Playing with Structures at the Nanoscale: Designing Catalysts by Manipulation of Clusters and Nanocrystals as Building Blocks

The purpose of this Concept is to highlight some of the most recent and promising methods for the preparation of tailored catalysts by designing and preparing the component building blocks and by assembling them in a controlled fashion. We want to emphasize how rational design and synthesis of catalysts must be coupled to precise catalytic and structural characterization of the systems in an ideal feedback loop. New catalyst design and preparation techniques, dictated by information about the active sites that the specific application requires, are frequently available. The building blocks for developing these novel catalysts include colloidal methods for the preparation of uniform nanostructures, physical methods for rational assembly of the building blocks (Langmuir–Blodgett, liquid–air self‐assembly), and development of rational interactions between the building blocks for enhanced activity of the assemblies. These methods, which apply techniques normally used in other fields of nanotechnology to catalysis, offer exciting opportunities to help improve currently available catalytic systems in terms of activity, stability and selectivity.     

Generation of Singlet Molecular Oxygen by Lipid Hydroperoxides and Nitronium Ion†

Singlet molecular oxygen is a reactive species involved in biological oxidative processes. The major cellular targets of singlet molecular oxygen are unsaturated fatty acids in the membrane, as well as nucleic acids and proteins. The aim of this study was to investigate whether lipids and commercial hydroperoxides generate singlet molecular oxygen, in presence of nitronium and activated nitronium ion. For this purpose, monomol light emitted in the near-infrared region (λ = 1270 nm) was used to monitor singlet molecular oxygen decay in different solvents, with different hydroperoxides and in the presence of azide. Direct measurements of the singlet molecular oxygen spectrum at 1270 nm recorded during the reaction between lipids and commercial hydroperoxides and nitronium ions unequivocally demonstrated the formation of this excited species.     

The Fluorenyl Cation

The fluorenyl cation is a textbook example for a 4π antiaromatic cation. However, contrasting results have been published on how the annelated benzene rings compensate the destabilizing effect of the 4π antiaromatic five‐membered ring in its core. Whereas previous attempts to synthesize this cation in superacidic media resulted in undefined polymeric material only, we herein report that it can be generated and isolated in amorphous water ice at temperatures below 30 K by photolysis of diazofluorene. Under these conditions, the fluorenylidene is protonated by water to give the fluorenyl cation, which could be characterized spectroscopically. Its absorption in the visible‐light range matches that previously obtained by ultrafast absorption spectroscopy, and furthermore, its IR spectrum could be recorded. The IR bands in amorphous ice very nicely match predictions from DFT and DFT/MM calculations, suggesting the absence of strong interactions between the cation and surrounding water molecules.     

Synthesis and Characterization of Far‐Red/NIR‐Fluorescent BODIPY Dyes,Solid‐State Fluorescence,and Application as Fluorescent Tags Attached to Carbon Nano‐onions

A series of π‐extended distyryl‐substituted boron dipyrromethene (BODIPY) derivatives with intense far‐red/near‐infrared (NIR) fluorescence was synthesized and characterized, with a view to enhance the dye’s performance for fluorescence labeling. An enhanced brightness was achieved by the introduction of two methyl substituents in the meso positions on the phenyl group of the BODIPY molecule; these substituents resulted in increased structural rigidity. Solid‐state fluorescence was observed for one of the distyryl‐substituted BODIPY derivatives. The introduction of a terminal bromo substituent allows for the subsequent immobilization of the BODIPY fluorophore on the surface of carbon nano‐onions (CNOs), which leads to potential imaging agents for biological and biomedical applications. The far‐red/NIR‐fluorescent CNO nanoparticles were characterized by absorption, fluorescence, and Raman spectroscopies, as well as by thermogravimetric analysis, dynamic light scattering, high‐resolution transmission electron microscopy, and confocal microscopy.     

A novel chemo-multienzymatic synthesis of bioactive cyclophellitol and epi-cyclophellitol in both enantiopure forms

A new route to synthesize cyclophellitol and epi-cyclophellitol from racemic starting materials in enantiopure forms has been developed. The synthesis involves a multi-enzymatic biotransformation pathway of the novel cyano-cyclitol (1R,4S,5R,6R)/(1S,4R,5S,6S)-4,5,6-trihydroxycyclohex-2-enecarbonitrile by a cooperative use of lipase, nitrile hydratase, and amidase.     

Reactivity of Functionalized Phosphonates 1. Acid-Base Properties and Reactivity of Methyl Esters of Alpha-Aminophosphonic Acids

Acid-base properties and reactivity of series of alpha-aminophosphonates has been investigated. The reaction of addition of the aminophosphonates to phenylisocyanate was used as a model reaction. The influence of steric and electronic effects of substituents at alpha-carbon or nitrogen in amino group on the mechanism inversion from AdN to AdE is discussed.     

New 9,10‐Secosteroids from Biotransformations of Bile Acids with Rhodococcus ruber

The biotransformations of cholic, deoxycholic, and hyocholic acids with Rhodococcus ruber are reported. In all biotransformations, the C₁₇‐side chain is partially degraded, and the new 9,10‐secosteroids 4a (54%) and 4b (55%) are obtained from cholic and deoxycholic acids, respectively. The loss of H₂O from C(11)? C(12) of secosteroids 4a and 4b affords the compounds 5a (5%) and 5b (20%), respectively. On the other hand, in the biotransformation of hyocholic acid with R. ruber the 9,10‐secosteroid 4c is not detected, but, rearranging to an intramolecular hemiacetal form, it evolves to the final furan derivative 6c (35%) by easy elimination of two molecules of H₂O. The new secosteroids were characterized by IR, NMR, and 2D‐NMR spectroscopy, and mass spectroscopy.     

Starshapedness of level sets of solutions to elliptic PDEs

We investigate how some geometric properties of the domain are inherited by level sets of solutions of elliptic equations. In particular we prove that, under suitable assumptions, solutions of elliptic Dirichlet problems in starshaped rings have starshaped level sets. Our results are applicable to a large class of operators, including fully-nonlinear ones.     

Comparative LC Enantioseparation of Novel PPAR Agonists on Cellulose- and Amylose-Based Chiral Stationary Phases

The LC enantiomeric separation of several dual PPARα/γ agonists on the commercially available Chiralcel OD and Chiralpak AD columns has been evaluated in normal phase mode using a mobile phase consisting in a mixture of n-hexane, 2-propanol and trifluoroacetic acid at constant volume ratio. Most compounds were separated as underivatized acids without requiring time consuming analysis. Some complementary selectivity was evidenced on the two investigated chiral stationary phases related to the different accessibility of the active sites of the helical cavities. Additional information on the chiral recognition mechanism were deduced from the chromatographic behaviour of some selected methyl esters.