Regioselective CH Bond Activation on Stabilized Nitrogen Ylides Promoted by Pd(II) Complexes: Scope and Limitations

The orthopalladation of N-ylides [H_<i>x</i>C_<i>y</i>N–CHC­(O)­Ar] (H_<i>x</i>C_<i>y</i>N = pyridine, benzylamine, imidazole, aniline, and phenylpyridine; Ar = aryl) has been studied. The incorporation of the Pd atom to these substrates is regioselective, since the orthopalladation is produced, in most of the cases, only at the aryl ring of the benzoyl group with concomitant C-bonding of the N-ylide. The X-ray structure of one representative example is reported. Factors governing the observed orientation are discussed, because this regioselectivity is worthy of note, considering the deactivating nature of the carbonyl group. Two exceptions to the general trend have been observed. The first one is the double metalation of the ylide [PhMe₂NCHC­(O)­Ph], which incorporates one Pd at each Ph. The second one is the palladation of the phenylpyridine derivative, which occurs at the pyridinic 2-phenyl ring and produces a six-membered palladacycle

Supplemental Material - A Scoping Review of the Community Health Worker Model Used for Food Systems Interventions Within the United States

Supplemental Material for A Scoping Review of the Community Health Worker Model Used for Food Systems Interventions Within the United States by Maria DeNunzio, Makenzie Miller, Melissa Chase, Vivica Kraak, Elena Serrano, and Sarah Misyak in American Journal of Health Promotion</p

Supplemental Material - A Scoping Review of the Community Health Worker Model Used for Food Systems Interventions Within the United States

Supplemental Material for A Scoping Review of the Community Health Worker Model Used for Food Systems Interventions Within the United States by Maria DeNunzio, Makenzie Miller, Melissa Chase, Vivica Kraak, Elena Serrano, and Sarah Misyak in American Journal of Health Promotion</p

IL-19 production after TLR activation in PBMC cultures from active CD patients (n = 3) and HC (n = 6).

<p>PBMC were cultured 24(A) and 48 h (B) with different TLR ligands (LPS, Pam3CSK4 or FSL-1) and IL-19 production was determined by ELISA as described in Materials and Methods. The viability of PBMC was determined by Trypan Blue (>99%). *p<0.05; **p<0.01; ***p<0.001.</p

Heat map image of IL-10 family cytokines.

<p>Monocytes mRNA was extracted from HC (n = 3) and active CD patients (n = 3) after 6 h of culture with medium in the absence or presence of Pam3CSK4 and FSL-1. A) Green denoted down-regulated and red up-regulated genes. B) logFC of IL-19 mRNA expression between CD and HC are shown. **p<0.01; ***p<0.001.</p

rhIL-19 up-regulates IL-4 production in activated T cells.

<p>PBMC from HC (n = 6) and active CD (n = 6) were activated and expanded with anti-CD3+anti-CD2+anti-CD28 as described in Materials and Methods. Supernatants were removed and IL-4 and IFNγ content were analyzed by ELISA. A) A) Up-regulation of IL-4 by rhIL-19 in HC cultures. B) IFNγ content in HC and CD patients in the presence or absence of rhIL-19.*p<0.05.</p

rhIL-19 up-regulates CTLA4 expression on CD4+CD25+CD127

<p>− <b>cells.</b> PBMC from HC (n = 4) and active CD (n = 3) were activated with anti-CD3+anti-CD2+anti-CD28 as described in Materials and Methods. The expression of CTLA4 (A) and GITR (B) was determined on CD4+CD25+CD127− cells by flow cytometry. *p<0.05.</p

rhIL-19 down-regulates TNFα production in cultures from HC after LPS activation.

<p>PBMC from HC and active CD patients were cultured with LPS (HC n = 10 and CD n = 5), Pam3CSK4 (HC n = 10 and CD n = 5) and FSL-1 (HC n = 5 and CD n = 3) for 24 h with or without rhIL-19 (400 ng/ml). A and B) TNFα and IL-10 production in cultures from HC after TLR activation with or without rhIL-19. D and E) TNFα and IL-10 production in cultures from active CD patients after TLR activation with or without rhIL-19. C and F) TNFα production from HC and active CD patients cultured with rhIL-10 (200 ng/ml). *p<0.05.</p

IL-10 regulates IL-19 expression.

<p>PBMC from A) HC (n = 3) and B) active CD patients (n = 3) were activated 24 h with TLR ligands (LPS, Pam3CSK4 and FSL-1) in the presence of rhIL-10 (200 ng/ml) and blocking anti-IL10 (500 ng/ml). Results are expressed as: (IL19 production with TLR+rhIL-10 or anti-IL10-IL-19 production with TLR)/IL-19 production with TLR.</p