Attention:The NSF Public Access Repository (PAR) system and access will be unavailable from 5:00 PM ET until 8:00 PM ET on Friday, September 11 due to maintenance. We apologize for the inconvenience.


Title: Efficient carbene transfer reactivity mediated by Fe( ii ) complexes supported by bulky alkoxides
The reaction of Fe(OR)2(THF)2(OR = bulky alkoxide ligand) with PhIC(CO2Me)2results in the formation of reactive remote carbene/vinyl radical intermediate that undergoes facile cyclopropanation or dimerization.  more » « less
Award ID(s):
2348382
PAR ID:
10588109
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
Chemical Communications
Date Published:
Journal Name:
Chemical Communications
Volume:
60
Issue:
55
ISSN:
1359-7345
Page Range / eLocation ID:
7033 to 7036
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. A new La(ii) synthesis involves SCXRD experiments on the La(iii) methyl complex La(SAriPr6)2CH3, AriPr6= C6H3-2,6-(C6H2-2,4,6-iPr3)2, with Cu Kα X-rays that results in homolytic La-CH3cleavage and formation of the La(ii) complex La(SAriPr6)2
    more » « less
  2. ABSTRACT Background0.55T systems offer unique advantages and may support expanded access to cardiac MRI. PurposeTo assess the feasibility of 0.55T cardiac MR Fingerprinting (MRF), leveraging a deep image prior reconstruction to mitigate noise. Study TypePhantom and prospective in vivo assessment. PopulationISMRM/NIST MRI system phantom and 18 healthy subjects (11 female; ages 28 ± 8 years). Field Strength and SequencesMRF, modified Look‐Locker inversion recovery (MOLLI), and T2‐prepared balanced steady state free precession (T2‐bSSFP) at 0.55T. AssessmentMRF T1and T2maps were reconstructed using (1) a low‐rank technique with sparse and locally low‐rank regularization (SLLR‐MRF) and (2) a deep image prior (DIP‐MRF). Accuracy and precision of MRF and conventional sequences were evaluated in a phantom. In vivo performance of MRF was evaluated in the 18 healthy subjects, with 7 subjects also undergoing conventional mapping. Myocardial T1and T2values were compared among methods and image quality scored by three readers (2, 3, and 4 years of experience) on a 5‐point scale. Statistical TestsLinear regression, Bland–Altman, intraclass correlation coefficient, and one‐way ANOVA withp < 0.05 considered significant. ResultsMean measurements in the left ventricular septum were 671 ± 31 ms (MOLLI), 761 ± 147 ms (SLLR‐MRF), and 686 ± 39 ms (DIP‐MRF) for T1, and 63.5 ± 5.7 ms (T2‐bSSFP), 47.5 ± 12.7 ms (SLLR‐MRF), and 45.2 ± 4.5 ms (DIP‐MRF) for T2. Compared to conventional mapping, DIP‐MRF exhibited significantly lower T2but no differences in T1(p > 0.99). Standard deviations within the myocardium were significantly lower with DIP‐MRF compared to SLLR‐MRF (39 vs. 147 ms for T1and 4.5 vs. 12.7 ms for T2). Overall image quality ratings were significantly lower for SLLR‐MRF (T1: 2.3, T2: 2.9), which were significantly lower compared to conventional mapping methods (T1: 3.4, T2: 3.9), and DIP‐MRF (T1: 3.8, T2: 4.1) received higher scores. Data ConclusionThis study demonstrated the feasibility of cardiac MRF on a commercial 0.55T system, enabled by a deep image prior reconstruction for denoising. Evidence Level2. Stage of Technical Efficacy1. 
    more » « less
  3. We present a new set of reference materials, the ND70‐series, forin situmeasurement of volatile elements (H2O, CO2, S, Cl, F) in silicate glass of basaltic composition. The materials were synthesised in piston cylinders at pressures of 1 to 1.5 GPa under volatile‐undersaturated conditions. They span mass fractions from 0 to 6%m/mH2O, from 0 to 1.6%m/mCO2and from 0 to 1%m/mS, Cl and F. The materials were characterised by elastic recoil detection analysis for H2O, by nuclear reaction analysis for CO2, by elemental analyser for CO2, by Fourier transform infrared spectroscopy for H2O and CO2, by secondary ion mass spectrometry for H2O, CO2, S, Cl and F, and by electron probe microanalysis for CO2, S, Cl and major elements. Comparison between expected and measured volatile amounts across techniques and institutions is excellent. It was found however that SIMS measurements of CO2mass fractions using either Cs+or Oprimary beams are strongly affected by the glass H2O content. Reference materials have been made available to users at ion probe facilities in the US, Europe and Japan. Remaining reference materials are preserved at the Smithsonian National Museum of Natural History where they are freely available on loan to any researcher. 
    more » « less
  4. To expand the range of donor atoms known to stabilize 4fn5d1Ln(ii) ions beyond C, N, and O first row main group donor atoms, the Ln(iii) terphenylthiolate iodides, LnIII(SAriPr6)2I (AriPr6= C6H3-2,6-(C6H2-2,4,6-iPr3)2, Ln = La, Nd) were reduced to LnII(SAriPr6)2complexes. 
    more » « less
  5. Abstract This study examined the effects of 24R,25‐dihydroxyvitamin D3(24R,25(OH)2D3) in estrogen‐responsive laryngeal cancer tumorigenesis in vivo, the mechanisms involved, and whether the ability of the tumor cells to produce 24R,25(OH)2D3locally is estrogen‐dependent. Estrogen receptor alpha‐66 positive (ER+) UM‐SCC‐12 cells and ER− UM‐SCC‐11A cells responded differently to 24R,25(OH)2D3in vivo; 24R,25(OH)2D3enhanced tumorigenesis in ER+ tumors but inhibited tumorigenesis in ER− tumors. Treatment with 17β‐estradiol (E2) for 24 h reduced levels of CYP24A1 protein but increased 24R,25(OH)2D3production in ER+ cells; treatment with E2for 9 min reduced CYP24A1 at 24 h and reduced 24R,25(OH)2D3production in ER− cells. These findings suggest the involvement of E2receptor(s) in addition to ERα66. To investigate if 24R,25(OH)2D3can act locally, ER+ and ER− cells were treated with 24R,25(OH)2D3after inhibiting putative 24R,25(OH)2D3receptors, and the cells were assessed for effects on DNA synthesis (proliferation) and p53 production (apoptosis). Specific inhibitors were used to assess downstream secondary messenger signaling pathways and requirements for palmitoylation and caveolae in both cell lines. The results show that 24R,25(OH)2D3binds to a complex of receptors, including TLCD3B2, VDR, and protein disulfide‐isomerase A3 (PDIA3) in ER+ UM‐SCC‐12 cells. The mechanism requires palmitoylation, and PLD, PI3K, and LPAR are involved. The anti‐tumorigenic effects of 24R,25(OH)2D3in ER− UM‐SCC‐11A cells involve a membrane‐receptor complex consisting of VDR, PDIA3, and ROR2 within caveolae to activate a yet‐to‐be‐elucidated downstream signaling cascade. This work demonstrates a driving mechanism for the therapeutic agent 24R,25(OH)2D3that may be used for laryngeal cancer patients. 
    more » « less