Spontaneous Vesicle Formation in Aqueous Mixtures of Cationic Surfactants and Partially Hydrolyzed Polyacrylamide

Spontaneous vesicle formation was observed in aqueous mixtures of partially hydrolyzed polyacrylamide and single-tailed cationic surfactants. The influences of pH, addition of long-chain alcohols, variation of hydrocarbon chain length, and head group size of the cationic surfactants were investigated systematically. It was found that 30-50% hydrolyzed degree of polyacrylamide and cationic surfactants with 10 or 12 methylene groups are suitable for vesicle formation in the mixed aqueous systems at pH 9.2. Addition of long-chain alcohols was found to be helpful for vesicle formation in some cases. The vesicle stability was also investigated at various temperatures and amounts of ethanol addition. Copyright 2001 Academic Press.     

Two novel dicoumaro-p-menthanes from Gerbera piloselloides (L.) CASS

Two new type dicoumarins (dicoumaro-p-menthanes), named dibothrioclinins I (1) and II (2) were isolated from the roots and rhizomes of Gerbera piloselloides (L.) CASS., collected in Yunnan Province, China. Their structures were elucidated on the basis of MS, 1D ((1)H-NMR, (13)C-NMR, DEPT and NOE) and 2D ((1)H-(1)H COSY, HMQC, HMBC) NMR spectral analyses. The relative structures of the two compounds were established by NOE difference spectroscopy and further confirmed by single-crystal X-ray diffraction studies.     

Calculations on the octupolar molecules with enhanced two-photon absorption cross sections based on the Zn (II) and Cu (I) as centers

The equilibrium geometries, electronic structures, as well as one- and two-photon absorption cross sections of a series of octupolar chromophores with Zn(2+) or Cu(+) as coordinate centers and 4,4'-bis(dibutylaminostyryl)-[2,2']-bis(bipyridyl) as ligands have been determined by using B3LYP/6-31G and ZINDO methods. These molecules are designed by controlled combination of two or three bipyridyl ligands with the metal centers. The results show that Zn(2+) is an effective template for the design of octupolar structures which enable it to form tetrahedral and octahedral coordinated complexes; while Cu(+) only exists in a tetrahedral coordinated complex, comparing the tetrahedral complex with Zn(2+) as the center with that of Cu(+) as the center, it is found that the complex with the Cu(+) center is a better two-photon absorption material than the former as far as the transparency/nonlinearity is concerned. Furthermore, for the same metal center of Zn(2+), both one- and two-photon absorptions of the tetrahedral complex are redshifted relative to those of the octahedral complex, is attributed to the spiroconjugation effect in the tetrahedral complex. Our theoretical findings are consistent with recent experimental observations and provide an important foundation for the design of improved transparency-nonlinearity two-photon absorption materials.     

Synthesis of substituted carbazoles by a vinylic to aryl palladium migration involving domino C-H activation processes

Substituted carbazoles are readily prepared in good yields by the palladium-catalyzed cross-coupling of alkynes and N-(3-iodophenyl)anilines. This process proceeds by carbopalladation of the alkyne, heteroatom-directed vinylic to aryl palladium migration, and ring closure involving two consecutive C-H activation processes. The process has also been expanded to the synthesis of an indole. [Structure: see text]     

Rheological properties of the aqueous mixtures of cationic-anionic surfactants

The rheological properties of the aqueous mixtures of cationic-anionic surfactants, both in single-phase systems and in aqueous two-phase systems, have been studied. Bizarre rheological properties —negative thixotropy, viscoelasticity and hihg viscosity of shear rate dependent at relatively low concentration — have been observed. An unusual viscosity change, that is, viscosity lowering with increasing concentration, was obtained. The negative thixotropy might be due to the existence of lamellar or sheet-like micelles, viscoelasticity might be induced by rodlike and lamellar or sheet-like micelles, the high viscosity might be a consequence of the formation of network by long rodlike micelles and the concentration-induced viscosity lowering could be interpreted in terms of the decrease of micellar dimensions with concentration.     

Trypsin activity assay in substrate-specific one- and two-dimensional gels: a powerful method to separate and characterize novel proteases in active form in biological samples

To separate and identify the proteases, a substrate-specific, sensitive assay in sodium dodecyl sulfate (SDS)-polyacrylamide gels after two-dimensional (2-D) electrophoresis has been developed. This method allows simultaneous determination of protease cleavage specificity, molecular weight, isoelectric point, and if necessary, amino acid sequencing. After isoelectric focusing in immobilized pH gradient (IPG) strips (pH 6-11) (first dimension), trypsin was electrophoresed in 12% SDS polyacrylamide gels (second dimension) copolymerized with Boc-Gln-Ala-Arg-MCA (4-methyl-coumaryl-7-amide). The gels were washed in cold 2.5% Triton X-100 and water, and incubated in assay buffer (6.3 mM Bicine, 100 mM NaCl). Trypsin cleavage of the peptide-MCA generated fluorescent 7-amino-4-methyl-coumarin. In 1-D gels, as low as 500 pg trypsin could be detected and trypsin band volumes correlated linearly with the amounts of trypsin (R(2) = 0.999). In 2-D gels, the lowest amount of trypsin detected was 1 ng. The linear regression of spot volume and loading amount was still good (R(2) = 0.974). To optimize renaturation conditions, 5x5 min washes with 2.5% Triton X-100 and water, respectively, gave the strongest band volume. For fluorescence development, an assay buffer at pH 9 was the best; incubation at 37 degrees C for 30 min was sufficient. The method has application for identifying novel proteases as it does not rely on antibodies.     

Baylis-Hillman reactions of N-tosyl aldimines and aryl aldehydes with 3-methylpenta-3,4-dien-2-one

The attempted Baylis-Hillman reactions of N-tosyl aldimines and aryl aldehydes with 3-methylpenta-3,4-dien-2-one gave the corresponding Baylis-Hillman adducts 3 and 6 in moderate to good yields in the presence of DMAP in DMSO, respectively. In the case of the aza-Baylis-Hillman reactions of N-tosyl aldimines with 3-methylpenta-3,4-dien-2-one catalyzed by PBu3, the corresponding aza-Baylis-Hillman derivatives 4 and 5 were formed at the same time.     

Immunosuppressive ent‐Kaurene Diterpenoids from Isodon serra

Three new enmein‐type ent‐kaurenoids, i.e., the two pairs 1 and 2 of 20‐epimers and the (20R)‐isomer 3 , besides the seven known diterpenoids 4 – 10 , were isolated from the aerial parts of Isodon serra. Their structures were elucidated by spectroscopic techniques and X‐ray diffraction. The immunosuppressive effect for T‐lymphocytes proliferation induced by Con A in BALB/c mouse was evaluated for the isolates 1 – 10 . They all displayed a remarkable inhibitory effect, with multi‐glycosides of Tripterygium wilfordii as positive reference substance (Table 3).     

Influences of hydration force and elastic strain energy on the stability of solid film in a very thin solid-on-liquid structure

Since hydration forces become very strong at short range and are particularly important for determining the magnitude of the adhesion between two surfaces or interaction energy, the influences of the hydration force and elastic strain energy due to hydration-induced layering of liquid molecules close to a solid film surface on the stability of a solid film in a solid-on-liquid (SOL) nanostructure are studied in this paper. The liquid of this thin SOL structure is a kind of water solution. Since the surface forces play an important role in the structure, the total free energy change of SOL structures consists of the changes in the bulk elastic energy within the solid film, the surface energy at the solid-liquid interface and the solid-air interface, and highly nonlinear volumetric component associated with interfacial forces. The critical wavelength of one-dimensional undulation, the critical thickness of the solid film, and the critical thickness of the liquid layer are studied, and the stability regions of the solid film have been determined. Emphasis is placed on calculation of critical values, which are the basis of analyzing the stability of the very thin solid film.     

Homolytic C-H and N-H bond dissociation energies of strained organic compounds

High-level computations at G3, CBS-Q, and G3B3 levels were conducted, and good-quality C-H and N-H bond dissociation energies (BDEs) were obtained for a variety of saturated and unsaturated strained hydrocarbons and amines for the first time. From detailed NBO analyses, we found that the C-H BDEs of hydrocarbons are determined mainly by the hybridization of the parent compound, the hybridization of the radical, and the extent of spin delocalization of the radical. The ring strain has a significant effect on the C-H BDE because it forces the parent compound and radical to adopt certain undesirable hybridization. A structure-activity relationship equation (i.e., BDE (C-H) = 61.1-227.8 (p(parent)% - 0.75)(2) + 152.9 (p(radical)% - 1.00)(2) + 40.4 spin) was established, and it can predict the C-H BDEs of a variety of saturated and unsaturated strained hydrocarbons fairly well. For the C-H BDEs associated with the bridgehead carbons of the highly rigid strained compounds, we found that the strength of the C-H bond can also be predicted from the H-C-C bond angles of the bridgehead carbon. Finally, we found that N-H BDEs show less dependence on the ring strain than C-H BDEs.