Comparison of the Peroxidase‐Like Activity of Unmodified,Amino‐Modified,and Citrate‐Capped Gold Nanoparticles

The origin of the peroxidase‐like activity of gold nanoparticles and the impact of surface modification are studied. Furthermore, some influencing factors, such as fabrication process, redox property of the modifier, and charge property of the substrate, are investigated. Compared to amino‐modified or citrate‐capped gold nanoparticles, unmodified gold nanoparticles show significantly higher catalytic activity toward peroxidase substrates, that is, the superficial gold atoms are a contributing factor to the observed peroxidase‐like activity. The different catalytic activities of amino‐modified and citrate‐capped gold nanoparticles toward 3,3′,5,5′‐tetramethylbenzidine (TMB) and 2,2′‐azino‐bis(3‐ethylbenzothiazoline‐6‐sulfonic acid) diammonium salt (ABTS) show that the charge characteristics of the nanoparticles and the substrate also play an important role in the catalytic reactions.     

Asymmetric Nucleophilic Monofluorobenzylation of Carbonyl Compounds: Synthesis of Enantiopure vic‐Fluorohydrins and α‐Fluorobenzylketones

Asymmetric nucleophilic monofluoroalkylation of a broad range of aldehydes with an α‐fluoro‐γ‐sulfinylbenzyl carbanion takes place with complete control of the facial selectivity at the carbanion and good to high anti‐diastereoselectivity to give easily separable mixtures of two optically pure 1,2‐fluorohydrin derivatives (up to 24:1 anti/syn). Separation and removal of the p‐tolylsulfinyl group with tBuLi provides enantiomerically pure anti‐1,2‐disubstituted‐1,2‐fluorohydrins, whereas α‐fluorobenzylketones can be obtained by desulfinylation of the mixture followed by pyridinium chlorochromate oxidation (one‐pot process).     

Intracrystalline Diffusion in Mesoporous Zeolites

Specially synthesized extra‐large crystallites of zeolite LTA with intentionally added mesoporosity are used for an in‐depth study of guest diffusion in hierarchical nanoporous materials by the pulsed field gradient NMR technique. Using propane as a guest molecule, intracrystalline mass transfer is demonstrated to be adequately described by a single effective diffusivity resulting from the weighted average of the diffusivities in the two (micro‐ and meso‐) pore spaces. Gas‐kinetic order‐of‐magnitude estimates of the diffusivities are in satisfactory agreement with the experimental data and are thus shown to provide a straightforward means for predicting and quantifying the benefit of hierarchically structured nanoporous materials in comparison with their purely microporous equivalent.     

Photoactivated Nitrene Chemistry to Prepare Gold Nanoparticle Hybrids with Carbonaceous Materials

Photolysis of organic solvent soluble aryl azide‐modified gold nanoparticles (N₃‐AuNPs) with a core size of 4.6±1.6 nm results in the generation of interfacial reactive nitrene intermediates. The high reactivity of the nitrenes is utilized to tether the AuNP to the native surface of carbon nanotubes, and reduce graphene oxide and micro‐diamond powder, likely via addition to π‐conjugated carbon skeleton or insertion into the functionalities at the surface, to yield the desired hybrid material without the need for pretreatment of the surface. The AuNP‐covalent hybrid materials are robust in that they survive vigorous washing and sonication. In the absence of photolysis no attachment occurs with the same N₃‐AuNP. The nanohybrid AuNP‐nanohybrid materials are characterized using a combination of TEM, powder XRD, XPS and UV/Vis and IR spectroscopies. All of the characterization studies confirm the uniform incorporation of the AuNP on the irradiated substrates.     

Theoretical Insight into the Origin of Large Stokes Shift and Photophysical Properties of Anilido‐Pyridine Boron Difluoride Dyes

The geometric and electronic structures and photophysical properties of anilido‐pyridine boron difluoride dyes 1 – 4 , a series of scarce 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) derivatives with large Stokes shift, are investigated by employing density functional theory (DFT) and time‐dependent DFT (TD‐DFT) calculations to shed light on the origin of their large Stokes shifts. To this end, a suitable functional is first determined based on functional tests and a recently proposed index—the charge‐transfer distance. It is found that PBE0 provides satisfactory overall results. An in‐depth insight into Huang–Rhys (HR) factors, Wiberg bond indices, and transition density matrices is provided to scrutinize the geometric distortions and the character of excited states pertaining to absorption and emission. The results show that the pronounced geometric distortion due to the rotation of unlocked phenyl groups and intramolecular charge transfer are responsible for the large Stokes shift of 1 and 2 , while 3 shows a relatively blue‐shifted emission wavelength due to its mild geometric distortion upon photoemission, although it has a comparable energy gap to 1 . Finally, compound 4 , which is designed to realize the rare red emission in BODIPY derivatives, shows desirable and expected properties, such as high Stokes shift (4847 cm^?1), red emission at 660 nm, and reasonable fluorescence efficiency. These properties give it great potential as an ideal emitter in organic light‐emitting diodes. The theoretical results could complement and assist in the development of BODIPY‐based dyes with both large Stokes shift and high quantum efficiency.     

Kinetics of Iterative Carbohydrate Transfer to Polysaccharide Catalyzed by Chondroitin Polymerase on a Highly Sensitive Flow‐Type 27 MHz Quartz‐Crystal Microbalance

Using a highly sensitive flow‐type 27 MHz quartz crystal microbalance, we could detect a small mass change during stepwise and alternating one‐sugar transfer of glucuronic acid (GlcA) and N‐acetylgalactosamine (GalNAc) to an acceptor, catalyzed by chondroitin polymerase from Escherichia coli strain K4 (K4CP), and analyze the elongation mechanism of K4CP. K4CP was found to bind strongly to a chondroitin acceptor (K_d=0.97 μM ). Although the binding affinity and the catalytic rate constant for each monomer were considerably different, the apparent catalytic efficiency (k_cat/K_m) was similar (6.3×10⁴ M ^?1 s^?1 for GlcA transfer and 3.4×10⁴ M ^?1 s^?1 for the GalNAc transfer). This is reasonable for the smooth alternating elongation of GlcA and GalNAc on the acceptor. This is the first study to report the determination of kinetic parameters for enzymatic, alternated, sugar elongation.     

Magnetism‐Tunable Oligoacene Dioxide Diradicals: Promising Magnetic Oligoacene‐Like Molecules

Graphene oxide has attracted intense research interest recently because the graphene oxide synthesis route, as a promising alternative for cost‐effective mass production of graphene, has been explored. To further study the oxidation process and possible mechanism and to explore applicability of the oxidized products, we have performed a computational study on three series of oligoacene dioxides, focusing on their structures and electronic properties. Taking 1,5‐dioxidized naphthalene as a starting point, three series of oligoacene dioxides are considered as follows: 1) middle insertion by 1–2 benzene rings; 2) single‐side expansion using 1–2 benzene rings; 3) double‐side expansion using two benzene rings. On the basis of density functional theory and complete active space self‐consistent field (CASSCF) calculations, we reveal that oligoacene dioxides in the middle insertion series have a triplet ground state, whereas those in the single‐side expansion series and the double‐side expansion series have open‐shell broken‐symmetry singlet diradical ground states except for their common origin naphthalene‐1,5‐dioxide whose ground state is triplet and which is also viewed as the origin of the middle insertion series. Magnetic coupling interactions of these oligoacene dioxides are also determined. This work should help people toward an atomistic understanding of the electronic structures and properties of possible intermediates or products and even the oxidation mechanism of graphene sheets, and provides a reasonable strategy of designing novel graphene‐oxide‐based magnetic materials.     

Effect of Residual Water and Microwave Heating on the Half‐Life of the Reagents and Reactive Intermediates in Peptide Synthesis

Precise microwave heating has changed the way many small molecules are being synthesized and, currently, the field of solid‐phase peptide synthesis is undergoing dramatic changes owing to the use of microwave heating. To fully reap the benefits of precise microwave heating for the formation of amide bonds in peptide synthesis, it is important to understand the kinetics of formation and break‐down of activated esters and their N‐acylation of the nascent peptide chain at elevated temperatures. Herein, we present systematic studies of, first, the rate of formation of activated esters by NMR spectroscopy and, second, their N‐acylation during peptide synthesis. A study of the amount of residual water in the solvents revealed a significant effect on electrophilic reagents and intermediates. This observation was expanded into a general study of microwave heating in peptide synthesis.     

Observable Structures of Small Neutral and Anionic Gold Clusters

Since gold clusters have mostly been studied theoretically by using DFT calculations, more accurate studies are of importance. Thus, small neutral and anionic gold clusters (Au_n and Au_n^?, n=4–7) were investigated by means of coupled cluster with singles, doubles, and perturbative triple excitations [CCSD(T)] calculations with large basis sets, and some differences between DFT and CCSD(T) results are discussed. Interesting isomeric structures that have dangling atoms were obtained. Structures having dangling atoms appear to be stable up to n=4 for neutral gold clusters and up to n=7 for anionic clusters. The relative stabilities and electronic properties of some isomers and major structures are discussed on the basis of the CCSD(T) calculations. This accurate structure prediction of small gold clusters corresponding to experimental photoelectron spectral peaks is valuable in the field of atom‐scale materials science including nanocatalysts.