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1.
Radiology ; 311(3): e231863, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38916503

RESUMEN

HISTORY: A 30-year-old female patient with a history of infertility and no pregnancy presented to the gynecologic endometriosis clinic for follow-up 1 month after oocyte retrieval, to be evaluated for pelvic optimization before potential embryo transfer, with worsening dysmenorrhea, dyspareunia, and overall pelvic pain. Eleven years prior, the patient had undergone left ovarian cystectomy for treatment of endometrioma, as well as excision of deep infiltrative endometriosis. The oocyte retrieval procedure, where more than 30 eggs were retrieved, was complicated by ovarian hyperstimulation syndrome and intraperitoneal bleeding, which necessitated admission to the intensive care unit (ICU) for 3 days. Following discharge from the ICU, the patient experienced occasional on-and-off pressure of the urinary bladder and persistent aching pelvic pain. At the 1-month follow-up appointment, the patient's vital signs were assessed (blood pressure, 142/94 mm Hg; pulse rate, 95 per minute; temperature, 96.8 °F [36 °C]). Routine blood investigations, including white blood cell count, were within normal limits. Physical examination showed the abdomen was soft but there was mild pelvic tenderness. The serum ß-human chorionic gonadotropin test result was negative for pregnancy, and urinalysis testing showed no leukocyte esterase or nitrites. MRI of the pelvis (Figs 1-3) was performed to evaluate the worsening pain.


Asunto(s)
Imagen por Resonancia Magnética , Humanos , Femenino , Adulto , Imagen por Resonancia Magnética/métodos , Endometriosis/diagnóstico por imagen , Endometriosis/cirugía , Endometriosis/complicaciones , Diagnóstico Diferencial , Dolor Pélvico/diagnóstico por imagen , Dolor Pélvico/etiología
2.
Clin Infect Dis ; 77(9): 1265-1272, 2023 11 11.
Artículo en Inglés | MEDLINE | ID: mdl-37310036

RESUMEN

BACKGROUND: Antimicrobial stewardship (AS) is an important topic in infectious diseases (ID) training, yet many ID fellowships lack formal training, and little is known about fellows' learning preferences. METHODS: We conducted 24 in-depth interviews with ID fellows across the United States during 2018 and 2019 to explore their experiences with and preferences for AS education during fellowship. Interviews were transcribed, deidentified, and analyzed to identify themes. RESULTS: Fellows had variable exposure to AS before and during fellowship, which impacted their knowledge about and attitude toward stewardship as a career; however, all fellows expressed the importance of learning general stewardship principles during fellowship. Some fellows' training included mandatory stewardship lectures and/or rotations, but most fellows felt their primary stewardship learning occurred through informal experiences in the clinical setting, such as holding the antimicrobial approval pager. Fellows expressed a preference for a standardized, structured curriculum that included in-person practical, interactive discussions with multidisciplinary faculty along with the opportunity to practice and apply their skills; however, they emphasized that time needed to be set aside for those educational activities. Although they wanted to learn the evidence and rationale for stewardship recommendations, they especially wanted training in and feedback on how to communicate stewardship recommendations to other health professionals, particularly in the setting of conflict. CONCLUSIONS: ID fellows believe that standardized AS curricula should be included in their fellowship training, and they prefer structured, practical, and interactive learning experiences.


Asunto(s)
Programas de Optimización del Uso de los Antimicrobianos , Enfermedades Transmisibles , Entrenamiento Simulado , Humanos , Estados Unidos , Curriculum , Educación de Postgrado en Medicina , Becas , Encuestas y Cuestionarios
3.
Am J Obstet Gynecol ; 228(2): 203.e1-203.e9, 2023 02.
Artículo en Inglés | MEDLINE | ID: mdl-36088988

RESUMEN

BACKGROUND: The supply of obstetrician-gynecologists and gynecologic oncologists across the United States has been described. However, these studies focused on reproductive-age patients and did not assess the growing demand for services to the advanced-age female population. OBJECTIVE: This study aimed to evaluate the supply of obstetrician-gynecologists and gynecologic oncologists who serve the US Medicare population per 100,000 female Medicare beneficiaries, over time and by state and region. STUDY DESIGN: The supply of obstetrician-gynecologists and gynecologic oncologists was extracted from the Physician and Other Supplier Public Use File database of Medicare Part B claims submitted to the US Centers for Medicare & Medicaid Services. Data were only available from 2012 to 2019. The supply of providers was divided by the number of original female Medicare beneficiaries obtained from the Kaiser Family Foundation; all values reported are providers per 100,000 female beneficiaries by state. Trends over time were assessed as the difference in provider-to-beneficiary ratio and the percentage change from 2012 to 2019. All data were collected in 2021. All analyses were performed with SAS, version 9.4. This study was exempt from institutional review board approval. RESULTS: In 2019, the average number of obstetrician-gynecologists per 100,000 female beneficiaries across all states was 121.32 (standard deviation±33.03). The 3 states with the highest obstetrician-gynecologist-to-beneficiary ratio were the District of Columbia (268.85), Connecticut (204.62), and Minnesota (171.60), and the 3 states with the lowest were Montana (78.37), West Virginia (82.28), and Iowa (83.92). The average number of gynecologic oncologists was 4.48 (standard deviation±2.08). The 3 states with the highest gynecologic oncologist-to-beneficiary ratio were the District of Columbia (11.30), Rhode Island (10.58), and Connecticut (9.24), and the 3 states with the lowest were Kansas (0.82), Vermont (1.41), and Mississippi (1.47). The number of obstetrician-gynecologists per 100,000 female beneficiaries decreased nationally by 8.4% from 2012 to 2019; the difference in provider-to-beneficiary ratio from 2012 to 2019 ranged from +29.97 (CT) to -82.62 (AK). Regionally, the Northeast had the smallest decrease in the number of obstetrician-gynecologists per 100,000 female beneficiaries (-3.8%) and the West had the largest (-18.2%). The number of gynecologic oncologists per 100,000 female beneficiaries increased by 7.0% nationally during the study period; this difference ranged from +8.96 (DC) to -3.39 (SD). Overall, the West had the smallest increase (4.7%) and the Midwest had the largest (15.4%). CONCLUSION: There is wide geographic variation in the supply and growth rate of obstetrician-gynecologists and gynecologic oncologists for the female Medicare population. This analysis provides insight into areas of the country where the supply of obstetrician-gynecologists and gynecologic oncologists may not meet current and future demand. The national decrease in the number of obstetrician-gynecologists is alarming, especially because population projections estimate that the proportion of elderly female patients will grow. Future work is needed to determine why fewer providers are available to see Medicare patients and what minimum provider-to-enrollee ratios are needed for gynecologic and cancer care. Once such ratios are established, our results can help determine whether specific states and regions are meeting demand. Additional research is needed to assess the effect of the COVID-19 pandemic on the supply of women's health providers.


Asunto(s)
COVID-19 , Oncólogos , Estados Unidos , Humanos , Femenino , Anciano , Medicare , Ginecólogos , Obstetras , Pandemias
4.
J Minim Invasive Gynecol ; 30(10): 782, 2023 10.
Artículo en Inglés | MEDLINE | ID: mdl-37541324

RESUMEN

OBJECTIVE: In patients with endometriosis, extra pelvic endometriosis is estimated to have an incidence of 11% and a rare subset of extra pelvic lesions include abdominal wall endometriosis with an incidence of 0.03% to 3.5% [1,2]. Evaluation for and surgical management of abdominal wall endometriosis are an essential skill set for the advanced gynecologic surgeon. In this video, we demonstrate a surgical technique for robot-assisted laparoscopic excision of abdominal wall endometriosis with intraoperative ultrasound-guided needle placement. DESIGN: Description and demonstration of surgical technique. SETTING: A patient with previous history of 2 cesarean sections and right lower quadrant cyclic abdominal wall pain; a tertiary care, academic center. INTERVENTIONS: Intraoperative ultrasound-guided needle placement to map location and boundaries of the lesion followed by minimally invasive resection of the lesion with the intermittent advancement and withdrawal of needles to confirm clear margins. CONCLUSION: Minimally invasive resection of abdominal wall endometriosis using intraoperative ultrasound-guided needle placement is an effective technique to guide surgical dissection and allow for clear surgical margins and successful treatment of this rare condition.


Asunto(s)
Pared Abdominal , Endometriosis , Laparoscopía , Robótica , Humanos , Femenino , Endometriosis/diagnóstico por imagen , Endometriosis/cirugía , Endometriosis/patología , Pared Abdominal/diagnóstico por imagen , Pared Abdominal/cirugía , Pared Abdominal/patología , Laparoscopía/métodos , Dolor Abdominal/cirugía
5.
Chem Soc Rev ; 51(3): 1045-1097, 2022 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-35005751

RESUMEN

A defining characteristic of nearly all catalytically functional MOFs is uniform, molecular-scale porosity. MOF pores, linkers and nodes that define them, help regulate reactant and product transport, catalyst siting, catalyst accessibility, catalyst stability, catalyst activity, co-catalyst proximity, composition of the chemical environment at and beyond the catalytic active site, chemical intermediate and transition-state conformations, thermodynamic affinity of molecular guests for MOF interior sites, framework charge and density of charge-compensating ions, pore hydrophobicity/hydrophilicity, pore and channel rigidity vs. flexibility, and other features and properties. Collectively and individually, these properties help define overall catalyst functional behaviour. This review focuses on how porous, catalyst-containing MOFs capitalize on molecular-scale confinement, containment, isolation, environment modulation, energy delivery, and mobility to accomplish desired chemical transformations with potentially superior selectivity or other efficacy, especially in comparison to catalysts in homogeneous solution environments.


Asunto(s)
Catálisis , Iones , Conformación Molecular
6.
J Am Chem Soc ; 144(27): 12092-12101, 2022 Jul 13.
Artículo en Inglés | MEDLINE | ID: mdl-35786950

RESUMEN

Ceria-based materials have been highly desired in photocatalytic reactions due to their redox properties and strong oxygen storage and transfer ability. Herein, we report the structures of one CeCe70 oxysulfate cluster and four MCe70 clusters (M = Cu, Ni, Co, and Fe) with the same Ce70 core. As noted, single-crystal X-ray diffraction confirmed the structures of CeCe70 and the MCe70 series, while Raman spectroscopy indicated an increase in oxygen defects upon the introduction of Cu and Fe ions. The clusters catalyzed the oxidation of 4-methoxybenzyl alcohol under ultraviolet light. CuCe70 and FeCe70 exhibited enhanced reactivity compared to CeCe70 and improved aldehyde selectivity compared to control experiments. In comparison with their homogeneous congeners, the CeCe70/MCe70 clusters altered the location of radical generation from the bulk solution to the clusters' surfaces. Mechanistic studies highlight the role of oxygen defects and specific transition metal introduction for efficient photocatalysis. The mechanistic pathway in this study provides insight into how to select or design a highly selective catalyst for photocatalysis.

7.
Gynecol Oncol ; 167(1): 81-88, 2022 10.
Artículo en Inglés | MEDLINE | ID: mdl-35909004

RESUMEN

OBJECTIVE: Endosalpingiosis is a poorly understood condition of ectopic epithelium resembling the fallopian tubes. It has been described as an incidental pathology finding, a disease similar to endometriosis, and in association with malignancy. The objective of this study is to determine if endosalpingiosis (ES) has an increased association with gynecologic malignancy when compared to endometriosis (EM). METHODS: This is a retrospective case-control analysis of patients with a histologic diagnosis of endosalpingiosis or endometriosis at three affiliated academic hospitals between 2000 and 2020. All ES patients were included, and 1:1 matching was attempted to obtain a comparable cohort of EM patients. Demographic and clinical data were obtained, and statistical analysis was performed. RESULTS: A total of 967 patients (515 ES and 452 EM) were included. ES patients were significantly older than EM patients (median age 52 vs 48 years, p < 0.001). The ES group had significantly more cancer diagnoses at surgery than the EM group (40.1% vs 18.1%, p < 0.001); this difference persisted in a sub-analysis excluding patients with known or suspected malignancy (20.9% vs 5.6%, p < 0.001). ES patients had lower overall survival (10-year freedom from death: 77.0% vs 90.5%, p < 0.001). After adjusting for confounders, multivariable analysis showed that ES patients had increased cancer diagnosed at surgery (OR = 2.48, p < 0.001) and greater risk of death (OR = 1.69, p = 0.017). CONCLUSIONS: Endosalpingiosis was found concurrently with malignancy in 40% of cases, and this effect was preserved in multi-variable and sub-group analyses. Further research consisting of longer follow-up and exploration of molecular relationships between ES and cancer are forthcoming.


Asunto(s)
Endometriosis , Enfermedades de las Trompas Uterinas , Neoplasias de los Genitales Femeninos , Enfermedades Urogenitales , Endometriosis/complicaciones , Endometriosis/diagnóstico , Endometriosis/epidemiología , Enfermedades de las Trompas Uterinas/diagnóstico , Enfermedades de las Trompas Uterinas/epidemiología , Trompas Uterinas/patología , Femenino , Neoplasias de los Genitales Femeninos/complicaciones , Neoplasias de los Genitales Femeninos/epidemiología , Humanos , Persona de Mediana Edad , Estudios Retrospectivos
8.
J Sex Med ; 19(10): 1553-1561, 2022 10.
Artículo en Inglés | MEDLINE | ID: mdl-35970712

RESUMEN

BACKGROUND: Studies have found that women with endometriosis have a higher risk of female sexual dysfunction (FSD). AIM: To evaluate the relationship between self-reported endometriosis and FSD utilizing validated surveys. METHODS: A cross-sectional analysis was conducted among sexually active women aged 18-90 who presented to 3 Mayo Clinic sites from 2015 to 2021. FSD was determined utilizing a combined endpoint of Female Sexual Function Index score ≤ 26.55 and Female Sexual Distress Scale-Revised score ≥ 11. Associations between history of endometriosis and FSD were evaluated by fitting 3 multivariable logistic models and were stratified by menopause status. In the first model, the association was adjusted for age, BMI, race/ethnicity, marital status, and education. The second model adjusted for the variables in Model 1 and hormone therapy, hormonal contraceptive use, self-reported history of abuse within the last year, and co-morbidities including the history of diabetes, heart disease, hypertension, osteoporosis, and stroke. The third model adjusted for the variables in Model 1, Model 2, and anxiety, depression, relationship satisfaction, and SSRI/SNRI use. OUTCOMES: The outcomes included self-reported endometriosis and female sexual dysfunction determined utilizing a combined endpoint of Female Sexual Function Index score ≤ 26.55 and Female Sexual Distress Scale-Revised score ≥ 11. RESULTS: Of 7118 patients (mean age 51.3), 92.2% were white, 78.4% were peri- or postmenopausal, 8.7% reported endometriosis history, and 57.2% met the criteria for FSD. Women with endometriosis were more likely to be overweight or obese, be smokers, have had a history of heart disease and osteoporosis, have had anxiety and depressed mood, have had a hysterectomy and bilateral salpingo-oophorectomy, and have used hormone therapy. Compared to those without endometriosis, women with endometriosis were significantly more likely to have FSD only among premenopausal women (74.2% vs 57.4%). Similarly, in multivariable analysis the relationship was only seen for premenopausal women in all 3 models (Model 1: OR 2.74 (95% CI 1.43-5.27); Model 2: OR 2.55 (95% CI 1.30-5.04); Model 3: OR 2.30 (95% CI 1.13-4.68)). CLINICAL IMPLICATIONS: These findings highlight the opportunity for healthcare practitioners to evaluate sexual function in premenopausal women with endometriosis. For peri and postmenopausal women with endometriosis, the risk of FSD was lower than for premenopausal women with endometriosis. STRENGTHS AND LIMITATIONS: This study analyzed the association between endometriosis and FSD in women by menopause status using validated tools that included a measure of distress associated with sexual dysfunction. Limitations include its cross-sectional design which does not allow for determination of the direction of this association. CONCLUSION: The risk for FSD associated with endometriosis depends on menopause status. Endometriosis increased the odds of FSD only in premenopausal women. Kling JM, Ghaith S, Smith T, et al. Evaluating the Link Between Self-Reported Endometriosis and Female Sexual Dysfunction. J Sex Med 2022;19:1533-1561.


Asunto(s)
Endometriosis , Cardiopatías , Osteoporosis , Inhibidores de Captación de Serotonina y Norepinefrina , Disfunciones Sexuales Psicológicas , Anticonceptivos , Estudios Transversales , Endometriosis/complicaciones , Endometriosis/epidemiología , Femenino , Hormonas , Humanos , Persona de Mediana Edad , Autoinforme , Disfunciones Sexuales Psicológicas/epidemiología , Disfunciones Sexuales Psicológicas/etiología , Encuestas y Cuestionarios
9.
Chem Rev ; 120(16): 8130-8160, 2020 08 26.
Artículo en Inglés | MEDLINE | ID: mdl-32207607

RESUMEN

Materials capable of the safe and efficient capture or degradation of toxic chemicals, including chemical warfare agents (CWAs) and toxic industrial chemicals (TICs), are critically important in the modern age due to continuous threats of these chemicals to human life, both directly and indirectly. Metal-organic frameworks (MOFs), atomically precise hybrid materials that are synthesized via the self-assembly of metal cations or clusters and organic linkers, offer a unique solid adsorbent design platform due to their great synthetic versatility. This review will focus on recent advancements in MOF-based adsorbent design for protection against chemical warfare agents (organophosphorus nerve agents, blistering agents, and their simulants) and toxic industrial chemicals such as H2S, NH3, SO2, CO, NO2, and NO.


Asunto(s)
Estructuras Metalorgánicas/química , Sustancias Protectoras/química , Adsorción , Amoníaco/química , Amoníaco/aislamiento & purificación , Monóxido de Carbono/química , Monóxido de Carbono/aislamiento & purificación , Sustancias para la Guerra Química/química , Sustancias para la Guerra Química/aislamiento & purificación , Sulfuro de Hidrógeno/química , Sulfuro de Hidrógeno/aislamiento & purificación , Estructuras Metalorgánicas/síntesis química , Óxido Nítrico/química , Óxido Nítrico/aislamiento & purificación , Dióxido de Nitrógeno/química , Dióxido de Nitrógeno/aislamiento & purificación , Sustancias Protectoras/síntesis química , Dióxido de Azufre/química , Dióxido de Azufre/aislamiento & purificación
10.
Curr Opin Obstet Gynecol ; 34(4): 204-209, 2022 08 01.
Artículo en Inglés | MEDLINE | ID: mdl-35895962

RESUMEN

PURPOSE OF REVIEW: Thoracic endometriosis is a rare disease that can lead to a variety of clinical manifestations. There are currently no guidelines for optimal diagnosis and management of the disease. The purpose of this review is to provide an overview of the diagnosis and surgical treatment of thoracic endometriosis. RECENT FINDINGS: Various imaging modalities, including computed tomography (CT), MRI and ultrasound, have been reported in the detection of thoracic endometriosis. MRI is the most sensitive imaging study and may aid in preoperative planning. Histopathology of a biopsied lesion remains the gold standard for diagnosis. Surgical management of thoracic endometriosis may involve laparoscopy and/or thoracoscopy, and surgical planning should include preparation for single ventilation capability. A multidisciplinary approach involving a gynaecologic surgeon and thoracic surgeon may be considered. Repairing diaphragm defects and pleurodesis are shown to decrease recurrent symptoms. SUMMARY: Although optimal diagnostic testing remains uncertain, a high clinical suspicion for thoracic endometriosis is critical to ensure prompt diagnosis and treatment in order to prevent recurrent symptoms and progression to more serious sequalae. Minimally invasive surgical techniques are becoming increasingly utilized and allow for thorough evaluation and treatment of thoracic endometriosis.


Asunto(s)
Endometriosis , Laparoscopía , Enfermedades Musculares , Diafragma/patología , Diafragma/cirugía , Endometriosis/diagnóstico , Endometriosis/patología , Endometriosis/cirugía , Femenino , Humanos , Procedimientos Quirúrgicos Mínimamente Invasivos , Enfermedades Musculares/cirugía
11.
J Minim Invasive Gynecol ; 29(5): 683-690, 2022 05.
Artículo en Inglés | MEDLINE | ID: mdl-35085838

RESUMEN

STUDY OBJECTIVE: Evaluate inter-rater and intrarater reliability of a novel scoring tool for surgical complexity assessment of endoscopic hysterectomy. DESIGN: Validation study. SETTING: Academic medical center. PARTICIPANTS: Total of 11 academic obstetrician-gynecologists with varying years of postresidency training, clinical practice, and surgical volumes. INTERVENTIONS: Application of a novel scoring tool to evaluate surgical complexity of 150 sets of images taken in a standardized fashion before surgical intervention (global pelvis, anterior cul-de-sac, posterior cul-de-sac, right adnexa, left adnexa). Using only these images, raters were asked to assess uterine size, number, and location of myomas, adnexal and uterine mobility, need for ureterolysis, and presence of endometriosis or adhesions in relevant locations. Surgical complexity was staged on a scale of 1 to 4 (low to high complexity). MEASUREMENTS AND MAIN RESULTS: Number of postresidency years in practice for participating surgeons ranged from 2 to 15, with an average of 8 years. A total of 8 obstetrician-gynecologists (72.7%) had completed a fellowship in minimally invasive gynecologic surgery. Six (54.6%) reported an annual volume of >50 hysterectomies. Raters reported that 95.4% of the images were satisfactory for assessment. Of the 150 sets of images, most were found to be stage 1 to 2 complexity (stage 1: 23.8%, stage 2: 41.6%, stage 3: 32.8%, stage 4: 1.8%). The level of inter-rater agreement regarding stage 1 to 2 vs 3 to 4 complexity was moderate (κ = 0.49; 95% confidence interval [CI], 0.42-0.56). Moderate inter-rater agreement was also found between surgeon raters with an annual hysterectomy volume >50 (κ = 0.49; 95% CI, 0.40-0.57) as well as between surgeon raters with fellowship experience (κ = 0.50; 95% CI, 0.42-0.58). Intrarater agreement averaged 80.2% among all raters and also achieved moderate agreement (mean weighted κ = 0.53; range, 0.38-0.72). CONCLUSION: This novel scoring tool uses clinical assessment of preintervention anatomic images to stratify the surgical complexity of endoscopic hysterectomy. It has rich and comprehensive evaluation capabilities and achieved moderate inter-rater and intrarater agreement. The tool can be used in conjunction with or instead of traditional markers of surgical complexity such as uterine weight, estimated blood loss, and operative time.


Asunto(s)
Fondo de Saco Recto-Uterino , Histerectomía , Femenino , Humanos , Variaciones Dependientes del Observador , Tempo Operativo , Reproducibilidad de los Resultados
12.
Angew Chem Int Ed Engl ; 61(19): e202202207, 2022 05 02.
Artículo en Inglés | MEDLINE | ID: mdl-35212125

RESUMEN

The fabrication of MOF polymer composite materials enables the practical applications of MOF-based technology, in particular for protective suits and masks. However, traditional production methods typically require organic solvent for processing which leads to environmental pollution, low-loading efficiency, poor accessibility, and loss of functionality due to poor solvent resistance properties. For the first time, we have developed a microbial synthesis strategy to prepare a MOF/bacterial cellulose nanofiber composite sponge. The prepared sponge exhibited a hierarchically porous structure, high MOF loading (up to ≈90 %), good solvent resistance, and high catalytic activity for the liquid- and solid-state hydrolysis of nerve agent simulants. Moreover, the MOF/ bacterial cellulose composite sponge reported here showed a nearly 8-fold enhancement in the protection against an ultra-toxic nerve agent (GD) in permeability studies as compared to a commercialized adsorptive carbon cloth. The results shown here present an essential step toward the practical application of MOF-based protective gear against nerve agents.


Asunto(s)
Estructuras Metalorgánicas , Agentes Nerviosos , Catálisis , Celulosa , Estructuras Metalorgánicas/química , Solventes
13.
J Am Chem Soc ; 143(49): 21056-21065, 2021 12 15.
Artículo en Inglés | MEDLINE | ID: mdl-34873904

RESUMEN

Heterometallic CeIV/M oxo clusters are underexplored yet and can benefit from synergistic properties from combining cerium and other metal cations to produce efficient redox catalysts. Herein, we designed and synthesized a series of new Ce12V6 oxo clusters with different capping ligands: Ce12V6-SO4, Ce12V6-OTs (OTs: toluenesulfonic acid), and Ce12V6-NBSA (NBSA: nitrobenzenesulfonic acid). Single crystal X-ray diffraction (SCXRD) for all three structures reveals a Ce12V6 cubane core formulated [Ce12(VO)6O24]18+ with cerium on the edges of the cube, vanadyl capping the faces, and sulfate on the corners. While infrared spectroscopy (IR), ultraviolet-visible spectroscopy (UV-vis), electrospray ionization mass spectrometry (ESI-MS), and proton nuclear magnetic resonance (1H NMR) proved the successful coordination of the organic ligands to the Ce12V6 core, liquid phase 51V NMR and small-angle X-ray scattering (SAXS) confirmed the integrity of the clusters in the organic solutions. Furthermore, functionalization of the Ce12V6 core with organic ligands both provides increased solubility in term of homogeneous application and introduces porosity to the assemblies of Ce12V6-OTs and Ce12V6-NBSA in term of heterogeneous application, thus allowing more catalytic sites to be accessible and improving reactivity as compared to the nonporous and less soluble Ce12V6-SO4. Meanwhile, the coordinated ligands also influenced the electronic environment of the catalytic sites, in turn affecting the reactivity of the cluster, which we probed by the selective oxidation of 2-chloroethyl ethyl sulfide (CEES). This work provides a strategy to make full use of the catalytic sites within a class of inorganic sulfate capped clusters via organic ligand introduction.

14.
J Am Chem Soc ; 143(3): 1503-1512, 2021 01 27.
Artículo en Inglés | MEDLINE | ID: mdl-33433209

RESUMEN

Interpenetration of two or more sublattices is common among many metal-organic frameworks (MOFs). Herein, we study the evolution of one zirconium cluster-based, 3,8-connected MOF from its non-interpenetrated (NU-1200) to interpenetrated (STA-26) isomer. We observe this transient catenation process indirectly using ensemble methods, such as nitrogen porosimetry and X-ray diffraction, and directly, using high-resolution transmission electron microscopy. The approach detailed here will serve as a template for other researchers to monitor the interpenetration of their MOF samples at the bulk and single-particle limits. We investigate the mechanical stability of both lattices experimentally by pressurized in situ X-ray diffraction and nanoindentation as well as computationally with density functional theory calculations. Both lines of study reveal that STA-26 is considerably more mechanically stable than NU-1200. We conclude this study by demonstrating the potential of these MOFs and their mixed phases for the capture of gaseous n-hexane, used as a structural mimic for the chemical warfare agent sulfur mustard gas.

15.
J Am Chem Soc ; 143(40): 16777-16785, 2021 10 13.
Artículo en Inglés | MEDLINE | ID: mdl-34590851

RESUMEN

The most recent global health crisis caused by the SARS-CoV-2 outbreak and the alarming use of chemical warfare agents highlight the necessity to produce efficient protective clothing and masks against biohazard and chemical threats. However, the development of a multifunctional protective textile is still behind to supply adequate protection for the public. To tackle this challenge, we designed multifunctional and regenerable N-chlorine based biocidal and detoxifying textiles using a robust zirconium metal-organic framework (MOF), UiO-66-NH2, as a chlorine carrier which can be easily coated on textile fibers. A chlorine bleaching converted the amine groups located on the MOF linker to active N-chlorine structures. The fibrous composite exhibited rapid biocidal activity against both Gram-negative bacteria (E. coli) and Gram-positive bacteria (S. aureus) with up to a 7 log reduction within 5 min for each strain as well as a 5 log reduction of SARS-CoV-2 within 15 min. Moreover, the active chlorine loaded MOF/fiber composite selectively and rapidly degraded sulfur mustard and its chemical simulant 2-chloroethyl ethyl sulfide (CEES) with half-lives less than 3 minutes. The versatile MOF-based fibrous composite designed here has the potential to serve as protective cloth against both biological and chemical threats.


Asunto(s)
Antibacterianos/farmacología , Antivirales/farmacología , Sustancias para la Guerra Química/química , Cloro/farmacología , Estructuras Metalorgánicas/farmacología , Ropa de Protección , Animales , Antibacterianos/síntesis química , Antivirales/síntesis química , Línea Celular , Cloro/química , Escherichia coli/efectos de los fármacos , Halogenación , Humanos , Estructuras Metalorgánicas/síntesis química , Pruebas de Sensibilidad Microbiana , Gas Mostaza/análogos & derivados , Gas Mostaza/química , Oxidación-Reducción , SARS-CoV-2/efectos de los fármacos , Staphylococcus aureus/efectos de los fármacos , Textiles , Circonio/química
16.
Coord Chem Rev ; 4292021 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-33678810

RESUMEN

Porphyrins are important molecules widely found in nature in the form of enzyme active sites and visible light absorption units. Recent interest in using these functional molecules as building blocks for the construction of metal-organic frameworks (MOFs) have rapidly increased due to the ease in which the locations of, and the distances between, the porphyrin units can be controlled in these porous crystalline materials. Porphyrin-based MOFs with atomically precise structures provide an ideal platform for the investigation of their structure-function relationships in the solid state without compromising accessibility to the inherent properties of the porphyrin building blocks. This review will provide a historical overview of the development and applications of porphyrin-based MOFs from early studies focused on design and structures, to recent efforts on their utilization in biomimetic catalysis, photocatalysis, electrocatalysis, sensing, and biomedical applications.

17.
Faraday Discuss ; 225: 9-69, 2021 02 01.
Artículo en Inglés | MEDLINE | ID: mdl-33242050

RESUMEN

As chemists and materials scientists, it is our duty to synthesize and utilize materials for a multitude of applications that promote the development of society and the well-being of its citizens. Since the inception of metal-organic frameworks (MOFs), researchers have proposed a variety of design strategies to rationally synthesize new MOF materials, studied their porosity and gas sorption performances, and integrated MOFs onto supports and into devices. Efforts have explored the relevance of MOFs for applications including, but not limited to, heterogeneous catalysis, guest delivery, water capture, destruction of nerve agents, gas storage, and separation. Recently, several start-up companies have undertaken MOF commercialization within industrial sectors. Herein, we provide a brief overview of the state of the MOF field from their design and synthesis to their potential applications, and finally, to their commercialization.

18.
J Minim Invasive Gynecol ; 28(5): 1107-1112, 2021 05.
Artículo en Inglés | MEDLINE | ID: mdl-33497728

RESUMEN

STUDY OBJECTIVE: To describe the gender makeup of historic fellow classes, as well as those in the roles of associate program director and program director. To determine the representation ratio of the current fellowship program leadership related to historic fellowship class gender proportion. DESIGN: Retrospective observational study. SETTING: Fellowship in minimally invasive gynecologic surgery (FMIGS) sites. PARTICIPANTS: No patient data were captured or used in this study. The subjects included all FMIGS fellows, program directors, and associate program directors for whom there was publicly available data from 2001 to present. INTERVENTIONS: Not applicable. MEASUREMENTS AND MAIN RESULTS: Most FMIGS fellow classes have consisted of mostly female surgeons ranging from 40% to 89% female. The representation ratios for the current program leadership are 0.57, 0.82, and 0.71 for program directors, associate program directors, and all leadership positions, respectively. CONCLUSION: Representation ratios indicate that the current gender makeup of program leadership is not representative of the gender makeup of graduated fellow classes.


Asunto(s)
Becas , Cirujanos , Femenino , Procedimientos Quirúrgicos Ginecológicos , Humanos , Liderazgo , Masculino , Procedimientos Quirúrgicos Mínimamente Invasivos
19.
J Minim Invasive Gynecol ; 28(10): 1680, 2021 10.
Artículo en Inglés | MEDLINE | ID: mdl-34023518

RESUMEN

STUDY OBJECTIVE: To demonstrate a technique for robot-assisted laparoscopic excision of abdominal wall endometriosis and mesh reinforcement of the subsequent defect. DESIGN: Description and demonstration of surgical technique. SETTING: Abdominal wall endometriosis most commonly takes hold after seeding of a previous cesarean scar [1-5]. As of 2018, 31.9% of deliveries in the United States were accomplished by cesarean section [6]. With endometriosis at an estimated incidence of 11% in the United States, evaluation for, and minimally invasive management of, abdominal wall endometriosis is becoming an essential skillset for the gynecologic surgeon [7]. INTERVENTIONS: Robot-assisted laparoscopic evaluation of size and location of lesion in relation to anatomic landmarks. Demonstration of techniques to identify borders of endometriotic lesion including clinical and microscopic. Minimally invasive resection of lesion with preservation of vital structures. Placement of abdominal wall mesh for reinforcement of rectus muscle and fascial defect. Peritoneal closure to minimize adhesions and herniation into defect. Brief review of alternative approaches to surgical management. CONCLUSION: Minimally invasive resection of abdominal wall endometriosis with subsequent mesh reinforcement provides a surgical option with less morbidity while still accomplishing successful treatment.


Asunto(s)
Pared Abdominal , Endometriosis , Procedimientos Quirúrgicos Robotizados , Robótica , Pared Abdominal/patología , Pared Abdominal/cirugía , Cesárea , Cicatriz/patología , Endometriosis/cirugía , Femenino , Humanos , Embarazo , Mallas Quirúrgicas
20.
J Minim Invasive Gynecol ; 28(7): 1343-1350, 2021 07.
Artículo en Inglés | MEDLINE | ID: mdl-32979533

RESUMEN

STUDY OBJECTIVE: To identify incidence of decision regret associated with surgery for endometriosis or chronic pelvic pain (CPP). DESIGN: Survey study. SETTING: Academic medical center. PATIENTS: All patients undergoing excisional surgery for endometriosis or CPP between January 2016 and June 2019. INTERVENTIONS: The women were contacted to complete 2 validated questionnaires: the Decision Regret and Patient Global Impression of Improvement scales. MEASUREMENTS AND MAIN RESULTS: A total of 253 patients were contacted, and 154 patients responded (60.8% response rate) to the survey. A total of 137 women (90%) agreed or strongly agreed that having excisional surgery was the right decision; 134 women (87%) indicated that they would choose to have surgery again. The survey responders did not differ from nonresponders in age (years, 33.9 vs 35; p = .25), robotic route of surgery (83.1% vs 78.8%; p = .66), or performance of hysterectomy (27.3% vs 26.3%; p = .85). The responders were more likely to have stage III/IV endometriosis (50.6% vs 29.3%; p <.01), more previous surgeries for endometriosis (median surgeries, 1 vs 0; p = .01), higher complication rate (8.4% vs 2.0%; p = .03), and pathology test results more frequently positive for endometriosis (87.7% vs 77.8%; p = .03). Overall, 25 patients (16.3%) reported some level of regret after excisional surgery for endometriosis or CPP. Regret was not associated with a lower Patient Global Impression of Improvement score (odds ratio [OR] 4.37; 95% confidence interval [CI], 0.81-23.7), age (OR 0.98; 95% CI, 0.93-1.04), time since surgery (OR 1; 95% CI, 0.97-1.04), number of previous surgeries (OR 1.08; 95% CI, 0.9-1.31), negative pathology test results (OR 2.82; 95% CI, 0.95-8.32), hysterectomy (OR 1.23; 95% CI, 0.45-3.32), or complications (OR 1.07; 95% CI, 0.22-5.16). CONCLUSION: Most women who pursue excisional surgery for endometriosis or CPP are satisfied with their decision. Regret was not associated with patient-reported lack of improvement, negative pathology test results, hysterectomy, or complications. Gynecologic surgeons should engage in shared decision-making with patients and feel comfortable offering surgical evaluation and management to patients with endometriosis or CPP when clinically indicated.


Asunto(s)
Dolor Crónico , Endometriosis , Dolor Crónico/etiología , Dolor Crónico/cirugía , Emociones , Endometriosis/complicaciones , Endometriosis/cirugía , Femenino , Humanos , Histerectomía/efectos adversos , Dolor Pélvico/etiología , Dolor Pélvico/cirugía
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