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1.
J Surg Res ; 291: 151-157, 2023 11.
Artigo em Inglês | MEDLINE | ID: mdl-37399633

RESUMO

INTRODUCTION: Parathyroidectomy is underperformed despite clear benefits in primary hyperparathyroidism (PHPT). We evaluated disparities in receipt of parathyroidectomy following PHPT diagnosis to explore barriers to care. METHODS: Adults diagnosed with PHPT 2013-2018 at a health system were identified. Recommended indications for parathyroidectomy include age ≤50 y, calcium >11 mg/dL, or the presence of nephrolithiasis, hypercalciuria, nephrocalcinosis, decreased glomerular filtration rate, osteopenia, osteoporosis, or pathological fracture 1 y prior to diagnosis. Kaplan-Meier analysis assessed rates of parathyroidectomy within 12 mo following diagnosis as well as median time to parathyroidectomy, and multivariable Cox proportional hazards analyses assessed factors associated with undergoing parathyroidectomy. RESULTS: Of 2409 patients, 75% were females, 12% aged ≤50 y, and 92% non-Hispanic White, while 52% had Medicaid/Medicare, 36% were commercial/self-pay or uninsured, and 12% unknown. Parathyroidectomy was performed within 1 y in 50% of patients. Within the 68% that met recommendations, parathyroidectomy was performed within 1 y in 54%; median time from diagnosis to surgery was shorter for males, patients aged ≤50 y, commercial/self-pay/no insurance patients (versus Medicaid/Medicare), and those with fewer comorbidities, P < 0.05. Multivariable analysis demonstrated non-Hispanic White patients and those with commercial/self-pay/uninsured were more likely to undergo parathyroidectomy after adjusting for comorbidity, age, and facility site. Among those strongly indicated, patients not on Medicare/Medicaid and aged ≤50 y were more likely to undergo parathyroidectomy after adjusting for race, comorbidity, and facility site. CONCLUSIONS: Disparities in parathyroidectomy for PHPT were observed. Insurance type was associated with undergoing parathyroidectomy; patients on governmental insurance were less likely to undergo surgery and waited longer for surgery despite strong indications. Barriers to referral and access to surgery should be investigated and addressed to optimize all patients' access to care.


Assuntos
Hiperparatireoidismo Primário , Cálculos Renais , Osteoporose , Estados Unidos/epidemiologia , Masculino , Adulto , Feminino , Humanos , Idoso , Hiperparatireoidismo Primário/cirurgia , Hiperparatireoidismo Primário/complicações , Paratireoidectomia , Medicare , Osteoporose/complicações , Osteoporose/diagnóstico , Osteoporose/cirurgia , Estudos Retrospectivos
2.
Chemistry ; 27(13): 4394-4400, 2021 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-33296102

RESUMO

The hybrid bidentate 1-(2-pyridyl)benzotriazole (pyb) ligand was introduced into 3d transition metal catalysis. Specifically, [CuII (OTf)2 (pyb)2 ]⋅2 CH3 CN (1) enables the synthesis of a wide range of propargylamines by the A3 coupling reaction at room temperature in the absence of additives. Experimental and high-level theoretical calculations suggest that the bridging N atom of the ligand imposes exclusive trans coordination at Cu and allows ligand rotation, while the N atom of the pyridine group modulates charge distribution and flux, and thus orchestrates structural and electronic precatalyst control permitting alkyne binding with simultaneous activation of the C-H bond via a transient CuI species.

3.
World J Surg ; 45(1): 188-194, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-33034710

RESUMO

BACKGROUND: The role of lymphadenectomy in adrenocortical carcinoma resection is controversial. Therefore, we conducted a population-based study to assess the association between positive lymph nodes (LN) and survival. METHODS: The Surveillance, Epidemiology, and End Results set of cancer registries were utilized. The associations between positive lymph nodes and tumor size, grade and laterality were assessed. Cancer specific survival (CSS) trends and factors affecting survival were analyzed. RESULTS: A total of 2170 adult patients were identified; 60% underwent resection. Among those resected, LN were examined in 23% and were positive in 25% of patients with LN examined. Patients with positive LN tended to have smaller tumors compared to those with negative LN (12 ± 5 vs 15 ± 11 cm, p = 0.02). The rate of positive LN was higher in right ACC, p = 0.03. Median overall CSS was 21 months, with significant differences between resection (42 months) and no resection (4 months), p < 0.01. Median CSS did not change over time when comparing ACC patients who underwent surgery before 2000, 2000-2009, and 2010-2016. On multivariable analysis including resection group, advanced age, grades III and IV, regional and distant stage, in addition to positive LN were associated with worse survival, p < 0.05. CONCLUSION: Lymphadenectomy is infrequently performed during ACC resection, and when performed, regional LN involvement tends to be associated with worse survival. Neoplasm size and grade were not associated with LN involvement and therefore, do not inform lymphadenectomy need. Further studies are needed to assess the indications for, and value of lymphadenectomy in ACC.


Assuntos
Neoplasias do Córtex Suprarrenal , Carcinoma Adrenocortical , Neoplasias do Córtex Suprarrenal/epidemiologia , Neoplasias do Córtex Suprarrenal/mortalidade , Neoplasias do Córtex Suprarrenal/patologia , Neoplasias do Córtex Suprarrenal/cirurgia , Carcinoma Adrenocortical/epidemiologia , Carcinoma Adrenocortical/mortalidade , Carcinoma Adrenocortical/patologia , Carcinoma Adrenocortical/cirurgia , Adulto , Idoso , Idoso de 80 Anos ou mais , Feminino , Humanos , Excisão de Linfonodo/estatística & dados numéricos , Linfonodos/patologia , Linfonodos/cirurgia , Masculino , Pessoa de Meia-Idade , Estadiamento de Neoplasias , Estudos Retrospectivos , Programa de SEER/estatística & dados numéricos , Adulto Jovem
4.
Ann Surg Oncol ; 27(10): 3851-3857, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32388739

RESUMO

BACKGROUND: Bilateral adrenalectomy (BA) is a curative treatment for hypercortisolism in patients with corticotropin (ACTH)-dependent Cushing syndrome. Indications include refractory Cushing's disease (CD) following failed pituitary surgery, and occult or unresectable ectopic ACTH-producing neoplasms (EA). METHODS: This was a single-center, retrospective review (1995-2017) of patients undergoing BA for CD or EA. Demographics, laboratory findings, and intraoperative and postoperative variables were analyzed. RESULTS: Of 137 patients, 83 (61%) had CD and 54 (39%) had EA; 87% of CD patients were female versus 46% of EA patients (p < 0.0001). Mean age at diagnosis was 40 ± 15 years for CD and 49 ± 18 years for EA (p = 0.004). Preoperative serum cortisol concentrations were higher in the EA cohort (63 ± 40 µg/dL) versus the CD cohort (33 ± 19 µg/dL) [p < 0.001], with no significant differences in serum ACTH. Time from diagnosis until adrenalectomy was 54 ± 69 months for CD versus 4 ± 13 for EA (p = 0.002). Most patients underwent minimally invasive surgery (MIS; 86% CD vs. 75% EA; p = 0.19). There was no difference between the rates of conversion to an open approach, intraoperative blood loss, or operative time between groups, and no difference between complications in CD versus EA (p = 1.0). Five-year survival was significantly shorter among the EA cohort (30% for EA vs. 80% for CD; p < 0.001). CONCLUSION: Patients with EA presented with higher serum cortisol levels compared with patients with CD. EA patients were more likely to require intraoperative transfusion and postoperative intensive care. BA in patients with CD and EA can be performed safely in an MIS fashion, with similar morbidity; however, survival at 5 years was significantly less in the EA cohort.


Assuntos
Neoplasias , Hipersecreção Hipofisária de ACTH , Adrenalectomia , Hormônio Adrenocorticotrópico , Adulto , Idoso , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Hipersecreção Hipofisária de ACTH/etiologia , Hipersecreção Hipofisária de ACTH/cirurgia , Estudos Retrospectivos , Resultado do Tratamento
5.
J Surg Res ; 245: 107-114, 2020 01.
Artigo em Inglês | MEDLINE | ID: mdl-31415931

RESUMO

BACKGROUND: To help control opioid overprescription, we conducted a large institutional, 3-site initiative to provide discharge prescribing guidelines for different procedures. Our aim is to refine institutional guidelines for parathyroidectomy. METHODS: Patients undergoing parathyroidectomy completed a 28-question survey about opioid consumption. Discharge opioid prescription amounts were converted into morphine milligram equivalents (MMEs) and reported as median and interquartile range (IQR). Consumption was dichotomized into top quartile MME users (Q4) versus standard users (Q1, Q3). Univariate analysis compared opioid consumption. RESULTS: A total of 91 patients were included; 90% were opioid-naive. While the median prescribed was 75 (IQR 75, 150) MME, the median consumed was 0 (IQR 0, 20). Top users reported higher pain scores [median (IQR): 2 (2, 4)] compared to standard users [1 (0, 3), P = 0.01]. However, there was no difference in opioid consumption between unilateral neck exploration, bilateral exploration, or thyroidectomy and parathyroidectomy, P = 0.11. There was no difference in opioid consumption by age, sex, or BMI (all P > 0.05). Of those receiving a prescription, 94.6% had left-over opioids at the time of survey, resulting in 82% of prescribed opioids being unused. CONCLUSIONS: Over half of patients undergoing parathyroidectomy did not consume any opioid, and very few needed more than 2 d of opioid. Moreover, most patients did not dispose the unused opioids, which put these pills at risk of diversion and misuse. Surgical approach did not change consumption, illustrating that these guidelines are applicable to thyroidectomy given the similarity between techniques. We recommend prescribing nonopioid analgesics for patients undergoing parathyroidectomy.


Assuntos
Analgésicos não Narcóticos/efeitos adversos , Analgésicos Opioides/uso terapêutico , Dor Pós-Operatória/tratamento farmacológico , Paratireoidectomia/efeitos adversos , Padrões de Prática Médica/normas , Adulto , Idoso , Idoso de 80 Anos ou mais , Prescrições de Medicamentos/normas , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Epidemia de Opioides/etiologia , Epidemia de Opioides/prevenção & controle , Medição da Dor , Dor Pós-Operatória/diagnóstico , Dor Pós-Operatória/etiologia , Guias de Prática Clínica como Assunto , Uso Indevido de Medicamentos sob Prescrição/prevenção & controle , Avaliação de Programas e Projetos de Saúde , Estudos Prospectivos , Estudos Retrospectivos , Tireoidectomia/efeitos adversos
6.
World J Surg ; 44(7): 2288-2294, 2020 07.
Artigo em Inglês | MEDLINE | ID: mdl-32128613

RESUMO

INTRODUCTION: Due to the rarity of malignant insulinoma, a lack of the literature describing factors affecting outcomes exists. Our aim was to review malignant insulinoma incidence, characteristics and survival trends. METHODS: We identified all patients with malignant insulinoma in the SEER registries from 1973 to 2015. Incidence, neoplasm characteristics and factors affecting cancer-specific survival (CSS) were described. RESULTS: A total of 121 patients were identified. The crude annual overall incidence was low (range 0.0-0.27 cases per million person years). The largest proportion had localized disease (40%), while 16% had regional disease, 39% distant metastatic disease, and stage was unreported in 5%. Most neoplasms were in the body/tail of the pancreas, followed by the head of the pancreas. Grade was reported in 40% of patients; only a single patient reported as having grade IV with the remainder all grades I/II. Surgical resection was performed in 64% of patients. Within surgical patients, the median primary neoplasm size was 1.8 cm. Regional lymph nodes were examined in 57.1% of surgical patients, while 34% of examined nodes were positive. The median CSS was 183 months. On multivariable analysis, surgical resection, male sex and absence of metastatic disease were associated with superior survival. CONCLUSION: While the greatest proportion of patients with malignant insulinoma present with localized disease, regional lymph node involvement was found in 34% of whose nodes were tested. Further studies are needed to assess the role of lymph node dissection in improving survival and preventing recurrence given the observed frequency of lymph node involvement.


Assuntos
Insulinoma , Tumores Neuroendócrinos , Neoplasias Pancreáticas , Humanos , Insulinoma/diagnóstico , Insulinoma/epidemiologia , Insulinoma/patologia , Insulinoma/cirurgia , Excisão de Linfonodo , Metástase Linfática , Tumores Neuroendócrinos/diagnóstico , Tumores Neuroendócrinos/epidemiologia , Tumores Neuroendócrinos/patologia , Tumores Neuroendócrinos/cirurgia , Neoplasias Pancreáticas/diagnóstico , Neoplasias Pancreáticas/epidemiologia , Neoplasias Pancreáticas/patologia , Neoplasias Pancreáticas/cirurgia , Prognóstico , Taxa de Sobrevida
7.
Pediatr Surg Int ; 36(2): 129-135, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31691026

RESUMO

BACKGROUND: Adrenalectomy for non-neuroblastic pathologies in children is rare with limited data on outcomes. We reviewed our experience of adrenalectomy in this unique population. METHODS: Retrospective study of children (age ≤ 18) who underwent adrenalectomy with non-neuroblastic pathology from 1988 to 2018. Clinical and operative details of patients were abstracted. Outcomes included length of stay and 30-day postoperative morbidity. RESULTS: Forty children underwent 50 adrenalectomies (12 right-sided, 18 left-sided, 10 bilateral). Six patients (15%) presented with an incidental adrenal mass while 4 (10%) had masses found on screening for genetic mutations or prior malignancy. The remaining 30 (75%) presented with symptoms of hormonal excess. Nineteen patients (48%) underwent genetic evaluation and 15 (38%) had genetic predispositions. Diagnoses included 9 patients (23%) with pheochromocytoma, 8 (20%) with adrenocortical adenoma, 8 (20%) with adrenocortical carcinoma, 7 (18%) with adrenal hyperplasia, 2 (5%) with metastasis, and 6 (14%) with additional benign pathologies. Of 50 adrenalectomies, twenty-five (50%) were laparoscopic. Median hospital length of stay was 3 days (range 0-11). Post-operative morbidity rate was 17% with the most severe complication being Clavien-Dindo grade II. CONCLUSION: Adrenalectomy for non-neuroblastic pathology can be done with low morbidity. Its frequent association with genetic mutations and syndromes requires surgeons to have knowledge of appropriate pre-operative testing and post-operative surveillance.


Assuntos
Neoplasias das Glândulas Suprarrenais/cirurgia , Adrenalectomia/métodos , Laparoscopia/métodos , Feocromocitoma/cirurgia , Adolescente , Neoplasias das Glândulas Suprarrenais/diagnóstico , Criança , Feminino , Humanos , Tempo de Internação , Masculino , Feocromocitoma/diagnóstico , Período Pós-Operatório , Estudos Retrospectivos
8.
J Org Chem ; 84(11): 6858-6867, 2019 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-31074278

RESUMO

A solvent-free methodology that yields trans-4,5-diaminocyclopent-2-enones, main domains of natural products and a variety of N-heterocycles, is described. The bimetallic catalyst [NiII2DyIII2L4(DMF)6] 2(OTf) 2(DMF) (1) promotes the domino reaction of furfural and amines, with loadings as low as 0.01%, under stirring or microwave-assisted conditions to afford the corresponding frameworks in very good to excellent yields. Crystallographic and theoretical studies shed light on the exclusive formation of the trans-diastereoisomers via a 4π-conrotatory electrocyclization process elucidating the key step in the catalytic process.

9.
Inorg Chem ; 56(9): 4898-4910, 2017 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-28394133

RESUMO

A family of benzotriazole based coordination compounds, obtained in two steps and good yields from commercially available materials, formulated as [CuII(L1)2(MeCN)2]·2ClO4·MeCN (1), [CuII(L1)(NO3)2]·MeCN (2), [ZnII(L1)2(H2O)2]·2ClO4·2MeCN (3), [CuII(L1)2Cl2]2 (4), [CuII5(L1)2Cl10] (5), [CuII2(L1)4Br2]·4MeCN·CuII2Br6 (6), [CuII(L1)2(MeCN)2]·2BF4 (7), [CuII(L1)2(CF3SO3)2] (8), [ZnII(L1)2(MeCN)2]·2CF3SO3 (9), [CuII2(L2)4(H2O)2]·4CF3SO3·4Me2CO (10), and [CuII2(L3)4(CF3SO3)2]·2CF3SO3·Me2CO (11), are reported. These air-stable compounds were tested as homogeneous catalysts for the A3 coupling synthesis of propargylamine derivatives from aldehyde, amine, and alkyne under a noninert atmosphere. Fine tuning of the catalyst resulted in a one-dimensional (1D) coordination polymer (CP) (8) with excellent catalytic activity in a wide range of substrates, avoiding any issues that would inhibit its performance.

10.
Inorg Chem ; 56(16): 9563-9573, 2017 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-28783350

RESUMO

Michael addition (MA) is one of the most well studied chemical transformation in synthetic chemistry. Here, we report the synthesis and crystal structures of a library of 3d/4f coordination clusters (CCs) formulated as [ZnII2YIII2L4(solv)X(Z)Y] and study their catalytic properties toward the MA of nitrostyrenes with barbituric acid derivatives. Each CC presents two borderline hard/soft Lewis acidic ZnII centers and two hard Lewis acidic YIII centers in a defect dicubane topology that brings the two different metals into a proximity of ∼3.3 Å. Density functional theory computational studies suggest that these tetrametallic CCs dissociate in solution to give two catalytically active dimers, each containing one 3d and one 4f metal that act cooperatively. The mechanism of catalysis has been corroborated via NMR, electron paramagnetic resonance, and UV-vis. The present work demonstrates for the first time the successful use of 3d/4f CCs as efficient and high diastereoselective catalysts in MA reactions.

11.
Environ Sci Technol ; 51(1): 616-624, 2017 01 03.
Artigo em Inglês | MEDLINE | ID: mdl-27976870

RESUMO

Fish can be exposed to a complex mixture of chemical contaminants, including pharmaceuticals, present in discharges of wastewater treatment works (WwTWs) effluents. There is little information on the effects of effluent exposure on fish metabolism, especially the small molecule signaling compounds which are the biological target of many pharmaceuticals. We applied a newly developed sensitive nanoflow-nanospray mass spectrometry nontargeted profiling technique to identify changes in the exposome and metabolome of roach (Rutilus rutilus) exposed to a final WwTWs effluent for 15 days. Effluent exposure resulted in widespread reduction (between 50% and 90%) in prostaglandin (PG) profiles in fish tissues and plasma with disruptions also in tryptophan/serotonin, bile acid and lipid metabolism. Metabolite disruptions were not explained by altered expression of genes associated with the PG or tryptophan metabolism. Of the 31 pharmaceutical metabolites that were detected in the effluent exposome of fish, 6 were nonsteroidal anti-inflammatory drugs but with plasma concentrations too low to disrupt PG biosynthesis. PGs, bile acids, and tryptophan metabolites are important mediators regulating a diverse array of physiological systems in fish and the identity of wastewater contaminants disrupting their metabolism warrants further investigation on their exposure effects on fish health.


Assuntos
Metabolômica , Águas Residuárias , Animais , Espectrometria de Massas , Metaboloma , Preparações Farmacêuticas , Poluentes Químicos da Água
12.
Surg Endosc ; 31(3): 1336-1341, 2017 03.
Artigo em Inglês | MEDLINE | ID: mdl-27444824

RESUMO

BACKGROUND: Patients with Barrett's esophagus (BE) and high-grade dysplasia (HGD) or intramucosal cancer (IMC) on endoscopic forceps biopsies are referred to endoscopic therapy even though forceps biopsies do not reflect the disease extent accurately. Endoscopic mucosal resection (EMR) and endoscopic ultrasound (EUS) are frequently used for staging prior to endoscopic therapy. Our aims were to evaluate: (1) if endoscopic forceps biopsies correlated with EMR histology in these patients; (2) the utility of EUS compared to EMR; and (3) if accuracy of EUS varied based on grade of differentiation of tumor. METHODS: This is a retrospective review of patients referred to endoscopic therapy of BE with HGD or early esophageal adenocarcinoma (EAC) who underwent EMR from 2006 to 2011. Age, race, sex, length of Barrett's segment, hiatal hernia size, number of endoscopies and biopsy results and EUS findings were abstracted. RESULTS: A total of 151 patients underwent EMR. In 50 % (75/151) of patients, EMR histology was consistent with endoscopic forceps biopsy findings. EMR resulted in change in diagnosis with upstaging in 21 % (32/151) and downstaging in 29 % (44/151). In patients with HGD on EMR, EUS staging was T0 in 74.1 % (23/31) but upstaged in 25.8 % (8/31). In patients with IMC on EMR, EUS findings were T1a in 23.6 % (9/38), upstaged in 18.4 % (7/38) and downstaged in 57.8 % (22/38). EUS accurately identified EMR histology in all submucosal cancers. Grade of differentiation was reported in 24 cancers on EMR histology. There was no correlation between grade and EUS staging. CONCLUSIONS: EUS is of limited utility in accurate staging of BE patients with HGD or early EAC. Endoscopic forceps biopsy correlated with EMR findings in only 50 % of patients. Irrespective of the endoscopic forceps biopsy results, all BE patients with visible lesions should be referred to EMR.


Assuntos
Esôfago de Barrett/patologia , Biópsia/métodos , Ressecção Endoscópica de Mucosa , Endossonografia , Neoplasias Esofágicas/patologia , Lesões Pré-Cancerosas/patologia , Adenocarcinoma/patologia , Adenocarcinoma/cirurgia , Idoso , Esôfago de Barrett/cirurgia , Estudos de Coortes , Detecção Precoce de Câncer , Neoplasias Esofágicas/cirurgia , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Lesões Pré-Cancerosas/cirurgia , Estudos Retrospectivos , Instrumentos Cirúrgicos
13.
Inorg Chem ; 55(14): 6988-94, 2016 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-27355452

RESUMO

A series of heterometallic coordination clusters (CCs) [Ni(II)2Ln(III)2(L1)4Cl2(CH3CN)2] 2CH3CN [Ln = Y (1Y), Sm (1Sm), Eu (1Eu), Gd (1Gd), or Tb (1Tb)] were synthesized by the reaction of (E)-2-(2-hydroxy-3-methoxybenzylidene-amino)phenol) (H2L1) with NiCl2·6(H2O) and LnCl3·x(H2O) in the presence of Et3N at room temperature. These air-stable CCs can be obtained in very high yields from commercially available materials and are efficient catalysts for the room-temperature domino ring-opening electrocyclization synthesis of trans-4,5-diaminocyclopent-2-enones from 2-furaldehyde and primary or secondary amines under a non-inert atmosphere. Structural modification of the catalyst to achieve immobilization or photosensitivity is possible without deterioration in catalytic activity.

14.
Anal Chem ; 87(2): 1158-65, 2015 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-25521704

RESUMO

Global urine metabolomics is a rapidly expanding field with the potential to discover biomarkers of disease and exposure. To date, most methods focus on rapid sample preparation, using neat or diluted urine, together with high-throughput analyses, and are poorly suited for detection of low abundance metabolites present in urine samples. In this study, novel methods have been developed to analyze urine by splitless nanoflowUHPLC-nanoESI-TOFMS (nUHPLC-nESI-TOFMS) after preconcentration by solid-phase extraction (SPE), thus enabling significant improvements in analytical sensitivity and coverage of the urinary metabolome. In initial work, urine samples were extracted by both anion and cation exchange mixed-mode polymeric SPE cartridges and qualitatively compared with those using conventional sample preparations using UHPLC-ESI-TOFMS analyses. Compared with neat or diluted urine samples, SPE concentration of urine resulted in detection of additional metabolites including bile acids, lipids, pharmaceuticals, and markers of lifestyle, with little loss of other components of the metabolome. Analyses of SPE preparations by nUHPLC-nESI-TOFMS revealed excellent retention time repeatability with <1% coefficient of variation (CV) for 96% of analyzed peaks. The repeatability of the MS response was <30% CV for >79% of MS features in both negative and positive nESI modes. Compared with UHPLC-ESI-TOFMS, analysis by the nanoplatform enabled detection of signaling molecules important in disease processes including sex steroids, glucocorticoids, eicosanoids, and neurotransmitter metabolites. The significant improvement in sensitivity arising from use of splitless nUHPLC-nESI-TOFMS analyses of SPE-concentrated samples represents a step change in coverage of the urinary metabolome, thereby increasing the potential for biomarker discovery.


Assuntos
Biomarcadores/urina , Cromatografia Líquida/métodos , Metabolômica/métodos , Nanotecnologia/métodos , Extração em Fase Sólida/métodos , Espectrometria de Massas por Ionização por Electrospray/métodos , Urinálise/métodos , Adulto , Feminino , Voluntários Saudáveis , Humanos , Masculino , Adulto Jovem
15.
Chemistry ; 21(17): 6358-61, 2015 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-25766091

RESUMO

Three isoskeletal tetranuclear coordination clusters with general formula [M(II) 2 Dy(III) 2 L4 (EtOH)6 ](ClO4 )2 ⋅2 EtOH, (M=Co, 1; M=Ni, 2) and [Ni(II) 2 Dy(III) 2 L4 Cl2 (CH3 CN)2 ]⋅2 CH3 CN (3), have been synthesized and characterized. These air-stable compounds, and in particular 3, display efficient homogeneous catalytic behavior in the room-temperature synthesis of trans-4,5-diaminocyclopent-2-enones from 2-furaldehyde and primary or secondary amines under a non-inert atmosphere.

16.
Environ Sci Technol ; 49(21): 12731-40, 2015 Nov 03.
Artigo em Inglês | MEDLINE | ID: mdl-26439915

RESUMO

In recent years, an intense debate about the environmental risks posed by neonicotinoids, a group of widely used, neurotoxic insecticides, has been joined. When these systemic compounds are applied to seeds, low concentrations are subsequently found in the nectar and pollen of the crop, which are then collected and consumed by bees. Here we demonstrate that the current focus on exposure to pesticides via the crop overlooks an important factor: throughout spring and summer, mixtures of neonicotinoids are also found in the pollen and nectar of wildflowers growing in arable field margins, at concentrations that are sometimes even higher than those found in the crop. Indeed, the large majority (97%) of neonicotinoids brought back in pollen to honey bee hives in arable landscapes was from wildflowers, not crops. Both previous and ongoing field studies have been based on the premise that exposure to neonicotinoids would occur only during the blooming period of flowering crops and that it may be diluted by bees also foraging on untreated wildflowers. Here, we show that exposure is likely to be higher and more prolonged than currently recognized because of widespread contamination of wild plants growing near treated crops.


Assuntos
Anabasina/toxicidade , Abelhas/metabolismo , Exposição Ambiental/análise , Flores/química , Animais , Brassica rapa/química , Produtos Agrícolas/química , Hordeum/química , Inseticidas/análise , Néctar de Plantas/química , Pólen/química , Sementes/química , Solo/química , Triticum/química
17.
Anal Bioanal Chem ; 407(26): 8151-62, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-26329280

RESUMO

To accurately estimate exposure of bees to pesticides, analytical methods are needed to enable quantification of nanogram/gram (ng/g) levels of contaminants in small samples of pollen or the individual insects. A modified QuEChERS extraction method coupled with ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) analysis was tested to quantify residues of 19 commonly used neonicotinoids and fungicides and the synergist, piperonyl butoxide, in 100 mg samples of pollen and in samples of individual bumblebees (Bombus terrestris). Final recoveries ranged from 71 to 102 % for most compounds with a repeatability of below 20 % for both pollen and bumblebee extracts spiked at 5 and 40 ng/g. The method enables the detection of all compounds at sub-ng/g levels in both matrices and the method detection limits (MDL) ranged from 0.01 to 0.84 ng/g in pollen and 0.01 to 0.96 ng/g in individual bumblebees. Using this method, mixtures of neonicotinoids (thiamethoxam, clothianidin, imidacloprid and thiacloprid) and fungicides (carbendazim, spiroxamine, boscalid, tebuconazole, prochloraz, metconazole, fluoxastrobin, pyraclostrobin and trifloxystrobin) were detected in pollens of field bean, strawberry and raspberry at concentrations ranging from MDL, and in some bees, the fungicides carbendazim, boscalid, tebuconazole, flusilazole and metconazole were present at concentrations between 0.80 to 30 ng/g. This new method allows the analysis of mixtures of neonicotinoids and fungicides at trace levels in small quantities of pollen and individual bumblebees and thus will facilitate exposure assessment studies.


Assuntos
Abelhas/química , Produtos Agrícolas/química , Fungicidas Industriais/análise , Inseticidas/análise , Pólen/química , Espectrometria de Massas em Tandem/métodos , Animais , Cromatografia Líquida de Alta Pressão/métodos , Fragaria/química , Guanidinas/análise , Imidazóis/análise , Limite de Detecção , Neonicotinoides , Nitrocompostos/análise , Oxazinas/análise , Piridinas/análise , Rubus/química , Tiametoxam , Tiazinas/análise , Tiazóis/análise
18.
Environ Sci Technol ; 48(9): 5203-10, 2014 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-24684439

RESUMO

Alcohol polyethoxylate (AEO) surfactants are widely used in household and industrial products, but the health effects arising from short-term exposure to sublethal concentrations are unknown. A metabolomic approach was used to investigate the biotransformation and effects of exposure to sublethal concentrations of hexaethylene glycol monododecylether (C12EO6) in juvenile sole, Solea senegalensis. After 5 days, C12EO6 was rapidly metabolized in the sole by oxidation, glucuronidation, and ethoxylate chain shortening. C12EO6 exposure at either 146 or 553 µg L(-1) resulted in significant metabolite disruption in liver and blood samples, including an apparent fold increase of >10(6) in the circulating levels of C24 bile acids and C27 bile alcohols, disturbance of glucocorticoid and lipid metabolism, and a 470-fold decrease in levels of the fatty acid transport molecule palmitoyl carnitine. Depuration resulted in rapid elimination of the surfactant and normalization of metabolites toward pre-exposure levels. Our findings show for the first time the ability of metabolomic analyses to discern effects of this AEO on metabolite homeostasis at exposure levels below its no effect concentrations for survival and reproduction in juvenile fish. The pronounced alteration in levels of liver metabolites, phospholipids, and glucocorticoids in S. senegalensis in response to surfactant exposure may indicate that this contaminant could potentially impact a number of health end points in fish.


Assuntos
Linguados/metabolismo , Metabolômica , Tensoativos/farmacologia , Animais , Biotransformação , Análise Multivariada , Espectrometria de Massas por Ionização por Electrospray
19.
Surg Clin North Am ; 104(4): 741-749, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38944495

RESUMO

Molecular testing for cytologically indeterminate thyroid nodules has demonstrated benefit by reducing the need for diagnostic thyroidectomies and reducing costs. Its use is currently recommended in practice guidelines from the American Thyroid Association and the American Association of Endocrine Surgeons when clinically appropriate. Moreover, there is growing evidence that molecular testing may provide prognostic information and can detect targetable genetic alterations which may expand treatment options for refractory advanced thyroid cancers.


Assuntos
Biomarcadores Tumorais , Neoplasias da Glândula Tireoide , Humanos , Neoplasias da Glândula Tireoide/diagnóstico , Neoplasias da Glândula Tireoide/genética , Neoplasias da Glândula Tireoide/terapia , Biomarcadores Tumorais/genética , Tireoidectomia , Prognóstico
20.
Am J Surg ; 228: 226-229, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37852845

RESUMO

BACKGROUND: We aim to evaluate the incidence of venous thromboembolism (VTE) following adrenalectomy. METHODS: A retrospective analysis of the Collaborative Endocrine Surgery Quality Improvement Program was performed to assess incidence for VTE, including pulmonary embolism or deep vein thrombosis, in adults undergoing adrenalectomy (2014-2022). RESULTS: 2567 patients undergoing adrenalectomy were included. Surgical approach was 10% open and 90% minimally invasive. Pathology was 13% malignant and 87% benign; 19% had hypercortisolism. VTE developed in 0.27% at a median of 8 days from surgery. The incidence was higher in primary adrenal malignancy compared to benign or metastases to the adrenals, p â€‹< â€‹0.01. VTE was associated with longer hospital stay, longer operative time, readmission, and mortality. VTE rates were similar for hypercortisolism vs no hypercortisolism and between patients with clinical vs subclinical hypercortisolism. CONCLUSION: Although VTE following adrenalectomy is rare, it is more common in cases of primary adrenal malignancy, those with longer operations, or those requiring prolonged hospitalization.


Assuntos
Neoplasias das Glândulas Suprarrenais , Síndrome de Cushing , Embolia Pulmonar , Tromboembolia Venosa , Adulto , Humanos , Tromboembolia Venosa/epidemiologia , Tromboembolia Venosa/etiologia , Incidência , Estudos Retrospectivos , Adrenalectomia/efeitos adversos , Síndrome de Cushing/complicações , Fatores de Risco , Complicações Pós-Operatórias/epidemiologia , Embolia Pulmonar/epidemiologia , Embolia Pulmonar/etiologia , Neoplasias das Glândulas Suprarrenais/cirurgia
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