Suppressed beta-hydride elimination in palladium-catalyzed cascade cyclization-coupling reactions: an efficient synthesis of 3-arylmethylpyrrolidines

[formula: see text] A novel type of palladium-catalyzed cascade cyclization-coupling reaction that proceeds with suppressed beta-hydride elimination has been found. One of the N-sulfonyl oxygens is suggested to coordinatively stabilize an alkylpalladium intermediate, thus preventing the intermediate from the usual beta-elimination. This is the first sequential palladium-catalyzed coupling reaction where the Suzuki and Heck reactions can compete. The reaction provides an efficient synthetic route to 4-methylene-3-arylmethylpyrrolidines, which are not readily available by other routes.     

Sequence- and site-specific photodissociation at 266 nm of protonated synthetic polypeptides containing a tryptophanyl residue

Photodissociation at 266 nm of protonated synthetic polypeptides containing a tryptophanyl residue was investigated using a homebuilt tandem time-of-flight mass spectrometer equipped with a matrix-assisted laser desorption/ionization source. Efficient photodissociation of the protonated peptides was demonstrated. Most of the intense peaks in the laser-induced tandem mass spectra were sequence ions. Furthermore, sequence ions due to cleavages at all the peptide bonds were observed; this is a feature of the technique that is particularly useful for peptide sequencing. Fragmentations at both ends of the tryptophanyl residue were especially prevalent, which can be useful for location of the tryptophanyl chromophore in a peptide.     

Osteoprotegerin is present on the membrane of osteoclasts isolated from mouse long bones

Osteoprotegerin (OPG), a member of the tumor necrosis factor receptor superfamily, is known to inhibit osteoclastogenesis by acting as a soluble decoy receptor for the receptor activator of NF-kappaB ligand (RANKL). We report the presence of OPG on the membrane of osteoclasts and the possibility of the direct action of OPG on them. Highly pure osteoclast precursors were isolated from mouse long bones and induced to differentiate into mature osteoclasts by M-CSF and soluble RANKL (sRANKL). The presence of OPG on the membrane of these cells was confirmed by western blotting and immunostaining. Furthermore, sRANKL was found to be bound to the OPG on the osteoclast precursors. These results suggest that OPG might have a new role during the differentiation of osteoclasts beyond its role as a soluble decoy receptor. The mechanism of the existence of OPG on osteoclast precursors remains to be found.     

Kinetics of the degradation of polystyrene in supercritical acetone

The kinetic analysis of the degradation of polystyrene (PS) in supercritical acetone has been studied using the nonisothermal weight loss technique with heating rates of 3, 5 and 7 °C/min. The weight loss data according to degradation temperature have been analyzed using the integral method based on Arrhenius form to obtain the kinetic parameters such as apparent activation energy and overall reaction order. The kinetic parameters obtained from this work were also compared with those of the thermal degradation of PS in nitrogen atmosphere. From this work, it was found that the activation energies of PS degradation in supercritical acetone were 73.3-200.7 kJ/mol and lower than those of the thermal degradation in nitrogen atmosphere.     

Thermally produced biodegradable scaffolds for cartilage tissue engineering

A novel process was developed to fabricate biodegradable polymer scaffolds for tissue engineering applications, without using organic solvents. Solvent residues in scaffolds fabricated by processes involving organic solvents may damage cells transplanted onto the scaffolds or tissue near the transplantation site. Poly(L-lactic acid) (PLLA) powder and NaCl particles in a mold were compressed and subsequently heated at 180 degrees C (near the PLLA melting temperature) for 3 min. The heat treatment caused the polymer particles to fuse and form a continuous matrix containing entrapped NaCl particles. After dissolving the NaCl salts, which served as a porogen, porous biodegradable PLLA scaffolds were formed. The scaffold porosity and pore size were controlled by adjusting the NaCl/PLLA weight ratio and the NaCl particle size. The characteristics of the scaffolds were compared to those of scaffolds fabricated using a conventional solvent casting/particulate leaching (SC/PL) process, in terms of pore structure, pore-size distribution, and mechanical properties. A scanning electron microscopic examination showed highly interconnected and open pore structures in the scaffolds fabricated using the thermal process, whereas the SC/PL process yielded scaffolds with less interconnected and closed pore structures. Mercury intrusion porosimetry revealed that the thermally produced scaffolds had a much more uniform distribution of pore sizes than the SC/PL process. The utility of the thermally produced scaffolds was demonstrated by engineering cartilaginous tissues in vivo. In summary, the thermal process developed in this study yields tissue-engineering scaffolds with more favorable characteristics, with respect to, freedom from organic solvents, pore structure, and size distribution than the SC/PL process. Moreover, the thermal process could also be used to fabricate scaffolds from polymers that are insoluble in organic solvents, such as poly(glycolic acid). Cartilage tissue regenerated from thermally produced PLLA scaffold.     

Effects of pH and Dye Concentration on the Optical and Structural Properties of Coumarin-4 Dye-Doped SiO2-PDMS Xerogels

Optical and structural properties of coumarin-4 dye-doped SiO₂-PDMS xerogels synthesized by acid catalyzed (one-step) and acid-base catalyzed (two-step) sol-gel routes with varying pH (0.6 to 7) and dye content ( 5 × 10^–4 to 5 × 10^–2 mole) are reported. Spectroscopic methods such as photo-luminescence, FT-IR and FT-Raman were used for characterizations. The acid catalyzed xerogels prepared with pH < 2.5 exhibited two fluorescence peaks, I at 390 nm and II at 480 nm. The acid-base catalyzed xerogels synthesized with pH < 2.5 also exhibited two peaks, I at 400 nm and II at 475 nm. Peak II was not observed for the samples with pH 2.5. This phenomenon was attributed to the existence of pH dependent different forms of coumarin-4 molecule. The concentration-quenching phenomenon was observed for the acid catalyzed xerogels prepared with different dye concentration. TheFT-IR spectra indicated the existence of hydrogen bonds between the carbonyl groups of dye molecules and the silanol groups of gel matrix. The hydrogen bonding was the highest for the samples with the extremity pH, 0.6 and 7, resulting in the highest dye/gel matrix interactions, hence, the highest fluorescence peaks. The Raman studies indicated that the samples prepared with pH < 2.5 possessed relatively more number of 3-membered siloxane rings than 4-membered siloxane rings. The ring statistics was reversed for the samples with pH > 2.5. The number of silanol groups was higher for the samples with pH > 2.5.     

An efficient synthesis of novel carbocyclic nucleosides with use of ring-closing metathesis from D-lactose

This paper describes an efficient synthetic route for various types of novel carbocyclic nucleosides. The required stereochemistry of the targeted nucleosides was successfully obtained with use of Grubbs cyclization and Trost allylic alkylation from the carbohydrate chiral template "D-lactose".     

Modular fluorescence sensors for saccharides

Modular and modular polymer supported fluorescence photoinduced electron transfer (PET) sensors 2 and 3 with two boronic acid receptor units, a pyren-1-yl fluorophore, and hexamethylene linker show selective saccharide binding in aqueous methanolic solution at pH 8.21.     

Two-Photon Excitation of 4'-Hydroxymethyl-4,5',8-Trimethylpsoralen

Abstract— Psoralens are a class of pharmaceutical agents commonly used to treat several cutaneous disorders. When irradiated with a mode-locked titanium: sapphire (Ti: sapphire) laser tuned to 730 nm, an aqueous solution of 4'-hydroxymethyl-4,5',8-trimethylpsoralen (HMT) emits blue light. The emission spectrum is centered at 452 nm and is identical to that obtained by one-photon excitation with UVA excitation, and its magnitude depends quad-ratically on the intensity of laser excitation. These results suggest that two-photon excitation occurs to a potentially photochemically active state. To estimate the two-photon absorption cross section, it was first necessary to measure the emission quantum yield of HMT using 365 nm excitation at room temperature that resulted in a value of 0.045 ± 0.007. The two-photon absorption cross section of HMT at 730 nm is therefore estimated to be 20 ± 10⁻⁵⁰ cm⁴ s (20 Göppert-Mayer). The excited-state photophysics and photochemistry of psoralens suggest potential applications to cutaneous phototherapy in diseases such as psoriasis and dystrophic epidermolysis bullosa.     

An improved method for constructing a full-length enriched cDNA library using small amounts of total RNA as a starting material

We have developed an improved method for constructing a full-length cDNA library using small quantity of material by modifying the original oligo-capping method. In our devised method, total RNAs are used in sequential oligo-capping steps directly without preliminary mRNA purification. Using this method, we constructed full- length cDNA libraries from 100 mg of total RNA. These libraries contained 8x10(5) to 8x10(6) independent clones with average insert sizes of 2.0 kb. Moreover, the number of full-length cDNAs containing the translation initiation codon ATG in the constructed libraries was estimated to 60-70%. In addition, 54% of the known cDNAs had a longer 5' end than the corresponding genes in the public database. Our results show that the method can be effectively used to construct full-length enriched cDNA libraries, especially, if starting material is limited.