Linezolid belongs to a class of antibiotics known as oxazolidinones. It is receiving great attent... more Linezolid belongs to a class of antibiotics known as oxazolidinones. It is receiving great attention due to its activity toward multidrugs resistant bacteria, and simple and cheap methods for the analysis of this compound in pharma-ceutical preparations are required. In this work, the electrochemistry of the antibiotic linezolid was investigated and a differential pulse voltammetric method based on the oxidation of the oxazolidinonic compound at a glassy carbon electrode has been developed and optimized for its determination; LOD of 50 mgL1 and a linearity up to 200 mgL1 were reported. The electrochemical process was studied by using different electrochemical techniques and confirmed by HPLC-MS/MS.
TiO2 sepiolite and zeolite composites, as well the corresponding N-doped composites, synthesized ... more TiO2 sepiolite and zeolite composites, as well the corresponding N-doped composites, synthesized through a sol–gel method, were tested for the photocatalytic degradation of a widespread fluoroquinolone antibiotic (ofloxacin) under environmental conditions. The catalysts were characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), and diffuse reflectance spectroscopy (DRS) analyses. A complete drug degradation occurred in 10–15 min in the presence of both TiO2 sepiolite and zeolite catalysts, and in 20–30 min with the N-doped ones. Sepiolite proved to be a better TiO2 support compared to the most common zeolite both in terms of adsorption capacity and photocatalytic efficiency in pollutants degradation. The influence of nitrogen doping (red shift from 3.2 to 3.0 eV) was also investigated. Although it was blurred by a marked increase of the particle dimension and thus a decrease of the specific surface area of the doped catalysts, it...
Abstract The performances of remediation processes initiated by ionizing radiation on ofloxacin a... more Abstract The performances of remediation processes initiated by ionizing radiation on ofloxacin are investigated in ambient conditions. The effectiveness of the decomposition of ofloxacin has been assessed both by γ-rays and electron beam in various aqueous solutions differentiated by the dissolved gases (Air or oxygen saturated) and H 2 O 2 . By HPLC it is shown that ofloxacin is removed according to a first order process vs. dose in any system. O 2 accelerates the decomposition rate, while H 2 O 2 does not seem to enhance any oxidation effect. The simultaneous oxidative-reductive treatment (no additive) demonstrated to have better mineralizing performances than the fully oxidative one (H 2 O 2 present). Mineralization by γ results to be more efficient than by EB. The Total Organic Carbon decrease was investigated in dependence of dose and of the • OH production rate. The latter parameter was changed over 7 orders of magnitude by controlling dose rate and/or by adding H 2 O 2 . A steep increase of acidity remarks the phases of fluorine-carbon bond break.
Environmental Science and Pollution Research, 2016
This is the first report on the photodegradation of ofloxacin under simulated solar light and in ... more This is the first report on the photodegradation of ofloxacin under simulated solar light and in actual environmental matrices in the presence of a g-C3N4 suspension. The catalyst, prepared from the polymerization of dicyandiamide (650 °C, reaction yield 60%), was characterized by means of powder X-ray diffraction (PXRD), UV-vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and BET surface area measurements. The experiments were carried out in a lab-scale batch reactor at concentrations in the range of micrograms/milligrams per liter. The course of the reaction was monitored by high-pressure liquid chromatography with UV-vis and fluorescence detectors. The g-C3N4-promoted photodegradation occurred at a rate 10 times faster than the direct photolysis and obeyed a first-order kinetics; in addition, the photodegradation kinetics of sonicated g-C3N4 resulted to be of the same order of that caused by P25 TiO2. Finally, the photochemical paths and the photoproducts have been identified and compared to those obtained by using P25 TiO2. From the results of this study, it can be concluded that g-C3N4 is a very attractive photocatalyst compared to P25 TiO2 in view of its ease of preparation, low cost, excellent oxidizing properties, large fraction of solar radiation absorbed, and intrinsically layered structure.
The photodegradation of Ciprofloxacin (CIP), Enrofloxacin (ENR), Danofloxacin (DAN), Marbofloxaci... more The photodegradation of Ciprofloxacin (CIP), Enrofloxacin (ENR), Danofloxacin (DAN), Marbofloxacin (MAR) and Levofloxacin (LEV), five widely used fluoroquinolones (FQs), was studied in urban WWTP secondary effluent, under solar light. The degradation profiles and the kinetic constants were determined at the micrograms per litre levels (20-50μgL(-1)). The photo-generated products were identified by high-pressure liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). The toxicity of the photoproducts was assessed by Vibrio fischeri light emission inhibition assay performed on irradiated and not-irradiated FQs solutions, at environmentally significant concentrations. Attention was focused on the evaluation of the photoproducts contribution to the overall biotoxic effect of these emerging pollutants. Data from chronic exposure experiments (24-48h) were primarily considered. Results confirmed the major usefulness of chronic toxicity data with respect to the acute assay ones and proved the not negligible biotoxicity of the FQs photodegradation products.
MAR and ENR adsorption and photodegradation were investigated on NaY zeolite derivatized with thr... more MAR and ENR adsorption and photodegradation were investigated on NaY zeolite derivatized with three different TiO2 catalysts (ZT1= NaY-P25 Degussa, ZT2= NaY amorphous TiO2, ZT3= NaY-anatase TiO2) after acidic washing. The obtained materials were characterized by XRD, SEM, diffuse reflectance analysis and BET. The adsorption isotherms, investigated in natural water at native pH, showed that FQs are adsorbed in remarkable amounts by ZT2 and ZT3, with sorption capacities significantly higher than those observed for ZT1 and untreated zeolite. Photodegradation kinetics of adsorbed FQs were investigated on each material and demonstrated that solid-state photoreaction of these antibiotics takes place effectively. The degradation rate was greatly enhanced on the TiO2-modified zeolites, with a large FQs removal in about 2 hours for a 3-6 mg g-1 load. A comparable degradation required about 15 hours on untreated zeolite. Modifications in the course of the photoreaction in the adsorbed state w...
Journal of Photochemistry and Photobiology A: Chemistry, 2015
ABSTRACT Fluoroquinolone antibiotics (FQs) are important “emerging” micropollutants, and their en... more ABSTRACT Fluoroquinolone antibiotics (FQs) are important “emerging” micropollutants, and their environmental diffusion is an issue of great concern. In this study, the photochemical degradation of marbofloxacin (MAR) and enrofloxacin (ENR) adsorbed on montmorillonite (MMT) and kaolinite (KAO) clays was investigated. Being FQs photosensitive molecules, the sunlight-induced degradation of clay-adsorbed FQs and of their photoproducts was monitored as function of irradiation time. The photoproducts were identified by high performance liquid chromatography electrospray tandem mass spectrometry (HPLC-ESI-MS/MS) and the photochemical pathways have been elucidated. X-ray diffraction (XRD) has been employed to deeply study the solid-state photodegradation process of MAR and ENR on MMT. Interestingly, the XRD results clearly evidenced a significative variation of the interlayer spacing of MMT not only as function of FQs adsorbed amounts, but also in relationship with their photodegradation, not investigated by means of XRD as yet. The results confirmed that FQs adsorption is a bulk phenomenon that occurs in the interlayer spacing of the MMT structure; moreover, it was proved that sunlight largely degraded the adsorbed FQs, both on the external surface and in the interlayer spacing.
Journal of Environmental Chemical Engineering, 2014
Abstract Adsorption and photocatalytic removal from water of marbofloxacin (MAR) and enrofloxacin... more Abstract Adsorption and photocatalytic removal from water of marbofloxacin (MAR) and enrofloxacin (ENR), two fluoroquinolone (FQ) antibiotics widely present in surface waters, were investigated on zeolite Y derivatized with three different TiO2 catalysts (P25 Degussa and TiO2 obtained by optimization of a sol–gel method). The prepared materials were characterized by X-rays powder diffraction (XRPD), scanning electron microscopy (SEM), BET analysis and diffuse reflectance spectroscopy (DRS). TiO2-derivatization improved the adsorption capacities of zeolite Y for FQs and promoted the sunlight-induced degradation of FQs adsorbed (solid-state photodegradation), not investigated in literature yet. A large FQs removal (3 mg g−1) occurred in about 2 h (residual adsorbed FQs
The photodegradation of the most prescribed glucocorticoids (GCs) was studied under relevant envi... more The photodegradation of the most prescribed glucocorticoids (GCs) was studied under relevant environmental conditions in the presence of suspended TiO2. The considered drugs included cortisone (CORT), hydrocortisone (HCORT), betamethasone (BETA), dexamethasone (DEXA), prednisone (PRED), prednisolone (PREDLO), and triamcinolone (TRIAM). The experiments were carried out at concentrations (50 µg L−1) close to the real ones in freshwater samples (tap and river) under simulated and natural sunlight, and their decomposition took place very efficiently under natural sunlight. The reactions were monitored by high-pressure liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). According to a pseudo-first-order decay, all drugs underwent degradation within 15 min, following different paths with respect to the direct photolysis. The observed kinetic constants, slightly lower in river than in tap water, varied from 0.29 to 0.61 min−1 with modest diff...
Photocatalysis by semiconductors is considered one of the most promising advanced oxidation proce... more Photocatalysis by semiconductors is considered one of the most promising advanced oxidation processes (AOPs) and TiO2 is the most well-studied material for the removal of contaminants from the aquatic system. Over the last 20 years, pharmaceuticals have been the most investigated pollutants. They re-enter the environment almost unmodified or slightly metabolized, especially in the aquatic environment, since the traditional urban wastewater treatment plants (WWTPs) are not able to abate them. Due to their continuous input, persistence in the environment, and unpleasant effects even at low concentrations, drugs are considered contaminants of emerging concern (ECs). Among these, we chose fluoroquinolone (FQ) antibiotics as an environmental probe for assessing the role of TiO2 photocatalysis in the degradation of recalcitrant pollutants under environmental conditions and detoxification of surface waters and wastewaters. Due to their widespread diffusion, their presence in the list of th...
International Journal of Environmental Research and Public Health
The photodegradation process of seven glucocorticoids (GCs), cortisone (CORT), hydrocortisone (HC... more The photodegradation process of seven glucocorticoids (GCs), cortisone (CORT), hydrocortisone (HCORT), betamethasone (BETA), dexamethasone (DEXA), prednisone (PRED), prednisolone (PREDLO) and triamcinolone (TRIAM) was studied in tap and river water at a concentration close to the environmental ones. All drugs underwent sunlight degradation according to a pseudo-first-order decay. The kinetic constants ranged from 0.00082 min−1 for CORT to 0.024 min−1 for PRED and PREDLO. The photo-generated products were identified by high-pressure liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). The main steps of the degradation pathways were the oxidative cleavage of the chain 17 for CORT, HCORT and the rearrangement of the cyclohexadiene moiety for the other GCs. The acute and chronic toxicity of GCs and of their photoproducts was assessed by the V. fischeri and P.subcapitata inhibition assays. The bioassays revealed no significant differences in...
Natural pesticides have attracted substantial interest due to the increase in organic agriculture... more Natural pesticides have attracted substantial interest due to the increase in organic agriculture and enhanced attention to environmental pollution. Plant Growth Promoting Bacteria (PGPB) are applied for both disease control and growth enhancement; PGPBs are known to elicit Induced Systemic Response (ISR) in plants. However, less is known about the effect of botanical pesticides, such as the azadirachtin-containing neem extracts, on plant metabolism. This study aimed to investigate the effects of foliar application of the above-mentioned natural pesticides on the metabolic profiling of tomato. Leaf application of Bacillus subtilis fostered Induced Systemic Resistance (ISR) in treated plants via the Jasmonic acid pathway, and enhanced production of secondary metabolites such as flavonoids, phytoalexins and auxins. Changes in sterols and terpenes, as well as an increase in glucosinolates were also observed. Interestingly, azadirachtin-treated tomatoes also showed an increase in ISR and our results revealed that most of the enriched metabolites are shared with a B. subtilis treatment, suggesting conserved biochemical responses. These (un)expected findings indicate that plants are not insensitive to application of natural pesticide and while Azadirachtin is applied as a direct pesticide, it also stimulates a defense response in tomatoes very similar to B. subtilis induced ISR.
Linezolid belongs to a class of antibiotics known as oxazolidinones. It is receiving great attent... more Linezolid belongs to a class of antibiotics known as oxazolidinones. It is receiving great attention due to its activity toward multidrugs resistant bacteria, and simple and cheap methods for the analysis of this compound in pharma-ceutical preparations are required. In this work, the electrochemistry of the antibiotic linezolid was investigated and a differential pulse voltammetric method based on the oxidation of the oxazolidinonic compound at a glassy carbon electrode has been developed and optimized for its determination; LOD of 50 mgL1 and a linearity up to 200 mgL1 were reported. The electrochemical process was studied by using different electrochemical techniques and confirmed by HPLC-MS/MS.
TiO2 sepiolite and zeolite composites, as well the corresponding N-doped composites, synthesized ... more TiO2 sepiolite and zeolite composites, as well the corresponding N-doped composites, synthesized through a sol–gel method, were tested for the photocatalytic degradation of a widespread fluoroquinolone antibiotic (ofloxacin) under environmental conditions. The catalysts were characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), and diffuse reflectance spectroscopy (DRS) analyses. A complete drug degradation occurred in 10–15 min in the presence of both TiO2 sepiolite and zeolite catalysts, and in 20–30 min with the N-doped ones. Sepiolite proved to be a better TiO2 support compared to the most common zeolite both in terms of adsorption capacity and photocatalytic efficiency in pollutants degradation. The influence of nitrogen doping (red shift from 3.2 to 3.0 eV) was also investigated. Although it was blurred by a marked increase of the particle dimension and thus a decrease of the specific surface area of the doped catalysts, it...
Abstract The performances of remediation processes initiated by ionizing radiation on ofloxacin a... more Abstract The performances of remediation processes initiated by ionizing radiation on ofloxacin are investigated in ambient conditions. The effectiveness of the decomposition of ofloxacin has been assessed both by γ-rays and electron beam in various aqueous solutions differentiated by the dissolved gases (Air or oxygen saturated) and H 2 O 2 . By HPLC it is shown that ofloxacin is removed according to a first order process vs. dose in any system. O 2 accelerates the decomposition rate, while H 2 O 2 does not seem to enhance any oxidation effect. The simultaneous oxidative-reductive treatment (no additive) demonstrated to have better mineralizing performances than the fully oxidative one (H 2 O 2 present). Mineralization by γ results to be more efficient than by EB. The Total Organic Carbon decrease was investigated in dependence of dose and of the • OH production rate. The latter parameter was changed over 7 orders of magnitude by controlling dose rate and/or by adding H 2 O 2 . A steep increase of acidity remarks the phases of fluorine-carbon bond break.
Environmental Science and Pollution Research, 2016
This is the first report on the photodegradation of ofloxacin under simulated solar light and in ... more This is the first report on the photodegradation of ofloxacin under simulated solar light and in actual environmental matrices in the presence of a g-C3N4 suspension. The catalyst, prepared from the polymerization of dicyandiamide (650 °C, reaction yield 60%), was characterized by means of powder X-ray diffraction (PXRD), UV-vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and BET surface area measurements. The experiments were carried out in a lab-scale batch reactor at concentrations in the range of micrograms/milligrams per liter. The course of the reaction was monitored by high-pressure liquid chromatography with UV-vis and fluorescence detectors. The g-C3N4-promoted photodegradation occurred at a rate 10 times faster than the direct photolysis and obeyed a first-order kinetics; in addition, the photodegradation kinetics of sonicated g-C3N4 resulted to be of the same order of that caused by P25 TiO2. Finally, the photochemical paths and the photoproducts have been identified and compared to those obtained by using P25 TiO2. From the results of this study, it can be concluded that g-C3N4 is a very attractive photocatalyst compared to P25 TiO2 in view of its ease of preparation, low cost, excellent oxidizing properties, large fraction of solar radiation absorbed, and intrinsically layered structure.
The photodegradation of Ciprofloxacin (CIP), Enrofloxacin (ENR), Danofloxacin (DAN), Marbofloxaci... more The photodegradation of Ciprofloxacin (CIP), Enrofloxacin (ENR), Danofloxacin (DAN), Marbofloxacin (MAR) and Levofloxacin (LEV), five widely used fluoroquinolones (FQs), was studied in urban WWTP secondary effluent, under solar light. The degradation profiles and the kinetic constants were determined at the micrograms per litre levels (20-50μgL(-1)). The photo-generated products were identified by high-pressure liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). The toxicity of the photoproducts was assessed by Vibrio fischeri light emission inhibition assay performed on irradiated and not-irradiated FQs solutions, at environmentally significant concentrations. Attention was focused on the evaluation of the photoproducts contribution to the overall biotoxic effect of these emerging pollutants. Data from chronic exposure experiments (24-48h) were primarily considered. Results confirmed the major usefulness of chronic toxicity data with respect to the acute assay ones and proved the not negligible biotoxicity of the FQs photodegradation products.
MAR and ENR adsorption and photodegradation were investigated on NaY zeolite derivatized with thr... more MAR and ENR adsorption and photodegradation were investigated on NaY zeolite derivatized with three different TiO2 catalysts (ZT1= NaY-P25 Degussa, ZT2= NaY amorphous TiO2, ZT3= NaY-anatase TiO2) after acidic washing. The obtained materials were characterized by XRD, SEM, diffuse reflectance analysis and BET. The adsorption isotherms, investigated in natural water at native pH, showed that FQs are adsorbed in remarkable amounts by ZT2 and ZT3, with sorption capacities significantly higher than those observed for ZT1 and untreated zeolite. Photodegradation kinetics of adsorbed FQs were investigated on each material and demonstrated that solid-state photoreaction of these antibiotics takes place effectively. The degradation rate was greatly enhanced on the TiO2-modified zeolites, with a large FQs removal in about 2 hours for a 3-6 mg g-1 load. A comparable degradation required about 15 hours on untreated zeolite. Modifications in the course of the photoreaction in the adsorbed state w...
Journal of Photochemistry and Photobiology A: Chemistry, 2015
ABSTRACT Fluoroquinolone antibiotics (FQs) are important “emerging” micropollutants, and their en... more ABSTRACT Fluoroquinolone antibiotics (FQs) are important “emerging” micropollutants, and their environmental diffusion is an issue of great concern. In this study, the photochemical degradation of marbofloxacin (MAR) and enrofloxacin (ENR) adsorbed on montmorillonite (MMT) and kaolinite (KAO) clays was investigated. Being FQs photosensitive molecules, the sunlight-induced degradation of clay-adsorbed FQs and of their photoproducts was monitored as function of irradiation time. The photoproducts were identified by high performance liquid chromatography electrospray tandem mass spectrometry (HPLC-ESI-MS/MS) and the photochemical pathways have been elucidated. X-ray diffraction (XRD) has been employed to deeply study the solid-state photodegradation process of MAR and ENR on MMT. Interestingly, the XRD results clearly evidenced a significative variation of the interlayer spacing of MMT not only as function of FQs adsorbed amounts, but also in relationship with their photodegradation, not investigated by means of XRD as yet. The results confirmed that FQs adsorption is a bulk phenomenon that occurs in the interlayer spacing of the MMT structure; moreover, it was proved that sunlight largely degraded the adsorbed FQs, both on the external surface and in the interlayer spacing.
Journal of Environmental Chemical Engineering, 2014
Abstract Adsorption and photocatalytic removal from water of marbofloxacin (MAR) and enrofloxacin... more Abstract Adsorption and photocatalytic removal from water of marbofloxacin (MAR) and enrofloxacin (ENR), two fluoroquinolone (FQ) antibiotics widely present in surface waters, were investigated on zeolite Y derivatized with three different TiO2 catalysts (P25 Degussa and TiO2 obtained by optimization of a sol–gel method). The prepared materials were characterized by X-rays powder diffraction (XRPD), scanning electron microscopy (SEM), BET analysis and diffuse reflectance spectroscopy (DRS). TiO2-derivatization improved the adsorption capacities of zeolite Y for FQs and promoted the sunlight-induced degradation of FQs adsorbed (solid-state photodegradation), not investigated in literature yet. A large FQs removal (3 mg g−1) occurred in about 2 h (residual adsorbed FQs
The photodegradation of the most prescribed glucocorticoids (GCs) was studied under relevant envi... more The photodegradation of the most prescribed glucocorticoids (GCs) was studied under relevant environmental conditions in the presence of suspended TiO2. The considered drugs included cortisone (CORT), hydrocortisone (HCORT), betamethasone (BETA), dexamethasone (DEXA), prednisone (PRED), prednisolone (PREDLO), and triamcinolone (TRIAM). The experiments were carried out at concentrations (50 µg L−1) close to the real ones in freshwater samples (tap and river) under simulated and natural sunlight, and their decomposition took place very efficiently under natural sunlight. The reactions were monitored by high-pressure liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). According to a pseudo-first-order decay, all drugs underwent degradation within 15 min, following different paths with respect to the direct photolysis. The observed kinetic constants, slightly lower in river than in tap water, varied from 0.29 to 0.61 min−1 with modest diff...
Photocatalysis by semiconductors is considered one of the most promising advanced oxidation proce... more Photocatalysis by semiconductors is considered one of the most promising advanced oxidation processes (AOPs) and TiO2 is the most well-studied material for the removal of contaminants from the aquatic system. Over the last 20 years, pharmaceuticals have been the most investigated pollutants. They re-enter the environment almost unmodified or slightly metabolized, especially in the aquatic environment, since the traditional urban wastewater treatment plants (WWTPs) are not able to abate them. Due to their continuous input, persistence in the environment, and unpleasant effects even at low concentrations, drugs are considered contaminants of emerging concern (ECs). Among these, we chose fluoroquinolone (FQ) antibiotics as an environmental probe for assessing the role of TiO2 photocatalysis in the degradation of recalcitrant pollutants under environmental conditions and detoxification of surface waters and wastewaters. Due to their widespread diffusion, their presence in the list of th...
International Journal of Environmental Research and Public Health
The photodegradation process of seven glucocorticoids (GCs), cortisone (CORT), hydrocortisone (HC... more The photodegradation process of seven glucocorticoids (GCs), cortisone (CORT), hydrocortisone (HCORT), betamethasone (BETA), dexamethasone (DEXA), prednisone (PRED), prednisolone (PREDLO) and triamcinolone (TRIAM) was studied in tap and river water at a concentration close to the environmental ones. All drugs underwent sunlight degradation according to a pseudo-first-order decay. The kinetic constants ranged from 0.00082 min−1 for CORT to 0.024 min−1 for PRED and PREDLO. The photo-generated products were identified by high-pressure liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). The main steps of the degradation pathways were the oxidative cleavage of the chain 17 for CORT, HCORT and the rearrangement of the cyclohexadiene moiety for the other GCs. The acute and chronic toxicity of GCs and of their photoproducts was assessed by the V. fischeri and P.subcapitata inhibition assays. The bioassays revealed no significant differences in...
Natural pesticides have attracted substantial interest due to the increase in organic agriculture... more Natural pesticides have attracted substantial interest due to the increase in organic agriculture and enhanced attention to environmental pollution. Plant Growth Promoting Bacteria (PGPB) are applied for both disease control and growth enhancement; PGPBs are known to elicit Induced Systemic Response (ISR) in plants. However, less is known about the effect of botanical pesticides, such as the azadirachtin-containing neem extracts, on plant metabolism. This study aimed to investigate the effects of foliar application of the above-mentioned natural pesticides on the metabolic profiling of tomato. Leaf application of Bacillus subtilis fostered Induced Systemic Resistance (ISR) in treated plants via the Jasmonic acid pathway, and enhanced production of secondary metabolites such as flavonoids, phytoalexins and auxins. Changes in sterols and terpenes, as well as an increase in glucosinolates were also observed. Interestingly, azadirachtin-treated tomatoes also showed an increase in ISR and our results revealed that most of the enriched metabolites are shared with a B. subtilis treatment, suggesting conserved biochemical responses. These (un)expected findings indicate that plants are not insensitive to application of natural pesticide and while Azadirachtin is applied as a direct pesticide, it also stimulates a defense response in tomatoes very similar to B. subtilis induced ISR.
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Papers by Luca Pretali