U-shaped stereoscopic design strategy toward N-doped nanographene segment.

There have been scarce reports about stereoscopic design of N-heteroacenes (NHAs), especially for the electron-deficient π-building blocks. Herein, we report the design and synthesis of a U-shaped bis(pyrene-quinoxaline) (BPQ). Single crystal X-ray diffraction reveals the herringbone stacking pattern and the presence of regular and incompletely closed pores.

Response mechanism of a highly efficient partial nitritation-anammox (PN/A) process under antibiotic stress: Extracellular polymers, microbial community, and functional genes.

The Partial nitritation-Anammox (PN/A) process can be restricted when treating high ammonia nitrogen wastewater containing antibiotics. This study aims to explore the response mechanism of the PN/A process under antibiotic stress. Results showed the PN/A process achieved a nitrogen removal rate higher than 1.01 ± 0.03 kg N/m3/d under long-term sulfamethazine stress. The increase of extracellular polymers from 22.52 to 43.96 mg/g VSS was conducive to resisting antibiotic inhibitory. The increase of Denitratisoma and SM1A02 abundance as well as functional genes nirS and nirK indicated denitrifiers should play an important role in the stability of the PN/A system under sulfamethazine stress. In addition, antibiotic-resistant genes (ARGs) sul1 and intI1 significantly increased by 8.78 and 5.12 times of the initial values to maintain the resistance of PN/A process to sulfamethazine stress. This study uncovers the response mechanism of the PN/A process under antibiotic stress, offering a scientific basis and guidance for further application in the future.

Highly Sensitive Pressure Sensor Based on Elastic Conductive Microspheres.

Elastic pressure sensors play a crucial role in the digital economy, such as in health care systems and human-machine interfacing. However, the low sensitivity of these sensors restricts their further development and wider application prospects. This issue can be resolved by introducing microstructures in flexible pressure-sensitive materials as a common method to improve their sensitivity. However, complex processes limit such strategies. Herein, a cost-effective and simple process was developed for manufacturing surface microstructures of flexible pressure-sensitive films. The strategy involved the combination of MXene-single-walled carbon nanotubes (SWCNT) with mass-produced Polydimethylsiloxane (PDMS) microspheres to form advanced microstructures. Next, the conductive silica gel films with pitted microstructures were obtained through a 3D-printed mold as flexible electrodes, and assembled into flexible resistive pressure sensors. The sensor exhibited a sensitivity reaching 2.6 kPa-1 with a short response time of 56 ms and a detection limit of 5.1 Pa. The sensor also displayed good cyclic stability and time stability, offering promising features for human health monitoring applications.

Microbial degradation mechanism and pathway of the insecticide thiamethoxam by isolated Bacillus Cereus from activated sludge.

The high water solubility and ecotoxicity of thiamethoxam (TMX) is a potential hazard to ecosystems and human health. Here, a strain of Bacillus cereus with high TMX degradation activity was isolated from the sediment of the A2O process in the wastewater treatment plant and was able to utilize TMX as its sole carbon source. Under different environmental conditions, the degradation efficiency of TMX by Bacillus cereus-S1 (strain S1) ranged from 41.0% to 68.9% after 216 h. The optimum degradation conditions were DO = 3.5 mg/L and pH 9.0. The addition of an appropriate carbon-to-nitrogen ratio could accelerate the degradation of TMX. A plausible biodegradation pathway has been proposed based on the identified metabolites and their corresponding degradation pathways. TMX can be directly converted into Clothianidin (CLO), TMX-dm-hydroxyl and TMX-Urea by a series of reactions such as demethylation, oxadiazine ring cleavage and C=N substitution by hydroxy group. The main products were TMX-dm-hydroxyl and TMX-Urea, the amount of CLO production is relatively small. This study aims to provide a new approach for efficient degradation of TMX; furthermore, strain S1 is a promising biological source for in situ remediation of TMX contamination.

Thiamethoxam adsorption by ZnCl2 modified cow manure biochar: Mechanism and quantitative prediction.

The overuse of thiamethoxam (THM) has threatened the survival of living organisms and it is necessary to find an environmentally friendly material to remove THM frequently detected in water. Biochar prepared from cow manure modified with ZnCl2 (Zn-CBC) was used to remove THM. Compared to the unmodified cow manure biochar (CBC), the removal ratio of THM by Zn-CBC was enhanced 35 times. In the mechanistic analysis, SEM and BET showed that Zn-CBC had a good pore structure and its specific surface area (166.502 m2 g-1) increased to 17 times that of CBC, indicating that Zn-CBC had good pore adsorption properties. The adsorption kinetic and isotherm implied that the main mechanism was chemisorption including π-π interaction and H-bonding. Furthermore, the stable graphitized structure of Zn-CBC allowed for efficient adsorption and reusability. In addition, this study constructed an intelligent prediction model using batch experiment data, and the high R2 (0.978) and low RMSE (0.057) implied that the model could accurately and quantitatively predict the adsorption efficiency. This paper provides a novel perspective to simultaneously remove the neonicotinoid insecticides and realize the resource utilization of cow manure.

Free nitrous acid prediction in ANAMMOX process using hybrid deep neural network model.

Free nitrous acid (FNA) is a critical metric for stabilization of ANAMMOX but can not be directly and immediately measured by sensors or chemical measurement method, which hinders the effective management and operation for ANAMMOX. This study focuses on FNA prediction using hybrid model based on temporal convolutional network (TCN) combined with attention mechanism (AM) optimized by multiobjective tree-structured parzen estimator (MOTPE), called MOTPE-TCNA. A case study in an ANAMMOX reactor is carried out. Results show that nitrogen removal rate (NRR) is highly correlated with FNA concentration, indicating that it can forecast the operational status by predicting FNA. Then, MOTPE successfully optimizes the hyperparameters of TCN, helping TCN achieve a high prediction accuracy, and AM furtherly improves model accuracy. MOTPE-TCNA obtains the highest prediction accuracy, whose R2 value gets 0.992, increasing 1.71-11.80% compared to other models. As a deep neural network model, MOTPE-TCNA has more advantages than traditional machine learning methods in FNA prediction, which is beneficial to maintain the stable operation and easy control for ANAMMOX process.

Targeting immunosuppressive Ly6C+ classical monocytes reverses anti-PD-1/CTLA-4 immunotherapy resistance.

Introduction: Despite significant clinical advancement with the use of immune checkpoint blockade (ICB) in non-small cell lung cancer (NSCLC) there are still a major subset of patients that develop adaptive/acquired resistance. Understanding resistance mechanisms to ICB is critical to developing new therapeutic strategies and improving patient survival. The dynamic nature of the tumor microenvironment and the mutational load driving tumor immunogenicity limit the efficacy to ICB. Recent studies indicate that myeloid cells are drivers of ICB resistance. In this study we sought to understand which immune cells were contributing to resistance and if we could modify them in a way to improve response to ICB therapy. Results: Our results show that combination anti-PD-1/CTLA-4 produces an initial antitumor effect with evidence of an activated immune response. Upon extended treatment with anti-PD-1/CTLA-4 acquired resistance developed with an increase of the immunosuppressive populations, including T-regulatory cells, neutrophils and monocytes. Addition of anti-Ly6C blocking antibody to anti-PD-1/CTLA-4 was capable of completely reversing treatment resistance and restoring CD8 T cell activity in multiple KP lung cancer models and in the autochthonous lung cancer KrasLSL-G12D/p53fl/fl model. We found that there were higher classical Ly6C+ monocytes in anti-PD-1/CTLA-4 combination resistant tumors. B7 blockade illustrated the importance of dendritic cells for treatment efficacy of anti-Ly6C/PD-1/CTLA-4. We further determined that classical Ly6C+ monocytes in anti-PD-1/CTLA-4 resistant tumors are trafficked into the tumor via IFN-γ and the CCL2-CCR2 axis. Mechanistically we found that classical monocytes from ICB resistant tumors were unable to differentiate into antigen presenting cells and instead differentiated into immunosuppressive M2 macrophages or myeloid-derived suppressor cells (MDSC). Classical Ly6C+ monocytes from ICB resistant tumors had a decrease in both Flt3 and PU.1 expression that prevented differentiation into dendritic cells/macrophages. Conclusions: Therapeutically we found that addition of anti-Ly6C to the combination of anti-PD-1/CTLA-4 was capable of complete tumor eradication. Classical Ly6C+ monocytes differentiate into immunosuppressive cells, while blockade of classical monocytes drives dendritic cell differentiation/maturation to reinvigorate the anti-tumor T cell response. These findings support that immunotherapy resistance is associated with infiltrating monocytes and that controlling the differentiation process of monocytes can enhance the therapeutic potential of ICB.

Design and 3D Printing of Stretchable Conductor with High Dynamic Stability.

As an indispensable part of wearable devices and mechanical arms, stretchable conductors have received extensive attention in recent years. The design of a high-dynamic-stability, stretchable conductor is the key technology to ensure the normal transmission of electrical signals and electrical energy of wearable devices under large mechanical deformation, which has always been an important research topic domestically and abroad. In this paper, a stretchable conductor with a linear bunch structure is designed and prepared by combining numerical modeling and simulation with 3D printing technology. The stretchable conductor consists of a 3D-printed bunch-structured equiwall elastic insulating resin tube and internally filled free-deformable liquid metal. This conductor has a very high conductivity exceeding 104 S cm-1, good stretchability with an elongation at break exceeding 50%, and great tensile stability, with a relative change in resistance of only about 1% at 50% tensile strain. Finally, this paper demonstrates it as a headphone cable (transmitting electrical signals) and a mobile phone charging wire (transmitting electrical energy), which proves its good mechanical and electrical properties and shows good application potential.

Enhanced biodegradation of thiamethoxam with a novel polyvinyl alcohol (PVA)/sodium alginate (SA)/biochar immobilized Chryseobacterium sp H5.

Long-term and extensive usage of thiamethoxam, the second-generation neonicotinoid insecticide, has caused a serious threat to non-target organisms and ecological security. Efficient immobilized microorganism techniques are a sustainable solution for bioremediation of thiamethoxam contamination. A Gram-negative aerobic bacterium Chryseobacterium sp H5 with high thiamethoxam-degrading efficiencies was isolated from activated sludge. Then we developed a novel polyvinyl alcohol (PVA)/sodium alginate (SA)/biochar bead with this functional microbe immobilization to enhance the biodegradation and removal of thiamethoxam. Results indicated that the total removal and biodegradation rate of thiamethoxam with PVA/SA/biochar (0.7 %) beads with Chryseobacterium sp H5 immobilization at 30 °C and pH of 7.0 within 7 d reached about 90.47 % and 68.03 %, respectively, much higher than that using PVA/SA immobilized microbes (75.06 %, 56.05 %) and free microbes (61.72 %). Moreover, the PVA/SA/biochar (0.7 %) immobilized microbes showed increased tolerance to extreme conditions. Biodegradation metabolites of thiamethoxam were identified and two intermediates were first reported. Based on the identified biodegradation intermediates, cleavage of C-N between the 2-chlorothiazole ring and oxadiazine, dichlorination, nitrate reduction and condensation reaction would be the major biodegradation routes of thiamethoxam. Results of this work suggested the novel PVA/SA/biochar beads with Chryseobacterium sp H5 immobilization would be helpful for the effective bioremediation of thiamethoxam contamination.

Novel hydrophilic straw biochar for the adsorption of neonicotinoids: kinetics, thermodynamics, influencing factors, and reuse performance.

Nitenpyram (NIT) is the most water-soluble neonicotinoid (NEO). It has been shown to pose a serious threat to human health and the environment but was always ignored due to its limited market share. There were few experts who studied NIT's transport behavior on biochar. In this study, two types of biochar were co-activated separately using zinc chloride combined with phosphoric acid and potassium hydroxide combined with acetic acid, marked as ZBC and KBC. Characterizations suggested that hydrophilic ZBC and KBC had more surface functional groups than unmodified biochar (BC), and specific surface areas of ZBC (456.406 m2·g-1) and KBC (750.588 m2·g-1) were significantly higher than of BC (67.181 m2·g-1). The pore structures of KBC and ZBC were hierarchical porous structures with different pore sizes and typical microporous structure, respectively. The adsorption performance of either NIT or IMI on KBC was better than that on ZBC. Only 0.4 g·L-1 of KBC can absorb 89.62% of NIT in just 5 min. The equilibrium adsorption amounts of NIT on ZBC and KBC were 17.995 mg·g-1 and 82.910 mg·g-1. Elovich and Langmuir models were used to evaluate the whole adsorption process, which was attributed to the chemisorption mechanism. In addition, removal rates of NIT were negatively correlated to NIT's initial concentration and positively correlated to the dose of biochar. pH had almost no effect on adsorption, but the presence of salt ions can inhibit the removal of NIT. Long-term stabilities of biochars were also acceptable. These findings will promote the development in the preparation of biochar fields and provide a positive reference value for NEO removal.

Computational Analysis of the Related Factors of Deep Vein Thrombosis (DVT) Formation in Patients Undergoing Hip Fracture Surgery.

A retrospective study was conducted on 51 patients undergoing hip fracture surgery to investigate the factors associated with the formation of deep venous thrombosis (DVT). The independent sample t-test and correlation analysis were used to sort out and analyze the data. The findings are as follows. (1) Different gender samples showed significant differences in the Caprini score and thrombus location. Most DVTs in females are located in the posterior tibial vein and intermuscular veins. The Caprini score of females was significantly higher than that of males. (2) Age displays a positive correlation with DVT, coronary heart disease, hypertension, and different surgical types, respectively. (3) There is a correlation between age and operation duration. (4) Hyperlipidemia and cerebrovascular disease show a positive correlation with DVT. (5) There was a significant negative correlation between the Caprini score and the quantification of D-dimer. This indicates that in this sample, the higher the patients' Caprini score is, the lower the quantitation of D-dimer will be. (6) Hyperlipidemia and cardiac insufficiency show a positive correlation with cerebrovascular disease. Patients with hyperlipidemia and cardiac insufficiency may also suffer from cerebrovascular diseases.

Detection of Neonicotinoids in agriculture soil and degradation of thiacloprid through photo degradation, biodegradation and photo-biodegradation.

The social and ecological influence of Neonicotinoids (NEOs) usage in agriculture sector is progressively higher. There are seven NEOs insecticides widely used for the insects control. Among the NEOs, thiacloprid (THD) was extensively used for insect control during crop cultivation. This study targets to analyse the contamination levels of NEOs in agricultural soil and identify photo-biodegradation of THD degradation using pure isolates and mixed consortium. The photo degradation (PD), biodegradation (BD) and photo-biodegradation (PBD) of THD were compared. The corn field agricultural soils were polluted by four NEOs, among them THD had greater contamination level (surface soil: 3901.2 ± 0.04 µg/g) and (sub-surface soil: 3988.6 ± 0.05 µg/g). Three soil free enriched bacterial strains following Bacillus atrophaeus (PB-2), Priestia megaterium (PB-3) (formerly known as Bacillus megaterium), and Peribacillus simplex (PB-4) (formerly known as Bacillus simplex) were identified by microbiological and molecular 16s rRNA gene sequencing. The PD, BD and PBD of THD were conducted and degradation rate was detected by instrument UPLC-MS-MS. The PBD process with blue-LEDs showed better THD degradation efficiency than PD and BD, where the specific THD degradation rate was 85 ± 0.2%, 87 ± 0.5%, and 89 ± 0.3%, respectively for PB-2, PB-3 and PB-4. Then, the photo-biodegradation performance is greater at 150, 175, 200 rpm, pH 7.0-9.0, and temperature 30-35 °C. After the PBD system deliver four intermediate metabolites, the THD degradation process maybe through nitro reduction, hydroxylation and oxidative cleavage pathway.

Water quality prediction model using Gaussian process regression based on deep learning for carbon neutrality in papermaking wastewater treatment system.

Wastewater recycling is the measure with enormous potentiality to achieve carbon neutrality in wastewater treatment plants. High-precision online monitoring can improve the stability of wastewater treatment system and help wastewater recycling. A new water quality prediction CSWLSTM-GPR model, which fused the spatial feature of convolutional neural network (CNN), the temporal feature of sharing-weight long short-term memory (SWLSTM) and the probabilistic reliability of Gaussian process regression (GPR), was applied for monitoring papermaking wastewater treatment system with high-precision point prediction and interval prediction. Compared with SWLSTM-GPR and CLSTM-GPR, RMSE of CSWLSTM-GPR reduced by more than 48.9% on effluent chemical oxygen demand (CODeff), MAE reduced by more than 49.3%, R2 increased by more than 25.14%, R increased by more than 7.07%. And for the effluent suspended solids (SSeff), CSWLSTM-GPR had better predictive results than SWLSTM-GPR and CSWLSTM-GPR. Compared with SWLSTM-GPR, RMSE, MAE, R, R2 of CSWLSTM-GPR on effluent suspended solids (SSeff) were improved by 4.8%, 6.1%, 29.01% and 31.15%, respectively. Simulation results showed convincing comprehensive forecasting ability were obtained and the true values frequently stayed within the water quality range obtained by CSWLSTM-GPR model, which provided important insights for online monitoring, wastewater recycling and carbon neutrality of papermaking industry.

Reducing Open-Circuit Voltage Deficit in Perovskite Solar Cells via Surface Passivation with Phenylhydroxylammonium Halide Salts.

Suppressing non-radiative recombination via passivating surface defects of perovskite films has demonstrated an excellent strategy for high-performance perovskite solar cells (PSCs). However, it is still hard to realize both high open-circuit voltage (Voc ) of >1.2 V and high power conversion efficiency (PCE) of >22%, because the optimized bandgap of perovskite films is less than 1.60 eV for efficient light harvesting and Voc deficit is generally unavoidable due to carriers recombination. Here, the surface of the perovskite film is treated with a series of phenylhydroxylammonium halide salts and it is found that all of them can remarkably prolong the carrier lifetime owing to their excellent capability of surface defects passivation. The best PSC with phenylbutylammonium bromide treatment realizes a PCE of 22.67% with a Voc of 1.216 V, corresponding to a small Voc deficit of ≈344 mV.

Crucial roles of 3D-MoO2-PBC cocatalytic electrodes in the enhanced degradation of imidacloprid in heterogeneous electro-Fenton system: Degradation mechanisms and toxicity attenuation.

Imidacloprid (IMI), as the most-consumed pesticide, has posed a severe threat to the water ecosystem due to its recalcitrance and inefficient elimination in the traditional wastewater treatment. Herein, a heterogeneous electro-Fenton (EF) system coupled with 3D-MoO2-porous biochar (PBC) cocatalytic electrodes, abbreviated as 3D-MPE-EF, is initially applied to promote the elimination of IMI in the agrochemical wastewater from pesticide production. The elimination rate of IMI by 3D-MPE-EF system is 18.15 times higher than that by traditional EF system at pH 7.0. The utilization of 3D-MoO2-PBC electrodes sufficiently compensates for inherent deficiencies of traditional EF system. The circular utilization of Fe is also addressed by 3D-MoO2-PBC cocatalytic electrodes to reduce the consumption of Fe2+ and the deposition of iron mud. Through comparison, MoO2 is considered the most appropriate cocatalyst in terms of the reutilization of Fe and degradation of IMI. Eight mechanisms are identified in the degradation pathways of IMI by UPLC-Q-TOF-MS. The ecotoxicities of IMI are remarkably attenuated in the 3D-MPE-EF system. This study provides insights into the roles of 3D-MoO2-PBC cocatalytic electrodes in the enhanced elimination of IMI in heterogeneous EF system.

Photo-biodegradation of imidacloprid under blue light-emitting diodes with bacteria and co-metabolic regulation.

Imidacloprid (IMI) is existence in the soil environment with a half-life habitually more than hundred days. This study targets to determine, identify and characterize photo-biodegradation bacteria from neonicotinoids (NEOs) contaminated agricultural field soils. The sub-surface soil had a higher level contamination of NEOs, in specifically greater concentration of IMI (3445.2 ± 0.09 µg/g) and thiacloprid (4084.4 ± 0.09 µg/g) has been found. Three bacteria Ralstonia pickettii (PBMS-2), Bacillus cereus (PBMS-3) and Shinella zoogloeoides (PBMS-4) was identified from soil-free stable enrichment cultures. The biodegradability of IMI (50 mg L-1) by three bacteria under different colors of light-emitting diodes (LEDs) with a constant 12 V power supply was tested and found that the blue-LEDs had greatest efficiency in supporting biodegradation of IMI which is called photo-biodegradation. In specific, the rate of photo-biodegradation of IMI by Ralstonia pickettii (87%), Bacillus cereus (80%) and Shinella zoogloeoides (80%) was measured. Besides this study also tested the effect of aeration (rpm), pH, and temperature on photo-biodegradation of IMI. There were seven intermediate metabolites were measured as biodegradation products of IMI under photo-biodegradation conditions and they are; IMI-urea, IMI-desnitro, 6-chloronicotinic acid, 6-hydroxy nicotinic acid, IMI- aminoguanidine, IMI-nitrosoguanidine and 4,5-hydroxy IMI, these metabolites are may non-toxic to the environment.

Contamination of drinking water by neonicotinoid insecticides in China: Human exposure potential through drinking water consumption and percutaneous penetration.

Neonicotinoids (NEOs) are the most widely used pesticides and have posed a serious threat to human health. However, data on human exposure to NEOs are extremely scarce. To bridge this gap, human exposure potential of NEOs through drinking water consumption and percutaneous penetration was evaluated with the influences of 17 age groups, 4 seasons, 6 regions, and 2 genders. The results showed that drinking water in the present study had an upper middle level of NEO contamination. Anthropogenic activity and weather condition played important roles in the regional distribution of NEOs in tap water. For both children and adults, NEOs intake from drinking water exposure (NDE) and percutaneous exposure (NPE) in the south regions of China are significantly higher than those in the north regions, while the order of NDE and NPE by season is summer > spring = autumn > winter. Furthermore, human age and gender also have remarkable impacts on NDE and NPE. The age groups of children subjected to the highest NDE and NPE were 9 months - 2 years old and 9-12 years old, respectively. This study provides insights into the role of seasonal and regional influence, age and gender in the risk of drinking water and percutaneous exposure to NEOs.

Contamination of neonicotinoid insecticides in soil-water-sediment systems of the urban and rural areas in a rapidly developing region: Guangzhou, South China.

Residues and distribution of neonicotinoid insecticides (NEOs) in soil-water-sediment systems of the urban and rural areas of Guangzhou, South China were investigated. A total of 104 soil samples from 7 different functional zones and 29 water/sediment samples from creeks were collected. The results showed that at least one neonicotinoid insecticide was detected in all samples. The summed levels of five target neonicotinoids (∑5neonics) were in the range of 0.003-229 ng/g dw for soil samples, 7.94-636 ng/L for water samples, and 0.017-31.3 ng/g dw for sediment samples, with a geometric mean of 0.59 ng/g dw, 153 ng/L and 1.11 ng/g dw, respectively. Soils from agricultural areas contained the highest residual NEOs, followed by commercial, traffic, residential, industrial, educational zones and parks. Among the seven different functional zones studied, imidacloprid was the most dominant NEO in the agricultural areas and commercial zones, whereas acetamiprid was dominant in the other five functional zones with different land-use types. Thiamethoxam and acetamiprid were the main NEOs in water and sediment samples collected from 29 creeks. The pollution of NEOs in soils, water and sediments from rural areas was higher than that in the counterparts from urban areas. Residual concentration of NEOs detected in soils, water and sediments showed significant correlations with each other. The distribution of NEOs in soil-water-sediment systems indicated that NEOs tended to concentrate in water, followed by sediments and soils, especially in urban areas. An evaluation of the exposure to the current level of the ∑5NEOs in Guangzhou suggests a significant risk for aquatic and soil organisms, particularly under chronic exposures. The results of the present study offer valuable data to better understand the contamination and ecological risks of neonicotinoid insecticides in the rapidly developing urbanized region of South China.

An Efficient Trap Passivator for Perovskite Solar Cells: Poly(propylene glycol) bis(2-aminopropyl ether).

Perovskite solar cells (PSCs) are regarded as promising candidates for future renewable energy production. High-density defects in the perovskite films, however, lead to unsatisfactory device performances. Here, poly(propylene glycol) bis(2-aminopropyl ether) (PEA) additive is utilized to passivate the trap states in perovskite. The PEA molecules chemically interact with lead ions in perovskite, considerably passivate surface and bulk defects, which is in favor of charge transfer and extraction. Furthermore, the PEA additive can efficiently block moisture and oxygen to prolong the device lifetime. As a result, PEA-treated MAPbI3 (MA: CH3NH3) solar cells show increased power conversion efficiency (PCE) (from 17.18 to 18.87%) and good long-term stability. When PEA is introduced to (FAPbI3)1-x(MAPbBr3)x (FA: HC(NH2)2) solar cells, the PCE is enhanced from 19.66 to 21.60%. For both perovskites, their severe device hysteresis is efficiently relieved by PEA.

A supramolecular chain of dimeric Dy single molecule magnets decorated with azobenzene ligands.

We report the synthesis, ab initio calculations, magnetic and optical characterization of a DyIII-based dimeric compound named DyAZO. The dimers self-organize into a supramolecular chain decorated with photo-isomerizable azobenzene ligands. DyAZO displays single-molecule magnet (SMM) behavior. However, ab initio calculations highlight a quite strong admixture of MJ states of the 6H15/2 level of DyIII ions, the presence of low-lying excited MJ states and antiferromagnetic Dy-Dy dipolar coupling. This favors zero-field fast tunneling. Accordingly the Dy-doped analogue YDyAZO (5.5% Dy doping) displays enhanced magnetic relaxation with a hysteresis that is observed at 0.5 K. The influence of the cis- to trans-isomerization of the decorating azobenzene ligand on magnetic properties has been tested for both solid samples and solutions of DyAZO and YDyAZO. This provides hints for the synthesis of future Dy-based photo-isomerizable molecules.