Multifunctional Modification of the Buried Interface in Mixed Tin-Lead Perovskite Solar Cells.

Mixed tin-lead perovskite solar cells can reach bandgaps as low as 1.2 eV, offering high theoretical efficiency and serving as base materials for all-perovskite tandem solar cells. However, instability and high defect densities at the interfaces, particularly the buried surface, have limited performance improvements. In this work, we present the modification of the bottom perovskite interface with multifunctional hydroxylamine salts. These salts can effectively coordinate the different perovskite components, having critical influences in regulating the crystallization process and passivating defects of varying nature. The surface modification reduced traps at the interface and prevented the formation of excessive lead iodide, enhancing the quality of the films. The modified devices presented fill factors reaching 81% and efficiencies of up to 23.8%. The unencapsulated modified devices maintained over 95% of their initial efficiency after 2000 h of shelf storage.

Suppressed Defects by Functional Thermally Cross-Linked Fullerene for High-Efficiency Tin-Lead Perovskite Solar Cells.

Mixed tin-lead (Sn-Pb) perovskites have attracted the attention of the community due to their narrow bandgap, ideal for photovoltaic applications, especially tandem solar cells. However, the oxidation and rapid crystallization of Sn2+ and the interfacial traps hinder their development. Here, cross-linkable [6,6]-phenyl-C61-butyric styryl dendron ester (C-PCBSD) is introduced during the quenching step of perovskite thin film processing to suppress the generation of surface defects at the electron transport layer interface and improve the bulk crystallinity. The C-PCBSD has strong coordination ability with Sn2+ and Pb2+ perovskite precursors, which retards the crystallization process, suppresses the oxidation of Sn2+, and improves the perovskite bulk and surface crystallinity, yielding films with reduced nonradiative recombination and enhanced interface charge extraction. Besides, the C-PCBSD network deposited on the perovskite surface displays superior hydrophobicity and oxygen resistance. Consequently, the devices with C-PCBSD obtain PCEs of up to 23.4% and retained 97% of initial efficiency after 2000 h of storage in a N2 atmosphere.

Inhibiting Interfacial Nonradiative Recombination in Inverted Perovskite Solar Cells with a Multifunctional Molecule.

Interface-induced nonradiative recombination losses at the perovskite/electron transport layer (ETL) are an impediment to improving the efficiency and stability of inverted (p-i-n) perovskite solar cells (PSCs). Tridecafluorohexane-1-sulfonic acid potassium (TFHSP) is employed as a multifunctional dipole molecule to modify the perovskite surface. The solid coordination and hydrogen bonding efficiently passivate the surface defects, thereby reducing nonradiative recombination. The induced positive dipole layer between the perovskite and ETLs improves the energy band alignment, enhancing interface charge extraction. Additionally, the strong interaction between TFHSP and the perovskite stabilizes the perovskite surface, while the hydrophobic fluorinated moieties prevent the ingress of water and oxygen, enhancing the device stability. The resultant devices achieve a power conversion efficiency (PCE) of 24.6%. The unencapsulated devices retain 91% of their initial efficiency after 1000 h in air with 60% relative humidity, and 95% after 500 h under maximum power point (MPP) tracking at 35 °C. The utilization of multifunctional dipole molecules opens new avenues for high-performance and long-term stable perovskite devices.

Controlling Tin Halide Perovskite Oxidation Dynamics in Solution for Perovskite Optoelectronic Devices.

As a leading contender to replace lead halide perovskites, tin-based perovskites have demonstrated ever increasing performance in solar cells and light-emitting diodes (LEDs). They tend to be processed with dimethyl sulfoxide (DMSO) solvent, which has been identified as a major contributor to the Sn(II) oxidation during film fabrication, posing a challenge to the further improvement of Sn-based perovskites. Herein, we use NMR spectroscopy to investigate the kinetics of the oxidation of SnI2, revealing that autoamplification takes place, accelerating the oxidation as the reaction progresses. We propose a mechanism consistent with these observations involving water participation and HI generation. Building upon these insights, we have developed low-temperature Sn-based perovskite LEDs (PeLEDs) processed at 60 °C, achieving enhanced external quantum efficiencies (EQEs). Our research underscores the substantial potential of low-temperature DMSO solvent processes and DMSO-free solvent systems for fabricating oxidation-free Sn-based perovskites, shaping the future direction in processing Sn-containing perovskite materials and optoelectronic devices.

Anlotinib in Chinese patients aged ≥70 years with advanced non-squamous non-small cell lung cancer without prior chemotherapy: a multicenter, single-arm pilot trial.

Background: Based on pharmacoeconomics, drug availability and actual treatment, optimal treatment regimens for Chinese non-small-cell lung carcinoma (NSCLC) patients over 70 years old are needed. Methods: This multicenter, single-arm pilot trial enrolled patients with advanced non-squamous NSCLC who refused systemic chemotherapy. Eligible patients received anlotinib (12 mg/day, d1-14, Q3W) until disease progression, intolerant toxicities, or withdrawal from the study. The primary endpoint was progression-free survival (PFS). Results: Forty-nine patients were screened between January 2019 and September 2021, of whom 40 patients were eligible. The median age was 76 years. With a median follow-up period of 16.20 (95% CI: 8.77, 25.10) months, the median PFS was 5.45 months (95% CI: 3.52-9.23) and the median overall survival was 10.32 months (95% CI: 6.44-12.78). Three patients achieved a partial response and 34 had stable disease, with an objective response rate of 7.5% and a disease control rate of 92.5%. Thirty-three (82.5%; 33/40) patients reported treatment-related adverse events (TRAEs) of any grade, and the incidence rate of grade ≥3 TRAEs was 35% (14/40). The most common grade ≥3 TRAEs were hypertension (4/40; 10.0%), hand-foot syndrome (3/40; 7.5%), and proteinuria (2/40; 5.0%). Conclusion: Anlotinib treatment was feasible and safe in Chinese elderly patients with advanced non-squamous NSCLC who did not receive any systemic chemotherapy.

Hydrogen Production via Electrolysis of Wastewater.

The high energy consumption of traditional water splitting to produce hydrogen is mainly due to complex oxygen evolution reaction (OER), where low-economic-value O2 gas is generated. Meanwhile, cogeneration of H2 and O2 may result in the formation of an explosive H2/O2 gas mixture due to gas crossover. Considering these factors, a favorable anodic oxidation reaction is employed to replace OER, which not only reduces the voltage for H2 production at the cathode and avoids H2/O2 gas mixture but also generates value-added products at the anode. In recent years, this innovative strategy that combines anodic oxidation for H2 production has received intensive attention in the field of electrocatalysis. In this review, the latest research progress of a coupled hydrogen production system with pollutant degradation/upgrading is systematically introduced. Firstly, wastewater purification via anodic reaction, which produces free radicals instead of OER for pollutant degradation, is systematically presented. Then, the coupled system that allows for pollutant refining into high-value-added products combined with hydrogen production is displayed. Thirdly, the photoelectrical system for pollutant degradation and upgrade are briefly introduced. Finally, this review also discusses the challenges and future perspectives of this coupled system.

Analysis of resistance risk and mechanism of the 14α-demethylation inhibitor ipconazole in Fusarium pseudograminearum.

Ipconazole is a broad-spectrum triazole fungicide that is highly effective against Fusarium pseudograminearum. However, its risk of developing resistance and mechanism are not well understood in F. pseudograminearum. Here, the sensitivities of 101 F. pseudograminearum isolates to ipconazole were investigated, and the average EC50 value was 0.1072 µg/mL. Seven mutants resistant to ipconazole were obtained by fungicide adaption, with all but one showing reduced fitness relative to the parental isolates. Cross-resistance was found between ipconazole and mefentrifluconazole and tebuconazole, but none between ipconazole and pydiflumetofen, carbendazim, fludioxonil, or phenamacril. In summary, these findings suggest that there is a low risk of F. pseudograminearum developing resistance to ipconazole. Additionally, a point mutation, G464S, was seen in FpCYP51B and overexpression of FpCYP51A, FpCYP51B and FpCYP51C was observed in ipconazole-resistant mutants. Assays, including transformation and molecular docking, indicated that G464S conferred ipconazole resistance in F. pseudograminearum.

Resistance risk, resistance mechanism and the effect on DON production of a new SDHI fungicide cyclobutrifluram in Fusarium graminearum.

Fusarium head blight in wheat is caused by Fusarium graminearum, resulting in significant yield losses and grain contamination with deoxynivalenol (DON), which poses a potential threat to animal health. Cyclobutrifluram, a newly developed succinate dehydrogenase inhibitor, has shown excellent inhibition of Fusarium spp. However, the resistance risk of F. graminearum to cyclobutrifluram and the molecular mechanism of resistance have not been determined. In this study, we established the average EC50 of a range of F. graminearum isolates to cyclobutrifluram to be 0.0110 µg/mL. Six cyclobutrifluram-resistant mutants were obtained using fungicide adaptation. All mutants exhibited impaired fitness relative to their parental isolates. This was evident from measurements of mycelial growth, conidiation, conidial germination, virulence, and DON production. Interestingly, cyclobutrifluram did not seem to affect the DON production of either the sensitive isolates or the resistant mutants. Furthermore, a positive cross-resistance was observed between cyclobutrifluram and pydiflumetofen. These findings suggest that F. graminearum carries a moderate to high risk of developing resistance to cyclobutrifluram. Additionally, point mutations H248Y in FgSdhB and A73V in FgSdhC1 of F. graminearum were observed in the cyclobutrifluram-resistant mutants. Finally, an overexpression transformation assay and molecular docking indicated that FgSdhBH248Y or FgSdhC1A73V could confer resistance of F. graminearum to cyclobutrifluram.

Adaptive Force Field Parameter Optimization for Expanding Reaction Simulations within Wide-Ranged Temperature.

Large-scale and long-term simulation of chemical reactions are key research topics in computational chemistry. However, there are still difficulties in simulating high-temperature reactions, such as polymer thermal decomposition. Herein, we introduce an adaptive potential parameter optimization framework designed to automatically fine-tune parameters, and the application of it to optimize ReaxFF parameters enhances the accuracy of chemical reaction simulations conducted at experimental temperatures. To achieve this, we leverage the power of Random Forests and interpretable machine learning techniques that enable the identification and selection of parameters that exert a substantial influence on the target attribute. By training deep neural network (NN) models, we established optimized parameter associations with reference properties. We train deep neural network (NN) models to establish the relationship between the optimized parameters and reference properties. We employ a Genetic Algorithm (GA) to utilize the surrogate NN model and the quantum mechanical targets to speed up the search for the optimal parameters. Our simulation results of resin pyrolysis show that the adaptive optimized ReaxFF can predict the peak temperature more accurately and obtain reasonable product composition under conditions that more closely resemble experimental scenarios. This work facilitates advances in force field parameter optimization for more accurate and universal reaction simulations.

Mefentrifluconazole-Resistant Risk and Resistance-Related Point Mutation in FpCYP51B of Fusarium pseudograminearum.

Mefentrifluconazole, a triazole fungicide, exhibits remarkable efficacy in combating Fusarium spp. The mean EC50 value of mefentrifluconazole against 124 isolates of Fusarium pseudograminearum was determined to be 1.06 µg/mL in this study. Fungicide taming produced five mefentrifluconazole-resistant mutants with resistance factors ranging from 19.21 to 111.34. Compared to the original parental isolates, the fitness of three resistant mutants was much lower, while the remaining two mutants displayed enhanced survival fitness. There was evidence of positive cross-resistance between tebuconazole and mefentrifluconazole. Mefentrifluconazole resistance in F. pseudograminearum can be conferred by FpCYP51BL144F, which was identified in four mutants according to molecular docking and site-directed transformation experiments. Overexpression of FpCYP51s was also detected in the resistant mutants. In conclusion, mefentrifluconazole has a low-to-medium resistance risk in F. pseudograminearum, and the L144F mutation in FpCYP51B and the increased expression level of FpCYP51s may be responsible for mefentrifluconazole resistance in F. pseudograminearum.

Resistance risk assessment of mefentrifluconazole in Corynespora cassiicola and the control of cucumber target spot by a two-way mixture of mefentrifluconazole and prochloraz.

The cucumber target spot, caused by Corynespora cassiicola, is a major cucumber disease in China. Mefentrifluconazole, a new triazole fungicide, exhibits remarkable efficacy in controlling cucumber target spot. However, the resistance risk and mechanism remain unclear. In this study, the inhibitory activity of mefentrifluconazole against 101 C. cassiicola isolates was determined, and the results indicated that the EC50 values ranged between 0.15 and 12.85 µg/mL, with a mean of 4.76 µg/mL. Fourteen mefentrifluconazole-resistant mutants of C. cassiicola were generated from six parental isolates in the laboratory through fungicide adaptation or UV irradiation. The resistance was relatively stable after ten consecutive transfers on a fungicide-free medium. No cross-resistance was observed between mefentrifluconazole and pyraclostrobin, fluopyram, prochloraz, mancozeb, or difenoconazole. Investigations into the biological characteristics of the resistant mutants revealed that six resistant mutants exhibited an enhanced compound fitness index (CFI) compared to the parental isolates, while others displayed a reduced or comparable CFI. The overexpression of CcCYP51A and CcCYP51B was detected in the resistant mutants, regardless of the presence or absence of mefentrifluconazole. Additionally, a two-way mixture of mefentrifluconazole and prochloraz at a concentration of 7:3 demonstrated superior control efficacy against the cucumber target spot, achieving a protection rate of 80%. In conclusion, this study suggests that the risk of C. cassiicola developing resistance to mefentrifluconazole is medium, and the overexpression of CcCYP51A and CcCYP51B might be associated with mefentrifluconazole resistance in C. cassiicola. The mefentrifluconazole and prochloraz two-way mixture presented promising control efficacy against the cucumber target spot.

Anchoring Charge Selective Self-Assembled Monolayers for Tin-Lead Perovskite Solar Cells.

Self-assembled monolayers (SAMs) have displayed great potential for improving efficiency and stability in p-i-n perovskite solar cells (PSCs). The anchoring of SAMs at the conductiv metal oxide substrates and their interaction with perovskite materials must be rationally tailored to ensure efficient charge carrier extraction and improved quality of the perovskite films. Herein, SAMs molecules with different anchoring groups and spacers to control the interaction with perovskite in the p-i-n mixed Sn-Pb PSCs are selected. It is found that the monolayer with the carboxylate group exhibits appropriate interaction and has a more favorable orientation and arrangement than that of the phosphate group. This results in reduced nonradiative recombination and enhanced crystallinity. In addition, the short chain length leads to an improved energy level alignment of SAMs with perovskite, improving hole extraction. As a result, the narrow bandgap (≈1.25 eV) Sn-Pb PSCs show efficiencies of up to 23.1% with an open-circuit voltage of up to 0.89 V. Unencapsulated devices retain 93% of their initial efficiency after storage in N2 atmosphere for over 2500 h. Overall, this work highlights the underexplored potential of SAMs for perovskite photovoltaics and provides essential findings on the influence of their structural modification.

Biotoxicity of Halide Perovskites in Mice.

Halide perovskites are crystalline semiconductors with exceptional optoelectronic properties, rapidly developing toward large-scale applications. Lead (II) (Pb2+ ) is the core element used to prepare halide perovskites. Pb2+ can displace key 2+ elements, including calcium, zinc and iron, that regulate vital physiological functions. Sn2+ can replace Pb2+ within the perovskite structure and, if accidentally dispersed in the environment, it readily oxidizes to Sn4+ , which is compatible with physiological functions and thus potentially safe. The 3+ salt bismuth (III) (Bi3+ ) is also potentially safe for the same reason and useful to prepare double perovskites. Here, this work studies the biotoxicity of Pb, Sn, and Bi perovskites in mice for the first time. This work analyses histopathology and growth of mice directly exposed to perovskites and investigate the development of their offspring generation. This study provides the screening of organs and key physiological functions targeted by perovskite exposure to design specific studies in mammalians.

High-Stable Lead-Free Solar Cells Achieved by Surface Reconstruction of Quasi-2D Tin-Based Perovskites.

Tin halide perovskites are an appealing alternative to lead perovskites. However, owing to the lower redox potential of Sn(II)/Sn(IV), particularly under the presence of oxygen and water, the accumulation of Sn(IV) at the surface layer will negatively impact the device's performance and stability. To this end, this work has introduced a novel multifunctional molecule, 1,4-phenyldimethylammonium dibromide diamine (phDMADBr), to form a protective layer on the surface of Sn-based perovskite films. Strong interactions between phDMADBr and the perovskite surface improve electron transfer, passivating uncoordinated Sn(II), and fortify against water and oxygen. In situ grazing incidence wide-angle X-ray scattering (GIWAXS) analysis confirms the enhanced thermal stability of the quasi-2D phase, and hence the overall enhanced stability of the perovskite. Long-term stability in devices is achieved, retaining over 90% of the original efficiency for more than 200 hours in a 10% RH moisture N2 environment. These findings propose a new approach to enhance the operational stability of Sn-based perovskite devices, offering a strategy in advancing lead-free optoelectronic applications.

Resistance to the DMI fungicide mefentrifluconazole in Monilinia fructicola: risk assessment and resistance basis analysis.

BACKGROUND: Brown rot disease, caused by Monilinia fructicola, poses a significant challenge to peach production in China. The efficacy of mefentrifluconazole, a new triazole fungicide, in controlling brown rot in peaches has been remarkable. However, the resistance risk and mechanism associated with this fungicide remain unclear. This study was designed to assess the resistance risk of M. fructicola to mefentrifluconazole and reveal the potential resistance mechanism. RESULTS: The mean median effective concentration (EC50 ) of 101 M. fructicola isolates to mefentrifluconazole was 0.003 µg mL-1 , and the sensitivity exhibited a unimodal distribution. Seven mefentrifluconazole-resistant mutants were generated from three parental isolates in the laboratory through fungicide adaption. The biological characteristics of the resistant mutants revealed that three of them exhibited enhanced survival fitness compared to the parental isolates, whereas the remaining four mutants displayed reduced survival fitness. Mefentrifluconazole showed strong positive cross-resistance with fenbuconazole, whereas no cross-resistance was observed with pyrimethanil, procymidone or pydiflumetofen. No overexpression of MfCYP51 gene was detected in the resistant mutants. Multiple sequence alignment revealed that three resistant mutants (MXSB2-2, Mf12-1 and Mf12-2) had a point mutation (G461S) in MfCYP51 protein. Molecular docking techniques confirmed the contribution of this point mutation to mefentrifluconazole resistance. CONCLUSION: The risk of M. fructicola developing resistance to mefentrifluconazole is relatively low-to-medium and point mutation G461S in MfCYP51 could confer mefentrifluconazole resistance in M. fructicola. This study provided essential data for monitoring the emergence of resistance and developing resistance management strategies for mefentrifluconazole. © 2023 Society of Chemical Industry.

Poly(3-hexylthiophene)/perovskite Heterointerface by Spinodal Decomposition Enabling Efficient and Stable Perovskite Solar Cells.

The best research-cell efficiency of perovskite solar cells (PSCs) is comparable with that of mature silicon solar cells (SSCs); However, the industrial development of PSCs lags far behind SSCs. PSC is a multiphase and multicomponent system, whose consequent interfacial energy loss and carrier loss seriously affect the performance and stability of devices. Here, by using spinodal decomposition, a spontaneous solid phase segregation process, in situ introduces a poly(3-hexylthiophene)/perovskite (P3HT/PVK) heterointerface with interpenetrating structure in PSCs. The P3HT/PVK heterointerface tunes the energy alignment, thereby reducing the energy loss at the interface; The P3HT/PVK interpenetrating structure bridges a transport channel, thus decreasing the carrier loss at the interface. The simultaneous mitigation of energy and carrier losses by P3HT/PVK heterointerface enables n-i-p geometry device a power conversion efficiency of 24.53% (certified 23.94%) and excellent stability. These findings demonstrate an ingenious strategy to optimize the performance of PSCs by heterointerface via Spinodal decomposition.

Three point mutations in AaCYP51 combined with induced overexpression of AaCYP51 conferred low-level resistance to mefentrifluconazole in Alternaria alternata.

Tomato early blight is a significant disease that causes substantial losses to tomato yield and quality. Mefentrifluconazole, an isopropanol-azole subgroup of triazole fungicides, has been registered in China for controlling various plant diseases, including tomato early blight, grape anthracnose, and apple brown spot. However, limited information is available on the mefentrifluconazole resistance risk and mechanism in plant pathogens. The sensitivity to mefentrifluconazole of 122 isolates of Alternaria alternata, one of the causal agents of tomato early blight, collected from different provinces in China, was evaluated. The results showed a unimodal curve for the sensitivity frequency, with an average EC50 of 0.306 µg/mL. Through fungicide adaption, six resistant mutants (N4, N5, T4, T5, NG1, and NG10) were obtained from three parental isolates, with a mutation frequency of 3.28 × 10-4 and resistance factors ranging between 19 and 147. The survival fitness of the resistant mutants, except for NG1, was significantly lower than that of their parental isolates. Positive cross-resistance was observed between mefentrifluconazole and difenoconazole or fenbuconazole, whereas no cross-resistance was found with three non-DMI fungicides. Furthermore, three distinct point mutations were detected in the AaCYP51 protein of the resistant mutants: I300S in T4 and T5; A303T in N4, NG1, and NG10; and A303V in N5. Compared to the parental isolates, the AaCYP51 gene was overexpressed in all six resistant mutants when treated with mefentrifluconazole. In summary, the resistance risk of A. alternata to mefentrifluconazole was low, and point mutations and overexpression of the AaCYP51 gene were identified as contributing factors to mefentrifluconazole resistance in A. alternata.

One-Step Solution Deposition of Tin-Perovskite onto a Self-Assembled Monolayer with a DMSO-Free Solvent System.

We show for the first time DMSO-free tin-based perovskite solar cells with a self-assembled hole selective contact (MeO-2PACz). Our method provides reproducible and hysteresis-free devices with MeO-2PACz, having the best device PCE of 5.8 % with a VOC of 638 mV.

Stabilization of Inorganic Perovskite Solar Cells with a 2D Dion-Jacobson Passivating Layer.

Inorganic metal halide perovskites such as CsPbI3 are promising for high-performance, reproducible, and robust solar cells. However, inorganic perovskites are sensitive to humidity, which causes the transformation from the black phase to the yellow δ, non-perovskite phase. Such phase instability has been a significant challenge to long-term operational stability. Here, a surface dimensionality reduction strategy is reported, using 2-(4-aminophenyl)ethylamine cation to construct a Dion-Jacobson 2D phase that covers the surface of the 3D inorganic perovskite structure. The Dion-Jacobson layer mainly grows at the grain boundaries of the perovskite, effectively passivating surface defects and providing favourable interfacial charge transfer. The resulting inorganic perovskite films exhibit excellent humidity resistance when submerged in an aqueous solution (isopropanol:water = 4:1 v/v) and exposed to a 50% humidity air atmosphere. The Dion-Jacobson 2D/3D inorganic perovskite solar cell (PSC) achieves a power conversion efficiency (PCE) of 19.5% with a Voc of 1.197 eV. It retains 83% of its initial PCE after 1260 h of maximum power point tracking under 1.2 sun illumination. The work demonstrates an effective way for stabilizing efficient inorganic perovskite solar cells.

Managing Excess Lead Iodide with Functionalized Oxo-Graphene Nanosheets for Stable Perovskite Solar Cells.

Stability issues could prevent lead halide perovskite solar cells (PSCs) from commercialization despite it having a comparable power conversion efficiency (PCE) to silicon solar cells. Overcoming drawbacks affecting their long-term stability is gaining incremental importance. Excess lead iodide (PbI2 ) causes perovskite degradation, although it aids in crystal growth and defect passivation. Herein, we synthesized functionalized oxo-graphene nanosheets (Dec-oxoG NSs) to effectively manage the excess PbI2 . Dec-oxoG NSs provide anchoring sites to bind the excess PbI2 and passivate perovskite grain boundaries, thereby reducing charge recombination loss and significantly boosting the extraction of free electrons. The inclusion of Dec-oxoG NSs leads to a PCE of 23.7 % in inverted (p-i-n) PSCs. The devices retain 93.8 % of their initial efficiency after 1,000 hours of tracking at maximum power points under continuous one-sun illumination and exhibit high stability under thermal and ambient conditions.