus discharged to waterbody, leading to a 20% decrease in the nitrogen/phosphorus ratio. In addition to many prominent factors like fertilizer use, the increasing impervious land area around cities is a notable factor driving the emissions, indicating the urgency to limit building expansion, especially in North China Plain and other less-developed regions. Improving land-use efficiency and consuming behaviors could reduce nitrogen and phosphorus emissions by 65-77% in 2030, but the nitrogen/phosphorus ratio will increase unintendedly due to larger reduction potentials for phosphorus, which may deteriorate the aquatic ecosystem. We highlight that nitrogen and phosphorus emissions should be reduced with coordinated but differentiated measures by prioritizing nitrogen reduction through cropland and food-system management.

3-(Methylthio)Propionic Acid from Bacillus thuringiensis Berliner Exhibits High Nematicidal Activity against the Root Knot Nematode Meloidogyne incognita (Kofoid and White) Chitwood.

Root knot nematodes cause serious damage to global agricultural production annually. Given that traditional chemical fumigant nematicides are harmful to non-target organisms and the environment, the development of biocontrol strategies has attracted significant attention in recent years. In this study, it was found that the Bacillus thuringiensis Berliner strain NBIN-863 exhibits strong fumigant nematicidal activity and has a high attraction effect on Meloidogyne incognita (Kofoid and White) Chitwood. Four volatile organic compounds (VOCs) produced by NBIN-863 were identified using solid-phase microextraction and gas chromatography-mass spectrometry. The nematicidal activity of four VOCs, namely, N-methylformamide, propenamide, 3-(methylthio)propionic acid, and phenylmalonic acid, was detected. Among these compounds, 3-(methylthio)propionic acid exhibited the highest direct contact nematicidal activity against M. incognita, with an LC50 value of 6.27 µg/mL at 24 h. In the fumigant bioassay, the mortality rate of M. incognita treated with 1 mg/mL of 3-(methylthio)propionic acid for 24 h increased to 69.93%. Furthermore, 3-(methylthio)propionic acid also exhibited an inhibitory effect on the egg-hatching of M. incognita. Using chemotaxis assays, it was determined that 3-(methylthio)propionic acid was highly attractive to M. incognita. In pot experiments, the application of 3-(methylthio)propionic acid resulted in a reduction in gall numbers, decreasing the number of galls per gram of tomato root from 97.58 to 6.97. Additionally, the root length and plant height of the treated plants showed significant increases in comparison with the control group. The current study suggests that 3-(methylthio)propionic acid is a novel nematicidal virulence factor of B. thuringiensis. Our research provides evidence for the potential use of NBIN-863 or its VOCs in biocontrol against root knot nematodes.

Heterojunction formed via 3D-to-2D perovskite conversion for photostable wide-bandgap perovskite solar cells.

Light-induced halide segregation constrains the photovoltaic performance and stability of wide-bandgap perovskite solar cells and tandem cells. The implementation of an intermixed two-dimensional/three-dimensional heterostructure via solution post-treatment is a typical strategy to improve the efficiency and stability of perovskite solar cells. However, owing to the composition-dependent sensitivity of surface reconstruction, the conventional solution post-treatment is suboptimal for methylammonium-free and cesium/bromide-enriched wide-bandgap PSCs. To address this, we develop a generic three-dimensional to two-dimensional perovskite conversion approach to realize a preferential growth of wider dimensionality (n ≥ 2) atop wide-bandgap perovskite layers (1.78 eV). This technique involves depositing a well-defined MAPbI3 thin layer through a vapor-assisted two-step process, followed by its conversion into a two-dimensional structure. Such a two-dimensional/three-dimensional heterostructure enables suppressed light-induced halide segregation, reduced non-radiative interfacial recombination, and facilitated charge extraction. The wide-bandgap perovskite solar cells demonstrate a champion power conversion efficiency of 19.6% and an open-circuit voltage of 1.32 V. By integrating with the thermal-stable FAPb0.5Sn0.5I3 narrow-bandgap perovskites, our all-perovskite tandem solar cells exhibit a stabilized PCE of 28.1% and retain 90% of the initial performance after 855 hours of continuous 1-sun illumination.

Antidepressants as Autophagy Modulators for Cancer Therapy.

Cancer is a major global public health problem with high morbidity. Depression is known to be a high-frequency complication of cancer diseases that decreases patients' life quality and increases the mortality rate. Therefore, antidepressants are often used as a complementary treatment during cancer therapy. During recent decades, various studies have shown that the combination of antidepressants and anticancer drugs increases treatment efficiency. In recent years, further emerging evidence has suggested that the modulation of autophagy serves as one of the primary anticancer mechanisms for antidepressants to suppress tumor growth. In this review, we introduce the anticancer potential of antidepressants, including tricyclic antidepressants (TCAs), tetracyclic antidepressants (TeCAs), selective serotonin reuptake inhibitors (SSRIs), and serotonin-norepinephrine reuptake inhibitors (SNRIs). In particular, we focus on their autophagy-modulating mechanisms for regulating autophagosome formation and lysosomal degradation. We also discuss the prospect of repurposing antidepressants as anticancer agents. It is promising to repurpose antidepressants for cancer therapy in the future.

Lattice Vacancy Induced Energy Renormalization of Photonic Quasiparticles in Two-Dimensional Semiconductors.

Coulomb interactions among dense charges and quasiparticle energy renormalization are at the center of quantum science because they significantly reshape the fundamental electronic and photonic properties of materials. While lattice vacancies are ubiquitous in solid materials, their physical effect on the Coulomb interaction among quasiparticles is normally weak and negligible. Here we show that in atomically thin semiconductors the presence of lattice vacancies emerges as an important but unexplored origin for the nontrivial renormalization of quasiparticle binding energies, due to the subtle modification of overall dielectric functions at low dimensionality. Such a renormalization effect leads to unusual reduction in the energy scales of photonic quasiparticles and red shifts of photoluminescence as the density of lattice vacancies increases. With strict configurative form factors derived, a dielectric screening model is also established for the generalized trilayer systems to capture the fine modification in the energy scales of quasiparticles and to elucidate the dielectric functions versus realistic Bohr lengths. This finding highlights the essential but commonly neglected role of lattice vacancies and deciphers the longstanding enigma of unpredictable photoluminescent line shifts in low-dimensional systems.

Simultaneous Photoluminescence and Photothermal Investigation of Individual CH3NH3PbBr3 Microcrystals.

The photoluminescence (PL) of CH3NH3PbBr3 (MAPbBr3), from thin films to nanoparticles, has been widely studied, providing information about charge carrier dynamics. However, the other energy dissipative channel, nonradiative relaxation, has not been thoroughly investigated due to a lack of proper technology. In this work, we simultaneously investigated the PL and photothermal (PT) properties of single MAPbBr3 microcrystals (MCs) by a home-built PL and PT microscope. In addition to the direct observation of the heterogeneity of the PL and PT images and kinetics of different MCs, we demonstrated the variation in the absorption of single MAPbBr3 MCs, which was believed to be constant. We also proved that more absorbed energy dissipated from the nonradiative channel at higher heating power. These results show that PL and PT microscopy is an effective and convenient method to investigate the charge carrier behaviors of optoelectronic materials at the single particle level for a deep understanding of their photophysical processes.

All-Optical Switching Based on Sub-Bandgap Photoactivation of Charge Trapping in Metal Halide Perovskites.

Controllable optical properties are crucial for the application of light-emitting materials in optical devices. In this work, controllable photoluminescence in metal halide perovskite crystals is realized via photoactivation of their defects. It is found that under continuous excitation, the photoluminescence intensity of a CH3 NH3 PbBr3 crystal can be fully controlled by sub-bandgap energy photon illumination. Such optically controllable emission behavior is rather general as it is observed also in CsPbBr3 and other perovskite materials. The switching mechanism is assigned to reversible light-induced activation/deactivation of nonradiative recombination centers, the presence of which relates to an excess of Pb during perovskite synthesis. Given the success of perovskites in photovoltaics and optoelectronics, it is believed that the discovery of green luminescence controlled by red illumination will extend the application scope of perovskites toward optical devices and intelligent control.

Identification of a novel prognostic ADME-related signature associated with tumor immunity for aiding therapy in head and neck squamous cell carcinoma.

The genes that control drug absorption, distribution, metabolism, and excretion (ADME) are also involved in carcinogenesis, cancer progression, and chemoresistance. However, no studies have systematically investigated the clinical significance and underlying functions of ADME genes in head and neck squamous cell carcinoma. Herein, we comprehensively explored the ADME genes in this disease, constructed and validated as a prognostic ADME gene signature (ADMEGS), using three ADME genes (ABCB1, ALDH1B1, and PON2) utilizing multiple datasets, including the training and test sets of The Cancer Genome Atlas and the Gene Expression Omnibus validation set. Moreover, we analyzed the relationship between the ADMEGS and clinical parameters, tumor immunity, and therapeutic response. We found that the ADMEGS was significantly correlated with the clinical, T, and N stages. Additionally, we were able to effectively differentiate tumor immune scores, immune cell infiltration statuses, and treatment responses based on the ADMEGS. As such, ADMEGS may be promising predictors for clinical outcome, tumor immunity, and treatment response.

Complete Genome Sequence of Brachybacterium sp. Strain NBEC-018, Isolated from Nematode-Infected Potatoes.

Brachybacterium species are ubiquitous Gram-positive bacteria. Here, we report the complete genome sequence of Brachybacterium sp. strain NBEC-018. The strain was isolated from rotten potatoes that were infected with potato rot nematodes (Ditylenchus destructor). The genome sequence will be beneficial to clarify the ecological role of Brachybacterium species.

Moisture-Dependent Blinking of Individual CsPbBr3 Nanocrystals Revealed by Single-Particle Spectroscopy.

All-inorganic metal halide perovskite nanocrystals (NCs) have been exceptional candidates for high-performance solution-processed optoelectronic and photonic devices compared with organometal halide perovskite NCs due to their superior stability. However, the interactions between all-inorganic perovskite NCs and moisture, which is an acknowledged detrimental factor, are still under debate, and detailed investigations to uncover such fundamentals remain to be performed. Herein, with wide-field fluorescence microscopy, the burst photoluminescence blinking responses of CsPbBr3 NCs were observed in ambient air, and moisture rather than oxygen was verified to be the key factor that leads to the enhanced PL intensity and reduced OFF duration. This behavior is rationalized through an effective passivation effect of the adsorbed water molecules on the surface halide vacancies on CsPbBr3 NCs. This work validates that ∼40% humidity atmospheres are helpful for better utilizing the all-inorganic perovskites, which is evidence of their promising prospect for application.

Optical Detection and Imaging of Nonfluorescent Matter at the Single-Molecule/Particle Level.

Since the first optical detection of single molecules in 1989, single-molecule spectroscopy has developed rapidly and been widely applied in many areas. However, the vast majority of matter is extremely inefficient at emitting photons in our physical world, which seriously limits the applications of optical methods based on photoluminescence. In addition to indirect detection by fluorescence labeling, many efforts have been made to directly image nonfluorescent matter at the single-particle or single-molecule level in different ways based on the absorption or scattering interaction between light and matter. Herein, we review five popular methods for imaging nonfluorescent particles/molecules, including dark-field microscopy (DFM), surface plasmon resonance microscopy (SPRM), surface enhanced Raman microscopy (SERM), interferometric scattering microscopy (iSCAT), and photothermal microscopy (PTM). After summarizing the principles and applications of these methods, we compare the advantages and disadvantages of each method and describe further potential development and applications.

Ultrasensitive detection of local acoustic vibrations at room temperature by plasmon-enhanced single-molecule fluorescence.

Sensitive detection of local acoustic vibrations at the nanometer scale has promising potential applications involving miniaturized devices in many areas, such as geological exploration, military reconnaissance, and ultrasound imaging. However, sensitive detection of weak acoustic signals with high spatial resolution at room temperature has become a major challenge. Here, we report a nanometer-scale system for acoustic detection with a single molecule as a probe based on minute variations of its distance to the surface of a plasmonic gold nanorod. This system can extract the frequency and amplitude of acoustic vibrations with experimental and theoretical sensitivities of 10 pm Hz-1/2 and 10 fm Hz-1/2, respectively. This approach provides a strategy for the optical detection of acoustic waves based on molecular spectroscopy without electromagnetic interference. Moreover, such a small nano-acoustic detector with 40-nm size can be employed to monitor acoustic vibrations or read out the quantum states of nanomechanical devices.

Electron-phonon coupling-assisted universal red luminescence of o-phenylenediamine-based carbon dots.

Due to the complex core-shell structure and variety of surface functional groups, the photoluminescence (PL) mechanism of carbon dots (CDs) remain unclear. o-Phenylenediamine (oPD), as one of the most common precursors for preparing red emissive CDs, has been extensively studied. Interestingly, most of the red emission CDs based on oPD have similar PL emission characteristics. Herein, we prepared six different oPD-based CDs and found that they had almost the same PL emission and absorption spectra after purification. Structural and spectral characterization indicated that they had similar carbon core structures but different surface polymer shells. Furthermore, single-molecule PL spectroscopy confirmed that the multi-modal emission of those CDs originated from the transitions of different vibrational energy levels of the same PL center in the carbon core. In addition, the phenomenon of "spectral splitting" of single-particle CDs was observed at low temperature, which confirmed these oPD-based CDs were unique materials with properties of both organic molecules and quantum dots. Finally, theoretical calculations revealed their potential polymerization mode and carbon core structure. Moreover, we proposed the PL mechanism of red-emitting CDs based on oPD precursors; that is, the carbon core regulates the PL emission, and the polymer shell regulates the PL intensity. Our work resolves the controversy on the PL mechanism of oPD-based red CDs. These findings provide a general guide for the mechanism exploration and structural analysis of other types of CDs.

Steric Engineering Enables Efficient and Photostable Wide-Bandgap Perovskites for All-Perovskite Tandem Solar Cells.

Wide-bandgap (WBG, ≈1.8 eV) perovskite is a crucial component to pair with narrow-bandgap perovskite in low-cost monolithic all-perovskite tandem solar cells. However, the stability and efficiency of WBG perovskite solar cells (PSCs) are constrained by the light-induced halide segregation and by the large photovoltage deficit. Here, a steric engineering to obtain high-quality and photostable WBG perovskites (≈1.8 eV) suitable for all-perovskite tandems is reported. By alloying dimethylammonium and chloride into the mixed-cation mixed-halide perovskites, wide bandgaps are obtained with much lower bromide contents while the lattice strain and trap densities are simultaneously minimized. The WBG PSCs exhibit considerably improved performance and photostability, retaining >90% of their initial efficiencies after 1000 h of operation at maximum power point. With the triple-cation/triple-halide WBG perovskites enabled by steric engineering, a stabilized power conversion efficiency of 26.0% in all-perovskite tandem solar cells is further obtained. The strategy provides an avenue to fabricate efficient and stable WBG subcells for multijunction photovoltaic devices.

Nonblinking Colloidal Quantum Dots via Efficient Multiexciton Emission.

Nonblinking colloidal quantum dots (QDs) are significant to their applications as single-photon sources or light-emitting materials. Herein, a simple heat-up method was developed to synthesize high-qualityWZ-CdSe/CdS core-shell colloidal QDs, which achieved a near-unity photoluminescence quantum yield (PLQY). It was found that the blinking behavior of such QDs was completely suppressed at high excitation intensities, and ultra-stable PL emission was observed. For this reason, a systematic investigation was conducted, revealing that the complete blinking suppression was attributed mainly to the efficient multiexciton emission at high excitation intensities. Such high-quality QDs with nonblinking behaviors and nearly ideal PL properties at high excitation intensities have massive potential applications in various robust conditions, including QD display screens, single-particle tracks, and single-photon sources.

Controllable Introduction of Surface Defects on CH3NH3PbI3 Perovskite.

One of the unique characteristics of semiconductors is the strong dependence of their properties on crystal defects and doping. However, due to the species diversity and low density, it is very difficult to control the type and concentration of the defects. In perovskite materials, crystal defects are randomly formed during the fast crystallization process, causing large heterogeneity of the samples. Here, in this work, we report a controllable method to introduce surface defects on CH3NH3PbI3 perovskite materials via the interaction with 1,4-benzoquinone (BQ) molecules on the gas and solid interface. After the adsorption of BQ molecules on the perovskite surface, surface defects can be generated by photoinduced chemical reactions. The concentration of the defects can thus be controlled by precisely regulating the laser irradiation time. The concentration of the defects can be characterized by a gradually decreased PL intensity and lifetime and was found to influence the atmospheric response and the subsequent acetone-induced degradation of the materials. These results demonstrate that crystal defects in perovskite materials can be controllably introduced, which provides a possible way to fully understand the correlation between the nature and chemical structure of these defects.

The prognosis of HPV-associated metastatic pharyngeal patients by primary and distant site.

OBJECTIVES: Human papillomavirus (HPV) positivity is a favorable prognostic factor in the general population of head and neck squamous cell carcinoma (HNSCC) patients. However, its impact on the survival of metastatic HNSCC of pharynx (mHNSC-P) patients is unclear. This study aims to investigate the associations between HPV status and survival in mHNSC-P patients. METHODS: 735 mHNSC-P patients diagnosed at first presentation from 2010 to 2016 were retrieved from the Surveillance, Epidemiology and End Result database (SEER). Chi-Squared test, univariate and multivariate cox proportional hazards model, Kaplan-Meier analysis, and log-rank test were applied to compare HPV-positive and -negative mHNSC-P patients. RESULT: Using univariate cox proportional hazards analysis, HPV status, primary site, T stage, treatment and distant metastatic site correlate with the overall survival (OS) and disease-specific survival (DSS) in mHNSC-P patients. Multivariate cox regression analysis shows that HPV-positive mHNSC-P patients experienced significantly better OS (HR: 0.62 CI: 0.51-0.76, p < 0.001) and DSS (HR: 0.73 CI: 0.58-0.91, p < 0.01) as compared to HPV-negative mHNSC-P patients. Subgroup analysis indicates that HPV-associated OS and DSS benefits exist in patients with metastatic HNSCC of oropharynx (mHNSC-OP) but not in patients with metastatic HNSCC of non-oropharynx (mHNSC-non-OP). Among mHNSC-OP patients, HPV positivity confers disease-specific survival benefit in patients with oligometastatic rather than polymetastatic patients. Furthermore, HPV associated OS and DSS advantages in mHNSC-OP with lung metastasis was observed. CONCLUSION: HPV-positive mHNSC-OP patients with lung metastasis show better survival than HPV-negative mHNSC-OP patients, providing key information to guide patient treatment approaches.

Circular RNA HECTD1 Mitigates Ulcerative Colitis by Promoting Enterocyte Autophagy Via miR-182-5p/HuR Axis.

OBJECTIVE: Ulcerative colitis (UC) is a chronic colitis with unknown etiology. Circular RNA (circRNA) has shown regulatory effect in many diseases, but the role of circRNA in UC is barely known. This study uncovers the function and regulatory mechanism of circRNA HECTD1 (circHECTD1) in UC. METHODS: Colonic mucosal tissues of 60 patients with active UC and 30 healthy controls were collected for H&E staining. Lipopolysaccharide (LPS) and dextran sulfate sodium (DSS) were used to induce inflammation and UC in Caco-2 cells and C57BL/6 mice where modification of circHECTD1, miR-182-5p and/or human antigen R (HuR) took place. The Caco-2 cells and the colon tissues of DSS-treated mice were collected for analysis of the expression levels of inflammatory cytokines, NLRP3 inflammasome, and autophagy-related proteins. The interactions among circHECTD1, miR-182-5p, and HuR were verified. RESULTS: The colonic mucosal tissues of UC patients showed impaired autophagy and decreased expressions of circHECTD1 and HuR. Overexpression of circHECTD1 or HuR or inhibition of miR-182-5p suppressed inflammation and promoted autophagy of LPS-induced Caco-2 cells. The expression of HuR was promoted by circHECTD1 via miR-182-5p in Caco-2 cells. Overexpression of circHECTD1 reduced colonic injuries and inflammation by promoting autophagy in DSS-treated mice. CONCLUSION: Overexpression of circHECTD1 alleviates UC by promoting HuR-dependent autophagy via miR-182-5p. This study highlights the therapeutic potential of circHECTD1 for UC and adds to the knowledge of circRNA in the pathogenesis of UC.