166 research outputs found
In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?
Numerical calculations of enhancement factors offered by dynamic nuclear polarization in solids under magic angle spinning (DNPâMAS) were performed to determine the optimal EPR parameters for a dinitroxide polarizing agent. We found that the DNP performance of a biradical is more tolerant to the relative orientation of the two nitroxide moieties than previously thought. Generally, any condition in which the gyy tensor components of both radicals are perpendicular to one another is expected to have nearâoptimal DNP performance. Our results highlight the important role of the exchange coupling, which can lessen the sensitivity of DNP performance to the interâradical distance, but also lead to lower enhancements when the number of atoms in the linker becomes less than three. Lastly, the calculations showed that the electron T1e value should be near 500â
ÎŒs to yield optimal performance. Importantly, the newest polarizing agents already feature all of the qualities of the optimal polarizing agent, leaving little room for further improvement. Further research into DNP polarizing agents should then target nonânitroxide radicals, as well as improvements in sample formulations to advance highâtemperature DNP and limit quenching and reactivity
Direct 17O Dynamic Nuclear Polarization of Single-Site Heterogeneous Catalysts
We utilize direct 17O DNP for the characterization of non-protonated oxygens in heterogeneous catalysts. The optimal sample preparation and population transfer approach for 17O direct DNP experiments performed on silica surfaces are determined and applied to the characterization of Zr- and Y-based mesoporous silica-supported single-site catalysts
Nucleophilicity of Neutral versus Cationic Magnesium Silyl Compounds
Charge and ancillary ligands affect the reactivity of monomeric tris(trimethylsilyl)silyl magnesium compounds. Diamine-coordinated (tmeda)Mg{Si(SiMe3)3}Me (tmeda = tetramethylethylenediamine; 2-tmeda) and (dpe)Mg{Si(SiMe3)3}Me (dpe =1,2-N,N-dipyrrolidenylethane; 2-dpe) are synthesized by salt elimination reactions of L2MgMeBr and KSi(SiMe3)3. Compounds 2-tmeda or 2-dpe react with MeI or MeOTf to give MeSi(SiMe3)3 as the product of SiâC bond formation. In contrast, 2-tmeda and 2-dpe undergo exclusively reaction at the magnesium methyl group with electrophiles such as Me3SiI, B(C6F5)3, HB(C6F5)2, and [Ph3C][B(C6F5)4]. These reactions provide a series of neutral, zwitterionic, and cationic magnesium silyl compounds, and from this series we have found that silyl group transfer is less effective with cationic magnesium compounds than neutral complexes
A need for âgood eyesâ: Experiences told by patients diagnosed with psychosis
This study highlights experiences of psychiatric care described by patients diagnosed with psychosis. The aim was to investigate how patients, based on earlier experiences, described their wishes and needs regarding the psychiatric care system. Data comprised material from four focus groups; analysis used an inductive thematic approach. Relationships with staff emerged as a recurring theme. During periods of psychosis, patients needed staff to act as âparental figures,â providing care, safety, and help in dealing with overwhelming stimulation from the outside word. In the ensuing struggle to devise a livable life, the need for relationships recurred. In this phase, staff needed to give their time, provide support through information, and mirror the patient's capacity and hope. The patient's trials were described as threatened by a lack of continuity and non-listening professionals. It was important for staff to listen and understand, and to see and respect the patients' viewpoints
Oncocytic intraductal carcinoma of salivary glands: a distinct variant with TRIM33âRET fusions and BRAF V600E mutations
Aims: Salivary gland intraductal carcinoma (IDC) is a complex ductal neoplasm surrounded by a layer of myoepithelial cells. Recent insights have shown that there are three different types: intercalated duct-like, with frequent NCOA4-RET fusions; apocrine, with salivary duct carcinoma-like mutations; and mixed intercalated duct-like/apocrine, with RET fusions, including TRIM27-RET. In addition, an oncocytic IDC has been described, but it remains unclear whether it represents a fourth variant or simply oncocytic metaplasia of another IDC type. Our aim was to more completely characterize oncocytic IDC.
Methods and results: Six IDCs with oncocytic changes were retrieved from the authors' archives, from three men and three women ranging in age from 45 to 75 years (mean, 63 years). Five arose in the parotid gland, with one in an accessory parotid gland. Four patients with follow-up were free of disease after 1-23 months. Several immunostains (S100, mammaglobin, androgen receptor, and p63/p40) and molecular tools (RNA sequencing, RET fluorescence in-situ hybridisation, BRAF V600E VE1 immunohistochemistry, and Sanger sequencing) were applied. Histologically, the tumours were variably cystic with solid intracystic nodules often difficult to recognise as intraductal. In all, tumour ducts were positive for S100 and mammaglobin, negative for androgen receptor, and completely surrounded by myoepithelial cells positive for p63/p40. Molecular analysis revealed TRIM33-RET in two of six cases, NCOA4-RET in one of six cases, and BRAF V600E in two of six cases. One case had no identifiable alterations.
Conclusions: Oncocytic IDC shares similarities with intercalated duct-like IDC. Although additional verification is needed, the oncocytic variant appears to be sufficiently unique to be now regarded as the fourth distinct subtype of IDC. Because of its indolent nature, oncocytic IDC should be distinguished from histological mimics
Coordinatively Saturated Tris(oxazolinyl)borato Zinc Hydride-Catalyzed Cross Dehydrocoupling of Silanes and Alcohols
The four-coordinate zinc compound ToMZnH (1, ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate) catalyzes selective alcoholysis of substituted hydrosilanes. The catalytic reaction of PhMeSiH2 and aliphatic alcohols favors the monodehydrocoupled product PhMeHSiâOR. With the aryl alcohol 3,5-C6H3Me2OH, the selectivity for mono(aryloxy)hydrosilane PhMeHSiOC6H3Me2 and bis(aryloxy)silane PhMeSi(OC6H3Me2)2 is controlled by relative reagent concentrations. Reactions of secondary organosilanes and diols provide cyclic bis(oxo)silacycloalkanes in high yield. The empirical rate law for the ToMZnH-catalyzed reaction of 3,5-dimethylphenol and PhMeSiH2 is âd[PhMeSiH2]/dt = kâČobs[ToMZnH]1[3,5-C6H3Me2OH]0[PhMeSiH2]1 (determined at 96 °C) which indicates that SiâO bond formation is turnover-limiting in the presence of excess phenol
Nomenclature revision for encapsulated follicular variant of papillary thyroid carcinoma:a paradigm shift to reduce overtreatment of indolent tumors
Although growing evidence points to highly indolent behavior of encapsulated follicular variant of papillary thyroid carcinoma (EFVPTC), most patients with EFVPTC are treated as having conventional thyroid cancer
Changing Epidemiology of Serious Bacterial Infections in Febrile Infants without Localizing Signs
Objective: Historically, management of infants with fever without localizing signs (FWLS) has generated much controversy, with attempts to risk stratify based on several criteria. Advances in medical practice may have altered the epidemiology of serious bacterial infections (SBIs) in this population. We conducted this study to test the hypothesis that the rate of SBIs in this patient population has changed over time. Patients and Methods: We performed a retrospective review of all infants meeting FWLS criteria at our institution from 1997â2006. We examined all clinical and outcome data and performed statistical analysis of SBI rates and ampicillin resistance rates. Results: 668 infants met criteria for FWLS. The overall rate of SBIs was 10.8%, with a significant increase from 2002â2006 (52/ 361, 14.4%) compared to 1997â2001 (20/307, 6.5%) (p = 0.001). This increase was driven by an increase in E. coli urinary tract infections (UTI), particularly in older infants (31â90 days). Conclusions: We observed a significant increase in E. coli UTI among FWLS infants with high rates of ampicillin resistance. The reasons are likely to be multifactorial, but the results themselves emphasize the need to examine urine in all febrile infants,90days and consider local resistance patterns when choosing empiric antibiotics
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