Small angle X-ray scattering study of an extremely elongated micelle system of CTAB-p-toluidine solution

Whenp-toluidine is added to an aqueous solution of CTAB, a remarkable increase of viscosity is accompanied by a spectacular elasticity. We detected the existence of extremely elongated rod-like micelles in electron micrographs. SAXS measurements indicate a closely packed array of cylindrical rod-like micelles, brought about when solutions flow through a thin capillary. A scattering maximum ofd=160 Å almost corresponds to the distance between the nearest neighbours of the cylindrical rod-like micelles. This value agrees with the diameter measured on electron micrographs. The second broad peak (d=75 Å) is assigned to a subsidiary maximum of the shape function of the cylinder with infinite length.     

Radical cyclocopolymerization of divinyl ether and maleic anhydride. A 13C-NMR study of the polymer structure

The structure of the 1:2 copolymer of divinyl ether and maleic anhydride was investigated by ¹³C-NMR spectroscopy. The polymer contains the bicyclic unit composed of one molecule of each monomer and the maleic anhydride unit. The carbon chemical shift for these units was calculated on the basis of the chemical shift of many model compounds. The major peaks of the cyclopolymer prepared in chloroform were consistent with the presence of the symmetrical bicyclic unit with cis junction and the trans monocyclic anhydride unit. The carbonyl carbon spectrum for the copolymer obtained in a mixed solvent of acetone and CS₂ suggested the predominant formation of the unsymmetrical bicyclic unit. The polymerization process was discussed on the basis of these results.     

Proton-block strategy for the synthesis of oligodeoxynucleotides without base protection,capping reaction,and P-N bond cleavage reaction

A new N-unprotected phosphoramidite method called the "proton-block" approach was developed for the chemical synthesis of oligodeoxynucleotides based on the hitherto simplest and rational principle of acid-base reactions. This concept involves protection of the nucleobases of deoxycytidine and deoxyadenosine with "protons" to convert them to unreactive protonated bases during condensation by use of promoters having pK(a) values lower than 2.8. This strategy was applied to the synthesis of d[CpT] and d[ApT] to check the side reactions associated with the base residues. In this "proton-block" method, 5-nitrobenzimidazolium triflate (NBT) was found to be the best promoter, and THF was superior to CH(3)CN as the solvent so that the concomitant detritylation due to the inherent acidity of the promoter could be greatly suppressed. Application of this strategy to the solid-phase synthesis gave d[CpT], d[ApT], d[ApA], d[CpC], and d[GpT] as almost single peaks in HPLC analysis. Similarly, d[ApApApT] and d[CpCpCpT] were successfully synthesized without significant side reactions. Finally, d[CpCpCpCpCpCpT] and d[ApApApApApApT] were obtained as the main products. In the case of a longer oligomer, d[CpApGpTpCpApGpTpCpApGpT], a mixed solvent of CH(3)CN-N-methylpyrrolidone (1:1, v/v) was superior to THF so that the desired oligodeoxynucleotide could be isolated in a satisfactory yield. These results suggest that DNA synthesis can be carried out simply by using the protonated bases at the oligomer level not only without base protection but also without the capping reaction and the posttreatment of branched chains with MeOH-benzimidazolium triflate that previously was requisite. It is concluded that most of the reactions and solvent effects involved in this strategy can be explained in terms of simple acid-base reactions. Some problems associated with the previous posttreatment are also discussed with our own results.     

Third- and fourth-order perturbation corrections to excitation energies from configuration interaction singles

Complete third-order and partial fourth-order Rayleigh-Schrodinger perturbation corrections to excitation energies from configuration interaction singles (CIS) have been derived and termed CIS(3) and CIS(4)(P). They have been implemented by the automated system TENSOR CONTRACTION ENGINE into parallel-execution programs taking advantage of spin, spatial, and index permutation symmetries and applicable to closed- and open-shell molecules. The consistent use of factorization, first introduced by Head-Gordon et al. in the second-order correction to CIS denoted CIS(D), has reduced the computational cost of CIS(3) and CIS(4)(P) from O(n(8)) and O(n(6)) to O(n(6)) and O(n(5)), respectively, with n being the number of orbitals. It has also guaranteed the size extensivity of excited-state energies of these methods, which are in turn the sum of size-intensive excitation energies and the ground-state energies from the standard M?ller-Plesset perturbation theory at the respective orders. The series CIS(D), CIS(3), and CIS(4)(P) are usually monotonically convergent at values close to the accurate results predicted by coupled-cluster singles and doubles (CCSD) with a small fraction of computational costs of CCSD for predominantly singly excited states characterized by a 90%-100% overlap between the CIS and CCSD wave functions. When the overlap is smaller, the perturbation theory is incapable of adequately accounting for the mixing of the CIS states through higher-than-singles sectors of the Hamiltonian matrix, resulting in wildly oscillating series with often very large errors in CIS(4)(P). Hence, CIS(3) and CIS(4)(P) have a rather small radius of convergence and a limited range of applicability, but within that range they can be an inexpensive alternative to CCSD.     

Radiation-induced copolymerizations of perfluorovinyl acetic acid and its methyl ester with α-olefin

Homopolymerizations and copolymerizations of perfluorovinyl acetic acid (FVA) and its methyl ester (MFVA) were carried out by γ radiation at a temperature of 25°C, a dose rate of 1 × 10⁶ rad/hr, and FVA/α-olefin and MFVA/α-olefin ratios of 10/90-90/10 in the monomer mixture. FVA and MFVA gave small quantities of brown and greasy low-molecular-weight homopolymers. The polymerization rates of both FVA and MFVA were extremely small, as shown by the maximum G value of monomer consumption of 12. FVA and MFVA reacted with α-olefin to form waxlike copolymers. The copolymerization rates of both FVA and MFVA with α-olefin were remarkably larger than those of the homopolymerizations, particularly with ethylene. The polymer compositions of FVA/ethylene or MFVA/ethylene was nearly 1/2 over a wide range of the monomer compositions. The Mayo–Lewis method gave negative r₁ (FVA) and r₁ (MFVA). The polymer composition curves could be well interpreted by introducing the penultimate model.     

Resonance Raman scattering with a forbidden but vibronically allowed electronic transition: Excitation profiles of combinations and overtones of copper tetraphenylporphyrin in the Q-band resonance

Resonance Raman scattering with the Q band of CuTPP shows a peculiar intensity pattern; bands due to combinations and overtones are strong, whereas the corresponding fundamentals are very weak. By a quantitative analysis of excitation profiles, this phenomenon has been fully accounted for on the basis of the vibronic theory of Raman intensities. Vibronic coupling parameters between the Q and B states of CuTPP have been obtained.     

Polymeric organosilicon systems. XVII. Synthesis and photochemical and conducting properties of poly[o-and m-(disilanylene)phenylene]s

Poly[o-(tetramethyldisilanylene)phenylene] ( 2a ), poly[o-(1,2-dimethyldiphenyldisilanylene)-phenylene] ( 2b ), poly[m-(tetramethyldisilanylene)phenylene] ( 2c ), and poly[m-(1,2-dimethyldiphenyldisilanylene)phenylene] ( 2d ) were prepared by the sodium condensation reaction of the corresponding 1,2-and 1,3-bis (chlorosilyl)benzenes in toluene. Irradiation of thin films of 2a-2d in air resulted in a rapid decrease of absorption maxima in the ultraviolet region. The photolysis of 2b and 2d in benzene afforded photodegradation products with low molecular weights. When thin films of 2b and 2d were doped with antimony pentafluoride vapor, films which have conductivities of semi-conductor level were obtained. © 1993 John Wiley & Sons, Inc.     

Structural assignment of n3-acylated uridine derivatives by means of 13c nmr spectroscopy

Diisopropylethylamine was effective as a base for acylation of 2′,3′,5′-tri-O-acetyluridine with various acid chlorides. The ¹³C NMR spectra of the products and related compounds showed clearly that the acyl groups intoduced to the uracil moiety are attached to the N³-nitrogen.     

Interactions of water-soluble polymers with small molecules II: Poly(2-diethylaminoethyl methacrylate)-methyl orange and its homolog systems at different temperatures

In order to investigate the interactions of poly(2-diethylaminoethyl methacrylate) (PDEAEMA) with methyl orange and its homologs in solution, temperature dependence of the complex formation has been examined in detail by the measurements of transmittance and specific conductance for the systems. Furthermore, the binding course of dyes to PDEAEMA has been studied on the basis of thermodynamic parameters obtained from equilibrium dialysis experiments at different temperatures. It was observed that the flocculation process shifted to lower dye concentrations in accordance with increasing hydrophobicity of the dyes in the order, methyl orange < ethyl orange < butyl orange, and the process of complex formation was characterized by three separate regions according to the slope of specific conductivity-mixing ratio curve for mixtures of PDEAEMA and dye. The temperature dependences of F,H and S suggest that, for dyes-PDEAEMA complex formation, the hydrophobic interaction is predominant at a low temperature but the electrostatic interaction becomes important as the temperature increases.