TY  - JOUR
A1  - Folikumah, Makafui Yao
A1  - Neffe, Axel T.
A1  - Behl, Marc
A1  - Lendlein, Andreas
T1  - Thiol Michael-Type reactions of optically active mercapto-acids in aqueous medium
JF  - MRS advances : a journal of the Materials Research Society
N2  - Defined chemical reactions in a physiological environment are a prerequisite for the in situ synthesis of implant materials potentially serving as matrix for drug delivery systems, tissue fillers or surgical glues. ‘Click’ reactions like thiol Michael-type reactions have been successfully employed as bioorthogonal reaction. However, due to the individual stereo-electronic and physical properties of specific substrates, an exact understanding their chemical reactivity is required if they are to be used for in-situ biomaterial synthesis. The chiral (S)-2-mercapto-carboxylic acid analogues of L-phenylalanine (SH-Phe) and L-leucine (SH-Leu) which are subunits of certain collagenase sensitive synthetic peptides, were explored for their potential for in-situ biomaterial formation via the thiol Michael-type reaction.

In model reactions were investigated the kinetics, the specificity and influence of stereochemistry of this reaction. We could show that only reactions involving SH-Leu yielded the expected thiol-Michael product. The inability of SH-Phe to react was attributed to the steric hindrance of the bulky phenyl group. In aqueous media, successful reaction using SH-Leu is thought to proceed via the sodium salt formed in-situ by the addition of NaOH solution, which was intented to aid the solubility of the mercapto-acid in water. Fast reaction rates and complete acrylate/maleimide conversion were only realized at pH 7.2 or higher suggesting the possible use of SH-Leu under physiological conditions for thiol Michael-type reactions. This method of in-situ formed alkali salts could be used as a fast approach to screen mercapto-acids for thio Michael-type reactions without the synthesis of their corresponding esters.
KW  - biomaterial
KW  - biomedical
KW  - biomimetic (chemical reaction)
KW  - chemical synthesis
Y1  - 2019
U6  - https://doi.org/10.1557/adv.2019.308
SN  - 2059-8521
VL  - 4
IS  - 46-47
SP  - 2515
EP  - 2525
PB  - Springer Nature Switzerland AG
CY  - Cham
ER  -