The utility and selectivity of the catalyst [Ru(COD)(L(1))Br2] (1) bearing a fused π-conjugated imidazo[1,2-a][1,8]naphthyridine-based abnormal N-heterocyclic carbene ligand L(1) is demonstrated toward selective oxidation of C═C bonds to aldehydes and C≡C bonds to α-diketones in an EtOAc/CH3CN/H2O solvent mixture at room temperature using a wide range of substrates, including highly functionalized sugar- and amino acid-derived compounds.
Ultrathin films of 2-ferrocenyl-1,3-dithiolane and 2-ferrocenyl-1,3-dithiane (Fcs), which are chemically inert at ambient conditions, are studied on the basal plane of highly oriented pyrolytic graphite (HOPG) using atomic force microscopy (AFM) and scanning tunneling microscopy (STM). Films are prepared by drop-casting using Fcs dissolved in different solvents. Films prepared from methanol and dichloromethane show structural polymorphs on HOPG, while those prepared from ethanol, acetone, and dimethylformamide show an exclusive selection of one of the polymorphs. The selection of growth patterns of Fcs shows interesting correlation to the bulk solubility of molecules in the corresponding solvents and the solvent boiling point. The growth of Fcs at the submonolayer coverage is templated by the surface symmetry, and the molecular level packing on the surface is understood using high-resolution AFM, STM, and the bulk crystal packing of the molecules.
Cesium lead halide perovskite nanocrystals (PNCs) have enjoyed enormous attention in optoelectronics and photovoltaics. However, instability under polar conditions and limited energy/charge transport due to long-chain capping ligands restrict their large-scale applications. We have engineered a short-chain multidentate bolaamphiphilic ligand (NKE-3), which provides synergistic passivation of the perovskite surface by one multidentate ionic terminal and localizes water molecules by another multidentate ionic terminal, leading to a watersuspended colloidal solution of PNCs. NKE-3 allows efficient long-range dipole-based fluorescence resonance energy transfer (FRET) from perovskites to Rhodamine B isothiocyanate (RITC) in water, with FRET efficiencies ranging from 96% to 98%. We calculated the FRET rate using the acceptor's rise-time component, as it ensures no contamination from FRET-inactive donors. Moreover, we tuned the emission maxima of PNCs through halide exchange to optimize FRET efficiency. Such energy funneling to a suitable molecular photocatalyst is imperative for PNCs' potential applications.
Strategically designed surface modifiers that produce
stable perovskite
nanocrystals (NCs) and allow efficient charge extraction in polar
solvents are critical for perovskite photocatalysis. We designed a
multifunctional bolaamphiphilic ligand (NKE-12) with multidentate
ionic groups at both ends, which significantly increases the colloidal
stability of CsPbBr3 NCs in an aqueous medium without affecting
their structural integrity and catalytic attributes. Ligand deconstruction
via K and E fragmented ligands revealed synergistic actions of the
cationic and anionic functionalities in surface passivation, phase
separation, and water localization away from the surface of NKE-12-modified
CsPbBr3 NCs. Multidimensional nuclear magnetic resonance
experiments and contact angle measurements further suggested surface
interactions and improved hydrophilicity via ionic terminal groups
that account for water stability. Photogenerated hole-transfer dynamics
of CsPbBr3/NKE-12 NCs to a probe molecule 6,7-dihydroxycoumarin
was studied using transient absorption spectroscopy. Overall, this
study paves the way for ligand design principles for surface engineering
to develop water-stable perovskite photocatalysts.
Cesium lead halide (CsPbX3) perovskites, having stood out for solar cell applications, are now garnering attention in the field of photocatalysis as well. With a fundamental challenge in photocatalysis of...
Ferrocenyl-Alkyl-Protected
Sugar (Fc-Sug) and Ferrocenyl-Oxo-Alkyl-Protected
Sugar (Fc-Oxo-Sug) were deposited on the basal plane of Highly Oriented
Pyrolytic Graphite (HOPG) using a drop-casting method. Ultrathin films
of these molecules were investigated using Atomic Force Microscopy
to understand the growth at low coverage. Both molecules are forming
highly ordered one-dimensional molecular islands, which are growing
from a dimer building block. The dimer and interdimer interactions
(along the length of islands) are stabilized by −C2O···H–C hydrogen bonding. Unlike for Fc-Sug,
the islands of Fc-Oxo-Sug are extended to tens of micrometers, and
the growth is only limited by terrace edges or other islands on the
surface. This exceptional growth of islands is understood in terms
of an additional −CO···H–C–
hydrogen bonding leading to stronger interdimer interactions along
the length of the islands compared to Fc-Sug.
High‐affinity binders for the C‐reactive protein (CRP), with dissociation constants in the pM to nM range and selectivities in human serum comparable to those of antibodies, were obtained by conjugation of 16 designed polypeptides to phosphocholine, a small molecule that binds CRP with a KD value of 5 μM (see picture). The polypeptides were not designed specifically to recognize CRP and bind by an adapted fit mechanism.
The ultrathin films of 2-ferrocenyl-1,3-dithiolane (FcS 2 C 3 ) and 2-ferrocenyl-1,3-dithiane (FcS 2 C 4 ) dropcasted from toluene on highly oriented pyrolytic graphite (HOPG) surface are investigated using atomic force microscopy (AFM). Two types of growth polymorphs have been observed, which are distinctly different based on their nature of growth and the molecular level packing. We have developed a new type of temperature-dependent desorption experiment named "microscopic thermal desorption analysis" (MTDA) for understanding the adsorption energetics related to the observed growth polymorphs on the surface. Using MTDA, we have calculated the adsorption energies of growth polymorphs of both molecules and further revealed that their formation requires an activation energy. The subtle relation between the adsorption energies and activation energies of growth polymorphs account for their average abundance on the surface. The experimental observations are further supported by density functional theory (DFT) calculations.
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