The deselenization of selenocysteine selectively removes the selenol group to give alanine under anaerobic conditions or serine aerobic (oxygen saturation).

Abstract Although native chemical ligation has enabled the synthesis of hundreds proteins, not all proteins are accessible through typical conditions. The challenging protein, 125‐residue human phosphohistidine phosphatase 1 (PHPT1), three cysteines near C‐terminus, which strategically placed for ligation. Herein, we report first sequential ligation/deselenization reaction. PHPT1 was prepared from unprotected peptide segments using two reactions at cysteine and alanine junctions....

Abstract N -heterocyclic carbenes (NHCs) have been widely utilized for the formation of self-assembled monolayers (SAMs) on various surfaces. The main methodologies preparation NHCs-based SAMs either requires inert atmosphere and strong base deprotonation imidazolium precursors or use specifically-synthesized such as NHC(H)[HCO 3 ] salts NHC–CO 2 adducts. Herein, we demonstrate an electrochemical approach surface-anchoring NHCs which overcomes need dry environment, addition exogenous...

The human body contains 25 selenoproteins, but challenges in their preparations have prevented biological characterizations thus far. Here we report the first total chemical syntheses of two selenoprotein M (SELM) and W (SELW).

The formation of flexible self-assembled monolayers (SAMs) in which an external trigger modifies the geometry surface-anchored molecules is essential for development functional materials with tunable properties. In this work, it demonstrated that NO2 -functionalized N-heterocyclic carbene (NHCs), were anchored on Au (111) surface, change their orientation from tilted into flat-lying position following trigger-induced reduction nitro groups. DFT calculations identified energetic driving force...

Studying nanoparticle (NP)-electrode interactions in single collision events is critical to understanding dynamic processes such as motion, adsorption, oxidation, and catalytic activity, which are abundant on electrode surfaces. Herein, NP-electrode electrostatic studied by tracking the oxidation of AgNPs at Au microelectrodes functionalized with charged self-assembled monolayers (SAMs). Tuning charge short alkanethiol-based selecting that can be partially or fully oxidized upon impact...

The development of chemically addressable N-heterocyclic carbene (NHC) based self-assembled monolayers (SAMs) requires in-depth understanding the influence NHC's anchoring geometry on its chemical functionality. Herein, it is demonstrated that reactivity surface-anchored NO2-functionalized NHCs (NO2–NHCs) can be tuned by modifying distance between functional group and reactive surface, which governed deposition technique. Liquid NO2–NHCs Pt(111) induced a SAM in NO2-aryl groups were...

N-heterocyclic carbenes (NHCs) have been extensively studied to modulate the reactivity of molecular catalysts, colloids, and their supported analogues, being isolated sites, clusters, or nanoparticles. While interaction NHCs on metal surfaces has discussed in great detail, showing specific coordination chemistry depending type NHC ligands, much less is known when dispersed oxide supports, as heterogeneous catalysts. Herein, we study ligands with Au surface sites silica, a nonreducible...

IR nanospectroscopy measurements revealed the influence of oxidizing reaction conditions on reactivity different surface sites Pt particles.

Fundamental understanding of the correlation between structure and reactivity chemically addressable N-heterocyclic carbene (NHC) molecules on various surfaces is essential for design functional NHC-based self-assembled monolayers. In this work, we identified ways by which deposition OH-NHCs Au(111) or Pt(111) modified anchoring geometry chemical surface-anchored NHCs. The properties NHCs were probed conducting X-ray photoelectron spectroscopy polarized near-edge absorption fine...

Adsorption of chiral molecules on heterogeneous catalysts is a simple approach for inducing an asymmetric environment to enable enantioselective reactivity. Although the concept induction straightforward, its practical utilization far from simple, and only few examples toward successful by surface anchoring modifiers have been demonstrated so far. Elucidating factors that lead therefore crucial step understanding mechanism which chirality transferred. Herein, we identify adsorption geometry...

N-heterocyclic carbenes (NHCs) have emerged as versatile ligands in organometallic chemistry, prized for their strong σ-donating and tunable electronic properties. They stabilize diverse motifs, well clusters, nanoparticles, particularly those based on the coin-age metals—Cu, Ag, Au. Importantly, carbene 13C NMR isotropic chemical shift (δiso) of NHC-coinage metal complexes varies significantly across these elements, reflecting nuanced interplay structural factors. Here, we investigate...

Promotional effects are ubiquitous across catalytic processes involving supported nanoparticles, where additional elements – so-called promoters enhance significantly the performances (activity, selectivity and stability) of nanoparticles. However, inherent complexity these catalysts makes it difficult to underline effect at molecular level. Surface organometallic chemistry (SOMC) is a powerful tool decouple by constructing better-defined model systems. In this study, we compare two SOMC...

N-heterocyclic carbenes (NHCs) are versatile ligands in organometallic chemistry, prized for their strong σ-donating and tunable electronic properties. They used to stabilize a wide range of motifs, including clusters nanoparticles, based particular on coinage metals—Cu, Ag, Au. Notably, the carbene 13C NMR isotropic chemical shift (δiso) NHC-coinage metal complexes varies significantly across these elements, reflecting nuanced interplay structural factors. Here, we study carbon NHC-Au(I)-X...

N-Heterocyclic carbenes (NHCs) are versatile ligands in organometallic chemistry, prized for their strong σ-donating and tunable electronic properties. They used to stabilize a wide range of motifs, including clusters nanoparticles, based particular on coinage metals─Cu, Ag, Au. Notably, the carbene 13C NMR isotropic chemical shift (δiso) NHC-coinage metal complexes varies significantly across these elements, reflecting nuanced interplay structural factors. Here, we study carbon NHC-Au(I)-X...

Metal–support interactions have been widely utilized for optimizing the catalytic reactivity of oxide-supported Au nanoparticles. Optimized was mainly detected with small (1–5 nm) nanoparticles and correlated to highly reactive sites at oxide–metal interface. However, catalytically active are not necessarily restricted interface but reside as well on surface. Uncovering interconnection between located those situated metal surface is crucial importance understanding reaction mechanism Herein,...

The preparation of bimetallic nanoporous networks (BNNs) that combine the high surface area and thermal stability inorganic nanostructures with unique catalytic properties systems is highly desirable. Here we show a simple versatile approach for synthesis Pt–Re BNN demonstrate influence conditions on structure, composition, reactivity. was prepared by reduction double complex [Pt(NH3)4][Re(Cl6)] salt crystals, in which two oppositely charged metal complexes are evenly distributed each unit...

Abstract Although native chemical ligation has enabled the synthesis of hundreds proteins, not all proteins are accessible through typical conditions. The challenging protein, 125‐residue human phosphohistidine phosphatase 1 (PHPT1), three cysteines near C‐terminus, which strategically placed for ligation. Herein, we report first sequential ligation/deselenization reaction. PHPT1 was prepared from unprotected peptide segments using two reactions at cysteine and alanine junctions....

Site-dependent selectivity in oxidation reactions on Pt nanoparticles was identified by conducting IR nanospectroscopy measurements while using allyl-functionalized N-heterocyclic carbenes (allyl-NHCs) as probe molecules. Following exposure to oxidizing conditions the allyl groups NHCs that were located center of oxidized hydroxyl those nanoparticle's periphery into carboxylic acid. The superior reactivity correlated higher density low coordinated atoms these surface sites.

Stilbene-functionalized NHC accumulated vertical adsorption geometry on Au film, enabling reversible changes in surface potential following photoisomerization. Stronger interaction with Pt film quenched stilbene-NHC influence potential.

Nanoparticle-imprinted matrices (NAIMs) are an innovative approach for the efficient and selective recognition of nanoparticles (NPs). The NAIM system comprises preparation thin films in which NPs embedded as a template. removal template forms nanometric voids, subsequently used reuptake identical to those imprinted. ability depends on several parameters such geometrical compatibility between voids imprinted NPs, thickness matrix, supramolecular interactions matrix NP capping agents. Herein,...

Identifying the influence of atomic order on catalytic reactivity bimetallic catalysts is essential for their rational design. However, synthesis atomically ordered nanostructures under mild conditions not trivial, and in many cases a mixture various compositions formed. Here we show simple highly versatile approach Pt–Co nanoporous network (BNN) demonstrate preparation BNN’s reactivity. High surface area Pt3Co BNN was prepared by reduction [Co(NH3)5Cl][PtCl4] double complex salt crystals....