Colloidal crystallization of thermo-sensitive gel spheres of poly (N-isopropyl acrylamide). Influence of degree of cross-linking of the gels

Morphology, phase diagram, and reflection spectroscopy of the colloidal crystals of thermo-sensitive gel spheres, poly (N-isopropylacrylamide) having degrees of cross-linking 10 and 2?mol.% (pNIPAm(200?C10) and pNIPAm(200?C2)) were studied. Giant colloidal single crystals formed at very low gel concentrations. Critical concentrations of melting increased as the degree of cross-linking decreased in the range from 10 to 0.5?mol.% and/or suspension temperature increased from 20 to 45?°C. The critical concentration decreased sharply as the suspensions were deionized with coexistence of the mixtures of cation- and anion-exchange resins. Density of a gel sphere (gel concentration in weight percent divided by that in volume percent) increased sharply as the degree of cross-linking and/or temperature increased. These results demonstrated that the colloidal crystallization takes place by the extended electrical double layers formed around the gel spheres in addition of the excluded-volume effect of the gels. Most of the researchers including the authors have believed that the crystallization of the gel spheres takes place by the excluded-volume effect. However, the present work clarified that the colloidal interfaces, which are inevitable for the formation of the electrical double layers, are formed firmly between the water phase and gel spheres, though the gel spheres contain a lot of water molecules in the sphere region.     

A photochromic ATP analogue driving a motor protein with reversible light-controlled motility: controlling velocity and binding manner of a kinesin-microtubule system in an in vitro motility assay

We synthesized two photochromic ATP analogues (ATP-Azos) featuring azobenzene derivatives tethered at the 2' position of the ribose ring. In the presence of the ATP-Azo tethering p-tert-butylazobenzene, we observed reversible photo-control of the motility, velocity and binding manner, of a kinesin-microtubule system in an in vitro motility assay.     

Synthesis and Mesomorphic Properties of Ferroelectric Liquid Crystals with a Fluorinated Asymmetric Frame (1)

New ferroelectric liquid crystals with a fluorinated asymmetric frame were synthesized utilizing optically active S-(-)-2-fluoroalkanols prepared from R-(+)-1,2-epoxyalkanes with pyridinium poly(hydrogen fluoride), and their mesomorphic and physical properties (phase behavior, spontaneous polarization, response time) were studied. The biphenyl-phenyl derivatives of three-ring systems exhibited enantiotropic chiral smectic C phase in a broad temperature range (108°C-185°C). The phenyl benzoate of two-ring systems exhibited chiral smectic C phase at temperature relatively close to room temperature, and were found to possess the spontaneous polarization larger than 35 nC/cm².     

Isolation, structure determination, and synthesis of allo-RA-V and neo-RA-V, RA-series bicyclic peptides from Rubia cordifolia L

Two bicyclic hexapeptides, allo-RA-V (4) and neo-RA-V (5), and one cyclic hexapeptide, O-seco-RA-V (6), were isolated from the roots of Rubia cordifolia?L. Their gross structures were elucidated on the basis of spectroscopic analysis and X-ray crystallography of compound 5. The absolute stereochemistry of compounds 4 and 5 were established by their total syntheses, and the absolute stereochemistry of compound 6 by chemical correlation with deoxybouvardin (3). Comparison of the 3D structures of highly active RA-VII (1) with less-active compounds 4 and 5 suggests that the orientation of the Tyr-5 and/or Tyr-6 phenyl rings plays a significant role in their biological activity. The isolation of peptides 4-6, along with compound 3, and the comparison of their structures seem to indicate that peptide 6 may be the common precursor to bicyclic peptides 3-5 in the plant.     

Fine Tuning of Vesicle Assembly and Properties Using Dual Hydrophilic Triblock Copolypeptides

The design, synthesis, and self‐assembly of the first dual hydrophilic triblock copolypeptide vesicles, ${\rm R}_{m}^{{\rm H}} {\rm E}_{n} {\rm L}_{o} $ and ${\rm K}_{m}^{{\rm P}} {\rm R}_{n}^{{\rm H}} {\rm L}_{o} $ , is reported. Variation of the two distinct hydrophilic domains is used to tune cellular interactions without disrupting the self‐assembled structure. The aqueous self‐assemblies of these triblock copolypeptides in water are characterized using microscopy and DLS. Cell culture studies are used to evaluate cytotoxicity as well as intracellular uptake of the vesicles. The ability of polypeptides to incorporate ordered chain conformations that direct self‐assembly, combined with the facile preparation of functional, multiblock copolypeptide sequences of defined lengths, allow the design of vesicles attractive for development as drug carriers.

     

Uniform Rates of Decay in Anisotropic Thermo-Viscoelasticity

We consider the anisotropic and inhomogeneous thermo-viscoelastic equation. We prove that the first and second-order energy decay exponentially as time goes to infinity provided the relaxation function also decays exponentially to zero. While if the relaxation functions decay polynomially to zero, then the energy decays also polynomially. That is, the kernel of the convolution defines the rate of decay of the solution.     

Chromatographic study of optical resolution : VI. Separation of isomers of facial tris(aminoacidato) mixed ligand chelates with d-tartrate and antimony d-tartrate adsorbed on an anion-exchange resin

A systematic study was made of the chromatographic separation of enantiomers of a series of fac-[Co(β-ala)_n(α-ala)_3−n] through an anion-exchange column adsorbing chiral and achiral anions such as d-tartrate, antimony d-tartrate, chloride and sulphate. It was found that both the retention volume and the separation factor of the enantiomeric pair increase with increasing number of β-ala ligands when eluted through the d-tartrate form of the resin. On the other hand, when eluted through the antimony d-tartrate form of the resin, the trend of the retention volumes and the separation factors is the reverse of that for the d-tartrate form. These results are discussed in comparison with the results obtained for the corresponding series of fac-[Co(β-ala)_n(gly)_3−n].     

Preparation and antitumor activity of 2'-O-, 3'-O- and 2',3'-di-O-substituted derivatives of etoposide.

The 2'-O-, 3'-O- and 2',3'-di-O-substituted derivatives (4a--p) of etoposide were prepared by nucleophilic substitution of 4'-O-benzyloxycarbonyletoposide (2) followed by deprotection. Controlled reaction (a limited amount of reagents and low temperature) was required for preparing the mono-O-substituted derivatives. In terms of ED125 values, doses which show 125% of T/C against P388 leukemia in mice, both the 2'-O-acetate (4a, ED125 = 0.18 mg/kg) and 3'-O-acetate (4b, 0.23 mg/kg) were nearly as active as etoposide (1, 0.19 mg/kg), while the 2',3'-di-O-acetate (4c, 1.9 mg/kg) was somewhat less potent. In the replacement with other substituents, antitumor activity of the 2'-O-substituted derivatives was affected much more by the difference of the substituents as compared with that of the corresponding 3'-O-substituted derivatives. In the 2',3'-di-O-substituted derivatives, the activity was decreased additively on the substituents.     

Dynamics of positive charge carriers on Si chains of polysilanes

The transient absorption of radical cations of a variety of substituted polysilanes is discussed quantitatively in terms of the molar extinction coefficient and oscillator strength by nanosecond pulse radiolysis. Oxygen-saturated polysilane solutions in benzene exhibit a strong transient absorption band ascribed to the polysilane radical cation. The transient species react with N,N,N',N'-tetramethyl-p-phenylene-diamine (TMPD) to produce TMPD radical cations. On the basis of the molar extinction coefficient of the TMPD radical cation, the molar extinction coefficients for the radical cations of polysilanes are found to increase in the range 3.3 x 10(4) to 2.0 x 10(5) M(-)(1) cm(-)(1) with increasing polymer segment length. The stepwise increase in the total oscillator strength with an increase in the number of phenyl rings directly bonded to the Si skeleton suggests the delocalization of the positive polaron state and/or the SOMO state over the phenyl rings, indicating the importance of phenyl rings in intermolecular hole transfer processes.