Excited states of phosphorescent platinum(II) complexes containing N wedge C wedge N-coordinating tridentate ligands: spectroscopic investigations and time-dependent density functional theory calculations

The absorption and emission spectra of the Pt(II) complexes containing N wedge C wedge N-coordinating tridentate ligands, platinum(II) 1,3-di(2-pyridyl)benzene chloride [Pt(dpb)Cl] and platinum(II) 3,5-di(2-pyridyl)toluene chloride [Pt(dpt)Cl], together with their corresponding free ligands, 1,3-di(2-pyridyl)benzene (dpbH) and 3,5-di(2-pyridyl)toluene (dptH), have been analyzed by density functional theory (DFT) for the ground state and time-dependent DFT (TDDFT) for the excited states. T(1)(A(1)) and S(1)(B(2)) of the complexes (in C(2)(v) symmetry) were assigned on the basis of the calculated excitation energies as well as comparison of the experimental spectroscopic properties and the calculated states' characteristics. The calculated excitation energies for T(1) and S(1) of the complexes as well as those for T(1) of the free ligands were in good agreement with their observed values within 600 cm(-1). The d-pi* characters of the excited states were evaluated from the change in electron densities between the ground and excited states by Mulliken population analysis; values of 25% for T(1) and 32% for S(1) were obtained for both complexes. The calculated values of d-pi* character were found to be consistent with the reported emission lifetimes as well as the observed emission energy shifts from the corresponding free ligands. Most spectroscopic properties of the complexes and the free ligands, which include solvatochromic shift, Stokes shifts, methyl substitution shifts, and emission spectra profiles, were well explained from the calculation results.     

2,2′-Isopropylidenebis[(4S,5R)-4,5-di(2-naphthyl)-2-oxazoline] ligand for asymmetric cyclization-carbonylation of meso-2-alkyl-2-propargylcyclohexane-1,3-diols

The oxidative cyclization-carbonylation of meso-2-alkyl-2-propargylcyclohexane-1,3-diols mediated by Pd(II) with chiral bisoxazoline (box ligand) afforded bicyclic-β-alkoxyacrylates. Based on a ligand screening, 2,2′-isopropylidenebis[(4S,5R)-4,5-di(2-naphthyl)-2-oxazoline] ligand has been developed. The products with a chiral quaternary carbon were obtained in 71-100% yields with 85-95% ee.     

Peroxotungstate immobilized on ionic liquid-modified silica as a heterogeneous epoxidation catalyst with hydrogen peroxide

Peroxotungstate immobilized on ionic liquid-modified SiO2 is capable of heterogeneously epoxidizing a wide range of olefins with the maintenance of the catalytic activity of homogeneous analogue. The epoxidation was immediately stopped by the removal of the catalyst, and no tungsten species could be found in the filtrate after the removal of the catalyst. These results can rule out any contribution to the observed catalysis from the tungsten species that leached into the reaction solution, and the observed catalysis is truly heterogeneous in nature. Furthermore, the catalyst was reusable without the loss of the catalytic performance.     

Profiling analysis of oligosaccharides in antibody pharmaceuticals by capillary electrophoresis

Carbohydrate chains in glycoprotein pharmaceuticals have important roles for the expression of their biological activities. Therefore, development of an assessment method for the carbohydrate chains is an important parameter for quality control of glycoprotein pharmaceuticals such as newly developed therapeutic antibodies. In this report, we applied capillary electrophoresis with laser-induced fluorescence detection to the analysis of carbohydrate chains after releasing with glycoamidase followed by derivatization with 3-aminobenzoic acid. We found that four major oligosaccharides present in antibody pharmaceuticals were successfully separated with good resolution. The present method showed good precision in both migration times and relative peak areas, and gave comparable accuracy with that using a derivatization method with 8-aminopyrene-1,3,6-trisulfonate.     

Temperature-dependence of mechanical and morphological properties of ultra-high molecular weight polyethylene cross-linked by electron beam irradiation

Cross-linking of ultra-high molecular weight polyethylene was performed with electron-beam irradiation in the range of radiation dose from 12 to 96 Mrad under nitrogen. Dry gel films and melt films were used as specimens. Two kinds of cross-linked specimens could be kept at 200°C for a prolonged time in an undeformed state and this tendency was independent of radiation dose. The elongation of the gel films hampered the heat-resistant effect and the drawn specimens were broken at temperatures lower than 175 °C. The elongation of the melt films could not be realized, because of a marked fixation of chains in the fiber network, even at a dose of 12 Mrad.     

Practical synthesis of a neuropeptide Y antagonist via stereoselective addition to a ketene

[Reaction: see text]. The synthesis of neuropeptide Y antagonist 1, currently under clinical investigation for the treatment of obesity, is described. The convergent synthesis from trans-spirolactone carboxylic acid intermediate 2a and aminopyrazole 3 is predicated on a stereoselective route to the former. The coupling reaction of ethyl 4-oxocyclohexanecarboxylate (10a) with lithiated isonicotinamide 11 was investigated in detail, but even optimized conditions only provided a 45:55 ratio of trans:cis isomers (12a:12b). While selective crystallization schemes were developed to isolate the thermodynamically less stable trans isomer 2a, improved stereocontrol was subsequentially achieved by the application of ketene chemistry. The ketene formation and quench was investigated under a variety of conditions aimed at maximizing the trans:cis ratio. Reacting a mixture of carboxylic acids 2a and 2b with POCl3 in THF, followed by concomitant addition of tert-butyl alcohol in the presence of TMEDA at 35 degrees C provided a 4:1 ratio of trans:cis tert-butyl esters (18a:18b) via in situ ketene formation. Ester hydrolysis, followed by selective crystallization of undesired 2b as the HCl salt, led to isolation of 2a in 47% overall yield. Aminopyrazole intermediate 3 was synthesized via the condensation reaction of 2-fluorophenylhydrazine hydrochloride (4a) with acrylonitrile derivative 5 in 65-70% yield. Coupling of advanced intermediates 2a and 3b via activation with thionyl chloride gave a 92% yield of 1.     

Ruthenium‐catalyzed fast living radical polymerization of methyl methacrylate: The R?Cl/Ru(Ind)Cl(PPh3)2/n‐Bu2NH initiating system

A fast living radical polymerization of methyl methacrylate (MMA) proceeded with the (MMA)₂? Cl/Ru(Ind)Cl(PPh₃)₂ initiating system in the presence of n‐Bu₂NH as an additive [where (MMA)₂? Cl is dimethyl 2‐chloro‐2,4,4‐trimethyl glutarate]. The polymerization reached 94% conversion in 5 h to give polymers with controlled number‐average molecular weights (M_n's) in direct proportion to the monomer conversion and narrow molecular weight distributions [MWDs; weight‐average molecular weight/number‐average molecular weight (M_w/M_n) ≤ 1.2]. A poly(methyl methacrylate) with a high molecular weight (M_n ～ 10⁵) and narrow MWD (M_w/M_n ≤ 1.2) was obtained with the system within 10 h. A similarly fast but slightly slower living radical polymerization was possible with n‐Bu₃N, whereas n‐BuNH₂ resulted in a very fast (93% conversion in 2.5 h) and uncontrolled polymerization. These added amines increased the catalytic activity through some interaction such as coordination to the ruthenium center. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 617–623, 2002; DOI 10.1002/pola.10148     

Visible light-responsive cell scaffolds with bilayer structures for single cell separation

Collagen is a major component of the extracellular matrix, and collagen gels have been used as cell scaffolds. We previously prepared gold nanoparticle (AuNP)-embedded collagen gels (AuCol) to serve as cell scaffolds that were sensitive to visible light. We performed single cell detachment from this cell scaffold using a microscope equipped with a laser irradiation system. In the present study, we adjusted hydrogel thickness and AuNP concentration in AuCol, with a goal of improving cell detachment efficiency. Thin hydrogels became blackened after the laser irradiation, and thick hydrogels with high AuNP concentrations were not permeable to the laser light. We, therefore, prepared bilayer gels, composed of AuCol as the upper layer and intact collagen gel (Col) as the bottom layer. These bilayer gels allowed more effective cell detachment, because they were thick and optically transparent. Our results indicated that an AuCol/Col ratio of 2 enabled the highest cell detachment efficiency. Essentially, no cell damage was observed in our system, suggesting that this is a cell-friendly single cell separation system.