The hydrogen bonding and amino-imino tautomerization of the alkoxy-aminopyridines and amino-methoxypyrimidines with acetic acid The effects of the methoxy group

The hydrogen bonding and amino-imino tautomerization of the systems of 2-amino-3-methoxypyridine (2A3MOP), 2-amino-6-methoxypyridine (2A6MOP), 2-amino-6-n-propoxypyridine (2A6NPOP), 2-amino-6-iso-propoxypyridine(2A6IPOP), 2-amino-4-methoxypyrimidine (2A4MOPM), 4-amino-2-methoxypyrimidine (4A2OPM), 4-amino-6-methoxypyrimidine (4A6MOPM), 2-amino-4-methoxy-6-methylpyrimidine (MMPM), and 2-amino-4,6-dimethoxypyrimidine (DMOPM), with acetic acid (AcOH) in n-hexane at room temperature were investigated by means of the UV absorption and fluorescence spectroscopy. From the UV absorption spectra the presence of the dual hydrogen-bonded complexes that linked by a 1:1 molar ratio with AcOH were found, since the enthalpy changes accompanying the hydrogen bond formation between 2A3MOP, 2A4MOPM, 4A2MOPM, 4A6MOPM, or MMPM, and AcOH were ca. 42.8-61.1kJmol(-1) in n-hexane. The fluorescence spectra of the 2A3MOP/AcOH, 2A4MOPM/AcOH, 4A6MOPM/AcOH, and MMPM/ AcOH systems revealed that the imino-tautomers were produced through double proton transfer in the amino hydrogen-bonded 1:1 complexes in the S1 state, but the imino-tautomer formation for the 4A2MOPM/AcOH system was not found on account of the steric hindrance due to the inversion of the methoxy group in the S1 state. The imino-tautomer for the MMPM/AcOH system fluoresces most intensely among these systems investigated. On the other hand, not only the formation of the corresponding amino dual hydrogen-bonded complex and but also that of imino-tautomer were prevented for the 2A6MOP/AcOH, 2A6NPOPM/AcOH, 2A6IPOP/AcOH, and DMOPM/AcOH systems, because of the steric hindrance of the methoxy group in both the S0 and S1 states. The theoretical approaches by an ab initio molecular orbital calculation were in accord with the experimental results.     

Lengths of chains of minimal rational curves on Fano manifolds

In this paper, we consider a natural question how many minimal rational curves are needed to join two general points on a Fano manifold X of Picard number 1. In particular, we study the minimal length of such chains in the cases where the dimension of X is at most 5, the coindex of X is at most 3 and X equips with a structure of a double cover. As an application, we give a better bound on the degree of Fano 5-folds of Picard number 1.     

A Novel Route for Fabricating Metal‐Polymer Composite Nanoparticles with Phase‐Separated Structures

Au nanoparticles (NPs) and polymer composite particles with phase‐separation structures were prepared based on phase separation structures. Au NPs were successfully synthesized in amphiphilic block‐copolymer micelles, and then composite particles were formed by a simple solvent evaporation process from Au NPs and polymer solution. The phase separated structures (Janus and Core‐shell) were controlled by changing the combination of polymers having differing hydrophobicity.

     

Phase Transition and Phase Transformation in Block Copolymer Nanoparticles

Block copolymer nanopaticles were prepared from the mixture solutions containing good/poor solvents by a simple evaporation process. The block copolymers formed disorder, unidirectionally stacked lamellar, and onion‐like structures in nanoparticles depending on preparation temperatures. Thermal annealing induced the disorder‐order phase transition and order‐order phase transformation in the block copolymer nanoparticles, even though the annealing temperature is lower than the of one polymer segment. The unusual thermal behaviors suggest that the glass transition temperature of the block copolymer is decreased by the effect of nanoparticle, whose surface areas are larger than their volumes.

     

Photoresist materials comprising photobase generators and epoxy resins bearing carboxylic acids to lead to marked enhancement of base‐catalyzed cross‐linking reactions

Most of the photopatterning materials based on epoxy resins utilize photoacid generators (PAGs), which generate superacids as catalysts. They have been used for high aspect ratio photoresists in the fabrication of MEMS devices. However, there is a drawback, in that the acidic species from PAGs will induce metal corrosion. One of the approaches to overcome this problem is the use of photobase generators (PBGs) because organic bases would induce no corrosion. Although there have been many previous investigations of PBGs, only a few articles have mentioned photoreactive materials relying on PBGs because of their low photosensitivity. We report here highly sensitive photopatterning materials comprising PBGs and an epoxy resin bearing carboxylic acid groups. As a result, the photopatterning materials showed higher photosensitivity than conventional epoxy resin systems. We obtained high‐photosensitivity (up to 900 mJ/cm²), high‐resolution (10‐μm line‐and‐space) patterning materials in films, 10 μm in thickness.     

Synthesis and Ni(0)-catalyzed oligomerization of isomeric 4,4‴-dichloroquaterphenyls

4,4?-Dichloro-1,1′ : 2′,1″ : 2″,1?-quaterphenyl ( 9 ), 4,4?-dichloro-1,1′ : 3′,1″ : 3″,1?-quaterphenyl ( 10 ), and 4,4?-dichloro-1,1′ : 4′,1″ : 4″,1?-quaterphenyl ( 11 ) were synthesized by Pd (0) catalyzed cross-coupling reaction of 4-chlorobenzeneboronic acid with 2,2′-, 3,3′-, and 4,4′-bis (trifluoromethanesulfonyloxy)biphenyl respectively. 4,4?-Dichloro-1,1′ : 2′,1″ : 2″,1?-quaterphenyl ( 9 ) and 4,4?-dichloro-1,1′ : 3′,1″ : 3″,1?-quaterphenyl ( 10 ) were oligomerized by Ni(0) catalyzed homocoupling reaction to yield white and soluble oligophenylenes. © 1993 John Wiley & Sons, Inc.     

Initiation and termination mechanism in the cooligomerization of the styrene–methyl methacrylate–carbon tetrachloride system

The analysis of the endgroups of the oligomers produced in the styrene (A)–CCl₄(S) system (system I), the methyl methacrylate(B)–CCl₄ system (system II), and the styrene–methyl methacrylate–CCl₄ system (system III) was carried out in order to clarify the mechanism of the initiation, transfer, and termination. In system I, the number of Cl atoms per oligomer molecule N_Cl increases with the molar ratio of [S]/[A] when the molar ratio of [S]/[A] is below unity and is about four when the molar ratio of [S]/[A] is above unity, and the number of initiator fragments per oligomer molecule N_I decreases with the increase in the molar ratio of [S]/[A]. In system II, N_Cl is about 0.45 over a considerably wide range of the molar ratio of [S]/[B]. In system III, N_Cl increases and N_I decreases with the increase in the molar ratios of [S]/([A] + [B]) and [A]/[B]. From the data of N_Cl and N_I, the fraction I_CC14 of the initiation by the tri-chloromethyl radical in the overall initiation reactions and the fraction T_CC14 of the chain transfer reaction of the growing radical of styrene in all the reactions which produce the cooligomer in the system III were calculated. I_CCl3 and T_CC14 both increase with the molar ratios [S]/([A] + [B]) and [A]/[B].     

Synthesis of aromatic polyethers by Scholl reaction. V. Synthesis and polymerization of 1,3-bis[4-(1-naphthoxy) benzoyl]benzene, 1,4-bis[4-(1-naphthoxy)benzoyl]benzene,bis[4-(1-naphthoxy)phenyl]methane, 1,3-bis[4-(1-naphthoxy) phenylmethyl]benzene,and 1,4-bis-[4-(1-naphthoxy)phenylmethyl]benzene

This article describes the synthesis and the cation-radical polymerization (Scholl reaction) of 1,3-bis[4-(1-naphthoxy) benzoyl] benzene ( 6 ) and 1,4-bis[4-(1-naphthoxy) benzoyl]- benzene ( 7 ) initiated by FeCI₃. This polymerization produced poly(ether ether ketone ketone)s (PEEKK) of number average molecular weight (M?_n) up to 5400 g/mol. The synthesis of bis[4-(1-naphthoxy) phenyl] methane ( 8 ), 1,3-bis[4-(1-napthoxy) phenylmethyl] benzene ( 9 ), and 1,4-bis[4-(1-naphthoxy) phenylmethyl] benzene ( 10 ) are also described. Polyethers of M?_n up to 15400 g/mol at a FeCl₃/monomer molar ratio of 2/1 were obtained. An increased polymerizability of the monomers 9 and 10 containing two CH₂ groups versus that of the corresponding monomers containing two carbonyl groups ( 6 and 7 ) was observed. This enhanced polymerizability was explained based on the increased nucleophilicity of monomers 9 and 10 .     

Fano 5-folds with nef tangent bundles and Picard numbers greater than one

We prove that smooth Fano 5-folds with nef tangent bundles and Picard numbers greater than one are rational homogeneous manifolds.