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Photocatalyzed degradation of phenol in aqueous solution over surface impregnated TiO2 (M = Cu, Cr, V) under UV-Vis (366 nm) and UV (254 nm) irradiation is described. Nanosized photocatalyts were prepared from TiO2-P25 by wet impregnation, and characterized by X-ray diffraction, X-ray fluorescence, transmission electron microscopy, UV-Vis diffuse reflectance spectroscopy, Raman spectroscopy, and adsorption studies. No oxide phases of the metal dopants were found, although their presence in the TiO2-P25 lattice induces tensile strain in Cu-impregnated TiO2-P25, whereas compressive strain in Cr- and V-impregnated TiO2-P25. Experimental evidences support chemical and mechanical stability of the photocatalysts. Type IV N2 adsorption–desorption isotherms, with a small H3 loop near the maximum relative pressure were observed. Metal surface impregnated photocatalysts are mesoporous with a similar surface roughness, and a narrow pore distribution around ca. 25 Å. They were chemically stable, showing no metal lixiviation. Their photocatalytic activity was followed by UV-Vis spectroscopy and HPLC–UV. A first order kinetic model appropriately fitted the experimental data. The fastest phenol degradation was obtained with M (0.1%)/TiO2-P25, the reactivity order being Cu > V >> Cr > TiO2-P25 under 366 nm irradiation, while TiO2-P25 > Cu > V > Cr, when using 254 nm radiation. TOC removal under 366 nm irradiation for 300 min showed almost quantitative mineralization for all tested materials, while 254 nm irradiation for 60 min led to maximal TOC removal (ca. 30%). Photoproducts and intermediate photoproducts were identified by HPLC–MS, and appropriate reaction pathways are proposed. The energy efficiency of the process was analysed, showing UV lamps are superior to UVA lamps, and that the efficiency of the surface impregnated catalyst varies in the order Cu > V > Cr.

Kinetic photodegradation of imazethapyr, a herbicide from imidazolinone class of pesticides, has been investigated in aqueous solution using slurry titanium dioxide (TiO2) and supported on Ahlstrom paper (flexible photocatalytic support). Two types of TiO2 e.g., Millennium PC500 (100% anatase) and Degussa P25 (80% anatase, 20% rutile) were used. Experiments were investigated to evaluate the effect of the adsorption, initial concentrations of the pesticide as well as catalyst doses on the photocatalytic degradation of imazethapyr. Kinetic parameters were experimentally determined and a half-order kinetic was observed. Regarding Langmuir–Hinshelwood model, the kinetic of the imazethapyr degradation was more efficient at higher pesticide concentrations and catalyst doses. Accordingly, Degussa P25 shows higher photocatalytic activity in regard to PC500 Millennium.

Imazethapyr herbicide [5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid] is widely used on agricultural field crops in Morocco. It is reported that soil properties largely enhance the sorption of the herbicide in soils, however understanding their impact in soils of Morocco is needed. The present article investigates the sorption behavior of imazethapyr herbicide toward six agricultural soils from Morocco in batch equilibrium experiments at pH 5 and evaluates the effect of the organic matter, the clay content, and the cation exchange capacity (CEC) on the sorption by applying simple and multiple linear regressions. Freundlich isotherm model described well the dynamic of imazethapyr sorption in all studied soils under the experimental conditions. The linear regressions showed significant differences between the soil properties and their impact on the sorption. While simple regression revealed strong positive correlations between the sorption and both the soil clay content (R2 = 0.91) and CEC (R2 = 0.92), the multiple regression revealed a noteworthy influence of soil organic matter when combined with clays. Our findings showed a weak adsorption of imazethapyr on the selected Moroccan soils, in addition to a potential role of clay minerals and CEC in the retention of the herbicide compared to the organic matter. The low adsorptive capacity of the Moroccan soils urges the necessity of minimizing herbicide application rates in agricultural regions to prevent environmental detrimental impacts.

Signal transducer and activator of transcription (STAT) proteins are cytoplasmic transcription factors known to play key roles in numerous physiological and pathological processes, from pathogen response to cancer modulation. However, the roles of some STAT family members, particularly STAT1 and STAT4, in the initiation and progression of bladder cancer (BC) have not been comprehensively studied. The present study investigated the expression pattern of STAT1 and STAT4 in the prognosis and survival of BC taking advantage of patients' specimens and cell lines. In our cohort, high mRNA expression of STAT1 was significantly associated with tumor invasiveness, recurrence and progression, and was shown to increase according to tumor stage in BC cell lines. However, it did not affect patient survival. By contrast, STAT4 exhibited its highest expression in early-stage tumors, without a significant link to the tumor stage. Moreover, it was found that increased STAT4 mRNA expression was associated with improved disease-free survival and overall survival in our cohort. Collectively, these findings suggest that STAT1 and STAT4 could be promising prognostic markers to enhance BC management., Competing Interests: The authors declare that they have no competing interests., (Copyright: © 2025 El Ahanidi et al.)

The transcription factor TWIST1 is a major regulator of Epithelial-Mesenchymal Transition, enhancing cancer cell mobility and invasive potential. Overexpression of TWIST1 is associated with tumor progression and poor prognosis. In our study, we explored the role of TWIST1 as both a prognostic biomarker and a therapeutic target in bladder cancer (BC), as well as the relationship between its promoter methylation and mRNA expression in bladder cancer patients. In cohort of 66 bladder cancer patients, we explored TWIST1 expression levels in tumor samples through RT-qPCR analysis; Our findings revealed a significant correlation between high TWIST1 expression levels and advanced bladder tumor stages, grades, and progression; suggesting its association with aggressive BC phenotypes. Importantly, patients with low TWIST1 expression exhibited significantly prolonged disease-free survival (DFS), indicating its potential as a prognostic marker for stratification and as a therapeutic target in advanced BC. In contrast, there was no direct correlation between TWIST1 promoter methylation status and TWIST1 expression levels in BC tumors. In summary, TWIST1 expression could play an important role as a molecular marker for BC patients' prognosis and overall survival prediction. Moreover, our results suggest that TWIST1 promoter methylation doesn't affect the gene expression in BC. Furthermore, understanding the molecular mechanisms driving TWIST1 dysregulation may uncover novel therapeutic targets to improve the management of BC., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2025. Published by Elsevier Inc.)

Background: Telomerase activity plays a crucial role in cancer development and progression. Thus, telomerase activation through the interplay of mutations and epigenetic alterations in the telomerase reverse transcriptase (TERT) promoter may provide further insight into bladder cancer induction and progression., Methods: In this study 100 bladder tumour tissues were selected, and four molecular signatures were analysed: THOR methylation status, TERT promotor mutation, telomere length, and TERT expression., Results: In our study, 88% of bladder cancer patients had an hypermethylation of the THOR region and 60% had mutations in the TERT promoter region. TERT promoter methylation was observed in all stages and grades of bladder cancer. While, TERT promoter mutations were detected in advanced stages and grades. In our cohort, high levels of TERT expression and long telomeres have been found in noninvasive cases of bladder cancer, with a significant association between TERT expression and Telomere length. Interestingly, patients with low TERT expression and cases with long telomeres had significantly longer Disease-free survival and overall survival., Conclusion: The methylation and mutations occurring in the TERT promoter are implicated in bladder carcinogenesis, offering added prognostic and supplying novel insight into telomere biology in cancer., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Secure extraction of Personally Identifiable Information (PII) from Electronic Health Records (EHRs) presents significant privacy and security challenges. This study explores the application of Federated Learning (FL) to overcome these challenges within the context of French EHRs. By utilizing a multilingual BERT model in an FL simulation involving 20 hospitals, each represented by a unique medical department or pole, we compared the performance of two setups: individual models, where each hospital uses only its own training and validation data without engaging in the FL process, and federated models, where multiple hospitals collaborate to train a global FL model. Our findings demonstrate that FL models not only preserve data confidentiality but also outperform the individual models. In fact, the Global FL model achieved an F1 score of 75,7%, slightly comparable to that of the Centralized approach at 78,5%. This research underscores the potential of FL in extracting PIIs from EHRs, encouraging its broader adoption in health data analysis.

One of the main challenges of photocatalysis is to find a stable and effective photocatalyst, that is active and effective under sunlight. Here, we discuss the photocatalytic degradation of phenol as a model pollutant in aqueous solution using NUV-Vis (>366 nm) and UV (254 nm) in the presence of TiO 2 -P25 impregnated with different concentrations of Co (0.1%, 0.3%, 0.5%, and 1%). The modification of the surface of the photocatalyst was performed by wet impregnation, and the obtained solids were characterized using X-ray diffraction, XPS, SEM, EDS, TEM, N 2 physisorption, Raman and UV-Vis DRS, which revealed the structural and morphological stability of the modified material. BET isotherms are type IV, with slit-shaped pores formed by nonrigid aggregate particles and no pore networks and a small H3 loop near the maximum relative pressure. The doped samples show increased crystallite sizes and a lower band gap, extending visible light harvesting. All prepared catalysts showed band gaps in the interval 2.3-2.5 eV. The photocatalytic degradation of aqueous phenol over TiO 2 -P25 and Co(X%)/TiO 2 was monitored using UV-Vis spectrophotometry: Co(0.1%)/TiO 2 being the most effective with NUV-Vis irradiation. TOC analysis showed ca. 96% TOC removal with NUV-Vis radiation, while only 23% removal under UV radiation.

Vascular endothelial growth factor (VEGF) and its receptors (VEGFR1 and VEGFR2) are the most important tissue factors involved in tumor growth and angiogenesis. The aim of this study was to evaluate the promoter mutational status of VEGFA and the expression levels of VEGFA, VEGFR1, and VEGFR2 in bladder cancer (BC) tissues and to correlate the results with the clinical-pathological parameters of BC patients. A total of 70 BC patients were recruited at the Urology Department of the Mohammed V Military Training Hospital in Rabat, Morocco. Sanger sequencing was performed to investigate the mutational status of VEGFA, and RT-QPCR was used to evaluate the expression levels of VEGFA, VEGFR1, and VEGFR2. Sequencing of the VEGFA gene promoter revealed the presence of -460T/C, -2578C/A, and -2549I/D polymorphisms, and statistical analyses showed a significant correlation between -460T/C SNP and smoking ( p = 0.02). VEGFA and VEGFR2 expressions were significantly up-regulated in patients with NMIBC ( p = 0.003) and MIBC ( p = 0.03), respectively. Kaplan-Meier analyses showed that patients with high VEGFA expression had significantly longer disease-free survival ( p = 0.014) and overall survival ( p = 0.009). This study was very informative, showing the implication of VEGF alterations in BC, suggesting that VEGFA and VEGFR2 expressions could be promising biomarkers for the better management of BC.

Background: Tumor recurrence and progression in non-muscle invasive bladder cancer (NMIBC), therapy failure, and severe side effects in muscle invasive bladder cancer (MIBC) are the major challenges in the clinical management of bladder cancer (BC). Here, we identify new molecular targetable signatures to improve BC patients' stratification and the outcome of current immunotherapies., Material and Methods: In a prospective cohort of 70 BC patients, we assessed the genetic and molecular regulation of TERT in maintaining telomere length in parallel to immune checkpoint and microRNA expression., Results: TERT was undetectable in healthy bladder tissues but upregulated in invasive BC stages and high tumor grade. Its expression was linked with the combined effect of the C250T mutation and THOR hypermethylation, associated with progressing tumors and maintaining of telomere length. In the same cohort, PD-L1 scored highest in NMIBC, while PD-L2 was upregulated in MIBC. We also show that miR-100-5p and 138-5p were highly expressed in healthy bladder specimens and cell line, while expression decreased in the BC tissues and BC cell lines. In line with the binding prediction for these miRNAs on target genes, miRs 100-5p and 138-5p expression strongly inverse correlated with TERT, PD-L1, and PD-L2 expression, but not PD1., Conclusion: We identify a loop involving TERT, PD1-ligands, and miR-138-5p in BC, that might represent not only a useful biomarker for improved diagnosis and patients' stratification but also as a promising axis that might be therapeutically targeted in situ ., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 El Ahanidi, El Azzouzi, Hafidi Alaoui, Tetou, Bensaid, Chaoui, Benbacer, Hassan, Oukabli, Michaud, Ameur, Al Bouzidi, El Mzibri, Jandus and Attaleb.)

Introduction: in cancer cells, activating mutations in PIK3CA and AKT1 genes, major players of PI3K-AKT-mTOR signalling pathway, are widely reported in many cancers and present attractive targets for the identification of new therapeutics and better cancer management. The present study was planned to evaluate the mutational status of PIK3CA and AKT1 genes in bladder cancer patients and to assess the association between these mutations and patients´ clinico-pathological features., Methods: in this prospective study, bladder cancer biopsies and matched urine sediments samples were collected form 70 patients. Mutations were assessed by deoxyribonucleic acid (DNA) sequencing and correlation with clinico-pathological data was performed using SPSS software., Results: AKT1 alterations were poorly detected. Only one patient with pT1 stage and high-grade tumour carried the E17K mutation. In PIK3CA exon 9, 2 point mutations, E545K and Q546E, and a SNP (E547E) were reported, whereas in exon 20, 2 point mutations (L989V and H1047R) and 2 SNPs (I1022I and T1025T) were detected. PIK3CA mutations were mainly observed in early stages and high-grade tumours. Statistical analysis showed no significant association between the studied AKT1 and PIK3CA mutations and patients´ clinico-pathological parameters (p > 0.05). Detection of these mutations in voided urine samples showed a high specificity (100%) for both genes and a moderate sensitivity: 100% for AKT1 and 66.7% for PIK3CA genes., Conclusion: this study shows clearly that mutations in AKT1 and PIK3CA are rare events and could not be considered as valuable biomarkers for bladder cancer management., Competing Interests: The authors declare no competing interests., (Copyright: Hajar El Ahanidi et al.)

α-Fe 2 O 3 nanoparticles were synthesized via a straightforward method. XRD, FTIR, SEM, ESR, and DRS techniques investigated the influence of various calcination temperatures on the crystal structure, optical, and photocatalytic properties of the samples. The obtained results demonstrated that the average crystallite size increased with the increase in the calcination temperature. Measured and computed optical properties were in accordance and the bandgap energy decreased with the increase in the calcination temperature. The highest photocatalytic degradation efficiency for diclofenac (DCF) was obtained with the sample calcinated at 300 °C (96%). The photocatalytic process occurs because of the presence of OH• radicals. The addition of H 2 O 2 led to the inhibition of OH• radicals that H 2 O 2 scavenged., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Promoter hypermethylation have been reported to play a key role in bladder cancer development and progression. The aim of this study is to evaluate the methylation status of hTERT, TWIST1, VIM and NID2 genes in bladder cancer. The methylation status was evaluated using the Methylation-Specific PCR (MSP) approach on 70 tumour biopsies from Moroccan bladder cancer patients. Overall, methylation frequencies of hTERT, TWIST1, VIM and NID2 genes, were 90%, 85.71%, 67.14% and 67.14%, respectively. Hypermethylation of all studied genes was found in all pathological grades and stages of bladder cancer. Nevertheless, statistical analysis showed no significant association between promoter methylation of hTERT, TWIST1, VIM and NID2 genes and tumours stage/grade (p value >0.05). Moreover, we have investigated the association between the methylation pattern of selected genes and the treatment outcome in a sub-group of non-muscle-invasive bladder cancer cases (52/70). Hypermethylation of hTERT, TWIST1, VIM and NID2 was detected in 83.34%; 66.67%; 83.34% and 58.34% of recurrent cases, respectively, and in 80%; 80%; 80% and 60% of progressive cases, respectively. Statistical analysis highlighted a significant association between TWIST1 hypermethylation and tumour recurrence (p = 0.041<0.05). Our results indicate that hypermethylation of hTERT, TWIST1, VIM and NID2 genes is a frequent epigenetic event in bladder cancer and could be a promising therapeutic target to prevent bladder cancer progression and metastasis., Competing Interests: Declaration of Competing Interest The authors declare that they have no conflict of interest., (Copyright © 2021. Published by Elsevier Inc.)

The removal of emerging contaminants (ECs) for water source reclamation, minimizing energy and chemical use, is an environmental concern worldwide. In this study, we used the technologically cleaner pyrolysis and hydrothermal carbonization (HTC) processes to convert olive oil production wastes into chars in order to simultaneously remove triclosan (TCS), ibuprofen (IBP) and diclofenac (DCF) from water. The chars prepared from olive stone (S), olive tree pruning (P) and pitted and reprocessed wet olive mill waste (H), as well as commercial biochars and a commercial active carbon (CAC), were characterized using different techniques and assayed as adsorbents. Pyrolysis temperatures had only a slight effect on the adsorption capacity of chars. The pseudo second-order reaction kinetic and the Freundlich equation provided the best fit for experimental data. The pH values of char suspensions were negatively correlated with their maximum adsorption capacities. The hydrochars synthetized at the lowest temperatures (≤ 240 °C), which had an acidic pH and were rich in oxygenated functional groups, recorded the highest adsorption rates (64% for DCF, 43% for IBP) and especially for TCS, with a rate of 98%, despite of a low surface area of 7.5 m 2 / g. This study demonstrates for the first time that unmodified hydrochars from pitted and reprocessed wet olive mill waste are inexpensive, sustainable and environmentally friendly adsorbents which can be used to remove ECs and other similar compounds in water treatments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The determination of reaction pathways and identification of products of pollutants degradation is central to photocatalytic environmental remediation. This work focuses on the photocatalytic degradation of the herbicide Imazapyr (2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl) pyridine-3-carboxylic acid) under UV-Vis and visible-only irradiation of aqueous suspensions of Ca x MnO y -TiO 2 , and on the identification of the corresponding degradation pathways and reaction intermediates. Ca x MnO y -TiO 2 was formed by mixing Ca x MnO y and TiO 2 by mechanical grinding followed by annealing at 500 °C. A complete structural characterization of Ca x MnO y -TiO 2 was carried out. The photocatalytic activity of the hetero-nanostructures was determined using phenol and Imazapyr herbicide as model pollutants in a stirred tank reactor under UV-Vis and visible-only irradiation. Using equivalent loadings, Ca x MnO y -TiO 2 showed a higher rate (10.6 μM·h -1 ) as compared to unmodified TiO 2 (7.4 μM·h -1 ) for Imazapyr degradation under UV-Vis irradiation. The mineralization rate was 4.07 µM·h -1 for Ca x MnO y -TiO 2 and 1.21 μM·h -1 for TiO 2 . In the Ca x MnO y -TiO 2 system, the concentration of intermediate products reached a maximum at 180 min of irradiation that then decreased to a half in 120 min. For unmodified TiO 2 , the intermediates continuously increased with irradiation time with no decrease observed in their concentration. The enhanced efficiency of the Ca x MnO y -TiO 2 for the complete degradation of the Imazapyr and intermediates is attributed to an increased adsorption of polar species on the surface of Ca x MnO y . Based on LC-MS, photocatalytic degradation pathways for Imazapyr under UV-Vis irradiation have been proposed. Some photocatalytic degradation was obtained under visible-only irradiation for Ca x MnO y -TiO 2 . Hydroxyl radicals were found to be main reactive oxygen species responsible for the photocatalytic degradation through radical scavenger investigations.

Pharmaceuticals, especially antibiotics, constitute an important group of aquatic contaminants given their environmental impact. Specifically, tetracycline antibiotics (TCs) are produced in great amounts for the treatment of bacterial infections in both human and veterinary medicine. Several studies have shown that, among all antibiotics, oxytetracycline hydrochloride (OTC HCl) is one of the most frequently detected TCs in soil and surface water. The results of the photocatalytic degradation of OTC HCL in aqueous suspensions (30 mg·L - 1 ) of 0.5 wt.% cobalt-doped TiO 2 catalysts are reported in this study. The heterogeneous Co-TiO 2 photocatalysts were synthesized by two different solvothermal methods. Evonik Degussa Aevoxide P25 and self-prepared TiO 2 modified by the same methods were used for comparison. The synthesized photocatalysts were characterized by X-ray powder diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), UV/vis diffuse reflectance spectroscopy (DRS), and N 2 adsorption (BET) for specific surface area determination. The XRD and Raman results suggest that Ti 4+ was substituted by Co 2+ in the TiO 2 crystal structure. Uv/visible spectroscopy of Co-TiO 2 -R showed a substantial redshift in comparison with bare TiO 2 -R. The photocatalytic performance of the prepared photocatalysts in OTC HCL degradation was investigated employing Uv/vis spectroscopy and high-performance liquid chromatography (HPLC). The observed initial reaction rate over Co-TiO 2 -R was higher compared with that of Co-TiO 2 , and the commercial P25. The enhanced photocatalytic activity was attributed to the high surface area (153 m 2 , and the commercial P25. The enhanced photocatalytic activity was attributed to the high surface area (153 m 2 ·g - 1 ) along with the impurity levels within the band gap (2.93 eV), promoting the charge separation and improving the charge transfer ability. From these experimental results, it can be concluded that Co-doping under reflux demonstrates better photocatalytic performances than with the hydrothermal treatment., Competing Interests: The authors declare no conflict of interest.

This study investigates the degradation of imazapyr herbicide from wastewater by photocatalytic ozonation using TiO2 as a semiconductor. Effects of operational parameters on imazapyr removal efficiency including TiO2 dosing, initial herbicide concentration and pH were also studied. Obtained results showed that more than 90% of removal efficiency representing the disappearance of imazapyr was maintained until 7 µM in the presence of 200 mgL-1of UV100-TiO2. Otherwise, the degradation of imazapyr followed the first-order kinetics with a photocatalytic rate constant of 0.247 min-1, and complete degradation was achieved within 20 min using photocatalytic ozonation for 5 µM of Imazapyr at pH 7.

Rationale: 5-Amino-4-chloro-2-phenyl-3(2H)-pyridazone (Chloridazon) is an important systemic herbicide; its transformation by different Advanced Oxidation Processes could result in the formation of different and complex products. These products, that need to be identified, may present a more toxic effect than the parent compound., Methods: The exact and unequivocal structural characterization of the detected by-products of Chloridazon was performed by in-depth analysis of the liquid chromatography/negative electrospray ionization tandem mass spectrometric (LC/ESI+/MS(2) ) fragmentation. Such a technique is a powerful and sensitive analytical tool to study environmental issues. The reactive radicals that induce the degradation of Chloridazon were generated by selective excitation of titanium dioxide as photocatalyst and also by UV photolysis of hydrogen peroxide., Results: Several processes are initiated by hydroxyl radical reaction with Chloridazon. Among them (i) hydroxylation of the phenyl group at the ortho, meta and para positions; (ii) a second hydroxylation process as a secondary reaction is also obtained within the phenyl moiety; (iii) scission of the phenyl-N bond through a hydrolysis process; and (iv) a substitution of the chlorine atom by a hydroxyl group., Conclusions: LC/ESI-Q-TOFMS appeared to be a valuable and precise tool for structural elucidation of the unknown by-products that were generated during hydroxyl radical reactions with Chloridazon. Several hydroxylated and dihydroxylated isomers were identified together with dechlorinated and bridge opening products., (Copyright © 2016 John Wiley & Sons, Ltd.)

Simulated sunlight irradiation causing degradation of amidosulfuron, a pyrimidinylsulfonylurea herbicide, has been investigated in aqueous solution. The main degradation products were followed up by ultrahigh-pressure liquid chromatography with a UV detector (UHPLC-UV) and identified by combining ultrahigh-pressure liquid chromatography-mass spectrometry (UHPLC-MS) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). On the basis of the retrosynthetic analysis, the most identified degradation products were mainly due to the losses of methylsulfamic acid (CH₅NO₃S), sulfocarbamic acid (CH₃NO₅S), carbamic acid (CH₃NO₂), methyl(methylsulfonyl)sulfamic acid (C₂H₇NO₅S₂), N-methylmethanesulfonamide (C₂H₇NO₂S), and sulfonic acid (H₂SO₄) molecules. Accordingly, O and S-demethylation as well as hydroxylation processes were also observed. Sum formulas of the main degradation products were assigned, and a mechanical pathway is proposed.

The hydrolysis of the herbicide safener mefenpyrdiethyl (1-(2, 4-dichlorophenyl)-4, 5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylic acid diethyl ester) was investigated in aqueous solutions in the pH range from 2 to 9 and the temperature range from 298 to 323 K. The kinetics of hydrolysis were pseudo first order and were found to be strongly pH and temperature dependent. While near-constant in acidic medium, the hydrolysis rates strongly increased in alkaline pH, and total hydrolysis was observed at pH 11. Two main hydrolysis products, mefenpyrethyl (monoester) and mefenpyr (dicarboxylic acid) were isolated by ultrahigh-pressure liquid chromatography (UHPLC) and characterized using high-resolution Fourier transform ion cyclotron resonance mass spectroscopy (ICR-FT/MS) as well as (1)H, (13)C and 2D NMR analyses. Additionally, a density functional theory (DFT) investigation explained the stability of the pesticide at pH 7 and the high reactivity of the pesticide in alkaline medium. The key nucleophilic reaction partner is hydroxyl ions instead of neutral water molecules. Furthermore, the calculated activation barrier for hydrolysis in alkaline medium is in agreement with the extrapolated and experimentally determined activation barrier at pH 14.

The photodecomposition of imazamox, a herbicide of the imidazolinone family, was investigated in pure water. The main photoproducts from the photolysis were followed over time by liquid chromatography mass spectrometry and structures were proposed from exact mass determinations obtained by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The method comprised exact mass determination with better than 0.2 ppm mass accuracy and a corresponding structural visualization taking care of respective isotopes with an adapted van Krevelen diagram that enabled a systematic approach to the characterisation of the elementary composition of each photoproduct. By taking advantage of the high resolving power of FT-ICR MS to make precise formula assignments, the derived 2D van Krevelen diagram (O/C; H/C; m/z) enabled one to structurally differentiate the formed photoproducts and to propose a degradation pathway for imazamox.

The authors report the case of a 40 years old woman with a fronto parietal tumefaction and intracranial hypertension caused by a paraganglioma of the cranial vault. The clinical follow up is marked by rapid local recurrence of the tumor after complete excision. Usually paragangliomas arise in any area of the body where paraganglionar structures are situated (glomus jugulare, carotid glomus, vagus nerve). Other rare locations have been reported and remain difficult to be explained. The location at the cranial vault is exceptional. this tumor would probably arise from the paraganglionar cells which migrate from the neural crest following the trigeminal branches particularly the ophtalmic division.