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1.
Cureus ; 12(9): e10533, 2020 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-33094073

RESUMO

Background Short-term medical missions (STMMs) are a highly debated and largely understudied form of international volunteer work. With growing dedication to health care abroad, research evaluating their impact is crucial to ensure continued interventions are effective in improving medical care. STMM care varies in length, frequency, size, location, services offered, and country of origin and destination. This makes systematic evaluation of STMMs difficult. In addition, the transient nature of patient visits makes trending STMM's impact on long-term health outcomes complex. Despite intermittent availability, primary care missions offering pharmaceutical supplies have the unique opportunity to provide continued care to the community via free prescription supplies each visit. Given the challenges with measuring long-term outcomes in this population, it is unknown if these donated medications have any impact on patient health outcomes. As medication noncompliance is known to hinder health outcomes, our study chose to evaluate patient medication habits to see if these prescription supplies were being utilized appropriately. To our knowledge, no study has surveyed medical mission patients to explore their access and utilization of medication. Methods A cross-sectional study was conducted using a patient survey to identify risks and/or factors associated with medication noncompliance in patients visiting the medical mission, Waves of Health (WOH). For over 10 years, WOH has organized biannual seven-day trips to the Dominican Republic. The multi-question survey was translated into the native language, Spanish with Dominican dialect. Noncompliance was defined through the survey question "Did you run out of your prescription medication at all during the past year?" Spanish speaking participants, of both sexes and age ≥18 years old, who visited the mission clinic in November 2019 met inclusion for this study. Patients from Haiti or age <18 years old were excluded. Participation was voluntary. Survey items were dichotomized for univariate analysis to identify factors associated with running out of medication. To explore predictors of running out of medicine, we performed multivariate logistic regression analysis by ENTER method.  Results Of 127 patients, over half (58.3% [74]) reported running out of medication. Inadequate access to healthcare, daily medication use, and rationing personal medications were all significantly associated with running out of medicine. Frequency of WOH visits was not associated with running out of medication. Multivariate regression showed that being on daily medication and rationing personal medications were statistically significant predictors of running out of medicines. Access to healthcare, frequency of WOH visits, and WOH medication supply were not predictors of running out of medication. Conclusion  Mission interventions to improve medication practices should be explored due to the high number of patients who reported improper utilization of medication. In order to improve health outcomes in primary care settings, patients must play an active role in their care and understand the importance of taking their medication as prescribed for optimal disease management. Primary care STMMs may relieve short-term health concerns, but without proper utilization of chronic disease medications, it is unclear if STMMs role is impactful in long-term health outcomes.

2.
Eur J Clin Microbiol Infect Dis ; 39(11): 2005-2011, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32638221

RESUMO

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), the etiologic agent for the 2019 coronavirus disease (COVID-19) pandemic, has caused a public health emergency. The need for additional research in viral pathogenesis is essential as the number of cases and deaths rise. Understanding the virus and its ability to cause disease has been the main focus of current literature; however, there is much unknown. Studies have revealed new findings related to the full transmission potential of SARS-CoV-2 and its subsequent ability to cause infection by different means. The virus is hypothesized to be of increased virulence compared with previous coronavirus that caused epidemics, in part due to its overall structural integrity and resilience to inactivation. To date, many studies have discussed that the rationale behind its transmission potential is that viral RNA has unexpectedly been detected in multiple bodily fluids, with some samples having remained positive for extended periods of time. Additionally, the receptor by which the virus gains cellular entry, ACE2, has been found to be expressed in different human body systems, thereby potentiating its infection in those locations. In this evidence-based comprehensive review, we discuss various potential routes of transmission of SARS-CoV-2-respiratory/droplet, indirect, fecal-oral, vertical, sexual, and ocular. Understanding these different routes is important as they pertain to clinical practice, especially in taking preventative measures to mitigate the spread of SARS-CoV-2.


Assuntos
Betacoronavirus/patogenicidade , Infecções por Coronavirus/transmissão , Infecções por Coronavirus/virologia , Pneumonia Viral/transmissão , Pneumonia Viral/virologia , Aerossóis , COVID-19 , Túnica Conjuntiva/virologia , Infecções por Coronavirus/epidemiologia , Infecções por Coronavirus/prevenção & controle , Fezes/virologia , Humanos , Transmissão Vertical de Doenças Infecciosas , Boca/virologia , Pandemias/prevenção & controle , Pneumonia Viral/epidemiologia , Pneumonia Viral/prevenção & controle , Sistema Respiratório/virologia , SARS-CoV-2 , Sêmen/virologia , Eliminação de Partículas Virais
3.
Abdom Radiol (NY) ; 44(7): 2392-2402, 2019 07.
Artigo em Inglês | MEDLINE | ID: mdl-30905044

RESUMO

PURPOSE: Although ultrasound has been widely used to evaluate transjugular intrahepatic portosystemic shunts (TIPS) patency, several studies have reported conflicting data regarding its performance. Therefore, we aimed to evaluate performance of ultrasound for detection of TIPS dysfunction by performing a meta-analysis. METHODS: Literature search was performed for studies evaluating ultrasound for TIPS dysfunction, stenosis, and occlusion using PubMed, EMBASE, Scopus, and Cochrane Library through February 2019. Pooled sensitivity, specificity, log diagnostic odds ratio (LDOR), and area under curve (AUC) of summary receiver-operating characteristic were calculated. Subgroup analyses were performed according to ultrasonographic criteria and type of stent. RESULTS: In total, 21 studies were evaluated. Pooled sensitivity, specificity, and LDOR of ultrasound for detection of TIPS dysfunction were 0.82 (0.67, 0.93), 0.58 (0.46, 0.70), and 1.77 (1.20, 2.35). Pooled sensitivity, specificity, and LDOR for TIPS stenosis were 0.80 (0.69, 0.90), 0.80 (0.69, 0.91), and 2.83 (1.88, 3.78). Pooled sensitivity, specificity, and LDOR for TIPS occlusion were 0.96 (0.92, 0.99), 1 (0.99, 1.00), and 6.28 (4.96, 7.60). AUCs of ultrasound for TIPS dysfunction, stenosis, and occlusion were 0.77, 0.86, and 0.95, respectively. CONCLUSIONS: Although ultrasound had excellent performance for TIPS occlusion and acceptable performance for TIP stenosis, most studies utilized bare metal stent, and therefore, application to current practice is limited. Ultrasound for TIPS dysfunction in the setting of covered metal stent appeared to have acceptable sensitivity of 0.82, but limited specificity of 0.58 and low LDOR of 1.77. A new noninvasive tool is needed for detection of TIPS dysfunction in the era of covered metal stent.


Assuntos
Veias Hepáticas/diagnóstico por imagem , Veias Hepáticas/cirurgia , Veia Porta/diagnóstico por imagem , Veia Porta/cirurgia , Derivação Portossistêmica Transjugular Intra-Hepática/métodos , Ultrassonografia/métodos , Varizes Esofágicas e Gástricas/terapia , Humanos , Hipertensão Portal/prevenção & controle , Reprodutibilidade dos Testes , Resultado do Tratamento
5.
Trends Biotechnol ; 32(9): 436-40, 2014 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-25150363

RESUMO

The approach to research and development in biomedical science is changing. Increasingly, academia and industry seek to collaborate, and share resources and expertise, by establishing partnerships. Here, we explore the co-development partnership landscape in the field of regenerative medicine, focusing on agreements involving one or more private entities. A majority of the largest biopharmaceutical companies have announced strategic partnerships with a specific regenerative medicine focus, signifying the growth and widening appeal of this emerging sector.


Assuntos
Comportamento Cooperativo , Indústria Farmacêutica , Parcerias Público-Privadas/organização & administração , Medicina Regenerativa/métodos , Pesquisa/organização & administração , Universidades , Parcerias Público-Privadas/tendências , Medicina Regenerativa/tendências , Pesquisa/tendências
6.
Stem Cells Dev ; 22 Suppl 1: 63-72, 2013 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-24304079

RESUMO

Increased global connectivity has catalyzed technological development in almost all industries, in part through the facilitation of novel collaborative structures. Notably, open innovation and crowd-sourcing-of expertise and/or funding-has tremendous potential to increase the efficiency with which biomedical ecosystems interact to deliver safe, efficacious and affordable therapies to patients. Consequently, such practices offer tremendous potential in advancing development of cellular therapies. In this vein, the CASMI Translational Stem Cell Consortium (CTSCC) was formed to unite global thought-leaders, producing academically rigorous and commercially practicable solutions to a range of challenges in pluripotent stem cell translation. Critically, the CTSCC research agenda is defined through continuous consultation with its international funding and research partners. Herein, initial findings for all research focus areas are presented to inform global product development strategies, and to stimulate continued industry interaction around biomanufacturing, strategic partnerships, standards, regulation and intellectual property and clinical adoption.


Assuntos
Terapia Baseada em Transplante de Células e Tecidos , Células-Tronco Pluripotentes , Pesquisa com Células-Tronco/legislação & jurisprudência , Humanos , Propriedade Intelectual , Pesquisa Translacional Biomédica/legislação & jurisprudência
7.
J Urol ; 186(1): 97-102, 2011 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-21571343

RESUMO

PURPOSE: Extramammary Paget's disease is a rare intra-epithelial malignancy that is occasionally associated with an invasive adenocarcinoma component as well as other secondary cancers. We investigated a consecutive series of patients referred for extramammary Paget's disease of the penis or scrotum at a single center in the contemporary era to determine the presence of secondary cancers and treatment outcomes. MATERIALS AND METHODS: Between December 1990 and February 2009, 20 patients with extramammary Paget's disease of the scrotum and/or penis were seen. Patients were investigated with computerized tomography of the abdomen/pelvis, chest x-ray, cystoscopy, colonoscopy and serum prostate specific antigen measurement to rule out obvious secondary cancer. Clinical charts were reviewed with institutional review board approval. Mean followup of treated cases was 48 months (range 7 to 208). RESULTS: Patients were 50 to 86 years old with a history of symptoms of between 6 months and 10 years. Eight patients had invasive adenocarcinoma, of whom 2 died of the disease and 3 who had disease at 5, 7 and 40 months, respectively, were undergoing multimodal therapy. No patient with confirmed intra-epidermal disease only died of the disease. Invasive disease predicted nodal and metastatic progression. CONCLUSIONS: Surgical resection to achieve tumor-free margins resulted in durable relapse-free survival of patients with intra-epidermal extramammary Paget's disease alone. Extramammary Paget's disease with invasion was associated with regional metastatic progression. The latter scenario as well as failure to treat localized extramammary Paget's disease alone was associated with a fatal outcome. Systemic chemotherapy should be further explored in patients with invasive adenocarcinoma or lymph node positive disease.


Assuntos
Neoplasias dos Genitais Masculinos , Doença de Paget Extramamária , Neoplasias Penianas , Escroto , Idoso , Idoso de 80 Anos ou mais , Neoplasias dos Genitais Masculinos/diagnóstico , Neoplasias dos Genitais Masculinos/terapia , Humanos , Masculino , Pessoa de Meia-Idade , Doença de Paget Extramamária/diagnóstico , Doença de Paget Extramamária/terapia , Neoplasias Penianas/diagnóstico , Neoplasias Penianas/terapia , Estudos Retrospectivos
8.
Lab Chip ; 10(9): 1113-9, 2010 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-20390128

RESUMO

Microfluidic image cytometry (MIC) has been developed to study phenotypes of various hPSC lines by screening several chemically defined serum/feeder-free conditions. A chemically defined hPSC culture was established using 20 ng mL(-1) of bFGF on 20 microg mL(-1) of Matrigel to grow hPSCs over a week in an undifferentiated state. Following hPSC culture, we conducted quantitative MIC to perform a single cell profiling of simultaneously detected protein expression (OCT4 and SSEA1). Using clustering analysis, we were able to systematically compare the characteristics of various hPSC lines in different conditions.


Assuntos
Técnicas de Cultura de Células/instrumentação , Separação Celular/instrumentação , Citometria de Fluxo/instrumentação , Perfilação da Expressão Gênica/instrumentação , Técnicas Analíticas Microfluídicas/instrumentação , Microscopia/instrumentação , Células-Tronco Pluripotentes/citologia , Células Cultivadas , Desenho de Equipamento , Análise de Falha de Equipamento , Humanos , Reprodutibilidade dos Testes , Sensibilidade e Especificidade
9.
Emerg Radiol ; 17(5): 347-52, 2010 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-20217446

RESUMO

The purpose of this work is to question the conventional theory that all pulmonary emboli (PE) are abnormal, and to test the hypothesis that small peripheral PE are a function of life. Most radiologists report any filling defect, independent of size, as clinically significant PE when detected in the pulmonary arteries. We sought to reinforce the theory that small dots in the pulmonary arteries are not clinically significant clots in the conventional setting. The necessity for anticoagulation should be balanced against the risk of bleeding. This retrospective HIPAA-compliant study was approved by the institutional review board; informed consent was not required. All patients diagnosed with PE by 16-slice or 64-slice multidetector computed tomography (CT) over a 6-month period who also had a lower extremity venous ultrasound (US) performed within 7 days of CT were identified. The study group included 26 women and 24 men (mean, 56 years; range, 21-90 years). The locations of the PE were plotted on a pulmonary arterial diagram, and width of the most proximal clot for each patient was measured. Of 1,273 consecutive CT studies, 101 were positive (7.9%) and 50 patients underwent lower extremity US. Thirty-three (66%) patients had PE in the central pulmonary arteries, of which 19 (58%) had deep vein thrombosis (DVT). Seventeen (34%) patients had peripheral PE; DVT was detected in 0 (0%) patients. The peripheral clots measured 1.0-3.8 mm (mean, 2.5 mm). These clots appeared focal and rounded with a "dot-like" appearance. Peripheral, focal filling defects in the pulmonary arteries, which we termed "dots," are not traditional embolic clots, are not associated with detectable lower-extremity clot load, and may represent "normal" embolic activity originating from the lower extremity venous valves. We suggest that more in-depth understanding about small peripheral PE is needed. The necessity of conventional anticoagulation should be critically reviewed in patients with subsegmental PE and minimal clot burden.


Assuntos
Embolia Pulmonar/diagnóstico por imagem , Adulto , Idoso , Idoso de 80 Anos ou mais , Reações Falso-Positivas , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Embolia Pulmonar/diagnóstico , Embolia Pulmonar/terapia , Radiografia , Estudos Retrospectivos
10.
J Am Chem Soc ; 131(42): 15212-24, 2009 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-19795866

RESUMO

Absolute rate constants were determined for the abstraction of hydrogen atoms from (OC)(3)Fe(mu-SH)(2)Fe(CO)(3) (Fe(2)S(2)H(2)) and (OC)(3)Fe(mu-SCH(3))(mu-SH)Fe(CO)(3) (Fe(2)S(2)MeH) by benzyl radicals in benzene. From the temperature-dependent rate data for Fe(2)S(2)H(2), DeltaH(++) and DeltaS(++) were determined to be 2.03 +/- 0.56 kcal/mol and -19.3 +/- 1.7 cal/(mol K), respectively, giving k(abs) = (1.2 +/- 0.49) x 10(7) M(-1) s(-1) at 25 degrees C. For Fe(2)S(2)MeH, DeltaH(++) and DeltaS(++) were determined to be 1.97 +/- 0.46 kcal/mol and -18.1 +/- 1.5 cal/(mol K), respectively, giving k(abs) = (2.3 +/- 0.23) x 10(7) M(-1) s(-1) at 25 degrees C. Temperature-dependent rate data are also reported for hydrogen atom abstraction by benzyl radical from thiophenol (DeltaH(++) = 3.62 +/- 0.43 kcal/mol, DeltaS(++) = -21.7 +/- 1.3 cal/(mol K)) and H(2)S (DeltaH(++) = 5.13 +/- 0.99 kcal/mol, DeltaS(++) = -24.8 +/- 3.2 cal/(mol K)), giving k(abs) at 25 degrees C of (2.5 +/- 0.33) x 10(5) and (4.2 +/- 0.51) x 10(3) M(-1) s(-1), respectively, both having hydrogen atom abstraction rate constants orders of magnitude slower than those of Fe(2)S(2)H(2) and Fe(2)S(2)MeH. Thus, Fe(2)S(2)MeH is 100-fold faster than thiophenol, known as a fast donor. All rate constants are reported per abstractable hydrogen atom (k(abs)/M(-1) s(-1)/H). DFT calculations predict S-H bond strengths of 73.1 and 73.2 kcal/mol for Fe(2)S(2)H(2) and Fe(2)S(2)MeH, respectively. Free energy and NMR chemical shift calculations confirm the NMR assignments and populations of Fe(2)S(2)H(2) and Fe(2)S(2)MeH isomers. Derived radicals Fe(2)S(2)H(*) and Fe(2)S(2)Me(*) exhibit singly occupied HOMOs with unpaired spin density distributed between the two Fe atoms, a bridging sulfur, and d(sigma)-bonding between Fe centers. The S-H solution bond dissociation free energy (SBDFE) of Fe(2)S(2)MeH was found to be 69.4 +/- 1.7 kcal/mol by determination of its pK(a) (16.0 +/- 0.4) and the potential for the oxidation of the anion, Fe(2)S(2)Me(-), of -0.26 +/- 0.05 V vs ferrocene in acetonitrile (corrected for dimerization of Fe(2)S(2)Me(*)). This SBDFE for Fe(2)S(2)MeH corresponds to a gas-phase bond dissociation enthalpy (BDE) of 74.2 kcal/mol, in satisfactory agreement with the DFT value of 73.2 kcal/mol. Replacement of the Fe-Fe bond in Fe(2)S(2)MeH with bridging mu-S (Fe(2)S(3)MeH) or mu-CO (Fe(2)S(2)(CO)MeH) groups leads to (DFT) BDEs of 72.8 and 66.2 kcal/mol, the latter indicating dramatic effects of the choice of bridge structure on S-H bond strengths. These results provide a model for the reactivity of hydrosulfido sites of low-valent heterogeneous FeS catalysts.

11.
Am J Pathol ; 175(4): 1653-61, 2009 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-19717643

RESUMO

B-cell lymphomas, the most frequent human immune system malignancies, often contain dysregulated TCL1 oncogene expression. TCL1 transgenic (TCL1-tg) mice develop a spectrum of B-cell malignancies, supporting an oncogenic role for TCL1 in B cells. Our prior global survey of DNA methylation patterns in TCL1-tg B-cell lymphomas identified many lymphoma-specific candidate hypermethylated genes, including Stk39. The Stk39 encoded protein, sterile 20-like-related proline-alanine-rich kinase (SPAK), regulates cell stress responses, and microarray studies identified reduced SPAK expression in metastatic prostate and treatment-resistant breast cancers, suggesting that its loss may have a role in cancer progression. Here we identified DNA hypermethylation and SPAK silencing in TCL1-tg B-cell lymphomas and SPAK silencing without DNA methylation in multiple subtypes of human B-cell lymphomas. SPAK knockdown by shRNA protected B cells from caspase-dependent apoptosis induced by DNA double-strand breaks but not apoptosis in response to osmotic or oxidative cell stressors. Caspase 3 activation by cleavage was impaired with SPAK repression in DNA damaged B cells. Interestingly, c-Jun NH(2)-terminal kinase is potentially activated by SPAK and pharmacological inhibition of c-Jun NH(2)-terminal kinase in SPAK-expressing B cells recapitulated the cell-protective phenotype of SPAK knockdown. Taken together, these data indicate that SPAK loss in B-cell lymphomas promotes increased cell survival with DNA damage and provides a potential mechanism for increased resistance to genotoxic stress in cancer.


Assuntos
Apoptose , Dano ao DNA , Inativação Gênica , Linfoma de Células B/enzimologia , Linfoma de Células B/patologia , Proteínas Serina-Treonina Quinases/metabolismo , Animais , Caspase 3/metabolismo , Quebras de DNA de Cadeia Dupla , Metilação de DNA , Ativação Enzimática , Humanos , Linfoma de Células B/genética , Camundongos , Camundongos Transgênicos , Proteínas Proto-Oncogênicas/metabolismo
12.
J Am Chem Soc ; 131(14): 5224-32, 2009 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-19309157

RESUMO

An extensive family of thermochemical data is presented for a series of complexes derived from Cp*Mo(mu-S)(2)(mu-SMe)(mu-SH)MoCp* and Cp*Mo(mu-S)(2)(mu-SH)(2)MoCp*. These data include electrochemical potentials, pK(a) values, homolytic solution bond dissociation free energies (SBDFEs), and hydride donor abilities in acetonitrile. Thermochemical data ranged from +0.6 to -2.0 V vs FeCp(2)(+/o) for electrochemical potentials, 5 to 31 for pK(a) values, 43 to 68 kcal/mol for homolytic SBDFEs, and 44 to 84 kcal/mol for hydride donor abilities. The observed values for these thermodynamic parameters are comparable to those of many transition metal hydrides, which is consistent with the many parallels in the chemistry of these two classes of compounds. The extensive set of thermochemical data is presented in free energy landscapes as a useful approach to visualizing and understanding the relative stabilities of all of the species under varying conditions of pH and H(2) overpressure. In addition to the previously studied homogeneous reactivity and catalysis, Mo(2)S(4) complexes are also models for heterogeneous molybdenum sulfide catalysts, and therefore, the present results demonstrate the dramatic range of S-H bond strengths available in both homogeneous and heterogeneous reaction pathways.


Assuntos
Molibdênio/química , Compostos de Sulfidrila/química , Sulfetos/química , Eletroquímica , Estrutura Molecular , Termodinâmica
13.
AJR Am J Roentgenol ; 191(3): 908-11, 2008 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-18716127

RESUMO

OBJECTIVE: Parathyroid adenomas cause hypercalcemia and are culprits in the development of renal stone disease. With serum assays available, early detection of parathyroid tumors is possible. We performed this retrospective review to determine whether the prevalence of nephrocalcinosis and nephrolithiasis is still increased in patients with primary hyperparathyroidism compared with those not affected by the disorder in view of the early detection of parathyroid adenomas. MATERIALS AND METHODS: We retrospectively reviewed the renal sonograms of 271 patients with surgically proven primary hyperparathyroidism. All patients had undergone renal imaging within 6 months before parathyroid surgery. Our control group consisted of 500 age-matched subjects who had right upper quadrant sonograms obtained for various reasons. RESULTS: Nineteen (7.0%) of the 271 patients with primary hyperparathyroidism had renal stones, and eight (1.6%) of the 500 subjects in the control group had stones. Pearson's chi-square analysis showed that this difference in prevalence is significant (p < 0.0001). CONCLUSION: Our results showed a fourfold increased prevalence of asymptomatic renal stone disease in patients with surgically proven primary hyperparathyroidism compared with subjects not affected by the disorder. The National Institutes of Health consensus conference on asymptomatic primary hyperparathyroidism recommended that patients with renal stone disease undergo parathyroid surgery. These patients should undergo surgery even if they have minimal or no elevation of the total serum calcium value and no other metabolic manifestations of hyperparathyroidism. The finding of nephrocalcinosis or nephrolithiasis is, therefore, a significant finding in evaluating patients for parathyroid surgery. Routine imaging of the kidneys is necessary when primary hyperparathyroidism is documented.


Assuntos
Hiperparatireoidismo/diagnóstico por imagem , Hiperparatireoidismo/epidemiologia , Cálculos Renais/diagnóstico por imagem , Cálculos Renais/epidemiologia , Medição de Risco/métodos , Ultrassonografia/estatística & dados numéricos , Adolescente , Adulto , Idoso , Idoso de 80 Anos ou mais , Comorbidade , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Prevalência , Estudos Retrospectivos , Fatores de Risco
14.
J Am Chem Soc ; 130(28): 8940-51, 2008 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-18564842

RESUMO

The reactivity of the S-H bond in Cp*Mo(mu-S) 2(mu-SMe)(mu-SH)MoCp* ( S 4 MeH) has been explored by determination of kinetics of hydrogen atom abstraction to form the radical Cp*Mo(mu-S) 3(mu-SMe)MoCp* ( S 4 Me*), as well as reaction of hydrogen with the radical-dimer equilibrium to reform the S-H complex. From the temperature dependent rate data for the abstraction of hydrogen atom by benzyl radical, Delta H (double dagger) and Delta S (double dagger) were determined to be 1.54 +/- 0.25 kcal/mol and -25.5 +/- 0.8 cal/mol K, respectively, giving k abs = 1.3 x 10 (6) M (-1) s (-1) at 25 degrees C. In steady state abstraction kinetic experiments, the exclusive radical termination product of the Mo 2S 4 core was found to be the benzyl cross-termination product, Cp*Mo(mu-S) 2(mu-SMe)(mu-SBz)MoCp* ( S 4 MeBz), consistent with the Fischer-Ingold persistent radical effect. S 4 Me* was found to reversibly dimerize by formation of a weak bridging disulfide bond to form the tetranuclear complex (Cp*Mo(mu-S) 2(mu-SMe)MoCp*) 2(mu-S 2) ( ( S 4 Me) 2 ). The radical-dimer equilibrium constant has been determined to be 5.7 x 10 (4) +/- 2.1 x 10 (4) M (-1) from EPR data. The rate constant for dissociation of the dimer was found to be 1.1 x 10 (3) s (-1) at 25 degrees C, based on variable temperature (1)H NMR data. The rate constant for dimerization of the radical has been estimated to be 6.5 x 10 (7) M (-1) s (-1) in toluene at room temperature, based on the dimer dissociation rate constant and the equilibrium constant for dimerization. Structures are presented for ( S 4 Me) 2 , S 4 MeBz, and the cationic Cp*Mo(mu-S 2)(mu-S)(mu-SMe)MoCp*(OTf) ( S 4 Me ( + )), a precursor of the radical and the alkylated derivatives. Evidence for a radical addition/elimination pathway at an Mo 2S 4 core is presented.


Assuntos
Alcenos/química , Compostos de Benzil/química , Molibdênio/química , Compostos de Enxofre/química , Radicais Livres/química , Cinética , Compostos de Sulfidrila/química , Sulfetos/química , Termodinâmica
15.
Chem Commun (Camb) ; (24): 2533-2534, 1999.
Artigo em Inglês | MEDLINE | ID: mdl-21394239

RESUMO

Strontium (Sr(2+)) can be selectively extracted from aqueous solutions into supercritical fluid CO(2) at 60 °C and 100 atm with dicyclohexano-18-crown-6 (DC18C6) using CF(3)(CF(2))(6)CO(2) (-) (PFOA(-)) or CF(3)(CF(2))(6)CF(2)SO(3) (-) (PFOSA(-)) as a counter anion; at a mole ratio of Sr(2+) : DC18C6 : PFOA(-) = 1:10:50, the extraction of Sr (5.6 × 10(-5) M) from water at pH 3 is near quantitative whereas Ca(2+) and Mg(2+) at equal concentration are only extracted to a level of 7 and 1%, respectively; PFOSA(-) is an effective counter anion for selective extraction of Sr(2+) from 1.3 M HNO(3) with DC18C6 in supercritical CO(2).

16.
s.l; s.n; 1983. 3 p. ilus.
Não convencional em Inglês | LILACS, Sec. Est. Saúde SP, SESSP-ILSLACERVO, Sec. Est. Saúde SP | ID: biblio-1242274

RESUMO

A case of tuberculosis involving facial skin, nasal cavity throat and eyes was found in a yong korean girl. We report the case because of its unusual clinical picture and to recall the morbidity of cutaneos tuberculosis in the present dermatological field.Skin tuberculosis is one of the oldest diseases in dermatology. But the invasion of the skin by tubercle bacilli still seen and all the types of so called reinfection tuberculosis of the skin are being found sporadically all over the world.Generally patients with skin tuberculosis adapt themselves to their disorder during the long course of the disease actually, mostof the tuberculous skin lesions do not cause great troubles to the patient allowing him or her to lead a normal life. Recently we found a case which was quite unusual and seriosly treatened the patients normal activity because of naasal obstruction and facial disfiguration.


Assuntos
Cavidade Nasal/lesões , Lúpus Vulgar/enfermagem , Lúpus Vulgar/fisiopatologia , Lúpus Vulgar/microbiologia , Lúpus Vulgar/prevenção & controle , Pele/lesões
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