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1.
Biomedicines ; 11(6)2023 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-37371716

RESUMO

Fibromyalgia is a common disease syndrome characterized by chronic pain and fatigue in conjunction with cognitive dysfunction such as memory difficulties. Patients currently face a difficult prognosis with limited treatment options and a diminished quality of life. Given its widespread use and potential efficacy in treating other types of pain, cannabis may prove to be an effective treatment for fibromyalgia. This review aims to examine and discuss current clinical evidence regarding the use of cannabis for the treatment of fibromyalgia. An electronic search was conducted on MEDLINE, EMBASE, Cochrane Central Register of Controlled Trials, Cochrane Database of Systematic Reviews, and Scopus using Medical Subject Heading (MeSH) terms on all literature published up to October 2022. A follow-up manual search included a complete verification of relevant studies. The results of four randomized controlled trials (RCTs) and five observational studies (a total of 564 patients) that investigated the effects of cannabis on fibromyalgia symptoms were included in this review. Of the RCTs, only one demonstrated that cannabinoids did not have a different effect than placebo on pain responses. Overall, this analysis shows low-quality evidence supporting short-term pain reduction in people with fibromyalgia treated with cannabinoid therapeutics. Although current evidence is limited, medical cannabis appears to be a safe alternative for treating fibromyalgia.

2.
Aesthet Surg J Open Forum ; 5: ojad004, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36789103

RESUMO

Background: Instagram (Menlo Park, CA) has become a popular means of advertisement for aesthetic surgery procedures, influencing patients' likelihood of undergoing a procedure. In this study, the authors aim to explore public interest in aesthetic procedures before and after the Instagram platform started gaining in popularity through Google Trends (Google, Mountain View, CA), a platform with previously demonstrated utility for tracking interest in surgical procedures. Objectives: The authors hypothesize that as a result of increased medical marketing on Instagram, there is an increase in public interest in elective procedures of plastic surgery. Methods: Trends in the United States for given search terms and volumes were gathered through Google Trends between April 2004 and January 2022. Search terms included popular aesthetic procedures based on the 2020 Aesthetic Plastic Surgery National Data Bank Statistics. The search volumes were normalized, and a bivariate regression analysis of panel data was then applied to the aggregate trendlines to determine whether a statistically significant change in search volume occurred following the increase in user traffic of the Instagram platform. Results: The authors found significant variations in search volume for plastic surgery procedures before and after April 2012. Blepharoplasty, Botox, brachioplasty, breast implant removal, breast reduction, brow lift, butt lift, hair transplantation, lip augmentation, male breast surgery, mastopexy, mentoplasty, otoplasty, platysmaplasty, rhinoplasty, and thighplasty (P < .000) had statistically significant increases in search volume, whereas buccal fat removal (P = .003) had a statistically significant decrease in search volume after April 2012. Conclusions: The authors observed a significant increase in public interest in both surgical and nonsurgical aesthetic procedures after Instagram gained popularity in the April of 2012.

3.
Aesthet Surg J Open Forum ; 5: ojac096, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36751431

RESUMO

Background: Patients routinely use social media to locate providers, review before-and-after photographs, and discuss experiences, making it a powerful marketing tool for plastic surgeons. A few studies have systematically evaluated plastic surgery app content. Objectives: This study aims to analyze engagement levels and content posted by top plastic surgeon influencers on Instagram (Menlo Park, CA). Methods: The authors conducted a cross-sectional study in February 2022 to identify the top 10 global plastic surgeons on Instagram. Influencers were ranked based on the number of followers, and their latest 20 posts were analyzed. A total of 200 posts were categorized by 2 independent trainees as one of the following: marketing, education, personal, and miscellaneous. The number of likes was recorded as a proxy for engagement, and the average engagement for each category was calculated. Results: The top 10 influencers work primarily in private practice focusing on aesthetic procedures. Out of 200 categorized posts on Instagram, marketing posts had the greatest presence (64.5%), followed by personal (20%), miscellaneous (11%), and educational (4.5%). More still images were posted (56.5%) than videos (43.5%). The highest average engagement was for personal content (P = .005). No significant differences in engagement levels were found between photo and video content (P = .24). Conclusions: Although most content posted related to marketing efforts, many influencers were also using social media to post about their personal lives and promote their ancillary businesses. Although marketing content was the most common, engagement levels were the highest for personal and educational content, and no significant differences in engagement were found between videos and photos.

4.
Aesthet Surg J ; 43(4): 393-404, 2023 03 15.
Artigo em Inglês | MEDLINE | ID: mdl-36342786

RESUMO

BACKGROUND: Traditional invasive suture suspension techniques have proven efficacy and durability. A previously described percutaneous placement of a neck suspension suture with light guidance has transformed this into a minimally invasive technique. This novel technique provides a major advance for minimally invasive neck rejuvenation. OBJECTIVES: The authors sought to describe their experience with light-guided percutaneous neck rejuvenation over the past 4.5 years, including technique, patient selection, safety profile, and expected outcomes. METHODS: Data were retrospectively reviewed for all patients who underwent the procedure with 5 surgeons across 4 aesthetic plastic surgery practices from January 2018 through May 2022. Inclusion criteria were mild to moderate neck laxity, prominent anterior platysma bands, and desire to improve neck contour. Patients undergoing concurrent skin incision >5 mm (ie, open rhytidectomy or platysmaplasty) were excluded. RESULTS: A total of 391 patients meeting criteria were identified during the study period. No hematomas were documented. Four patients (1%) developed infection at the suture site, 1 resolving on antibiotics and 3 requiring suture removal. Eighteen (4.6%) developed recurrent platysmal bands, and 7 (1.8%) had residual loose skin. Four (1%) experienced transient marginal mandibular neuropraxia. Mean length of follow-up time was 240 days. CONCLUSIONS: Light-guided percutaneous suture suspension is a safe and viable option for improving neck contours. Although it does not address extensive skin laxity or excess submental fat, it can be combined with energy-based tissue tightening, submental liposuction, or skin excision. In selected patients, this minimally invasive procedure provides predictable results with a low risk of complications.


Assuntos
Procedimentos de Cirurgia Plástica , Ritidoplastia , Humanos , Estudos Retrospectivos , Rejuvenescimento , Pescoço/cirurgia , Ritidoplastia/efeitos adversos , Ritidoplastia/métodos , Suturas
5.
Curr Opin Pediatr ; 33(6): 570-575, 2021 12 01.
Artigo em Inglês | MEDLINE | ID: mdl-34636348

RESUMO

PURPOSE OF REVIEW: The purpose of this review is to describe recent findings on the clinical presentation, pathogenesis, and management of fetal alcohol spectrum disorders (FASDs). Alcohol causes a range of physical, developmental, and cognitive impairments on the developing fetus. Individuals exposed to alcohol prenatally have a wide variability in dysmorphic and neurologic features. Hence, a greater understanding of the mechanisms through which alcohol induces defects in the developing fetus is imperative in developing therapies that prevent alcohol-induced effects. RECENT FINDINGS: Current research has focused on leveraging technology to developing tools that can aid in the diagnostic process, defining patterns of neurocognition and neuroimaging specific to FASD, developing neurobehavioral and pharmacologic interventions, and expanding access to care. SUMMARY: FASDs are a common cause of neurodevelopmental impairment in school-age children, and their recognition is essential to provide early interventions in order to optimize the outcome for these individuals when they reach adulthood. Although previously thought to be the result of irreversible neurologic injury from prenatal alcohol exposure, recent evidence points to the benefits of applying principles regarding neuroplasticity in improving the lives for patients and their families.


Assuntos
Transtornos do Espectro Alcoólico Fetal , Efeitos Tardios da Exposição Pré-Natal , Adulto , Criança , Feminino , Transtornos do Espectro Alcoólico Fetal/diagnóstico , Transtornos do Espectro Alcoólico Fetal/terapia , Humanos , Gravidez , Efeitos Tardios da Exposição Pré-Natal/diagnóstico
6.
Adv Funct Mater ; 31(22)2021 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-36213489

RESUMO

Advanced wound scaffolds that integrate active substances to treat chronic wounds have gained significant recent attention. While wound scaffolds and advanced functionalities have previously been incorporated into one medical device, the wirelessly triggered release of active substances has remained the focus of many research endeavors. To combine multiple functions including light-triggered activation, anti-septic, angiogenic, and moisturizing properties, we have developed a 3D printed hydrogel patch encapsulating vascular endothelial growth factor (VEGF) decorated with photoactive and antibacterial tetrapodal zinc oxide (t-ZnO) microparticles. To achieve the smart release of VEGF, t-ZnO was modified by chemical treatment and activated through UV/visible light exposure. This process would also make the surface rough and improve protein adhesion. The elastic modulus and degradation behavior of the composite hydrogels, which must match the wound healing process, were adjusted by changing t-ZnO concentrations. The t-ZnO-laden composite hydrogels can be printed with any desired micropattern to potentially create a modular elution of various growth factors. The VEGF decorated t-ZnO-laden hydrogel patches showed low cytotoxicity and improved angiogenic properties while maintaining antibacterial functions in vitro. In vivo tests showed promising results for the printed wound patches, with less immunogenicity and enhanced wound healing.

7.
Am J Med Genet A ; 182(10): 2243-2252, 2020 10.
Artigo em Inglês | MEDLINE | ID: mdl-32677343

RESUMO

Fetal alcohol spectrum disorders (FASD) describe a range of physical, behavioral, and neurologic deficits in individuals exposed to alcohol prenatally. Reduced palpebral fissure length is one of the cardinal facial features of FASD. However, other ocular measurements have not been studied extensively in FASD. Using the Fetal Alcohol Syndrome Epidemiologic Research (FASER) database, we investigated how inner canthal distance (ICD), interpupillary distance (IPD), and outer canthal distance (OCD) centiles differed between FASD and non-FASD individuals. We compared ocular measurement centiles in children with FASD to non-FASD individuals and observed reductions in all three centiles for ICD, IPD, and OCD. However, when our non-FASD children who had various forms of growth deficiency (microcephaly, short-stature, or underweight) were compared to controls, we did not observe a similar reduction in ocular measurements. This suggests that reductions in ocular measurements are a direct effect of alcohol on ocular development independent of its effect on growth parameters, which is consistent with animal models showing a negative effect of alcohol on developing neural crest cells. Interpupillary distance centile appeared to be the most significantly reduced ocular measure we evaluated, suggesting it may be a useful measure to be considered in the diagnosis of FASD.


Assuntos
Consumo de Bebidas Alcoólicas/genética , Transtornos do Espectro Alcoólico Fetal/genética , Microcefalia/genética , Crista Neural/crescimento & desenvolvimento , Consumo de Bebidas Alcoólicas/efeitos adversos , Consumo de Bebidas Alcoólicas/epidemiologia , Animais , Criança , Olho/metabolismo , Olho/patologia , Face/patologia , Feminino , Transtornos do Espectro Alcoólico Fetal/epidemiologia , Transtornos do Espectro Alcoólico Fetal/etiologia , Transtornos do Espectro Alcoólico Fetal/patologia , Humanos , Masculino , Troca Materno-Fetal/genética , Microcefalia/induzido quimicamente , Microcefalia/epidemiologia , Crista Neural/patologia , Gravidez
8.
Am J Med Genet A ; 182(9): 2021-2026, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-32524756

RESUMO

Angelman syndrome (AS) is caused by several genetic mechanisms that impair the expression of maternally-inherited UBE3A through deletions, paternal uniparental disomy (UPD), UBE3A pathogenic variants, or imprinting defects. Current methods of differentiating the etiology require molecular testing, which is sometimes difficult to obtain. Recently, computer-based facial analysis systems have been used to assist in identifying genetic conditions based on facial phenotypes. We sought to understand if the facial-recognition system DeepGestalt could find differences in phenotype between molecular subtypes of AS. Images and molecular data on 261 individuals with AS ranging from 10 months through 32 years were analyzed by DeepGestalt in a cross-validation model with receiver operating characteristic (ROC) curves generated. The area under the curve (AUC) of the ROC for each molecular subtype was compared and ranked from least to greatest differentiable phenotype. We determined that DeepGestalt demonstrated a high degree of discrimination between the deletion subtype and UPD or imprinting defects, and a lower degree of discrimination with the UBE3A pathogenic variants subtype. Our findings suggest that DeepGestalt can recognize subclinical differences in phenotype based on etiology and may provide decision support for testing.


Assuntos
Síndrome de Angelman/genética , Aprendizado Profundo , Impressão Genômica/genética , Dissomia Uniparental/genética , Adolescente , Adulto , Síndrome de Angelman/classificação , Síndrome de Angelman/diagnóstico , Síndrome de Angelman/patologia , Criança , Pré-Escolar , Face/patologia , Feminino , Humanos , Lactente , Masculino , Herança Materna/genética , Fenótipo , Ubiquitina-Proteína Ligases/genética , Dissomia Uniparental/diagnóstico , Dissomia Uniparental/patologia , Adulto Jovem
9.
Rev. chil. pediatr ; 88(6): 765-770, dic. 2017. graf
Artigo em Espanhol | LILACS | ID: biblio-900049

RESUMO

Resumen Introducción: El dengue perinatal es una patología de la que poco se sabe, los reportes disponibles describen riesgo de resultados perinatales adversos. Objetivo: Reportar un caso de dengue perinatal, como diagnóstico diferencial de sepsis neonatal, que debe tenerse en cuenta en zonas endémicas. Caso clínico: Recién nacido de una mujer de 23 años quien a las 36 semanas de gestación presentó cuadro de dengue con antígeno Non-Structural Protein 1 (NS1) positivo y anticuerpos anti-dengue negativos. Al sexto día de enfermedad dio a luz a un recién nacido sano, quien, al segundo día de vida, presentó fiebre sin otros hallazgos patológicos al examen físico, asociado a trombocitopenia severa (17.900 plaquetas/uL) y aumento de la proteína C reactiva, antígeno viral NS1 positivo e in-munoglobulina G (IgG) anti dengue positiva. Fue manejado con antibióticoterpia con ampicilina y gentamicina por protocolo de la institución para sepsis neonatal probable. El neonato mostró me joría clínica, con estabilidad hemodinámica y aumento significativo de plaquetas, siendo dado de alta. Conclusiones: El dengue en el embarazo trae consigo el riesgo de resultados perinatales adver sos, particularmente bajo peso al nacer y parto pre-término. Los hijos de madres diagnosticadas con dengue al final del embarazo deberían ser observados estrechamente con realización de hemograma seriado en los primeros días de vida, debido al riesgo de transmisión vertical.


Abstract Introduction: Few reports are available about perinatal dengue, with controversial results in regards the risk of perinatal outcome. Objective: To report a case of perinatal dengue as a differential diagno sis with neonatal sepsis, which must be considered in endemic areas. Clinical case: Male newborn of a 23 year-old female, who presented a Non-Structural Protein 1 (NS1) antigen positive to dengue at 36 weeks of gestation and negative anti-dengue antibodies. At day six of the illness a healthy newborn was born. On the second day of life the neonate presented fever with no other pathological findings on the physical exam, associated with severe thrombocytopenia (17,900 platelets/uL), increased C-reactive protein, a positive NS1 antigen, and positive anti-dengue immunoglobulin G (IgG). He was treated with ampicillin and gentamicin according the Institution protocol of neonatal sepsis. The newborn showed clinical improvement, with hemodynamic stability and significant increase of platelets, receiving the medical discharge. Conclusions: Dengue in pregnancy produces the risk of adverse perinatal outcomes, particularly low birth weight and preterm delivery. Children of mothers diagnosed with dengue at the end of pregnancy should be observed closely with serial hemograms during child's first days of life, due to the high risk of vertical transmission.


Assuntos
Humanos , Masculino , Feminino , Gravidez , Recém-Nascido , Adulto Jovem , Complicações Infecciosas na Gravidez/diagnóstico , Transmissão Vertical de Doenças Infecciosas , Dengue/diagnóstico , Dengue/transmissão , Diagnóstico Diferencial , Sepse Neonatal/diagnóstico
10.
Rev Chil Pediatr ; 88(6): 765-770, 2017 Dec.
Artigo em Espanhol | MEDLINE | ID: mdl-29546926

RESUMO

INTRODUCTION: Few reports are available about perinatal dengue, with controversial results in regards the risk of perinatal outcome. OBJECTIVE: To report a case of perinatal dengue as a differential diagno sis with neonatal sepsis, which must be considered in endemic areas. CLINICAL CASE: Male newborn of a 23 year-old female, who presented a Non-Structural Protein 1 (NS1) antigen positive to dengue at 36 weeks of gestation and negative anti-dengue antibodies. At day six of the illness a healthy newborn was born. On the second day of life the neonate presented fever with no other pathological findings on the physical exam, associated with severe thrombocytopenia (17,900 platelets/uL), increased C-reactive protein, a positive NS1 antigen, and positive anti-dengue immunoglobulin G (IgG). He was treated with ampicillin and gentamicin according the Institution protocol of neonatal sepsis. The newborn showed clinical improvement, with hemodynamic stability and significant increase of platelets, receiving the medical discharge. CONCLUSIONS: Dengue in pregnancy produces the risk of adverse perinatal outcomes, particularly low birth weight and preterm delivery. Children of mothers diagnosed with dengue at the end of pregnancy should be observed closely with serial hemograms during child's first days of life, due to the high risk of vertical transmission.


Assuntos
Dengue/diagnóstico , Transmissão Vertical de Doenças Infecciosas , Complicações Infecciosas na Gravidez/diagnóstico , Dengue/transmissão , Diagnóstico Diferencial , Feminino , Humanos , Recém-Nascido , Masculino , Sepse Neonatal/diagnóstico , Gravidez , Adulto Jovem
11.
J Pharm Biomed Anal ; 124: 207-215, 2016 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-26962721

RESUMO

Quality control of solid dosage forms involves the analysis of end products according to well-defined criteria, including the assessment of the uniformity of dosage units (UDU). However, in the case of break-scored tablets, given that tablet splitting is widespread as a means to adjust doses, the uniform distribution of the active pharmaceutical ingredient (API) in all the possible fractions of the tablet must be assessed. A general procedure to accomplish with both issues, using Raman spectroscopy, is presented. It is based on the acquisition of a collection of spectra in different regions of the tablet, that later can be selected to determine the amount of API in the potential fractions that can result after splitting. The procedure has been applied to two commercial products, Sintrom 1 and Sintrom 4, with API (acenocoumarol) mass proportion of 2% and 0.7% respectively. Partial Least Squares (PLS) calibration models were constructed for the quantification of acenocoumarol in whole tablets using HPLC as a reference analytical method. Once validated, the calibration models were used to determine the API content in the different potential fragments of the scored Sintrom 4 tablets. Fragment mass measurements were also performed to estimate the range of masses of the halves and quarters that could result after tablet splitting. The results show that Raman spectroscopy can be an alternative analytical procedure to assess the uniformity of content, both in whole tablets as in its potential fragments, and that Sintrom 4 tablets can be perfectly split in halves, but some cautions have to be taken when considering the fragmentation in quarters. A practical alternative to the use of UDU test for the assessment of tablet fragments is proposed.


Assuntos
Análise Espectral Raman/métodos , Comprimidos , Cromatografia Líquida de Alta Pressão , Análise dos Mínimos Quadrados , Controle de Qualidade
12.
Phys Chem Chem Phys ; 16(35): 19001-10, 2014 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-25093656

RESUMO

Computational screening throughout a database containing ∼138 000 metal-organic frameworks (MOFs) has been performed to select candidate structures for hydrogen storage. A total of 231 structures (of which 79 contain paddle-wheel units) have been selected that meet the gravimetric and volumetric targets at 100 atm and 77 K. Grand Canonical Monte Carlo simulations have been performed to calculate the isotherms and select structures which meet the targets at 50 atm, and also to check the adsorption in the low pressure regime (1 atm). From this a reduced set of 18 structures has been analysed in more detail, regarding not only gravimetric and volumetric uptake but also pore size distribution and pore volume. A few structures with 3% gravimetric uptake at 1 atm and 77 K perform at the best level found so far.

13.
J Plant Physiol ; 171(15): 1354-61, 2014 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-25046756

RESUMO

The effect of NAA (1-naphthaleneacetic acid) on organic acid exudation in white lupin plants grown under phosphorus deficiency was investigated. Plants were sampled periodically for collecting of organic acids (citrate, malate, succinate), and also were used to study the effect on proton extrusion and release of Na(+), K(+), Ca(2+) and Mg(2+). The tissues were later processed to quantify the organic acids in tissues, the phosphorus content and the effects on plant biomass. The exogenous addition of NAA led to an increase in organic acid exudation, but this response was not proportional to the concentration of the dose applied, noticing the largest increments with NAA 10(-8)M. In contrast the increase in root weight was proportional to the dose applied, which shows that with higher doses the roots produced are not of proteoid type. Proton extrusion and the release of cations were related to the NAA dose, the first was proportional to the dose applied and the second inversely proportional. Regarding the analysis of tissues, the results of citrate and phosphorus content in shoots show that the overall status of these parts are the main responsible of the organic acids exuded. NAA served as an enhancer of the organic acid exudation that occurs under phosphorus deficient conditions, with a response that depends on the dose applied, not only in its magnitude, but also in the mechanism of action of the plant hormone.


Assuntos
Ácidos Indolacéticos/farmacologia , Lupinus/efeitos dos fármacos , Ácidos Naftalenoacéticos/farmacologia , Reguladores de Crescimento de Plantas/farmacologia , Biomassa , Ácidos Carboxílicos/metabolismo , Cátions/metabolismo , Ácido Cítrico/metabolismo , Lupinus/crescimento & desenvolvimento , Lupinus/metabolismo , Malatos/metabolismo , Fósforo/deficiência , Fósforo/metabolismo , Exsudatos de Plantas/análise , Raízes de Plantas/efeitos dos fármacos , Raízes de Plantas/metabolismo , Brotos de Planta/efeitos dos fármacos , Brotos de Planta/metabolismo , Prótons , Ácido Succínico/metabolismo
14.
Chem Soc Rev ; 42(1): 114-27, 2013 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-22996379

RESUMO

Despite the sustained use of forcefield methodologies to study SiO(2) polymorphs few reviews on the subject are available in the literature. The present study is an attempt to help fill this gap, focusing on classical forcefields used to reproduce and predict properties of pure silica zeolites (or zeosils) such as cell parameters, SiO distance and especially pore size. Instead of an exhaustive study we have focused on an application where diffusion of hydrocarbons makes important the use of pure silica zeolites. A particular area of interest is small pore zeosils containing 8-rings as the largest window, which are industrially interesting for their ability to perform kinetic separations of mixtures of C3 hydrocarbon molecules whose dimensions are of similar characteristics. A set of forcefields have been selected from the literature to analyze their accuracy and transferability when predicting structural, mechanical and dynamical properties of small pore pure silica zeolites and their performance at selective diffusion of C3 hydrocarbons.

15.
Phys Chem Chem Phys ; 14(7): 2508-17, 2012 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-22252608

RESUMO

The confinement effects upon hydrogen adsorption in Cu(II)-paddle wheel containing metal-organic frameworks (MOFs) were evaluated and rationalized in terms of the structural properties (cavity types and pore diameters) of PCN-12, HKUST-1, MOF-505, NOTT-103 and NOTT-112. First-principles calculations were employed to identify the strongest adsorption positions at the paddle wheel inorganic building unit (IBU). The adsorption centres due to confinement were located through analysis of 3D occupancy maps obtained from the hydrogen trajectories computed via molecular dynamics simulations. It was found that the confinement enhances the adsorption on the weakest adsorption centres around the IBU in regions close to the narrowest windows and promotes the formation of new adsorption regions into the small cavities. Our results indicate that at low pressure, the high H(2) uptake in these materials is partly due to the presence of small cavities (5.3-8.5 Å) or narrow windows where the long-range contribution to the adsorption becomes important. Conversely, confinement effects in cavities with diameters >12 Å were not observed.

16.
Phys Chem Chem Phys ; 13(37): 16558-68, 2011 Oct 06.
Artigo em Inglês | MEDLINE | ID: mdl-21860867

RESUMO

The adsorption of hydrogen in MOFs takes place mainly close to the inorganic secondary building unit (IBU). The adsorption capacities on MIL-88, UiO-66, MIL-47 and MFU-1 were investigated. Quantum chemical calculations at the ab initio HF/MP2 theoretical level were employed to estimate the maximum uptake of H(2) molecules per metallic centre. Extrapolating the results on small clusters to the unit cell of each particular MOF, the H(2) uptakes (gravimetric and volumetric) were estimated. The loading of hydrogen per metal atom (H(2) molecules/M-atom) and the density of metal atoms (M-atoms Å(-3)) were defined as useful parameters to assess hydrogen storage properties and to estimate the optimum density that the material should have to be a good H(2) adsorbent. It was found that values above 3 H(2) molecules/M-atom and around 0.004 M-atoms Å(-3) for MOFs with densities around 0.7-1.0 g cm(-3) are required to reach the 2015 storage targets.

17.
Phys Chem Chem Phys ; 11(40): 9250-8, 2009 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-19812846

RESUMO

High concentrations of molecular hydrogen adsorption on MOF-5 were evaluated at the semiempirical PM6 (periodic and cluster) and ab initio MP2 (cluster) theoretical levels. From the semiempirical calculations, an uptake of 3.9% weight on the inorganic building unit of MOF-5 was estimated, in good agreement with a recent accurate estimation of 4.5-5.2%. Although PM6 allows a correct estimation of the maximum uptake, the adsorption energy was overestimated and hence ab initio calculations, including a correlation treatment at the MP2 level as well as corrections for basis set superposition error, were performed with full optimisation, including the 6-31G basis set, which rendered an adsorption energy (per hydrogen molecule) of -0.14 kcal mol(-1). The crucial role of the quality of the basis set, as well as the importance of simulating high hydrogen loading (resembling experimental measurements), are remarked. Single point calculations (using the 6-31G geometry) with improved basis sets 6-31G(d,p) and 6-31++G(d,p) yielded adsorption energies of -0.33 and -0.57 kcal mol(-1), the latter in reasonable agreement with a recent experimental estimation of -1.0 kcal mol(-1). The role of the intermolecular hydrogen interactions is highlighted in this study, since many previous computational studies were performed at low hydrogen loadings, far from the experimental uptake conditions.

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