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1.
Diagnostics (Basel) ; 13(23)2023 Nov 21.
Artículo en Inglés | MEDLINE | ID: mdl-38066732

RESUMEN

Images from 64 patients undergoing an enhanced abdominal-pelvis scan at portal phase in dual-energy CT mode for the diagnosis of colitis or bowel obstruction were retrospectively analyzed. Acquisitions were performed on a third-generation dual-source CT (DSCT) 100/Sn150 kVp. Mixed images were generated, as well as virtual monoenergetic images (VMIs) at 40/50/60/70 keV. Objective image quality was assessed on VMIs and mixed images by measuring contrast, noise and contrast-to-noise ratio (CNR). Noise, smoothing and overall image quality were subjectively analyzed by two radiologists using Likert scales. For both patient groups, the noise decreased significantly according to the energy level from 40 to 60 keV by -47.2 ± 24.0% for bowel obstruction and -50.4 ± 18.2% for colitis. It was similar between 60 and 70 keV (p = 0.475 and 0.059, respectively). Noise values were significantly higher in VMIs than in mixed images, except for 70 keV (p = 0.53 and 0.071, respectively). Similar results were observed for contrast values, with a decrease between 40 and 70 keV of -56.3 ± 7.9% for bowel obstruction -56.2 ± 10.9% for colitis. The maximum CNR value was found at 60 keV compared to other energy levels and mixed images, but there was no significant difference with the other energy levels apart from 70 keV (-9.7 ± 9.8%) for bowel obstruction and 40 keV (-6.6 ± 8.2%) and 70 keV (-5.8 ± 9.2%) for colitis. The VMIs at 60 keV presented higher scores for all criteria for bowel obstruction and colitis, with no significant difference in smoothing score compared to mixed images (p = 0.119 and p = 0.888, respectively).

2.
Diagn Interv Imaging ; 104(5): 248-257, 2023 May.
Artículo en Inglés | MEDLINE | ID: mdl-36740536

RESUMEN

PURPOSE: The purpose of this study was to evaluate whether concomitant left gastric vein embolization (LGVE) during transjugular intrahepatic portosystemic shunt (TIPS) for acute variceal hemorrhage could reduce the risk of bleeding recurrence. MATERIAL AND METHOD: A national multicenter observational study was conducted in 14 centers between January 2019 and December 2020. All cirrhotic patients who underwent TIPS placement for acute variceal bleeding were included. During TIPS procedure, size of left gastric vein (LGV), performance of LGVE, material used for LGVE and portosystemic pressure gradient (PPG) before and after TIPS placement were collected. A propensity score for the occurrence of LGVE was calculated to assess effect of LGVE on rebleeding recurrence at six weeks and one year. RESULTS: A total of 356 patients were included (mean age 57.3 ± 10.8 [standard deviation] years; 283/356 [79%] men). Median follow-up was 11.2 months [interquartile range: 1.2, 13.3]. The main indication for TIPS was pre-emptive TIPS (162/356; 46%), rebleeding despite secondary prophylaxis (105/356; 29%), and salvage TIPS (89/356; 25%). Overall, 128/356 (36%) patients underwent LGVE during TIPS procedure. At six weeks and one year, rebleeding-free survival did not differ significantly between patients who underwent LGVE and those who did not (6/128 [5%] vs. 15/228 [7%] at six weeks, and 11/128 [5%] vs. 22/228 [7%] at one year, P = 0.622 and P = 0.889 respectively). A total of 55 pairs of patients were retained after propensity score matching. In patients without LGVE, the rebleeding rate was not different from those with LGVE (3/55 [5%] vs. 4/55 [7%], P > 0.99, and 5/55 [9%] vs. 6/55[11%], P > 0.99, at six weeks and one year respectively). Multivariable analysis identified PPG after TIPS placement as the only predictor of bleeding recurrence (hazard ratio = 1.09; 95% confidence interval: 1.02-1.18; P = 0.012). CONCLUSION: In this multicenter national real-life study, we did not observe any benefit of concomitant LGVE during TIPS placement for acute variceal bleeding on bleeding recurrence rate.


Asunto(s)
Várices Esofágicas y Gástricas , Derivación Portosistémica Intrahepática Transyugular , Masculino , Humanos , Persona de Mediana Edad , Anciano , Femenino , Várices Esofágicas y Gástricas/complicaciones , Várices Esofágicas y Gástricas/cirugía , Derivación Portosistémica Intrahepática Transyugular/métodos , Hemorragia Gastrointestinal/etiología , Hemorragia Gastrointestinal/cirugía , Recurrencia , Vena Porta
4.
J Pers Med ; 12(10)2022 Oct 12.
Artículo en Inglés | MEDLINE | ID: mdl-36294840

RESUMEN

Background: This study aimed to retrospectively analyze dosimetric indicators recorded since 2012 for thoracic, abdominal or pelvic embolizations to evaluate the contribution of new tools and technologies in dose reduction. Methods: Dosimetric indicators (dose area product (DAP) and air kerma (AK)) from 1449 embolizations were retrospectively reviewed from August 2012 to March 2022. A total of 1089 embolizations were performed in an older fixed C-Arm system (A1), 222 in a newer fixed C-Arm system (A2) and 138 in a 4DCT system (A3). The embolization procedures were gathered to compare A1, A2 and A3. Results: DAP were significantly lower with A2 compared to A1 for all procedures (median −50% ± 5%, p < 0.05), except for uterine elective embolizations and gonadal vein embolization. The DAP values were significantly lower with A3 than with A1 (p < 0.001). CT scan was used for guidance in 90% of embolization procedures. Conclusions: The last C-Arm technology allowed a median reduction of 50% of the X-ray dose. The implementation of a CT scan inside the IR room allowed for more precise 3D-guidance with no increase of the dose delivered.

5.
J Patient Saf ; 18(8): e1238-e1242, 2022 12 01.
Artículo en Inglés | MEDLINE | ID: mdl-35858479

RESUMEN

OBJECTIVES: Several studies have suggested a strong relationship between the number of peripherally inserted central catheter (PICC) lumens and the risk of complications. The purpose of this study is to evaluate the impact of the intervention of a clinical pharmacist (CP) on the number of lumens of PICC inserted and assess PICC-related complications. METHOD: This prospective monocentric study included all consecutive patients from 5 different units who underwent PICC insertions from September 2017 to March 2018. In the intervention group, the CP validated the pertinence of each PICC request according to the patients' records, choice of device (single or double lumen), and incompatibilities between treatments. The control group consisted of patients who underwent PICC insertions without a CP intervention. Complications were prospectively recorded up to PICC removal. Multivariate analyses adjusted for sex, age, and PICC line duration were performed. RESULTS: In the intervention group, 207 PICCs were inserted, 81.2% (n = 168) were single-lumen devices and 18.8% (n = 39) were double-lumen devices. In the control group (n = 77), the use of single-lumen PICCs was significantly lower (n = 48, 62.3%; P = 0.002). After intervention, the overall complication incidence rate decreased from 4.42 to 3.23 per 1000 catheter days ( P = 0.082). Considering the overall population, 216 single-lumen PICCs were inserted with significantly fewer complications than double-lumens (respectively n = 16, 16/216 = 7.4%, versus n = 15, 15/68 = 22.1%, P = 0.002). The adjusted odds ratio of double-lumen PICC was 3.83 (95% confidence interval, 1.46-10.07; P = 0.007). CONCLUSIONS: Our study showed the intervention of a CP in the PICC insertion process could increase the use of single-lumen PICCs and tended to reduce associated complications.


Asunto(s)
Cateterismo Venoso Central , Humanos , Cateterismo Venoso Central/efectos adversos , Proyectos Piloto , Estudios Prospectivos , Factores de Riesgo , Catéteres , Preparaciones Farmacéuticas
6.
Clin Nucl Med ; 47(7): 640-643, 2022 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-35353745

RESUMEN

ABSTRACT: A transarterial left hepatic artery radioembolization involving 90Y microspheres was performed on a cirrhotic man with hypermetabolic 18F-FDG segment III hepatocellular carcinoma. During the 18F-FDG PET/CT follow-up, the disappearance of the hypermetabolic lesion was initially observed. Then, a focal segment III hypermetabolism reappeared mimicking a recurrence before disappearing without any treatment. Finally, the hepatic MRI demonstrated that the transitory segment III hypermetabolism matched a thrombus of the dilated recanalized umbilical vein.


Asunto(s)
Carcinoma Hepatocelular , Neoplasias Hepáticas , Trombosis , Trombosis de la Vena , Carcinoma Hepatocelular/patología , Fluorodesoxiglucosa F18 , Humanos , Neoplasias Hepáticas/patología , Masculino , Tomografía Computarizada por Tomografía de Emisión de Positrones , Trombosis/diagnóstico por imagen , Venas Umbilicales/patología , Radioisótopos de Itrio/uso terapéutico
7.
Diagn Interv Imaging ; 103(7-8): 338-344, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35183486

RESUMEN

PURPOSE: The purpose of this study was to compare peak skin dose (PSD) and dose map calculated by Dose-Tracking-System® (DTS) software and measured with radiochromic films in patients undergoing abdominopelvic embolization. MATERIAL AND METHODS: The PSD measured by radiochromic films (PSDFilm) or calculated by DTS software (PSDDTS) were compared in patients who underwent abdominopelvic embolization between September 2020 and April 2021. Concordance between PSDFilm and PSDDTS was computed using the Lin's concordance correlation coefficient and the clinical concordance using Bland Altman analysis. PSD values were compared using the paired Mann-Whitney-Wilcoxon test. RESULTS: A total of 40 patients were included. There were 32 men and 8 women with a mean age of 73.0 ± 14.6 (SD) years (age range: 30-92 years). Median PSDFilm was 756 mGy (IQR: 390; 1094) and median PSDDTS was 768 mGy (IQR: 421; 1076), resulting in a median difference of -5% (IQR: -10%; 0%) between PSDFilm and PSDDTS (P = 0.024). The concordance correlation between PSDFilm and PSDDTS was substantial in patients (0.986; 95% CI: 0.977-0.992). Bland Altman analysis showed that PSDDTS was underestimated compared to PSDFilm by -36 mGy (95% CI: -68--4). Visually similar dose maps were found with DTS and radiochromic films. CONCLUSION: Real-time DTS software allows computing PSD with high accuracy and generating adequate dose map. PSDDTS was slightly underestimated compared to PSDFilm requiring the use of a correction factor for the PSDDTS to avoid lack of follow-up for some patients.


Asunto(s)
Embolización Terapéutica , Dosimetría por Película , Adulto , Anciano , Anciano de 80 o más Años , Embolización Terapéutica/métodos , Femenino , Dosimetría por Película/métodos , Humanos , Masculino , Persona de Mediana Edad , Dosis de Radiación , Piel , Programas Informáticos
8.
Cardiovasc Intervent Radiol ; 45(1): 1-11, 2022 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-34796373

RESUMEN

PRIMARY OBJECTIVE: Recently, selective internal radiation therapy using yttrium-90 (Y90) glass microspheres (TheraSphere™) was approved for reimbursement by health authorities in France. The PROACTIF study aims to gather data on effectiveness, patient quality of life, and safety with use of Y90 glass microspheres in real-world clinical settings in France. INCLUSION CRITERIA: Patient with a diagnosis of hepatocellular carcinoma (HCC), intrahepatic cholangiocarcinoma (iCC), and/or metastatic colorectal cancer (mCRC) who was treated with a dose of Y90 glass microspheres that has been reimbursed in France and who do not oppose use of their personal medical data. EXCLUSION CRITERIA: If data collection is opposed, treatment is reimbursed but not administered, or treatment is administered but not reimbursed. OUTCOME MEASURES: Primary outcome measures include overall survival from time of Y90 glass microsphere treatment and quality of life, as assessed using the Functional Assessment of Cancer Therapy- Hepatobiliary questionnaire. ESTIMATED NUMBER OF PATIENTS TO BE INCLUDED: This is an open study and there is no set number of patients; 115 have already been enrolled. PLANNED SUBGROUP ANALYSES: Analyses will be stratified by disease state (HCC, iCC, or mCRC). Subgroups to be analyzed include age group, unilobar/bilobar disease at baseline, Eastern Cooperative Oncology Group (ECOG) status at baseline, liver tumor burden at baseline, target lesion size, and standard versus multi-compartment personalized dosimetry treatment. PLANNED RECRUITMENT AND OBSERVATION PERIOD: Recruitment includes patients who are prescribed and treated with a commercial vial of Y90 glass microspheres between 01 January 2019 and 31 December 2024. TRIAL REGISTRATION: ClinicalTrials.gov Identifier: NCT04069468.


Asunto(s)
Neoplasias de los Conductos Biliares , Carcinoma Hepatocelular , Colangiocarcinoma , Neoplasias Colorrectales , Embolización Terapéutica , Neoplasias Hepáticas , Conductos Biliares Intrahepáticos , Carcinoma Hepatocelular/radioterapia , Colangiocarcinoma/radioterapia , Ensayos Clínicos Fase IV como Asunto , Neoplasias Colorrectales/radioterapia , Humanos , Neoplasias Hepáticas/radioterapia , Microesferas , Estudios Prospectivos , Calidad de Vida , Sistema de Registros , Resultado del Tratamiento , Radioisótopos de Itrio/uso terapéutico
9.
Eur Radiol ; 30(9): 5071-5081, 2020 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-32333144

RESUMEN

OBJECTIVES: To validate the performance of an automatic tool to estimate a patient's peak skin dose (PSD) and a skin dose map from data collected by a radiation dose management system (RDMS) during interventional procedures. METHODS: In total, 288 eligible consecutive patients undergoing abdominopelvic embolisation or planned coronary angioplasty using radiochromic films were screened between June 2018 and March 2019. For 98 included patients, PSD was measured using radiochromic films (PSDFilm) and computed by RDMS (PSDRDMS) using one flat and two anthropomorphic phantoms. Statistical concordance between PSDFilm and PSDRDMS was computed with Lin's concordance correlation coefficient and clinical concordance with the Bland and Altman graphic; values were compared using the paired Mann-Whitney-Wilcoxon test. RESULTS: In total, 190/288 patients were excluded and 98 patients were analysed (69 men, mean age 66 ± 14 years). The PSDFilm median (1st; 3rd quartile) was 0.59 Gy (0.40; 1.08). PSDRDMS was 0.62 Gy (0.43; 1.22) for the flat phantom and 0.62 Gy (0.42; 1.19) for anthropomorphic phantoms. The concordance between PSDFilm and PSDRDMS was good for both phantoms (flat: 0.94 [0.91; 0.95]; anthropomorphic 0.94 [0.91; 0.96]). Compared with the values of PSDFilm, the values of PSDRDMS were significantly increased by 5% (- 4%; 16%) for flat phantom (p = 0.001) and 7% (- 6%; 22%) for anthropomorphic phantoms (p = 0.002) for vascular procedures and 9% (- 4%; 26%, p = 0.01) and 6% (- 4%; 23%, p = 0.02) for cardiac procedures, respectively. Dose map representations matched for most patients. The gaps identified were due to table displacement during fluoroscopy events and the use of a wedge filter. CONCLUSIONS: The RDMS skin dose map tool allowed the computation of the PSD and skin dose distribution for all patients with fewer constraints than radiochromic films. However, the computed PSD was overestimated, increasing the number of patients requiring follow-up. KEY POINTS: • A good concordance correlation was identified between the peak skin dose (PSD) values measured with radiochromic films and estimated with the radiation dose management system (RDMS) skin dose map tool. • Differences were related to table displacement during fluoroscopy events and the use of a wedge filter, which are not accounted in the Digital Imaging and Communications in Medicine Radiation Dose Structured Reports. • For all procedures, the estimated PSDs were significantly higher than the measured PSDs by 5% (- 4%; 18%) for flat phantom (p < 0.001) and 6% (- 5%; 22%) for anthropomorphic phantoms (p < 0.001).


Asunto(s)
Fluoroscopía/métodos , Dosis de Radiación , Radiometría/métodos , Piel , Adulto , Anciano , Anciano de 80 o más Años , Angiografía Coronaria , Embolización Terapéutica/métodos , Femenino , Humanos , Masculino , Persona de Mediana Edad , Intervención Coronaria Percutánea/métodos , Fantasmas de Imagen , Dosímetros de Radiación
10.
Phys Med ; 66: 77-87, 2019 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-31563728

RESUMEN

OBJECTIVE: To assess the interactive Skin Dose Map® tool (SDMTool) integrated to the radiation dose management system (RDMS) DoseWatch® with Gafchromic® films for implementation in routine practice. METHODS: A retrospective dose estimation software SDMTool was used to calculate Peak Skin Dose (PSD) and display the patient skin dose distribution. PSD was calculated with a triangle mesh of 0.055 cm2 resolution on ICRP 110 male anthropomorphic phantom and with a square ROI of 1 cm2 on flat phantom. The tool uses Radiation Dose Structured Reports (RDSR) data to model exposure events and calculate the PSD per event. The PSD and the skin dose distribution estimated with SDMTool were evaluated in comparison with Gafchromic® films positioned under the PMMA phantom (20 cm) for 13 configurations. Measurements were performed on a Philips system. Statistical analysis were carried out to compare PSDFilm and PSDSDM. RESULTS: Average differences between PSDFilm and PSDSDM were 6% ±â€¯6% (range from -3% to 22%) for flat phantom and 5% ±â€¯7% (range from -3% to 25%) for ICRP phantom. Concordance was good between the measured PSDFilm and the estimated PSDSDM with Lin's coefficient estimation and 95% Confidence Interval of 0.979 [0.875; 0.984] for flat phantom and 0.977 [0.877; 0.985] for ICRP phantom. Dose map representations are concordant for 11 of the 13 tests on PMMA phantom. Disparities arose from the limitations of the RSDR format: table displacement during fluoroscopy events and the use of wedge filter. CONCLUSION: The results found in this experimental evaluation show that the SDMTool is a suitable alternative to Gafchromic® film to calculate PSD.


Asunto(s)
Dosimetría por Película/instrumentación , Dosis de Radiación , Piel/efectos de la radiación , Fantasmas de Imagen , Programas Informáticos
11.
Presse Med ; 48(6): 706-713, 2019 Jun.
Artículo en Francés | MEDLINE | ID: mdl-31151848

RESUMEN

Aortic pathologies benefit from imaging innovation and interventional radiology developments in order to improve patient management. At the early phase, vital risk should be considered. Whole body CT scan evaluate the complete aorta and its branches to assess the pathology and to choose the best approach between surgery or interventional radiology (fenestration, stentgraft, peripheral stenting). Algorithms, based on the understanding of the complications mechanisms and evolutive risk, modified the management specifically for aortic dissection. At chronic phase, GPs and angiologists should follow their patients in order to detect aortic complications and to treat cardiovascular risk factors. MRA is well indicated if possible.


Asunto(s)
Aorta Torácica , Enfermedades de la Aorta/diagnóstico , Enfermedades de la Aorta/cirugía , Enfermedad Aguda , Algoritmos , Enfermedad Crónica , Humanos
12.
J Obstet Gynaecol Res ; 42(1): 95-8, 2016 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-26555234

RESUMEN

A 27-year-old woman underwent a first vaginal delivery at our institution. She returned four days after delivery, presenting with abdominal pain and an unexplained drop in her hemoglobin value, without external bleeding. The initial computed tomography abdominal scan revealed an isolated diffuse hemoperitoneum. A laparoscopy did not find the cause of bleeding. A second computed tomography scan, performed 15 days later, revealed hemoperitoneum associated with a false aneurysm of the right uterine artery. Treatment consisted of embolization of the uterine arteries, with clinical success. False aneurysms are a rare cause of intra-abdominal non-exteriorized bleeding in late post-partum hemorrhage.


Asunto(s)
Aneurisma Falso/terapia , Hemoperitoneo/terapia , Hemorragia Posparto/terapia , Embolización de la Arteria Uterina , Adulto , Aneurisma Falso/complicaciones , Femenino , Hemoperitoneo/etiología , Humanos , Hemorragia Posparto/etiología , Resultado del Tratamiento
13.
Nat Mater ; 14(4): 447-51, 2015 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-25559425

RESUMEN

Nanosized faujasite (FAU) crystals have great potential as catalysts or adsorbents to more efficiently process present and forthcoming synthetic and renewable feedstocks in oil refining, petrochemistry and fine chemistry. Here, we report the rational design of template-free nanosized FAU zeolites with exceptional properties, including extremely small crystallites (10-15 nm) with a narrow particle size distribution, high crystalline yields (above 80%), micropore volumes (0.30 cm(3) g(-1)) comparable to their conventional counterparts (micrometre-sized crystals), Si/Al ratios adjustable between 1.1 and 2.1 (zeolites X or Y) and excellent thermal stability leading to superior catalytic performance in the dealkylation of a bulky molecule, 1,3,5-triisopropylbenzene, probing sites mostly located on the external surface of the nanosized crystals. Another important feature is their excellent colloidal stability, which facilitates a uniform dispersion on supports for applications in catalysis, sorption and thin-to-thick coatings.

14.
J Am Chem Soc ; 133(46): 18950-6, 2011 Nov 23.
Artículo en Inglés | MEDLINE | ID: mdl-21995563

RESUMEN

The present study demonstrated the possibility to form a secondary system of parallel macropores in zeolite crystals. The secondary pore formation was predetermined by the creation of defect zones in ZSM-5 crystals. A high energy (238)U ion beam was employed to form latent tracks in zeolite crystals, which were further subjected to attack with diluted HF solution and thus developed to uniformally sized macropores. The selective extraction of material from latent tracks was due to the higher etching velocity of highly agitated zones created by heavy ion bombardment. The combination of complementary methods unambiguously demonstrated the formation of hierarchical zeolite material comprising parallel macropores that extended through the entire crystal. The catalytic tests revealed improved activity at retained selectivity in the reaction of m-xylene conversion. The possibility to control the number of macropores per unit of crystal surface and thus the catalytic performance of the material was demonstrated. This model material is expected to bring better understanding to the effect of a secondary pore system in the catalytic performance of hierarchical zeolites obtained by the top-down or bottom-up approach.

15.
J Cardiovasc Med (Hagerstown) ; 12(12): 883-4, 2011 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-22002258

RESUMEN

The case of a woman with anomalous origin of the circumflex coronary artery that communicates with the left ventricle via a fistula, revealed by typical angina, is described and the several pathomechanisms involved are discussed.


Asunto(s)
Fístula Arterio-Arterial/diagnóstico por imagen , Anomalías de los Vasos Coronarios/diagnóstico por imagen , Ventrículos Cardíacos/anomalías , Anciano , Angina de Pecho/etiología , Angiografía Coronaria , Femenino , Ventrículos Cardíacos/diagnóstico por imagen , Humanos
16.
Langmuir ; 25(10): 5825-34, 2009 May 19.
Artículo en Inglés | MEDLINE | ID: mdl-19536912

RESUMEN

Five silica samples (four precipitated silicas provided by commercial suppliers and one with the MCM-41 structure) have been studied by infrared spectroscopy and by a homemade thermogravimetry-infrared spectrum (TG-IR) setup. The silanol amount, accessibility to water, and different alcohols, and the affinity to water of these various silicas were compared and quantified. TG-IR measurements allowed the precise determination of the integrated molar absorption coefficient of the (nu+delta)OH band, epsilon(nu+delta)OH=(0.16+/-0.01) cm micromol(-1). It is independent of the sample origin and the concentration of silanol groups on silicas. For the precipitated dried samples evacuated at room temperature, the silanol concentration COH varies between 3.6 and 7.0 mmol g(-1). It is 5.3 mmol g(-1) in the case of the MCM-41 sample. Exchange experiments with D2O, followed by back-exchanges with different alcohols (methanol, propan-2-ol, 2-methyl-propan-2-ol, and 3-ethyl-pentan-3-ol) have been followed by infrared spectroscopy. All of the silanols of the MCM-41 sample are accessible to water and alcohol molecules. By contrast, about 20% of the silanols in precipitated samples are not exchanged by D2O (internal silanols). Accessibility decreases with alcohol size; the main effect is relative to methanol. Taking into account the sample specific surface areas and the silanol accessibility to D2O, the surface silanol density of precipitated silicas is close to 8 OH per nm2, at maximum coverage. At variance, the silanol surface density of the MCM silica is much lower, 4 OH per nm2. The TG-IR setup has also been used to determine the amount of water adsorbed on silicas through the intensity of the deltaH2O band. It varies linearly with the concentration of adsorbed water, whatever the silica sample. The integrated molar absorption coefficient of two bands, epsilondeltaH2O=(1.53+/-0.03) cm micromol(-1) and epsilon(nu+delta)H2O=(0.22+/-0.01) cm micromol(-1), have been determined. The number of H2O molecules adsorbed per nm2 has been compared on the five samples under an equilibrium pressure of 13 hPa at room temperature. Taking into account the number of silanols accessible to D2O for each sample, the silica-water affinity has been defined by the H2O/(SiOHsurf) ratio. It is close to 0.8-0.9 for the precipitated samples but lower (0.7) in the case of the MCM one. This result is explained by the more important amount of isolated silanol groups presented by this sample.

17.
Chemistry ; 14(20): 6205-12, 2008.
Artículo en Inglés | MEDLINE | ID: mdl-18491305

RESUMEN

A non-aqueous sol-gel Al-based fluoride has been subjected to the microwave solvothermal process. The final material depends on the temperature heat treatment used. Three types of material have been prepared: 1) for low temperature heat treatment (90 degrees C) X-ray amorphous alkoxy fluoride was obtained; 2) for the highest temperature used (200 degrees C) the metastable form beta-AlF3 was obtained with a very large surface area of 125 m2 g(-1). The mechanism of the amorphous=crystalline transformation has been rationalised by the occurrence of a decomposition reaction of the gel fluoride induced by the microwave irradiation. 3) Finally, at intermediate temperature (180 degrees C) a multi-component material mixture exhibiting a huge surface area of 525 m2 g(-1) has been obtained and further investigated after mild post-treatment fluorination using F2 gas. The resulting aluminium-based fluoride still possesses a high-surface-area of 330 m2 g(-1). HRTEM revealed that the solid is built from large particles (50 nm) identified as alpha-AlF3, and small ones (10 nm), relative to an unidentified phase. This new high-surface-area material exhibits strong Lewis acidity as revealed by pyridine adsorption and catalytic tests. By comparison with other materials, it has been shown that whatever the composition/structure of the Al-based fluoride materials, the number of strong Lewis acid sites is related to the surface area, highlighting the role of surface reconstruction occurring on a nanoscopic scale on the formation of the strongest Lewis acid sites.

18.
J Am Chem Soc ; 128(10): 3218-27, 2006 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-16522102

RESUMEN

A study of the zeotypic giant pores chromium(III) tricarboxylate Cr(III)3OF(x)(OH)(1-x)(H2O)2 x {C6H3-(CO2)3}2 x nH2O (MIL-100) has been performed. First, its thermal behavior, studied by X-ray thermodiffractometry and infrared spectroscopy, indicates that the departure of water occurs without any pore contraction and no loss in crystallinity, which confirms the robustness of the framework. In a second step, IR spectroscopy has shown the presence of three distinct types of hydroxy groups depending on the outgassing conditions; first, at high temperatures (573 K), only Cr-OH groups with a medium Brønsted acidity are present; at lower temperatures, two types of Cr-H2O terminal groups are observed; and at room temperature, their relatively high Brønsted acidity allows them to combine with H-bonded water molecules. Finally, a CO sorption study has revealed that at least three Lewis acid sites are present in MIL-100 and that fluorine atoms are located on a terminal position on the trimers of octahedra. A first result of grafting of methanol molecules acting as basic organic molecules on the chromium sites has also been shown, opening the way for a postsynthesis functionalization of MIL-100.

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