Photocatalytic Water Splitting Promoted by 2D and 3D Porphyrin Covalent Organic Polymers Synthesized by Suzuki-Miyaura Carbon-Carbon Coupling

[EN] This work deals with the synthesis of metal-free and porphyrin-based covalent organic polymers (COPs) by the Suzuki-Miyaura coupling carbon-carbon bond forming reaction to study the photocatalytic overall water splitting performance. Apart from using 5,10,15,20-Tetrakis-(4-bromophenyl)porphyrin, we have chosen different cross-linker monomers to induce 2-dimensional (2D) or 3-dimensional (3D) and different rigidity in their resulting polymeric molecular structure. The synthesised COPs were extensively characterised to reveal that the dimensionality and flexibility of the molecular structure play an intense role in the physical, photochemical, and electronic properties of the polymers. Photoinduced excited state of the COPs was evaluated by nanosecond time-resolved laser transient absorption spectroscopy (TAS) by analysing excited state kinetics and quenching experiments, photocurrent density measurements and photocatalytic deposition of Ru3+ to RuO2, and photocatalysis. In summary, TAS experiments demonstrated that the transient excited state of these polymers has two decay kinetics and exhibit strong interaction with water molecules. Moreover, photocurrent and photocatalytic deposition experiments proved that charges are photoinduced and are found across the COP molecular network, but more important charges can migrate from the surface of the COP to the medium. Among the various COPs tested, COP-3 that has a flexible and 3D molecular structure reached the best photocatalytic performances, achieving a photocatalytic yield of 0.4 mmol H-2 x g(COP-3)(-1) after 3 h irradiation.Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa with grant code RTI2018-098237-CO21), Generalitat Valenciana (Prometeo 2017/083) and European Union [APOSTD2018/216] are gratefully acknowledged.Nóvoa-Cid, M.; Melillo, A.; Ferrer Ribera, RB.; Alvaro Rodríguez, MM.; Garcia-Baldovi, H. (2022). Photocatalytic Water Splitting Promoted by 2D and 3D Porphyrin Covalent Organic Polymers Synthesized by Suzuki-Miyaura Carbon-Carbon Coupling. Nanomaterials. 12(18):1-19. https://doi.org/10.3390/nano12183197119121

Occurrence of tetracyclines and sulfonamides in manures, agricultural soils and crops from different areas in Galicia (NW Spain)

Antibiotics released to the environment are causing public health and sustainability concerns. Taking that into account, we studied the presence of tetracyclines (Tetracycline, Oxytetracycline, Chlortetracycline and Doxycycline) and sulfonamides (Sulfadiazine, Sulfamethazine, Sulfachlorpyridazine and Sulfamethoxypyridazine) in manures, soils and crops from Galicia (Spain), where a high number of cattle, pig and poultry farms exist. We used the HPLC-MS/MS technique to analyze 40 samples of cattle, pig and poultry manure, as well as 65 soil samples, and 27 vegetation samples. The presence of antibiotics was detected in 42% of the manures, 17% of the soils and 44% of crop samples, with maximum concentrations of 106.0 mg kg−1 for individual antibiotics in manures and 0.6 mg kg−1 in soils and plants. The simultaneous presence of several antibiotics was infrequent in soils (only three soils presented two or three antibiotics), and more common in manures and plants, some of them with up to five antibiotics. Pig slurries showed the highest antibiotic concentrations, as well as the highest number of different antibiotics. Crops fertilized with these slurries also showed the highest number of different antibiotics. Antibiotics were detected in 71% of grass and corn samples, and in 33% of wheat grain samples, while they were not detected in potato samples. These results can be very relevant taking into account potential environmental and public health repercussions of antibiotics in soil and water, as well as antibiotics uptake and accumulation in plants, and subsequent incorporation to the food chain.Ministerio de Economía y Competitividad | Ref. CGL2015-67333-C2-1-RMinisterio de Economía y Competitividad | Ref. CGL2015-67333-C2-2-

Occurrence of tetracyclines and sulfonamides in manures, agricultural soils and crops from different areas in Galicia (NW Spain)

Antibiotics released to the environment are causing public health and sustainability concerns. Taking that into account, we studied the presence of tetracyclines (Tetracycline, Oxytetracycline, Chlortetracycline and Doxycycline) and sulfonamides (Sulfadiazine, Sulfamethazine, Sulfachlorpyridazine and Sulfamethoxypyridazine) in manures, soils and crops from Galicia (Spain), where a high number of cattle, pig and poultry farms exist. We used the HPLC-MS/MS technique to analyze 40 samples of cattle, pig and poultry manure, as well as 65 soil samples, and 27 vegetation samples. The presence of antibiotics was detected in 42% of the manures, 17% of the soils and 44% of crop samples, with maximum concentrations of 106.0 mg kg−1 for individual antibiotics in manures and 0.6 mg kg−1 in soils and plants. The simultaneous presence of several antibiotics was infrequent in soils (only three soils presented two or three antibiotics), and more common in manures and plants, some of them with up to five antibiotics. Pig slurries showed the highest antibiotic concentrations, as well as the highest number of different antibiotics. Crops fertilized with these slurries also showed the highest number of different antibiotics. Antibiotics were detected in 71% of grass and corn samples, and in 33% of wheat grain samples, while they were not detected in potato samples. These results can be very relevant taking into account potential environmental and public health repercussions of antibiotics in soil and water, as well as antibiotics uptake and accumulation in plants, and subsequent incorporation to the food chain.This work was supported by the Spanish Ministry of Economy and Competitiveness [grant numbers CGL2015-67333-C2-1-R and CGL2015-67333-C2-2-R]. M. Conde-Cid holds a pre-doctoral contract (FPU15/0280, Spanish Government). The sponsor had not involvement in study design; in the collection, analysis and interpretation of data; in the writing of the report, and in the decision to submit the article for publication.S

Experimental data and model prediction of tetracycline adsorption and desorption in agricultural soils

In this work, tetracycline (TC) adsorption and desorption were studied, and the soil properties that most influenced the process were identified. Batch experiments were carried out on 63 crop soil samples, which showed a wide range of values in their physicochemical characteristics. Adsorption curves fit well to the Freundlich equation, with KF values varying between 901 and 9202 Ln μmol1−n kg−1. Kd values ranged between 53 and 6899 L kg−1 for an initial concentration (Co) of 400 μM, whereas the adsorption capacity (qa) ranged from 8541 to 14,852 μmol kg−1. TC retention on soils was high, with adsorption values always higher than 58%, and desorption values lower than 9%. Bivariate correlations and multiple linear regressions were performed to identify those soil variables having a greater influence on TC adsorption and desorption. The results indicate that organic carbon, clay, exchangeable aluminum, available phosphorus, effective cation exchange capacity content, and pH are the main characteristics affecting TC adsorption and desorption. The models, developed by means of multiple linear regression, gave satisfactory and robust predictions for TC adsorption and desorption, using easily determinable soil characteristics as input.Ministerio de Economía y Competitividad | Ref. CGL2015-67333-C2-1-RMinisterio de Economía y Competitividad | Ref. CGL2015-67333-C2-2-