Direct one-pot introduction of 2-methylpyridines to Baylis-Hillman adducts via base-mediated 3-aza-Cope rearrangement

An efficient and regioselective introduction method of 2-methylpyridines to the secondary position of Baylis-Hillman adducts has been developed. A base treatment of 2-methylpyridinium salt of Baylis-Hillman bromide generated N-allylenamine intermediate which underwent a facile 3-aza-Cope rearrangement under mild conditions to produce the product.     

Compatibilizing effects for improving mechanical properties of biodegradable poly (lactic acid) and polycarbonate blends

Mechanical, morphological and rheological properties of polycarbonate (PC) and poly (lactic acid) (PLA) blends with compatibilizers have been investigated. Three types of compatibilizers were used: poly(styrene-g-acrylonitrile)-maleic anhydride (SAN-g-MAH), poly(ethylene-co-octene) rubber-maleic anhydride (EOR-MAH) and poly(ethylene-co-glycidyl methacrylate) (EGMA). The maximum value of the mechanical properties such as impact and tensile strengths of the PC/PLA (70/30, wt%) blend before or after hydrolysis was observed when the SAN-g-MAH was used as a compatibilizer at the amount of 5 phr. From the interfacial tension between PC and PLA which was determined from the weighted relaxation spectra using Palierne emulsion model, minimum value of interfacial tension (0.08 mN/m) was observed when the SAN-g-MAH (5 phr) was used. From the morphological studies of the PC/PLA (70/30) blends, the PLA droplet size showed minimum (0.19 μm) at the 5.0 phr SAN-g-MAH. From the results of mechanical, morphological and rheological properties of the PC/PLA (70/30) blend, it is suggested that the SAN-g-MAH is the most effective compatibilizer to improve the mechanical strength of the PC/PLA (70/30) blends among the compatibilizers used in this study, especially at the amount of 5 phr.     

Investigation of the evaporation of rare earth chlorides in a LiCl–KCl molten salt

Uranium dendrites which were deposited at a solid cathode of an electrorefiner contained a certain amount of salts. These salts should be removed for the recovery of pure metal using a cathode processor. In the uranium deposits from the electrorefining process, there are actinide chlorides and rare earth chlorides in addition to uranium chloride in the LiCl–KCl eutectic salt. The evaporation behaviors of the actinides and rare earth chlorides in the salts should be investigated for the removal of salts in the deposits. Experiments on the salt evaporation of rare earth chlorides in a LiCl–KCl eutectic salt were carried out. Though the vapor pressures of the rare earth chlorides were lower than those of the LiCl and KCl, the rare earth chlorides were co-evaporized with the LiCl–KCl eutectic salt. The Hertz–Langmuir relation was applied for this evaporation, and also the evaporation rates of the salt were obtained. The co-evaporation of the rare earth chlorides and LiCl–KCl eutectic were also discussed.     

Noncovalent endo-binding of fullerenes to diprotonated bisporphyrins

Noncovalent binding of fullerenes to bisporphyrins was studied in the gas phase by energy-dependent collision-induced dissociation (CID) with Xe under single-collision conditions. The electrospray ionization mass spectra of calix[4]arene-linked bisporphyrins show that bisporphyrins take up to 3-4 protons, depending on the type of meso-substituents. Of the protonated bisporphyrins, the diprotonated species form stable 1:1 complexes with fullerenes (C(60) and C(70)). CID cracking patterns of the diprotonated bisporphyrins indicate that each monomeric porphyrin moiety is singly protonated. CID yield-energy curves obtained from the 1:1 diprotonated bisporphyrin-fullerene complexes suggest that a fullerene occupies the endo-binding site intercalated between the two singly protonated porphyrin moieties. In the cases of 1:2 diprotonated bisporphyrin-fullerene complexes, CID results show that one fullerene binds inside (endo-binding) and the other outside (exo-binding). The exo-binding mode is energetically almost identical to the binding of fullerenes to singly protonated porphyrin monomers. The endo-binding energy is at least twice the exo-binding energy. To gain insights into the binding mode, we optimized structures of diprotonated bisporphyrins and their 1:1 endo-complexes with fullerenes, and calculated the endo-binding energy for C(60), C(70) (end-on), and C(70) (side-on). The endo-binding of fullerenes to diprotonated bisporphyrins nearly doubles the π-π interactions while reducing the electrostatic repulsion between the two singly protonated porphyrin moieties. The side-on binding of C(70) is favored over the end-on binding because the former exerts less steric strain to the lower rim of calixarene.     

Magnetic field induced aggregation of nanoparticles for sensitive molecular detection

A molecular detection method utilizing the magnetically induced aggregation of silver nanoparticle (NP)-embedded silica NPs for SERS activation is described. Here, silver embedded magnetic NPs (Ag-M-dots) composed of a magnetic core and silica shells, on whose surface silver NPs were formed, were used. Because the magnetic field induced aggregated Ag-M-dots exhibit a strong SERS signal compared to the dispersed Ag-M-dots, the system allows for the detection of adsorbed Raman label compound even at the 100 fM level. Adenine was tested as a model biocompound and its Raman spectrum could be observed at concentrations as low as 1 pM. The experimental results were supported by the theoretical calculations.     

Photofragmentation in selected tautomers of protonated adenine

The photofragmentation by UV excitation of selectively prepared 1(+) and 3(+) tautomers of protonated adenine is studied after excitation at a 266 and 263 nm wavelengths with two different experimental set-ups located in Seoul and Orsay. While the production of 1(+) tautomers with an electrospray ion source is now well accepted, calculations were used to ascribe the preparation of 3(+) tautomers from cold adenine dimers. The fragmentation patterns are rather similar for both tautomers, suggesting similar mechanisms as a statistical fragmentation in the ground electronic state after internal conversion.     

The origin of dips for the graphene-based DNA sequencing device

We recently proposed an ultrafast DNA sequencing method that electrically distinguishes different nucleobases on a graphene nanoribbon (GNR), utilizing π-π interaction. Analyzing the molecular orbitals (MOs) and the features of dips in conductance for our GNR-based sequencing device, we prove that the Fano resonance is responsible for the characteristic dips of each nucleobase.