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1.
World J Urol ; 42(1): 172, 2024 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-38506927

RESUMO

PURPOSE: To compare the outcomes of patients undergoing robotic YV plasty for bladder neck contracture (BNC) vs. vesico-urethral anastomotic stricture (VUAS). METHODS: A retrospective study included male patients who underwent robotic YV plasty for BNC after endoscopic treatment of BPH or VUAS between August 2019 and March 2023 at a single academic center. The primary assessed was the patency rate at 1 month post-YV plasty and during the last follow-up visit. RESULTS: A total of 21 patients were analyzed, comprising 6 in the VUAS group and 15 in the BNC group. Patients with VUAS had significantly longer operative times (277.5 vs. 146.7 min; p = 0.008) and hospital stay (3.2 vs. 1.7 days; p = 0.03). Postoperative complications were more common in the VUAS group (66.7% vs. 26.7%; p = 0.14). All patients resumed spontaneous voiding postoperatively. Five patients (23.8%) who developed de novo stress urinary incontinence had already an AUS (n = 1) or required concomitant AUS implantation (n = 3), all of whom were in the VUAS group (83.3% vs. 0%; p < 0.0001). The proportion of patients improved was similar in both groups (PGII = 1 or 2: 83.3% vs. 80%; p = 0.31). Stricture recurrence occurred in 9.5% of patients in the whole cohort, with no significant difference between the groups (p = 0.50). Long-term reoperation was required in three VUAS patients, showing a statistically significant difference between the groups (p = 0.05). CONCLUSION: Robotic YV plasty is feasible for both VUAS and BNC. While functional outcomes and stricture-free survival may be similar for both conditions, the perioperative outcomes were less favorable for VUAS patients.


Assuntos
Contratura , Procedimentos Cirúrgicos Robóticos , Estreitamento Uretral , Obstrução do Colo da Bexiga Urinária , Humanos , Masculino , Bexiga Urinária/cirurgia , Constrição Patológica/etiologia , Constrição Patológica/cirurgia , Procedimentos Cirúrgicos Robóticos/efeitos adversos , Estudos Retrospectivos , Obstrução do Colo da Bexiga Urinária/cirurgia , Obstrução do Colo da Bexiga Urinária/complicações , Contratura/cirurgia , Estreitamento Uretral/etiologia , Estreitamento Uretral/cirurgia , Prostatectomia/efeitos adversos
2.
bioRxiv ; 2023 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-38076793

RESUMO

The recognition of core promoter sequences by the general transcription factor TFIID is the first step in the process of RNA polymerase II (Pol II) transcription initiation. Metazoan holo-TFIID is composed of the TATA binding protein (TBP) and of 13 TBP associated factors (TAFs). Inducible Taf7 knock out (KO) results in the formation of a Taf7-less TFIID complex, while Taf10 KO leads to serious defects within the TFIID assembly pathway. Either TAF7 or TAF10 depletions correlate with the detected TAF occupancy changes at promoters, and with the distinct phenotype severities observed in mouse embryonic stem cells or mouse embryos. Surprisingly however, under either Taf7 or Taf10 deletion conditions, TBP is still associated to the chromatin, and no major changes are observed in nascent Pol II transcription. Thus, partially assembled TFIID complexes can sustain Pol II transcription initiation, but cannot replace holo-TFIID over several cell divisions and/or development.

3.
Aesthetic Plast Surg ; 47(6): 2283-2294, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37684416

RESUMO

INTRODUCTION: Most of the time, female-to-male (FtoM) chest surgery involves mastectomy techniques and free transplantation of the nipple-areola complex. With the increasing prevalence of gender dysphoria and the demand for female-to-male gender reassignment surgery, the need for FtM top surgery is also rising. To meet this demand, we present a new approach: the PIPe technique, based on a fasciocutaneous flap with a posteroinferior pedicle. MATERIALS AND METHODS: All patients with FtoM gender dysphoria undergoing surgery using the posteroinferior pedicle flap technique in the Plastic Surgery Department at Rennes University Hospital Center were included. The procedure involved extensive liposuction of the lower internal and external mammary quadrants, followed by liposuction of deep tissues in the upper quadrants, except in the pedicle area. After removing skin from the lower quadrants down to the dermis and de-epithelializing the posteroinferior pedicle flap, the thoracic flap was lowered and the areola transposed. RESULTS: From July 2022 to March 2023, fifteen patients underwent surgery, and their results were collected prospectively. The average age was 25 years, the mean weight was 76.6 kg, and the average BMI was 28.1 kg/m2. The average operating time was 102 min, and the mean weight excised was 459.5 g. The average length of hospital stay was 3.3 days, and the drainage duration was 2.4 days. No major complications were reported, and there were no cases of reintervention or recurrence. CONCLUSIONS: Our study presents a novel surgical approach utilizing the posteroinferior pedicle technique. Its key benefit lies in the preservation of neurovascular function, which makes it an attractive option for patients seeking to retain nipple sensitivity. This procedure is reliable, reproducible, and recommended as a first-line treatment for grade II and III gynecomastia due to its low rate of major complications and favorable functional and aesthetic outcomes. LEVEL OF EVIDENCE IV: This journal requires that authors assign a level of evidence to each article. For a full description of these Evidence-Based Medicine ratings, please refer to the Table of Contents or the online Instructions to Authors www.springer.com/00266 .


Assuntos
Neoplasias da Mama , Mamoplastia , Cirurgia de Readequação Sexual , Humanos , Masculino , Feminino , Adulto , Neoplasias da Mama/cirurgia , Mamoplastia/métodos , Mastectomia , Estudos Retrospectivos , Mamilos/cirurgia , Estética , Resultado do Tratamento
4.
Prog Urol ; 33(11): 541-546, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37516600

RESUMO

OBJECTIVES: Transcutaneous posterior tibial nerve stimulation (TC-PTNS) is a validated option for lower urinary tract symptoms (LUTS) management, with a short-term success rate of around 60% and few adverse events. Our goal was to report the efficacy and safety results of TC-PTNS using the newly issued device TENSI+ for LUTS management. PATIENTS AND METHODS: A multicenter, retrospective study was conducted in 7 urology departments in France. All patients treated with TC-PTNS for LUTS using the TENSI+ device between September 2021 and February 2022 were included. All patients received supervised at-home training by a specialized nurse. All patients were asked to do daily, 20minutes sessions of TC-PTNS. Patient demographics, history, initial symptoms and previous treatment were collected at inclusion. A follow-up visit was scheduled at 3 months. Efficacy was evaluated through treatment persistence at 3 months and PGI-I (Patient Global Impression of Improvement) score. Adverse events were recorded. RESULTS: One hundred and three patients (86 women and 17 men) were included. All patients had overactive bladder symptoms, 64 suffered from urgency incontinence, and 24 had associated voiding symptoms. Eighteen patients had neurogenic background, and 30 previously received anticholinergics. After a median follow-up of 12 [10-21]weeks, 70 patients were still using the device (68%). PGI-I score reflected an improvement in 70.9% and was 1, 2 and 3 in 28, 26 and 19 patients respectively, while 24 were unchanged and 6 were worse. No clinical baseline parameter was predictive of success. Adverse events included pain at stimulation site (two cases) and pelvic pain (two patients), which rapidly resolved after treatment interruption. CONCLUSIONS: TC-PTNS with TENSI+ device is an effective option for LUTS management, with results that seem similar to other TC-PTNS approaches. Adverse events were mild and reversible after treatment interruption.


Assuntos
Sintomas do Trato Urinário Inferior , Estimulação Elétrica Nervosa Transcutânea , Bexiga Urinária Hiperativa , Masculino , Humanos , Feminino , Estimulação Elétrica Nervosa Transcutânea/efeitos adversos , Estimulação Elétrica Nervosa Transcutânea/métodos , Estudos Retrospectivos , Bexiga Urinária Hiperativa/terapia , Sintomas do Trato Urinário Inferior/etiologia , Sintomas do Trato Urinário Inferior/terapia , Nervo Tibial
5.
Int J Urol ; 30(11): 1008-1013, 2023 11.
Artigo em Inglês | MEDLINE | ID: mdl-37439555

RESUMO

OBJECTIVES: The purpose of this study was to report the rate of stress urinary incontinence (SUI) recurrence after sling revision, and to determine predictive factors of SUI recurrence. METHODS: We conducted a retrospective cohort study in a single academic center between 2005 and 2022, of patients who underwent sling revision. Four surgical techniques were used for sling revision (loosening, section, partial, and total excision). The primary endpoint was recurrence of SUI at 3 months postoperatively, and the other outcome of interest was the rate of subsequent anti-incontinence surgical procedure. RESULTS: Sixty-nine patients were included for analysis. SUI recurred in 46.4% of patients. Fifteen patients underwent a subsequent anti-incontinence procedure (21.8%). The time to revision was significantly longer in the group with recurrent SUI (median: 84.5 vs. 44.8 months; p = 0.004). The recurrence rate differed significantly depending on the revision technique: 7.7% after sling loosening, 22.2% after sling section, 60% after partial excision, and 66.7% after complete sling removal (p = 0.001). The risk of SUI recurrence was lower for those whose indication of reoperation was voiding dysfunction (27.3% vs. 66.7%; p = 0.002), and was higher for those who underwent a trans-obturator tap rather than a tension-free vaginal tape revision (68.4% vs. 35.7%; p = 0.02). In multivariate analysis, only the revision technique remained significantly associated with the risk of recurrence of SUI (complete excision vs. section: odds ratio = 4.66; p = 0.04). CONCLUSION: The risk of SUI recurrence may differ widely according to the techniques used, and it seems that the less extensive the surgical procedure is, the lower the risk is.


Assuntos
Slings Suburetrais , Incontinência Urinária por Estresse , Incontinência Urinária , Feminino , Humanos , Incontinência Urinária por Estresse/cirurgia , Incontinência Urinária por Estresse/etiologia , Estudos Retrospectivos , Slings Suburetrais/efeitos adversos , Fatores de Risco , Reoperação/efeitos adversos , Reoperação/métodos , Incontinência Urinária/etiologia , Resultado do Tratamento , Recidiva
6.
Int Urogynecol J ; 34(10): 2479-2485, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37204473

RESUMO

INTRODUCTION AND OBJECTIVES: Almost two decades after the description of robotic vesicovaginal fistula repair (R-VVF), the literature remains limited. The aims of this study are to report the outcomes of R-VVF and to compare the transvesical versus extravesical techniques. METHODS: We performed an observational, retrospective, multicenter study, including all patients who underwent R-VVF from March 2017 to September 2021 at four academic institutions. All abdominal VVF repair over the study period were performed using a robotic approach. The success of R-VVF was defined as the absence of clinical recurrence. The outcomes of the extravesical versus transvesical techniques were compared. RESULTS: Twenty-two patients were included. The median age was 43 years old (IQR 38-50). Fistulas were supratrigonal and trigonal in 18 and 4 cases respectively. Five patients had undergone previous attempts of fistula repair (22.7%). The fistulous tract was systematically excised, and an interposition flap was used in all but two cases (90.9%). The transvesical and extravesical techniques were used in 13 and 9 cases respectively. There were four postoperative complications, three minor and one major. None of the patients had vesicovaginal fistula recurrence after a median follow-up of 15 months. CONCLUSIONS: The present series, one of the largest R-VVF reported to date, is consistent with the few series already published with a 100% cure rate. Systematic excision of the fistulous tract and the high rate of flap interposition may explain the high success rate. The transvesical and extravesical approaches yielded similar outcomes.

7.
World J Urol ; 41(4): 1187-1192, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36808530

RESUMO

PURPOSE: Neurogenic bladder associated with spina bifida disease remains a major cause for mortality or morbidity due to kidney damages. However, we currently do not know which urodynamic findings are associated with an higher risk of upper tract damages in spina bifida patients. The objective of the present study was to evaluate urodynamic findings associated with functional kidney failure and/or with morphological kidney damages. METHODS: A large single-center restrospective study was conducted in our national referral center for spina bifida patients using our patients' files. All urodynamics curves were assessed by the same examinator. Functional and/or morphological evaluation of the upper urinary tract were done at the same moment as the urodynamic exam (between 1 week before and 1 month after). Kidney function was assessed using creatinine serum levels or 24 h urinary creatinine levels (creatinine clearance) for walking patients, or with the 24 h urinary creatinine level for wheelchair-users. RESULTS: We included 262 spina bifida patients in this study. Fifty-five patients had a poor bladder compliance (21.4%) and 88 of them had detrusor overactivity (33.6%). Twenty patients had a stage 2 kidney failure (eGFR < 60 ml/min) and 81 patients out of 254 (30.9%) had an abnormal morphological examination. There were three urodynamic findings significantly associated with UUTD: bladder compliance (OR = 0.18; p = 0.007), Pdetmax (OR = 14.7; p = 0.003) and detrusor overactivity (OR = 1.84; p = 0.03). CONCLUSION: In this large series of spina bifida patients, maximum detrusor pressure and bladder compliance are the main urodynamic findings determinants of UUTD risk.


Assuntos
Insuficiência Renal , Disrafismo Espinal , Bexiga Urinaria Neurogênica , Humanos , Adulto , Creatinina , Disrafismo Espinal/complicações , Bexiga Urinária , Bexiga Urinaria Neurogênica/complicações , Insuficiência Renal/complicações , Urodinâmica , Fatores de Risco
8.
Photochem Photobiol Sci ; 21(8): 1497-1510, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35532879

RESUMO

Plants play a central role in the photochemistry of chemicals in the environment. They represent a major atmospheric source of volatile organic compounds (VOCs) but also an important environmental surface for the deposition and photochemical reactions of pesticides, gaseous and particulate pollutants. In this review, we point out the role of plant leaves in these processes, as a support affecting the reactions physically and chemically and as a partner through the release of natural constituents (water, secondary metabolites). We discuss the influence of the chosen support (leaves, needle surfaces or fruit cuticles, extracted cuticular waxes and model surfaces) and other factors (additives, pesticides mixture, and secondary metabolites) on the photochemical degradation kinetics and mechanisms. We also show how plants can be a source of photochemically reactive species which can act as photosensitizers promoting the photodegradation of pesticides or the formation and aging of secondary organic aerosols (SOA) and secondary organic materials (SOM). Understanding the fate of chemicals on plants is a research area located at the interface between photochemistry, analytical chemistry, atmospheric chemistry, microbiology and vegetal physiology. Pluridisciplinary approaches are needed to deeply understand these complex phenomena in a comprehensive way. To overcome this challenge, we summarize future research directions which have been clearly overlooked until now.


Assuntos
Pesquisa Interdisciplinar , Praguicidas , Aerossóis/química , Fotoquímica , Plantas
9.
Neurourol Urodyn ; 41(2): 601-608, 2022 02.
Artigo em Inglês | MEDLINE | ID: mdl-34962653

RESUMO

AIM: The objective of the present study was to compare the outcomes of open versus laparoscopic versus robotic cystectomy and ileal conduit for neurogenic lower urinary tract dysfunction (NLUTD). METHODS: The charts of all patients who underwent cystectomy and ileal conduit for NLUTD between January 2004 and November 2020 in an academic center were retrospectively reviewed. The approach was either open, laparoscopic or robot-assisted depending on the period (i.e., three consecutive era). For the robotic approach, the diversion was done either intracorporeally or extracorporeally. We compared the perioperative and late postoperative outcomes between the three groups. RESULTS: After exclusion of 10 patients with non-neurogenic benign conditions, 126 patients were included over the study period. The most frequent neurological conditions were multiple sclerosis (36.5%) and spinal cord injury (25.4%). The approach was open, laparoscopic or robot-assisted in 31 (24.6%), 26 (20.6%) and 69 (54.7%) cases respectively. Seventy-two patients experienced a 90-day postoperative complication (57.1%) of which 22 had a major complication (Clavien 3 or higher, 17.5%) including one death (0.8%). The rate of major postoperative complications was significantly lower in the robotic group (23% vs. 23% vs. 10%; p = 0.049) while the rate of overall complications was comparable across the three groups (58.1% vs. 53.9% vs. 60.6%; p = 0.84). After a median follow-up of 23 months, 22 patients presented a late complication (17.6%), mainly incisional hernia (5; 4%) and uretero-ileal stricture (9; 7.2%). The rate of late complications did not differ significantly between the three approaches. CONCLUSION: Cystectomy and ileal conduit for neurogenic bladder is associated with a relatively high perioperative morbidity. The robot-assisted approach may decrease the risk of major postoperative complications.


Assuntos
Laparoscopia , Procedimentos Cirúrgicos Robóticos , Robótica , Neoplasias da Bexiga Urinária , Bexiga Urinaria Neurogênica , Derivação Urinária , Cistectomia/efeitos adversos , Humanos , Laparoscopia/efeitos adversos , Complicações Pós-Operatórias/epidemiologia , Complicações Pós-Operatórias/etiologia , Complicações Pós-Operatórias/cirurgia , Estudos Retrospectivos , Procedimentos Cirúrgicos Robóticos/efeitos adversos , Resultado do Tratamento , Neoplasias da Bexiga Urinária/cirurgia , Bexiga Urinaria Neurogênica/etiologia , Derivação Urinária/efeitos adversos
10.
Sci Total Environ ; 807(Pt 1): 150716, 2022 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-34626636

RESUMO

Among the numerous studies devoted to the photodegradation of pesticides, very scarce are those investigating the effect of plant volatiles. Yet, pesticides can be in contact with plant volatiles after having been spread on crops or when they are transported in surface water, making interactions between the two kinds of chemicals possible. The objectives of the present study were to investigate the reactions occurring on plants. We selected thyme as a plant because it is used in green roofs and two pesticides: the fungicide chlorothalonil for its very oxidant excited state and the insecticide imidacloprid for its ability to release the radical NO2 under irradiation. Pesticides were irradiated with simulated solar light first in a solvent ensuring a high solubility of pesticides and plant volatiles, and then directly on thyme's leaves. Analyses were conducted by headspace gas chromatography-mass spectrometry (HS-GC-MS), GC-MS and liquid chromatography-high resolution mass spectrometry (LC-HRMS). In acetonitrile, chlorothalonil photosensitized the degradation of thymol, α-pinene, 3-carene and linalool with high quantum yields ranging from 0.35 to 0.04, and was photoreduced, while thymol underwent oxidation, chlorination and dimerization. On thyme's leave, chlorothalonil was photoreduced again and products arising from oxidation and dimerization of thymol were detected. Imidacloprid photooxidized and photonitrated thymol in acetonitrile, converting it into chemicals of particular concern. Some of these chemicals were also found when imidacloprid was irradiated dispersed on thyme's leaves. These results show that photochemical reactions between pesticides and the plants secondary metabolites can take place in solution as on plants. These findings demonstrate the importance to increase our knowledge on these complex scenarios that concern all the environmental compartments.


Assuntos
Praguicidas , Thymus (Planta) , Cromatografia Gasosa-Espectrometria de Massas , Praguicidas/análise , Plantas , Timol
11.
Water Res ; 206: 117775, 2021 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-34706320

RESUMO

Metrafenone (MF), as a new type of benzophenone fungicide, has been widely used in agriculture and is persistent in the environment. Understanding its photochemical fate is essential for the comprehensive evaluation of its ecological risk. In the present work, we reported a detailed study on the photochemical transformation of MF in aqueous solution under irradiation (at λ > 290 nm using a high pressure mercury lamp). MF was relatively photo-reactive showing a low polychromatic quantum yield of photolysis (1.06 × 10-4, 20 µM) counterbalanced by a significant light absorption above 290 nm. A series of photoproducts were identified by high resolution mass spectrometry (HR-MS) analysis, and three different pathways, including oxidation of the methyl group, debromination and replacement of bromine by hydroxyl group were proposed. Among them, debromination was identified as the dominating process that could be achieved via homolytic C-Br bond cleavage from singlet and triplet MF, as confirmed by laser flash photolysis (LFP) experiments and density functional theory (DFT) calculations. Toxicity assessment revealed that photochemical degradation reduced the ecotoxicity of MF efficiently. Nitrate ions and humic acid promoted the MF photolysis, while bicarbonate exhibited no effect. Results obtained in this work would increase our understanding on the environmental fate of MF in sunlit surface waters.


Assuntos
Fungicidas Industriais , Poluentes Químicos da Água , Benzofenonas , Bromo , Carbono , Cinética , Fotólise , Poluentes Químicos da Água/análise
12.
Urology ; 158: 215-221, 2021 12.
Artigo em Inglês | MEDLINE | ID: mdl-34537197

RESUMO

OBJECTIVE: To describe and assess the outcomes of dorsal onlay oral mucosa graft urethroplasty for female urethral stricture. METHODS: We retrospectively reviewed the charts of all female patients who underwent dorsal onlay oral (buccal or lingual) mucosa urethroplasty for urethral stricture between 2011 and 2020 at two academic institutions. The primary endpoint was clinical success defined as any subjective improvement in LUTS self-assessed by the patients 1-3 months after catheter removal. Four surgeons performed the urethroplasties using a standardized technique: suprameatal incision, dissection and longitudinal opening of the dorsal aspect of the urethra, harvest of the oral mucosa graft, graft onlay sutured into the urethral opening. RESULTS: Nineteen patients were included. The clinical success rate was 94.7% at 1-3 months and 90.9% at 1 year. After a median follow-up of 12 months (range 1-49) there was one recurrence (5.3%), clinical success was achieved in 17 patients (89.5%) and both the maximum urinary flow rate and post void residual were significantly improved (15.2 vs 7.4 ml/s preoperatively; P = .008 and 71.5 vs 161.1 ml preoperatively; P = .001 respectively). The de novo stress urinary incontinence rate was 15.7% at 1-3 months and 9.1% at 1 year. CONCLUSION: Dorsal onlay oral mucosa graft urethroplasty for female urethral stricture appears feasible across multiple surgeons and is associated with a low perioperative morbidity, satisfactory functional outcomes and a low recurrence rate. Other series with larger sample size and longer follow-up are needed to confirm these findings.


Assuntos
Mucosa Bucal/transplante , Uretra/cirurgia , Estreitamento Uretral/cirurgia , Idoso , Feminino , Humanos , Pessoa de Meia-Idade , Estudos Retrospectivos , Resultado do Tratamento , Procedimentos Cirúrgicos Urológicos/métodos
13.
Water Res ; 202: 117395, 2021 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-34273776

RESUMO

The present study aimed to investigate the changes in the chemical composition, and in the optical and photooxidant properties of Suwannee River Natural Organic Matter (SRNOM) induced by UVC (254 nm) treatment. The extent of the photodegradation was first assessed by UV-visible/fluorescence spectroscopies and organic carbon analysis. An in-depth investigation of the chemical changes was also conducted using liquid chromatography-mass spectrometry and gas chromatography-mass spectrometry after derivatizations. A series of mono, di and tricarbonyls and mono and dicarboxylic acids in C1C6 were identified in samples irradiated from 1 to 4 h. After 3 h of irradiation, carbonyls accounted for 46% of the organic carbon remaining in solution whereas carboxylic acids represented about 2%. Then, we investigated the modifications of the photooxidant properties of SRNOM induced by these chemical changes. At 254 nm, UVC pre-irradiated SRNOM photodegraded glyphosate 29 times faster than original SRNOM and the reaction was fully inhibited by 2-propanol (5 × 10-3 M). This enhanced photooxidant properties at 254 nm toward glyphosate was therefore reasonably due to •OH radicals formation, as confirmed by additional ESR measurements. A mechanism involving a chain reaction was proposed based on independent experiments conducted on carbonyl compounds, particularly pyruvic acid and acetone. The findings of this study show that UVC pre-treatment of NOM can enhance the removal of water pollutants and suggests a possible integration of a NOM pre-activation step in engineered water treatment sytems.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Fotólise , Rios , Raios Ultravioleta
14.
J Chromatogr A ; 1650: 462251, 2021 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-34062482

RESUMO

The carbon dots (CDs) from natural nanographite oxide mixture (NGO-MIX) and from its fraction NGO (3.5-10K) recovered after ultrafiltration and dialysis were analyzed by 3D-excitation/emission matrix and high-performance size exclusion chromatography (HPSEC) combined with online fluorescence and absorbance detections. HPSEC chromatograms obtained simultaneously with absorption within the wavelength range 200-500 nm and fluorescence detection at λexc/λem = 270/450 nm/nm showed that NGO-MIX sample is not homogeneous and consist of well resolved CDs fractions with different sizes, absorption spectra and distinct fluorescence and non-fluorescence properties. Despite the twice higher fluorescence intensity of fraction NGO (3.5-10K) compared to the NGO-MIX, some impurity of non-fluorescent components was detected by HPSEC. The absorbance spectra of chromatographic peaks, extracted from the data of multi-wavelength absorbance detector, demonstrated different combinations of absorbance maxima. It means that different chromatographic peaks correspond to sized and chemically different CDs fractions. This study demonstrated for the first time the possibility of separating oxidized nanographite into homogeneous free from non-fluorescent material CDs fractions with their simultaneous spectroscopic characterization.


Assuntos
Carbono , Técnicas de Química Analítica , Cromatografia em Gel , Pontos Quânticos , Carbono/análise , Carbono/isolamento & purificação , Técnicas de Química Analítica/instrumentação , Técnicas de Química Analítica/métodos , Fluorescência , Compostos Orgânicos/análise , Pontos Quânticos/análise , Análise Espectral
15.
Molecules ; 26(9)2021 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-33922609

RESUMO

Psychoactive drugs are classified as contaminants of emerging concern but there is limited information on their fate in surface waters. Here, we studied the photodegradation of three psychoactive drugs (sertraline, clozapine, and citalopram) in the presence of organic matter (WEOM) extracted under mild conditions from sediment of Lake Pamvotis, Greece. Spectral characterization of WEOM confirmed its humic-like nature. Preliminary experiments using chemical probes showed that WEOM was able to produce oxidant triplet excited state (3WEOM*), singlet oxygen (1O2), and hydroxyl radicals under irradiation with simulated solar light. Then, WEOM at 5 mgC L-1 was irradiated in the presence of the three drugs. It enhanced their phototransformation by a factor of 2, 4.2, and 16 for sertraline, clozapine, and citalopram, respectively. The drastic inhibiting effect of 2-propanol (5 × 10-3 M) on the reactions demonstrated that hydroxyl radical was the key intermediate responsible for drugs photodegradation. A series of photoproducts were identified by ultra-high performance liquid chromatography (UHPLC) coupled to high resolution mass spectrometry (HR-MS). The photodegradation of the three drugs proceeded through several pathways, in particular oxidations of the rings with or without O atom inclusion, N elimination, and substitution of the halogen by OH. The formation of halogenated aromatics was observed for sertraline. To conclude, sedimental natural organic matter can significantly phototransform the studied antidepressant drugs and these reactions need to be more investigated. Finally, ecotoxicity was estimated for the three target analytes and their photoproducts, using the Ecological Structure Activity Relationships (ECOSAR) computer program.


Assuntos
Radical Hidroxila/química , Fotólise , Psicotrópicos/química , Poluentes Químicos da Água/química
16.
Sci Total Environ ; 780: 146451, 2021 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-33773343

RESUMO

Ambroxol (AMB) is a drug commonly used for chronic bronchitis prevention. Once released in surface water, this recalcitrant chemical becomes a hazardous pollutant. Here, we investigated the ability of 1% Mn-doped TiO2 (Mn-TiO2) to mineralize AMB by photocatalysis. We studied the morphology, and the physical and electrochemical properties of Mn-TiO2 using X-ray diffraction, Scanning electron microscopy, Transmission electron microscopy, X-ray fluorescence, BET method, UV-visible, and electrochemical study and optimized the AMB degrading experimental conditions through response surface methodology (RSM). Mn-TiO2 at the dose of 0.625 g·L-1 allowed the complete photodegradation of AMB (30 ppm) at pH 7 under UVA light irradiation for 30 min while total mineralization in CO2 (>96%) was achieved after 24 h of irradiation. Mn-TiO2 was 1.6-time more efficient than TiO2 Degussa P25. Product studies were also carried out by liquid chromatography coupled to electrospray high resolution mass spectrometry. Twenty-one photodegradation products were detected and identified. In addition, ionic chromatography analyses revealed the release of Br-, NH4+, and NO3- at respectively 97, 63 and 35% of the total Br, and N initially present in AMB. Finally, the reusability of the photocatalyst was also tested. After four cycles, the almost complete photodegradation of AMB was achieved showing that Mn-TiO2 was highly stable. This work brings new physical characteristics on Mn-TiO2 photocatalyst. Moreover, it is the first study investigating the photocatalytic degradation of recalcitrant AMB drug.


Assuntos
Ambroxol , Poluentes Químicos da Água , Catálise , Projetos de Pesquisa , Titânio , Difração de Raios X
17.
Molecules ; 26(4)2021 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-33572434

RESUMO

Perfluoroalkyl substances (PFAS) represent one of the most recalcitrant class of compounds of emerging concern and their removal from water is a challenging goal. In this study, we investigated the removal efficiency of three selected PFAS from water, namely, perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and pefluorooctanesulfonic acid (PFOS) using a custom-built non-thermal plasma generator. A modified full factorial design (with 2 levels, 3 variables and the central point in which both quadratic terms and interactions between couple of variables were considered) was used to investigate the effect of plasma discharge frequency, distance between the electrodes and water conductivity on treatment efficiency. Then, the plasma treatment running on optimized conditions was used to degrade PFAS at ppb level both individually and in mixture, in ultrapure and groundwater matrices. PFOS 1 ppb exhibited the best degradation reaching complete removal after 30 min of treatment in both water matrices (first order rate constant 0.107 min-1 in ultrapure water and 0.0633 min-1 in groundwater), while the degradation rate of PFOA and PFHxA was slower of around 65% and 83%, respectively. During plasma treatment, the production of reactive species in the liquid phase (hydroxyl radical, hydrogen peroxide) and in the gas phase (ozone, NOx) was investigated. Particular attention was dedicated to the nitrogen balance in solution where, following to NOx hydrolysis, total nitrogen (TN) was accumulated at the rate of up to 40 mgN L-1 h-1.


Assuntos
Ácidos Alcanossulfônicos/metabolismo , Caproatos/metabolismo , Caprilatos/metabolismo , Fluorocarbonos/metabolismo , Água Subterrânea/química , Gases em Plasma/química , Poluentes Químicos da Água/metabolismo , Purificação da Água/métodos , Ácidos Alcanossulfônicos/análise , Ácidos Alcanossulfônicos/isolamento & purificação , Caproatos/análise , Caproatos/isolamento & purificação , Caprilatos/análise , Caprilatos/isolamento & purificação , Fluorocarbonos/análise , Fluorocarbonos/isolamento & purificação , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/isolamento & purificação
18.
J Agric Food Chem ; 68(52): 15409-15417, 2020 Dec 30.
Artigo em Inglês | MEDLINE | ID: mdl-33337882

RESUMO

Plant defense inducers (PDIs) are booming and attractive protection agents designed to immunostimulate the plant to reduce subsequent pathogen colonization. The structure-PDI activity relationships of four flavan-3-ols: Epicatechin (EC), Epigallocatechin (EGC), Epicatechin gallate (ECG), Epigallocatechin gallate (EGCG) and Gallotannic acid (GTA) were investigated in both whole plant and suspension cell systems. ECG, EGCG, and GTA displayed elicitor activities. Their infiltration into tobacco leaves induced hypersensitive reaction-like lesions with topical scopoletin and PR-target transcript accumulations. On the contrary, EC and EGC infiltrations fail to trigger the biochemical changes in tobacco tissues. The tobacco BY-2 cells challenged with ECG, EGCG, or GTA led to alkalinization of the BY-2 extracellular medium while EC and EGC did not trigger any pH variation. This work provides evidence that the esterified gallate pattern is as an essential flavonoid entity to induce plant defense reactions in tobacco. The phytoprotective properties of the esterified gallate-free EC and the esterified gallate-rich GTA were evaluated on the tobacco/Phytophthora parasitica var. nicotianae (Ppn) pathosystem. Tobacco treatment with EC did not induce significant protection against Ppn compared to GTA which shows antimicrobial properties on Ppn and decreases the infection on GTA-infiltrated and -sprayed wild-type leaves. GTA protection was impaired in the transgenic NahG tobacco plants, suggesting that protection was mediated by salicylic acid.


Assuntos
Flavonoides/química , Flavonoides/farmacologia , Doenças das Plantas/imunologia , Catequina/análogos & derivados , Catequina/química , Catequina/farmacologia , Estrutura Molecular , Phytophthora/fisiologia , Doenças das Plantas/microbiologia , Folhas de Planta/efeitos dos fármacos , Folhas de Planta/imunologia , Folhas de Planta/microbiologia , /microbiologia
19.
Environ Sci Pollut Res Int ; 27(21): 26385-26394, 2020 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-32363461

RESUMO

Wetlands are recognized for the importance of their hydrological function and biodiversity, and there is now a consensus to protect and restore them as well as to complete the knowledge on their functioning. Here, we studied the dissolved organic matter (DOM) of a wetland composed of the Auzon cut-off meander, the Allier River, the alluvial fluvial flow, and watershed aquifer. Water was sampled at different locations, in spring, summer, and autumn. For each sample, DOM was characterized for its chemical and optical properties and its photooxidant capacity through its ability to generate DOM triplet excited states (3DOM*) and singlet oxygen upon simulated solar light exposure. UV-visible and fluorescence indices revealed that DOM was mainly microbial-derived whatever the sampling sites with spatial and temporal variations in terms of aromaticity (5.5-22%), specific UV absorbance at 254 nm (0.28-2.82 L m-1mgC-1), ratio of the absorbance at 254 and 365 nm (4.6-10.8), fluorescence index (1.35-166), and biological index (0.812-2.25). All the samples generated 3DOM* and singlet oxygen, rates of formation of which showed parallel variations. Using principal component analysis (PCA), we found positive correlations between the sensitizing properties of DOM samples and parameters associated to the abundance of low molecular weight and low absorbing chromophores. Moreover, the parameter variation across the wetland reinforced the hydrological movements observed in a previous study, suggesting that these parameters could be used as water connection tracers.


Assuntos
Rios , Áreas Alagadas , França , Estações do Ano , Oxigênio Singlete
20.
Spectrochim Acta A Mol Biomol Spectrosc ; 238: 118450, 2020 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-32413721

RESUMO

The analytical high performance size exclusion liquid chromatography (SEC-HPLC) with multi-wavelength absorbance and fluorescence detections and fluorescence 3D-excitation/emission matrix (EEM) were used for the analysis of average molecular size (MS), molecular size distribution of aliphatic/aromatic compounds and fluorophores in dissolved organic matter (DOM) from Suwannee River (SRDOM) and two Karelian lakes (Vodoprovodnoe Lake - L1DOM and Onego Lake - L2DOM). The average MS of DOM samples varied in the order SRDOM > L1DOM > L2DOM. The absorbance ratios A250/A365 and A210/A254 have been used for the DOM samples characterization. The absorbance ratio A250/A365 provided significant information about average MS of the bulk aquatic DOMs but was not exactly correlated with the results of SEC-HPLC data. The absorbance ratio A210/A254 in combination with SEC was well correlated with the content of DOM aliphatic/aromatic compounds and could be used as an important water quality index to estimate the level of protein-like material in the aquatic DOM. Regardless of the origin (river or lakes), different geographical locations and different average MS of DOM, several similar types of humic-like SEC-separated fluorophores were found within the samples. In all DOM samples the decrease of the fluorophores emission maxima paralleled the decrease of their relative MS. The combination of SEC-HPLC with multi-wavelength fluorescence and absorbance detection and EEM analyses appears very useful for DOM characterization and for tracking of microbial activity resulting from anthropogenic and/or eutrophic impact in aquatic environments.

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