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.     

Stereocontrolled approaches to 9(0)-methanoprostacyclin

A stable PGI₂ analog (methanoprostacyclin $\text{2}$) was synthesized starting from 5-norbornene-2,3-dicarboxylic anhydride.     

Crystal and molecular structure of 6-0-acetylgrayanotoxin III

The crystal and molecular structure of a grayanotoxin III derivative, 6-0-acetylgrayanotoxin III is presented. The crystal is orthorhombic, space group P2₁2₁2₁, witha=15.582(3),b=21.304(3),c=6.339(3)Å,V=2104(1) ų Z=4. The structure was solved by direct methods and refined by full matrix least-squares methods to a finalR=0.047 for 1763 independent reflections withF ₀>3 (F ₀) The molecule is based on a tetracyclic structure consisting of two five-membered, one six-membered, and one seven-membered ring with various conformations.     

Hydration of short-chain poly(oxyethylene) in carbon tetrachloride: an infrared spectroscopic study

Hydration of short-chain poly(oxyethylene)s, CH(3)(OCH(2)CH(2))(m)OCH(3) (abbreviated as C(1)E(m)()C(1)) (m = 1-3), in carbon tetrachloride has been studied by infrared spectroscopy. The O-H stretching vibrations of water in ternary solutions with H(2)O:C(1)E(m)C(1):CCl(4) mole ratios of 0.000418:0.005:0.995 to 0.000403:0.04:0.96 were analyzed. Two types of hydrogen bonds are formed in the interaction between water and C(1)E(m)C(1) in carbon tetrachloride; one is a monodentate hydrogen bond, in which only one of the O-H bonds of a water molecule participates in hydrogen bonding, and the other is a bidentate hydrogen bond, in which both of the O-H bonds of a water molecule participate in hydrogen bonding by bridging oxygen atoms separated by two or more monomer units on the polymer chain. An important finding is that the bidentate hydrogen-bond bridge is not formed between the nearest-neighbor oxygen atoms. This experimental observation supports the results of previous molecular dynamics simulations. The shortest oligomer of poly(oxyethylene), i.e., CH(3)OCH(2)CH(2)OCH(3) (1,2-dimethoxyethane) with a single monomer unit, is suggested not to be an adequate model for this polymer with respect to hydrogen bonding to water. The hydrogen bonding in a 1:1 C(1)E(m)C(1)-water adduct in carbon tetrachloride represents primitive incipient hydration of poly(oxyethylene). The present results indicate that both monodentate and bidentate hydrogen bonds are important and the latter is destabilized more rapidly than the former with increasing temperature. This dehydration process can be a potential mechanism of the poly(oxyethylene)-water phase separation.     

Effects of Bis(aromatic) Pendants on Recognition of Nucleobase Thymine by Zn2+ -1,4,7,10-tetraazacyclododecane (Zn2+ -cyclen)

We have previously shown that the nucleobase thymine binding to Zn²⁺ -cyclen (cyclen=1,4,7,10-tetraazacyclododecane) complex became stronger by appending acridine, naphthalene, or quinoline rings to the cyclen. Amongst these, the pendant bis((1-naphthyl)methyl) or bis((4-quinolyl)methyl) groups yielded the most effective thymine-recognizing Zn²⁺ -cyclen complexes [J. Am. Chem. Soc., 121 (1999) 5426]. The present study was undertaken to find causes of the bis(aromatic) ring effect by X-ray crystal structure analysis and NMR studies. The crystal structure of the Zn²⁺ -bis((1-naphthyl)methyl)-cyclen complex with a deprotonated 1-methylthymine (1-MeT) failed to show the anticipated evidence for the double ~ - ~ stacking interactions between the two naphthalenes and the Zn 2+ -bound 1-MeT m (1-MeT m =N(3')-deprotonated 1-MeT). Crystal data: formula C₃₆ H₄₇ N₇ O₇ Zn, M r =755.19, monoclinic, space group P2₁/ c (No. 14), a =15.438(2) Å, b =14.093(3) Å, c =16.726(2) Å, g =90.53(1) V =3638.7(8) Å 3 Z =4, R =0.035, R _w =0.049. However, the ¹H NMR studies of Zn²⁼ -bis((4-quinolyl)methyl)-cyclen with 1-MeT in varying H₂O/CH₃ CN solution showed increasing upfield shifts of Me(5') and H(6') of the Zn²⁺ -bound 1-MeT in more aqueous media, indicating that the double intercalation with the two quinolines became more significant in more protic environments. We conclude that the double ~ - ~ stacking effect accounts for the enhanced recognition of thymine base by the appended bis((1-naphthyl)methyl) or bis((4-quinolinyl)methyl) groups.     

Conformation and Atropisomeric Properties of Indometacin Derivatives

The stereochemistry around the N‐benzoylated indole moiety of indometacin was studied by restricting the rotation about the N? C7′ and/or C7′? C1′ bond. In the 2′,6′‐disubstituted ones, an atropisomeric property was found and the atropoisomers were separated and isolated as stable forms. Their biological abilities to inhibit cyclooxygenase‐1 (COX‐1) and cyclooxygenase‐2 (COX‐2) were examined. Only the aR‐isomer showed specific inhibition of COX‐1, and COX‐2 was not inhibited by either atropisomer. Conformational analysis in NMR studies and X‐ray crystallography, and CD spectra in combination with calculations were utilized to elucidate the bioactive conformations.     

Infrared spectroscopic study of molecular interaction of tacticity-controlled poly(N-isopropylacrylamide) in a cast film deposited on a solid substrate

Analytical results of a series of poly(N-isopropylacrylamide) (PNiPA) with different tacticities using infrared spectroscopy are presented for studying the influence of the solvation and molecular interactions between the polymeric chains. Infrared spectra of solid matter samples of the compounds exhibit a systematic band intensity change for three band components at 1,680, 1,659, and 1,628 cm⁻¹ involved in the amide I band. The three components correspond to the free, half, and full hydrogen bondings of the secondary amide group, which reflect the molecular configuration depending on the tacticity. When cast films of the compounds prepared on a solid surface are analyzed by infrared transmission spectrometry, another factor of the solvent used for the film preparation is found to be another factor which plays an important role in determining the molecular architecture in the films. This molecular imprint mechanism after the solvation is confirmed by measuring infrared multiple-angle incidence resolution spectra of annealed films. The molecular interactions in the polymeric samples have been revealed by the use of infrared spectroscopy and the tacticity-controlled samples.     

Blue shift of the isolated CD stretching band of CH2DOH in water induced by changes in the hydrogen-bonding pattern

The wavenumber shift in the CD stretching (ν(CD)) band of the monodeuterated methanol (CH(2)DOH) has been monitored in water-methanol mixtures. For the pure liquid, two dominant bands are observed at 2148 and 2176 cm(-1) in the ν(CD) region. The matrix isolation technique and spectral simulation based on quantum chemical calculations have revealed that these two bands are categorized into the C(1) mode and originate from methanol molecules participating in different hydrogen(H)-bonding patterns. The simulation results for methanol clusters have suggested that the 2148 cm(-1) band is concerned with the end-donor species in the H-bonding network. The relative intensity of the band near 2148 cm(-1) decreases with increasing water concentration, indicating that the population of the end-donor species decreases by the addition of water. This spectral change causes the blue shift in the mean center of the ν(CD) band of CH(2)DOH in water.     

Thermoreversible gelation of isotactic-rich poly(N-isopropylacrylamide) in water

We report the experimentally determined phase diagram for an aqueous solution of isotactic-rich poly(N-isopropylacrylamide) (PNiPAM) composed of the sol-gel transition curve and the cloud-point curve. The meso diad content of isotactic-rich PNiPAM is 64%, and it is soluble in water at low temperatures, but undergoes a sol-to-gel transition with increasing temperature in the investigated concentration range of 1.8 wt. %-6.0 wt. %. With a further increase in temperature, the system becomes turbid. The gel formation and clouding behavior are thermally reversible. This is the first observation of thermoreversible gelation under the cloud-point temperature for an aqueous solution of PNiPAM. On the basis of the determined phase diagram, we carried out light scattering experiments to characterize the sol-gel transition behavior as a function of temperature.