scholarly journals Effect of pH on the Properties of Hydrogels Cross-Linked via Dynamic Thia-Michael Addition Bonds

Author(s):  
Thomas M. FitzSimons ◽  
Eric V. Anslyn ◽  
Adrianne M. Rosales
2000 ◽  
Vol 24 (4) ◽  
pp. 467-476 ◽  
Author(s):  
Sabine Vollenweider ◽  
Hans Weber ◽  
Stephanie Stolz ◽  
Aurore Chetelat ◽  
Edward E. Farmer
Keyword(s):  

2020 ◽  
Author(s):  
Kiron Kumar Ghosh ◽  
Alexander Uttry ◽  
Francesca Ghiringhelli ◽  
Arup Mondal ◽  
Manuel van Gemmeren

We report the ligand enabled C(sp3)–H activation/olefination of free carboxylic acids in the γ-position. Through an intramolecular Michael-addition, δ-lactones are obtained as products. Two distinct ligand classes are identified that enable the challenging palladium-catalyzed activation of free carboxylic acids in the γ-position. The developed protocol features a wide range of acid substrates and olefin reaction partners and is shown to be applicable on a preparatively useful scale. Insights into the underlying reaction mechanism obtained through kinetic studies are reported.<br>


2019 ◽  
Author(s):  
Nobutaka Fujieda ◽  
Miho Yuasa ◽  
Yosuke Nishikawa ◽  
Genji Kurisu ◽  
Shinobu Itoh ◽  
...  

Cupin superfamily proteins (TM1459) work as a macromolecular ligand framework with a double-stranded beta-barrel structure ligating to a Cu ion through histidine side chains. Variegating the first coordination sphere of TM1459 revealed that H52A and H54A/H58A mutants effectively catalyzed the diastereo- and enantio-selective Michael addition reaction of nitroalkanes to an α,β-unsaturated ketone. Moreover, in silico substrate docking signified C106N and F104W single-point mutations, which inverted the diastereoselectivity of H52A and further improved the stereoselectivity of H54A/H58A, respectively.


HortScience ◽  
1998 ◽  
Vol 33 (3) ◽  
pp. 550a-550 ◽  
Author(s):  
Royal G. Fader ◽  
Martin J. Bukovac

We have reported that NH4NO3 (AN, 8 mM, pH 4.2), applied as simulated spray droplets, enhanced penetration of 14C-NAA through isolated leaf and fruit cuticles. One explanation for this response is that AN depresses NAA (pKa= 4.2) dissociation, increasing the nondissociated moiety, which penetrates more readily than the anion (NAA'). Direct measurement of AN (concn. 0-800 mM) effect on NAA (215 μM) dissociation as indexed by change in solution pH revealed no significant effect, with a pH change from 4.19 to 4.05. This change is not sufficient to account for the observed enhancement. When 14C-NAA, buffered (20 mM sodium citrate) at pH 3.2, 4.2, 5.2, 6.2, was partitioned against chloroform, there was a marked increase in NAA partitioning into chloroform as pH was decreased. AN (8 mM) did not alter this partition behavior, also indicating no effect on NAA dissociation. However, in cuticle penetration studies, using a finite dose system with 14C-NAA buffered at pH 3.2, 4.2, 5.2, 6.2, and in the presence and absence of 8 mM AN, there was no marked or consistent pH or AN (-70 to + 232 % of no AN control) effect on penetration as indexed by initial slope (4-12 h) or penetration after 120 h. The possible effects of AN and buffer on penetration of 14C-NAA from the droplet deposit will be discussed.


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