- Impact of Molecular Architecture and Adsorption Density on Adhesion of Mussel-Inspired Surface Primers with Catechol-Cation Synergy
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Marine mussels secrete proteins rich in residues containing catechols and cationic amines that displace hydration layers and adhere to charged surfaces under water via a cooperative binding effect known as catechol-cation synergy. Mussel-inspired adhesives containing paired catechol and cationic functionalities are a promising class of materials for biomedical applications, but few studies address the molecular adhesion mechanism(s) of these materials. To determine whether intramolecular adjacency of these functionalities is necessary for robust adhesion, a suite of siderophore analog surface primers was synthesized with systematic variations in intramolecular spacing between catechol and cationic functionalities. Adhesion measurements conducted with a surface forces apparatus (SFA) allow adhesive failure to be distinguished from cohesive failure and show that the failure mode depends critically on the siderophore analog adsorption density. The adhesion of these molecules to muscovite mica in an aqueous electrolyte solution demonstrates that direct intramolecular adjacency of catechol and cationic functionalities is not necessary for synergistic binding. However, we show that increasing the catechol-cation spacing by incorporating nonbinding domains results in decreased adhesion, which we attribute to a decrease in the density of catechol functionalities. A mechanism for catechol-cation synergy is proposed based on electrostatically driven adsorption and subsequent binding of catechol functionalities. This work should guide the design of new adhesives for binding to charged surfaces in saline environments.
- Degen, George D.,Stow, Parker R.,Lewis, Robert B.,Andresen Eguiluz, Roberto C.,Valois, Eric,Kristiansen, Kai,Butler, Alison,Israelachvili, Jacob N.
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supporting information
p. 18673 - 18681
(2019/11/28)
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- The first total synthesis of gobichelin B: A mixed-ligand siderophore of: Streptomyces sp. NRRL F-4415
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The first total synthesis of a structurally diverse mixed ligand siderophore, gobichelin B produced by Streptomyces sp. NRRL F-4415, is reported. The systematic assembly of the building blocks to synthesize Gob-B 1st half and Gob-B 2nd half and subsequent coupling of these two fragments followed by global deprotection using Pearlman's catalyst led to the isolation of gobichelin B in excellent yield and purity.
- Sridhar, Perali Ramu,Venkatesh,Kalesha, Shaik,Sudharani, Chalapala
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p. 3732 - 3740
(2018/05/30)
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- Solution-phase synthesis of a muramyl dipeptide analogue MDA
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The solution-phase synthesis of a muramyl dipeptide (MDP) analogue of Nα-[4-chlorocinnamoyl-l-alanyl-d-isoglutaminyl]-l-lysine (MDA, 2) is reported that possesses the features of easy feasibility, safety and low cost in large scale of synthesis.
- Zhao, Nan,Ma, Yao,Liu, Gang
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scheme or table
p. 1443 - 1446
(2012/06/04)
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- Substituted pyridines having antiangiogenic activity
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Compounds having the formula are angiogenesis inhibitors. Also disclosed are compositions containing the compounds, methods of making the compounds, and methods of treatment using the compounds.
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- Nε-carbonyl> Derivatives of Tri-L-lysine and Tetra-L-lysine as Potential Intermediates in the Block Polymer Synthesis of Macromolecular Drug Conjugates
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Tri-L-lysine and tetra-L-lysine derivatives were synthesized with Nε-carbonyl>(Nε-Teoc) protecting groups an all the lysines, or on all but the N-terminal lysine, and with Nα-(tert-butyloxycarbonyl) (Nα-Boc) or Nα-(9-fluorenylmethyloxycarbonyl) (Nα-Fmoc) groups on the N-terminal lysines.Treatment of the Boc/Teoc peptides with p-toluenesulfonic or 2,4,6-trimethylbenzenesulfonic acid led to Boc cleavage with Teoc retention only when the Teoc/Boc ratio was 1:1 or 2:1.In contrast, treatment of the Fmoc/Teoc peptides with liquid ammonia in a sealed vessel cleaved the Fmoc group without significant loss of Teoc groups even when the Fmoc/Teoc ratio was 3:1, showing that Fmoc and Teoc groups provide more selectivity than the Boc and Teoc combination.Nα-Fmoc and Nε-Teoc groups were both stable under catalytic hydrogenolysis conditions.This made it possible to prepare Nα-Fmoc-tri-L-lysine and Nα-Fmoc-tetra-L-lysine derivatives with Nε-Teoc groups on all but the N-terminal lysine and demonstrated that the triad Fmoc/Cbz/Teoc is superior to Boc/Cbz/Teoc in peptide synthesis involving the orthogonal protection strategy.
- Rosowsky, Andre,Wright, Joel E.
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p. 5551 - 5558
(2007/10/02)
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- Novel Preparation of N-Protected Amino Acid Active Esters Using 1,2,2,2-Tetrachloroethyl Carbonates
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1,2,2,2-Tetrachloroethyl chloroformate reacts with substituted phenols or N-hydroxy imides to yield crystalline and stable mixed aryl or oximido tetrachloroethyl carbonates.When allowed to react with an N-protected amino acid derivative, these compounds proved to be efficient for the syntheses of the corresponding active esters.A series of active esters including p-nitrophenol, trichlorophenol, pentafluorophenol, and N-hydroxysuccinimide derivatives were prepared by this new procedure.
- Jaoudai, Mahmoud,Martinez, Jean,Castro, Bertrand
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p. 2364 - 2367
(2007/10/02)
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