Versatile and practical chiral shift reagent with hydrogen-bond donor/acceptor sites in a macrocyclic cavity

[structure: see text] Bifunctional macrocycle 1 with C2 symmetry was newly synthesized. NMR studies demonstrated that receptor 1 functions as a chiral shift reagent (solvating agent) that is highly effective for a wide range of chiral compounds having a carboxylic acid, oxazolidinone, lactone, alcohol, sulfoxide, sulfoximine, isocyanate, or epoxide functionality. Binding constants were determined to investigate the binding behavior of 1.     

Three‐center Coulomb repulsion integrals with Slater functions

The translation method for products of two Slater functions is improved and combined with the short–long range separation in order to develop a robust and efficient algorithm for the evaluation of three‐center Coulomb integrals with Slater functions. Several tests are carried out showing that the algorithm reported here yields integrals with an absolute error below 10^?12 hartree and a computational cost of a few microseconds per integral. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Thermal conductivity of high strength polyethylene fiber in low temperature

High strength polyethylene fiber (Toyobo, Dyneema® fiber, hereinafter abbreviated to DF) used as reinforcement of fiber‐reinforced plastics for cryogenic use has a high thermal conductivity. To understand the thermal conductivity of DF, the relation between fiber structure and thermal conductivity of several kinds of polyethylene fibers having different modulus from 15 to 134 GPa (hereinafter abbreviated to DFs) was investigated. The mechanical series‐parallel model composed of crystal and amorphous was applied to DFs for thermal conductivity. This mechanical model was obtained by crystallinity and crystal orientation angle measured by solid state NMR and X‐ray. Thermal conductivity of DF in fiber direction was dominated by that of the continuous crystal region. The thermal conductivity of the continuous crystal part estimated by the mechanical model increases from 16 to 900 mw/cmK by the increasing temperature from 10 to 150K, and thermal diffusivity of the continuous crystal part was estimated to about 100 mm²/s, which is almost temperature independent. The phonon mean free path of the continuous crystal region of DF obtained by thermal diffusivity is almost temperature independent and its value about 200 Å. With the aforementioned, the mechanical series‐parallel model composed of crystal and amorphous regions could be applied to DFs for thermal conductivity. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1495–1503, 2005     

N-functionalization of chitosan with bis-O-glycosylated derivative of 2,2-bis(methylol)propionic acid

A glycosylated 2,2-bis(methylol)propionic acid (bis-MPA) derivative as a versatile glycodendritic building block was synthesized by direct O-glycosylation of benzyl protected bis-MPA with d-glucose pentaacetate. After removal of the benzyl protection group by hydrogenation, the obtained bis-O-glycosylated bis-MPA unit with free carboxyl group was applied for modification of trityl protected chitosan by amidation. The removal of the 6-O-trityl protection group on chitosan backbone under acidic conditions yields acetyl protected glycosylated chitosan that forms gel in water. The acetyl protection group of d-glucose was removed under alkaline conditions to form glycosylated chitosan which is water-soluble at physiological conditions and, thus, it is suitable for further investigation as a potential carrier in drug delivery systems.     

Synthesis and Catalytic Performance of Hierarchically Porous MIL‐100(Fe)@polyHIPE Hybrid Membranes

Metal‐organic frameworks (MOFs) nanoparticles in combination with a nonionic surfactant (Pluronic L‐121) are used to stabilize dicyclopentadiene (DCPD)‐in‐water high internal phase emulsions (HIPEs). The resulting HIPEs containing the MIL‐100(Fe) nanoparticles (MIL: Materials of Institut Lavoisier) at the interface between the oil‐ and the water‐phases are then cured, and 100 μm thick, fully open, hierarchically porous hybrid membranes are obtained. The properties of the MIL‐100(Fe)@pDCPD polyHIPE membranes are characterized and it is found that up to 14 wt% of the MIL‐100(Fe) nanoparticles are incorporated in the hybrid material resulting in an increase of the microporosity up to 130 m² g⁻¹. Hybrid membranes show an appealing catalytic activity in Friedel–Crafts alkylation in a batch mode as well as in a flow‐through mode, thereby demonstrating the preserved accessibility of Lewis acidic sites in the MOF nanostructures.

     

Bifunctional Catalysts Based on m‐Phenylene‐Bridged Porphyrin Dimer and Trimer Platforms: Synthesis of Cyclic Carbonates from Carbon Dioxide and Epoxides

Highly active bifunctional diporphyrin and triporphyrin catalysts were synthesized through Stille coupling reactions. As compared with a porphyrin monomer, both exhibited improved catalytic activities for the reaction of CO₂ with epoxides to form cyclic carbonates, because of the multiple catalytic sites which cooperatively activate the epoxide. Catalytic activities were carefully investigated by controlling temperature, reaction time, and catalyst loading, and very high turnover number and turnover frequency were obtained: 220 000 and 46 000 h^?1, respectively, for the magnesium catalyst, and 310 000 and 40 000 h^?1, respectively, for the zinc catalyst. Results obtained with a zinc/free‐base hybrid diporphyrin catalyst demonstrated that the Br^? ions on the adjacent porphyrin moiety also function as nucleophiles.     

Facile Synthesis of Azahelicenes and Diaza[8]circulenes through the Intramolecular Scholl Reaction

Carbazole-based aza[7]helicenes and hetero[9]helicenes were successfully obtained via the intramolecular Scholl reaction of 3,6-bis(biphenyl-2-yl)carbazole congeners, while the reaction of 3,6-bis(naphthylphenyl)-appended carbazole gave a triple helicene via an unexpected simultaneous double aryl rearrangement. DFT calculations suggested that the rearrangement proceeded via an arenium cation intermediate. In addition, the reaction of methoxy-appended substrate gave an azahepta[8]circulene via the concurrent C−C bond formation. These helical dyes showed circularly polarized luminescence. The azahepta[8]circulene was further transformed into deeply saddle-distorted dibenzodiaza[8]circulenes as the first example of its solution-based synthesis and unambiguous structural determination.     

DAMQT 2.1.0: A new version of the DAMQT package enabled with the topographical analysis of electron density and electrostatic potential in molecules

DAMQT‐2.1.0 is a new version of DAMQT package which includes topographical analysis of molecular electron density (MED) and molecular electrostatic potential (MESP), such as mapping of critical points (CPs), creating molecular graphs, and atomic basins. Mapping of CPs is assisted with algorithmic determination of Euler characteristic in order to provide a necessary condition for locating all possible CPs. Apart from the mapping of CPs and determination of molecular graphs, the construction of MESP‐based atomic basin is a new and exclusive feature introduced in DAMQT‐2.1.0. The GUI in DAMQT provides a user‐friendly interface to run the code and visualize the final outputs. MPI libraries have been implemented for all the tasks to develop the parallel version of the software. Almost linear scaling of computational time is achieved with the increasing number of processors while performing various aspects of topography. A brief discussion of molecular graph and atomic basin is provided in the current article highlighting their chemical importance. Appropriate example sets have been presented for demonstrating the functions and efficiency of the code. © 2015 Wiley Periodicals, Inc.     

An improved program for molecular calculations with B functions

An improved version of a previously reported program for molecular calculations with B functions is presented. In this version, new algorithms for the three- and four-center electron repulsion integrals are used. The mathematical aspects of the algorithms are recognized and their performance analyzed. The results on full molecular calculations confirm the higher efficiency of the new algorithms in comparison with the old ones.     

Optical pulse narrowing using a Fabry-Perot resonator

An optical pulse narrowing technique by spectral windowing using a Fabry-Perot resonator is demonstrated. A 150 ps pulse from a mode-locked Ar ion laser has been compressed by a factor of 2.7.