Synthesis of novel heterogeneous photocatalysts based on Rose Bengal for effective wastewater disisnfection and decontamination

[EN] Anionic photosensitizers such as rose Bengal (RB) exhibit low efficiency in the photoinactivation of Gram-negative bacteria. Different strategies have been developed to improve their efficiency being the most effec-tive the addition of the photosensitizer to organic cationic materials. In this context, we have designed the synthesis of a novel heterogeneous photocatalyst based on silica in which the oxidizing properties of singlet oxygen photogenerated by RB have been combined with the chemoattraction of the bacteria to the cationic chains and their biocidal action. Thus, RB and cationic chains have been covalently linked to glass wool to obtain a photocatalyst that showed a highly efficient photodynamic activity against the Gram-positive (Enterococcus faecalis) and Gram-negative (Escherichia coli) bacteria. In addition, the new heterogeneous photocatalyst also resulted to be efficient in the decontamination of drugs such as diclofenac under visible light irradiation.We gratefully acknowledge the Universidad Complutense de Madrid, Ministerio de Universidades and recovery plan Next GenerationEU for financial support for postdoctoral contract 'Margarita Salas' for the requalification of the Spanish University System (2021-2023) , and the Spanish Ministry of Science and Innovation (PID2019-110441RB-C33 financed by MCIN/AEI/10.13039/501100011033) .Blázquez-Moraleja, A.; Moya Sanz, MDP.; Marín García, ML.; Bosca Mayans, F. (2023). Synthesis of novel heterogeneous photocatalysts based on Rose Bengal for effective wastewater disisnfection and decontamination. Catalysis Today. 413. https://doi.org/10.1016/j.cattod.2022.11.00941

Synthesis and biological evaluation of new analogues of the active fungal metabolites N-(2-methyl-3-oxodecanoyl)-2-pyrroline and N-(2-methyl-3-oxodec-enoyl)-2-pyrroline

[EN] To evaluate the effect of simplifying the ß-ketoamide system present in active isolated metabolites from Penicillium brevicompactum (2 and 3) on the activity, new analogues with a monocarbonylic amide functionality have been obtained. In this way, the insecticidal and fungicidal activities have been improved in relation to the natural products taken as lead molecules. Thus, two of the synthetic analogues (5a and 5b) showed very important insecticidal activities against third-instar nymphs of Oncopeltus fasciatus Dallas, with acute LD50 values of 3.0 and 1.5 ¿g/cm2, respectively. Moreover, some analogues showed good levels of fungicidal activity against a wide range of commercially important and taxonomically diverse fungi; remarkably, compound 7c has proved to be highly active against Colletotrichum gloesporoides and Colletotrichum coccodes, with ED50 values of 2.04 and 11.7 ¿g/mL, respectively.Moya Sanz, MDP.; Cantin Sanz, A.; Miranda Alonso, MÁ.; Primo Millo, J.; Primo Yufera, E. (1999). Synthesis and biological evaluation of new analogues of the active fungal metabolites N-(2-methyl-3-oxodecanoyl)-2-pyrroline and N-(2-methyl-3-oxodec-enoyl)-2-pyrroline. JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY. 47(9):3866-3871. doi:10.1021/jf990115q3866387147

What is the most effective percentage of Rose Bengal on polyamide fabrics for the visible-light photoinactivation of Gram-positive bacteria?

[EN] Heterogeneous photocatalysts based on fabric materials have achieved great relevance for water disinfection. However, studies have yet to be performed looking for the best percentage of a photosensitizer on fabric, considering the 1O2 generation efficiency as well as the charge distribution of the dye fabrics surface for bacterial inactivation. Therefore, polyamide fabrics (PAF) dyed at different Rose Bengal (RB) percentages (RB-PAF) as an anionic photosensitizer were prepared to determine the best value for photodynamic inactivation of Gram-positive bacteria (Enterococcus faecalis). Time-resolved and steady-state emission measurements, as well as laser flash photolysis experiments, were also performed. RB-PAF at a percentage of 1% (on-weigth-of-fiber, o.w. f.) showed 100% inactivation efficiency against E. faecalis (reduction of more than 6 log10 units in the viable count) in only 15 min. Contrarily, fabrics with RB values of 0.5 or 3% (o.w.f.) showed no bacterial inactivation or only a small activity (1 log10 unit reduction), respectively. Results revealed that the effects observed by RB-PAF are mediated by 3RF* and the subsequent generation of 1O2. The insignificant photooxygenation of 9,10-dimethyl anthracene observed for RB-PAF at 0.5% explains the lack of bacterial inactivation, while the low effect observed for RB-PAF at 3% is produced by electrostatic repulsions between the anionic RB and the bacteria surface. These results reveal that in order to design newly dyed fabrics for disinfection, it is important to optimize the percentage of dye to avoid aggregation of photosensitizers and to obtain an adequate net negative charge distribution in the antimicrobial fabrics.We are grateful for the CONACYT doctoral fellowship for J. F. (709358), and we also thank the Universidad Complutense de Madrid, Ministry of Universities, and Next GenerationEu recovery plan for financial support for the postdoctoral contract "Margarita Salas" for the requalification of the Spanish University System (CT31/21, 2021-2023), the Spanish Ministry of Science and Innovation (PID2019-110441RB-C33 funded by MCIN/AEI/10.13039/ 501100011033), and to the Valencian Agency for Innovation (INNEST/ 2021/75). Finally, we would also like to thank the CRUE-Universitat Politecnica de Valencia for funding the open access fee.Flores, J.; Blázquez-Moraleja, A.; Bonet-Aracil, M.; Moya Sanz, MDP.; Bosca Mayans, F.; Marín García, ML. (2023). What is the most effective percentage of Rose Bengal on polyamide fabrics for the visible-light photoinactivation of Gram-positive bacteria?. Journal of Environmental Chemical Engineering. 11(5). https://doi.org/10.1016/j.jece.2023.11063911

Laboratory evaluation of the compatibility of a new attractant contaminant device ciontaining Metarhizium anisopliae with Ceratitis capitata sterile males

[EN] Laboratory experiments were conducted to evaluate the compatibility of using the entomopathogenic fungus Metarhizium anisopliae, to be dispensed in a new attractant contaminant device (ACD), jointly with sterilized Ceratitis capitata males, as an integrated approach to control this major pest. The exposure of sterile Vienna 8 (V8) strain and wild type (WT) males to the contaminating part (infective dish) of the ACD showed similar susceptibility levels to the fungal strain (LT50 value of 4.52 and 4.72 days, respectively). Sterile V8 males were significantly less attracted to the infective dish (18.4%) than WT males (28.5%). As the success of Sterile Insect Technique (SIT) heavily relies on the mating success of sterile males in the field, mating performance of infected males was assessed. Around 85% of the females were mated, independently of the male strain and treatment (fungus-treated or untreated males) indicating that mating performance was unaffected by the fungus under laboratory conditions. Females showed a greater tendency to remate if previously mated to fungus-treated males, either V8 or WT. Our data suggest that this M. anisopliae based-ACD does not impair the performance of C. capitata sterile males and, therefore, it could be used combined with area wide SIT-based programs, providing that these results are validated in field conditions. The implications of this combined strategy to control C. capitata are discussed. (C) 2014 Elsevier Inc. All rights reserved.This work was partially supported by the "Comision Interministerial de Ciencia y Tecnologia" (CICYT, Spain) (Grant: AGL2006-13346-C02-02).San Andrés Aura, V.; Ayala Mingol, I.; Abad Payá, MDC.; Primo Millo, J.; Casteñera, P.; Moya Sanz, MDP. (2014). Laboratory evaluation of the compatibility of a new attractant contaminant device ciontaining Metarhizium anisopliae with Ceratitis capitata sterile males. Biological Control. 72:54-61. https://doi.org/10.1016/j.biocontrol.2014.02.007S54617

Role of age and comorbidities in mortality of patients with infective endocarditis

[Purpose]: The aim of this study was to analyse the characteristics of patients with IE in three groups of age and to assess the ability of age and the Charlson Comorbidity Index (CCI) to predict mortality. [Methods]: Prospective cohort study of all patients with IE included in the GAMES Spanish database between 2008 and 2015.Patients were stratified into three age groups:<65 years,65 to 80 years,and ≥ 80 years.The area under the receiver-operating characteristic (AUROC) curve was calculated to quantify the diagnostic accuracy of the CCI to predict mortality risk. [Results]: A total of 3120 patients with IE (1327 < 65 years;1291 65-80 years;502 ≥ 80 years) were enrolled.Fever and heart failure were the most common presentations of IE, with no differences among age groups.Patients ≥80 years who underwent surgery were significantly lower compared with other age groups (14.3%,65 years; 20.5%,65-79 years; 31.3%,≥80 years). In-hospital mortality was lower in the <65-year group (20.3%,<65 years;30.1%,65-79 years;34.7%,≥80 years;p < 0.001) as well as 1-year mortality (3.2%, <65 years; 5.5%, 65-80 years;7.6%,≥80 years; p = 0.003).Independent predictors of mortality were age ≥ 80 years (hazard ratio [HR]:2.78;95% confidence interval [CI]:2.32–3.34), CCI ≥ 3 (HR:1.62; 95% CI:1.39–1.88),and non-performed surgery (HR:1.64;95% CI:11.16–1.58).When the three age groups were compared,the AUROC curve for CCI was significantly larger for patients aged <65 years(p < 0.001) for both in-hospital and 1-year mortality. [Conclusion]: There were no differences in the clinical presentation of IE between the groups. Age ≥ 80 years, high comorbidity (measured by CCI),and non-performance of surgery were independent predictors of mortality in patients with IE.CCI could help to identify those patients with IE and surgical indication who present a lower risk of in-hospital and 1-year mortality after surgery, especially in the <65-year group

Photoreactivity of new rose bengal-SiO2 heterogeneous photocatalysts with and without a magnetite core for drug degradation and disinfection

[EN] The main drawback of homogeneous photocatalysis is the difficult separation of the photocatalysts from the reaction media after treatment completion; thus, heterogeneous photocatalysis represents a step forward in this technology. Moreover, heterogeneous catalysts incorporating magnetic properties further facilitate their separation and recovery. In this context, some photocatalyst of Rose Bengal (RB) on heterogeneous supports have been synthesized but how derivatization influences its mechanism of action against organic pollutants degradation and water disinfection still deserves a deeper investigation. In this context, new heterogeneous nanosized photocatalysts incorporating Rose Bengal (RB) have been prepared. The first one was based on the covalent anchoring to SiO2 nanoparticles and the second one incorporates a magnetite core. They have demonstrated to efficiently achieve photodegradation of ACF, DCF, and OFX under visible-light irradiation, with greater efficiency in the case of DCF. Interestingly, the photostability of RB is higher in heterogeneous than in homogeneous media. The presence of magnetite core in the heterogeneous photocatalyst facilitates its recovery from the medium but the photophysical properties of RB remain unchanged. These new photocatalysts also show a great efficiency in the photoinactivation of Enterococcus faecalis Gram-positive bacteria but not for the Gram-negative Escherichia coli and Pseudomonas aeruginosa. Analysis of all constants involving the photosensitized degradations of ACF, DCF, and OFX has evidenced that electron transfer process between RB, in homogeneous solutions and as a heterogeneous photocatalyst, and the three drugs is the initial step of their oxidations. In view of the results achieved, we believe that they could be used as a starting point for the development of new RB heterogeneous photocatalyst with adjustable oxidizing properties.PhD Scholarship from CONACYT for Flores-Garcia J. (709358), and the Spanish Ministry of Science and Innovation (PID2019-110441RB-C33 financed by MCIN/AEI/10.13039/501100011033) are gratefully acknowledged.Flores, J.; Moya Sanz, MDP.; Bosca Mayans, F.; Marín García, ML. (2023). Photoreactivity of new rose bengal-SiO2 heterogeneous photocatalysts with and without a magnetite core for drug degradation and disinfection. Catalysis Today. 413-415:1-9. https://doi.org/10.1016/j.cattod.2023.01.00119413-41

Susceptibility of Ceratitis capitata Wiedeman (Diptera:Tephritidae) to entomopathogenic fungi and their extracts

[EN] The effectiveness of seven strains of entomopathogenic fungi against Ceratitis capitata adults was evaluated in the laboratory. Adults were susceptible to five of seven aqueous suspensions of conidia. Metarhizium anisopliae and strain CG-260 of Paecilomyces fumosoroseus were the most pathogenic fungi, with 10- day LD50 values of 5.1 and 6.1 3 103 conidia/fly, respectively, when applied topically. Sublethal effects on fecundity and fertility of the fungal-exposed females were also studied. The most effective fungus in reducing fecundity was P. fumosoroseus CECT 2705, with reductions on the order of 65% at 1 3 106 conidia/fly. M. anisopliae and Aspergillus ochraceus also showed significant reductions of fecundity (40–50% for most of the assayed concentrations). Fertility was moderately affected by the fungi. M. anisopliae at 1 3 106 conidia/fly was the most effective fungus, showing egg eclosion reduction of over 50% compared with the control. In addition, culture broth dichloromethane extracts from the entomopathogenic fungi were tested for insecticide activity against C. capitata, including effects on fecundity and fertility. The extract from M. anisopliae was the most toxic, resulting in about 90% mortality at a concentration of 25 mg/g of diet; under these conditions, fecundity and fertility of treated females were reduced by 94 and 53%, respectively, compared with untreated controls. © 2000 Academic PressThe authors acknowledge the financial support of Comisión Interministerial de Ciencia y Tecnología (CICYT) and Consejería de Agricultura P. y A. de la C. Valenciana.Castillo López, MÁ.; Moya Sanz, MDP.; Hernández Giménez, E.; Primo Yufera, E. (2000). Susceptibility of Ceratitis capitata Wiedeman (Diptera:Tephritidae) to entomopathogenic fungi and their extracts. Biological Control. 19(3):274-282. doi:10.1006/bcon.2000.0867,S27428219

Novel inhibitors of the mitochondrial respiratory chain: Oximes and pyrrolines isolated from Penicillium brevicompactum and synthetic analogues

[EN] The capacity of inhibition of the mammalian mitochondrial respiratory chain of brevioxime 5a, a natural insecticide compound isolated from Penicillium brevicompactum culture broth, and another 15 analogue compounds, other oximes 5b and 5c; two diastereomeric pyrrolidines 1c' and 1c"; five pyrrolines 3c', 3c" (diastereomers between them), 3a, 3b, and 6; two oxazines 4c' and 4c" (also diastereomers between them); and four pyrrol derivatives 7-10, are analyzed in this paper. Compounds 3b, 3c', 3c", 4c', 4c", 5b, 5c, 6, and 10 were found to be inhibitors of the integrated electron transfer chain (NADH oxidase activity) in beef heart submitochondrial particles (SMP), establishing that all of them except compound 3b and 6 only affected to complex I of the mitochondrial respiratory chain. The most potent product was 5b, with an IC50 of 0.27 mu M, similar to the IC50 values of other known complex I inhibitors. The diastereomeric pairs 1 c'/1c", 3c'/3c", 4c'/4c", and 5c have not been previously described. Chemical characterization, on the basis of spectral data, is also shown.We acknowledge the Fundacio¿n Jose¿ y Ana Royo for a postdoctoral grant to M.C.G., and the Conserjer&#305;¿a de Educacio¿n y Ciencia de la C. Valenciana for the doctoral grant to M.P.L. This work has been supported by Oficina de Ciencia y Tecnolog&#305;¿a. I+D projects of the Generalitat Valenciana (Project GV01- 293), the Conselleria d Agricultura, Pesca i Alimentacio¿ (Project GVCAPA00-0529), and Fondos Europeos de Desarrollo Regional (FEDERFSE) of the European Union through the Fondo de Investigacio¿n Sanitaria (FIS 01/0406).Cantin Sanz, A.; López-Gresa, MP.; Gonzalez Más, MC.; Moya Sanz, MDP.; Miranda Alonso, MÁ.; Primo Millo, J.; Romero, V.... (2005). Novel inhibitors of the mitochondrial respiratory chain: Oximes and pyrrolines isolated from Penicillium brevicompactum and synthetic analogues. Journal of Agricultural and Food Chemistry. 53(21):8296-8301. https://doi.org/10.1021/jf058075fS82968301532

Role of age and comorbidities in mortality of patients with infective endocarditis.

The aim of this study was to analyse the characteristics of patients with IE in three groups of age and to assess the ability of age and the Charlson Comorbidity Index (CCI) to predict mortality. Prospective cohort study of all patients with IE included in the GAMES Spanish database between 2008 and 2015.Patients were stratified into three age groups: A total of 3120 patients with IE (1327  There were no differences in the clinical presentation of IE between the groups. Age ≥ 80 years, high comorbidity (measured by CCI),and non-performance of surgery were independent predictors of mortality in patients with IE.CCI could help to identify those patients with IE and surgical indication who present a lower risk of in-hospital and 1-year mortality after surgery, especially in th

Contemporary use of cefazolin for MSSA infective endocarditis: analysis of a national prospective cohort

Objectives: This study aimed to assess the real use of cefazolin for methicillin-susceptible Staphylococcus aureus (MSSA) infective endocarditis (IE) in the Spanish National Endocarditis Database (GAMES) and to compare it with antistaphylococcal penicillin (ASP). Methods: Prospective cohort study with retrospective analysis of a cohort of MSSA IE treated with cloxacillin and/or cefazolin. Outcomes assessed were relapse; intra-hospital, overall, and endocarditis-related mortality; and adverse events. Risk of renal toxicity with each treatment was evaluated separately. Results: We included 631 IE episodes caused by MSSA treated with cloxacillin and/or cefazolin. Antibiotic treatment was cloxacillin, cefazolin, or both in 537 (85%), 57 (9%), and 37 (6%) episodes, respectively. Patients treated with cefazolin had significantly higher rates of comorbidities (median Charlson Index 7, P <0.01) and previous renal failure (57.9%, P <0.01). Patients treated with cloxacillin presented higher rates of septic shock (25%, P = 0.033) and new-onset or worsening renal failure (47.3%, P = 0.024) with significantly higher rates of in-hospital mortality (38.5%, P = 0.017). One-year IE-related mortality and rate of relapses were similar between treatment groups. None of the treatments were identified as risk or protective factors. Conclusion: Our results suggest that cefazolin is a valuable option for the treatment of MSSA IE, without differences in 1-year mortality or relapses compared with cloxacillin, and might be considered equally effective