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1.
Ann Surg Open ; 5(1): e362, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38883966

RESUMO

Background: High-volume pancreatic surgery centers require a significant investment in expertise, time, and resources to achieve optimal patient outcomes. A detailed understanding of the economics of major pancreatic surgery is limited among many clinicians and hospital administrators. A greater consideration of these financial aspects may in fact have implications for enhancing clinical care and for a broader sustainability of high-volume pancreatic surgery programs. Methods: In this retrospective observational study, patients who underwent pancreaticoduodenectomy (PD), total pancreatectomy, or distal pancreatectomy at one academic medical center during the fiscal year 2021 were evaluated. Detailed hospital charges and professional fees were obtained for patients using the Qlik perioperative database. Clinical data for the study cohort were gathered from a prospectively maintained, IRB-approved pancreatic surgery database. Charges for the 91-day perioperative period were included. A P < 0.05 was considered significant. Results: During the study period, 159 evaluable patients underwent 1 of 3 designated pancreatic resections included in the analysis. Ninety-seven patients (61%) were diagnosed with adenocarcinoma and 70% (n = 110) underwent PD. The total charges (combined professional and hospital charges) for the cohort encompassing the entire perioperative period were $20,661,759. The median charge per patient was $130,306 (interquartile range [IQR], $34,534). The median direct cost of care was $23,219 (IQR, $6321) and the median contribution margin per case was $10,092 (IQR, $22,949). The median surgeon professional fee charges were $7700 per patient (IQR, $1296) as compared to $3453 (IQR, $1,144) for professional fee receipts (45% of the surgeon charge). The differences between the professional fee charges and receipts per patient were also considerable for other health care professionals such as anesthesiologists ($4945 charges vs $1406 receipts [28%]) and pathologists ($3035 charges vs $680 receipts [22%]). The surgeon professional fees were only 6% of the total charges, while the professional fees for anesthesiology and pathology were 4% and 2% of the total charges, respectively. Supply charges were 3% of the total charges. Longer operative time was correlated with increased hospital and anesthesia charges, without a significant increase in surgeon charges (P < 0.001, P < 0.001, and P = 0.2, respectively). Male sex, diabetes, and low serum albumin correlated with greater total hospital charges (P = 0.01, P = 0.01, and P = 0.03, respectively). Conclusions: The role of the surgeon in the perioperative clinical care of major pancreatic resection patients is crucial and important and is by no means limited to the operative day. Nevertheless, in the context of the current US health care system, the reimbursement to the surgeon in the form of professional fees is a relatively small fraction of the total health care receipts for these patients. This imbalance necessitates a substantial financial partnership between hospitals and their pancreatic surgery units to ensure the long-term viability of these programs.

2.
Org Lett ; 25(49): 8787-8791, 2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-38052021

RESUMO

The reduction of nitroarenes using KBH4 and I2 is described. BI3 is generated in situ and was shown to be the active reductant. Conditions were optimized for BI3 generation and then applied to a wide range of nitroarenes, including traditionally challenging substrates. The method constitutes a practical reduction option which produces low-toxicity boric acid and potassium iodide upon workup.

3.
Transgend Health ; 8(5): 420-428, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37810940

RESUMO

Purpose: To describe barriers to care for a cohort of transgender and nonbinary (TNB) youth and examine factors associated with delays in receiving puberty blockers (PBs) or gender-affirming hormones (GAHs). Methods: We used longitudinal data from a prospective cohort of TNB youth seeking care at a multidisciplinary pediatric gender clinic between August 2017 and June 2018. We calculated the time between (i) initial clinic contact, (ii) phone intake, (iii) first medical appointment, and (iv) initiating PBs/GAHs. We estimated Kaplan-Meier curves for each time-to-care interval and used Cox regression models to estimate hazard ratios (HRs) for factors hypothesized to be barriers and facilitators of care. Results: Our cohort included 104 youth aged 13-20 years. The median time from contacting the clinic to initiating PBs/GAHs was 307 days (range, 54-807). Lower income level, Medicaid insurance, and lack of family support were associated with longer times from contacting the clinic to completing the first medical appointment. In addition, older youth experienced longer times to first medical appointment relative to youth aged 13-14 years. Youth younger than 18 years of age who did not complete a mental health assessment before their first medical appointment experienced delays from first medical appointment to initiating PBs/GAHs (HR=0.44, 95% confidence interval, 0.22-0.88). Conclusion: Certain subsets of youth disproportionately experienced delays in receiving gender-affirming medications, and these factors varied by stage of care engagement. Given the association between gender-affirming care and improved mental health, identifying sociostructural and clinic-level barriers to care is critically important to facilitating more equitable access.

4.
Org Biomol Chem ; 20(11): 2187-2193, 2022 03 16.
Artigo em Inglês | MEDLINE | ID: mdl-35229853

RESUMO

The synthesis and bioactivity of neurotrophic banglenes and derivatives is described, establishing a structure-activity relationship which enables future mechanistic studies. Neuritogenesis assays indicate that (-) trans-banglene is the active enantiomer. Assays performed with and without NGF protein suggest that neurotrophic activity and potentiation of NGF activity by (-) trans-banglene might be distinct unassociated processes. Interestingly, (-) trans-banglene potentiation of NGF-induced neuritogenesis is unaffected by the presence of Erk1/2, Akt and Pkc inhibitors.


Assuntos
Neurônios
5.
Chemistry ; 27(42): 10839-10843, 2021 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-34137084

RESUMO

The facile production of ArCF2 X and ArCX3 from ArCF3 using catalytic iron(III)halides is reported, which constitutes the first iron-catalyzed halogen exchange for non-aromatic C-F bonds. Theoretical calculations suggest direct activation of C-F bonds by iron coordination. ArCX3 and ArCF2 X products of the reaction are synthetically valuable due to their diversification potential. In particular, chloro- and bromodifluoromethyl arenes (ArCF2 Cl, ArCF2 Br respectively) provide access to a myriad of difluoromethyl arene derivatives (ArCF2 R). To optimize for mono-halogen exchange, a statistical method called Design of Experiments was used. Optimized parameters were successfully applied to electron rich and electron deficient aromatic substrates, and to the late stage diversification of flufenoxuron, a commercial insecticide. These methods are highly practical, being run at convenient temperatures and using inexpensive common reagents.


Assuntos
Halogênios , Ferro , Catálise , Elétrons , Indicadores e Reagentes
6.
Environ Sci Technol ; 54(19): 12484-12492, 2020 10 06.
Artigo em Inglês | MEDLINE | ID: mdl-32936620

RESUMO

Photochemical processing taking place in atmospheric aqueous phases serves as both a source and a sink of organic compounds. In aqueous environments, acid-base chemistry and, by extension, aqueous-phase pH, are an important yet often neglected factors to consider when investigating the kinetics of organic compounds. We have investigated the aqueous-phase OH-oxidation of pinic acid, cis-pinonic acid, limononic acid, and formic acid (FA) as a function of pH. We have also extended our studies to other organic acids (OAs) present in the water-soluble fraction of secondary organic aerosol (SOA) arising from the ozonolysis of α-pinene. Although all the OAs exhibited larger OH reactivities at pH 10, the pH dependence was dramatically different between FA, the smallest OA, and those that contained more than eight carbons. A kinetic box model was also employed to characterize our photoreactor and to provide confidence to our results. Our finding shows that the atmospheric lifetimes of small OAs (e.g., FA) are highly sensitive to cloud water pH. However, those of larger OAs and many other OAs in α-pinene SOA are affected to a much less extent. These results are of great importance for the simplification of cloud water chemistry models.


Assuntos
Compostos Orgânicos , Água , Aerossóis , Concentração de Íons de Hidrogênio , Monoterpenos
7.
Org Lett ; 20(20): 6332-6335, 2018 10 19.
Artigo em Inglês | MEDLINE | ID: mdl-30265548

RESUMO

A protocol for the regioselective cleavage of unsymmetrical alkyl ethers to generate alkyl alcohol and alkyl bromide products is described. A mixture of trihaloboranes triggers this conversion and exhibits improved reactivity profiles (regioselectivity and yield) compared with BBr3 alone. Additionally, this procedure allows the efficient synthesis of (B-Cl) dialkyl boronate esters. There are limited methods to generate acyclic dialkoxyboryl chlorides, and these intermediates constitute important synthons in main-group chemistry.

8.
ACS Chem Biol ; 10(9): 1958-63, 2015 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-26061479

RESUMO

The design and synthesis of a fluorescent sensor of diphosphate esters along with its application for in-gel detection is described. Dinuclear zinc complex 1 selectively binds diphosphate esters in the presence of various other functional groups, including monophosphate esters. Complex 1 also constitutes a competent stain for visualization of pyrophosphorylated proteins in polyacrylamide gels. This reagent will facilitate the validation and exploration of protein pyrophosphorylation.


Assuntos
Difosfatos/análise , Proteínas de Escherichia coli/química , Escherichia coli/química , Corantes Fluorescentes/química , Fosfoproteínas/química , Proteínas de Saccharomyces cerevisiae/química , Saccharomyces cerevisiae/química , Resinas Acrílicas/química , Eletroforese em Gel de Poliacrilamida , Fosfopeptídeos/química , Fosforilação , Espectrometria de Fluorescência , Coloração e Rotulagem
10.
Org Lett ; 14(16): 4293-6, 2012 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-22568515

RESUMO

Stereospecific nickel-catalyzed cross-coupling reactions of benzylic 2-methoxyethyl ethers are reported for the preparation of enantioenriched 1,1-diarylethanes. The 2-methoxyethyl ether serves as a traceless directing group that accelerates cross-coupling. Chelation of magnesium ions is proposed to activate the benzylic C-O bond for oxidative addition.


Assuntos
Derivados de Benzeno/química , Compostos Heterocíclicos/síntese química , Níquel/química , Catálise , Etano/análogos & derivados , Etano/síntese química , Etano/química , Compostos Heterocíclicos/química , Estrutura Molecular , Oxirredução
11.
Chem Commun (Camb) ; 48(10): 1496-8, 2012 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-21984365

RESUMO

Ketones react with allyl acetate to generate tertiary homoallylic alcohols in the presence of a rhodium catalyst and bis(pinacolato)diboron. A range of substrates, including aryl, alkyl and cyclic ketones react smoothly under these conditions. Diastereoselective allylation reactions of functionalized ketones such as pregnenolone acetate are also reported.


Assuntos
Cetonas/química , Compostos Organometálicos/química , Propanóis/síntese química , Ródio/química , Acetatos/química , Alquilação , Compostos Alílicos/química , Catálise , Estrutura Molecular , Oxirredução , Propanóis/química , Estereoisomerismo
13.
J Colloid Interface Sci ; 337(1): 88-96, 2009 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-19527906

RESUMO

This paper describes colloidal particles that are designed to induce hyper-intensity contrast (T(1) relaxation) in MRI. The contrast agents consist of discrete gadolinium complexes tethered to 10 nm diameter silver nanoparticles. The gadolinium complexes (1) [Gd(DTPA-bisamido cysteine)](2-) and (2) [Gd(cystine-NTA)(2)](3-), undergo chemisorption to particle surfaces through thiol or disulfide groups, respectively, to form two new contrast agents. The resulting nanoparticulate constructs are characterized on the basis of their syntheses, composition, spectra and contrast enhancing power. The average r(1) relaxivities of the of the surface bound complexes (obtained at 9.4 T and 25 degrees C) are 10.7 and 9.7 s(-1) mM(-1), respectively, as compared to 4.7 s(-1) mM(-1) for the clinical agent Magnevist. Correspondingly, the respective whole particle relaxivities are 27927 and 13153 s(-1) mM(-1).


Assuntos
Meios de Contraste/química , Ouro/química , Elementos da Série dos Lantanídeos/química , Imageamento por Ressonância Magnética/métodos , Nanopartículas Metálicas , Espectroscopia de Ressonância Magnética , Microscopia Eletrônica de Transmissão , Espectrofotometria Ultravioleta
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