共查询到20条相似文献,搜索用时 0 毫秒
1.
Saito N Shigeno M Yamaguchi M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(29):8994-9004
A methodology for the formation of fibers/gels and vesicles by molecular assembly and for controlling their properties is presented. Two-component systems of pentamer (P)-5 and tetramer (M)-4 pseudoenantiomeric ethynylhelicenes with decyloxycarbonyl (D) and 4-methyl-2-(2-methylpropyl)-1-pentyloxycarbonyl (bD) side-chains have been examined. Distinct aggregates were formed by changing the solvent for the three combinations of (P)-bD-5/(M)-bD-4, (P)-D-5/(M)-bD-4, and (P)-D-5/(M)-D-4. In toluene, (P)-bD-5/(M)-bD-4, (P)-D-5/(M)-bD-4, and (P)-D-5/(M)-D-4 all formed gels and fibrous assemblies were observed by AFM. The minimum gel-forming concentration (MGC) decreased in the order (P)-bD-5/(M)-bD-4>(P)-D-5/(M)-bD-4>(P)-D-5/(M)-D-4. In diethyl ether, vesicular formation was observed by dynamic light scattering (DLS), AFM, and TEM, and the size of the vesicles decreased in the order (P)-bD-5/(M)-bD-4>(P)-D-5/(M)-bD-4>(P)-D-5/(M)-D-4. Both fiber/gel and vesicle formation were accompanied by enhanced CDs and redshifted UV/Vis absorption bands with a change in color to deep yellow. These are novel two-component oligomeric systems that form assemblies of fibers/gels or vesicles depending on the solvent, and the structures and properties of the assemblies can be fine-tuned by changing the combination of oligomers. In m-difluorobenzene, a homogeneous solution was obtained with (P)-D-5/(M)-bD-4, which again exhibits enhanced CDs and redshifted UV/Vis absorptions. Vapor pressure osmometry analysis showed the formation of a bimolecular heteroaggregate. The study has indicated that pseudoenantiomeric oligomers form hetero-double-helices that hierarchically assemble to form fibers/gels and vesicles. 相似文献
2.
3.
This report discusses the effect of fluoroalkyl chain on the mesomorphism. Several homologues of novel triphenylene compounds possessing fluoroalkylated side chains were synthesized. Studies of X-ray diffraction, DSC and texture observations by polarized microscope revealed that these homologues show hexagonal columnar (Colh) mesophase. These homologues made columnar mesophase stabilize and the melting point increase, as compared with corresponding alkyloxytriphenylenes. In the case of fluoroalkyloxytriphenylenes possessing fluoromethylene side chains, the increase of the fluoromethylene chain length stabilized columnar mesophase, made the phase transition enthalpy (Colh-Iso) and entropy (Colh-Iso) increase. It is considered that these results are due to the fluorophilic interaction, and that the fluorophilic interaction is important for stabilizing columnar mesophase. 相似文献
4.
Two types of homologues (symmetrical and asymmetrical in rotational symmetry) of novel triphenylene compounds possessing fluoroalkyl and alkyl side chains were synthesized via an alternative method. X-ray diffraction and DSC measurements showed that these homologues are thermotropic liquid crystals with a hexagonal columnar (Colh) mesophase. The phase transition temperatures (Colh-Iso) for both symmetrical and asymmetrical fluoroalkyloxytriphenylenes increase to about 180°C, and are independent of fluoromethylene chain and the rotational symmetry of chemical structure. The Colh phase of symmetrical and asymmetrical fluoroalkyloxytriphenylenes possessing three fluoroalkyl side chains are more stable than fluoroalkyloxytriphenylenes possessing six fluoroalkyl side chains and alkyloxytriphenylenes. The X-ray diffraction patterns for symmetrical and asymmetrical fluoroalkyloxytriphenylenes, fluoroalkyloxytriphenylenes and alkyloxytriphenylenes in the wide-angle region are compared. 相似文献
5.
Sugiura H Nigorikawa Y Saiki Y Nakamura K Yamaguchi M 《Journal of the American Chemical Society》2004,126(45):14858-14864
Optically active acyclic ethynylhelicene oligomers were synthesized in high yields by a two-directional method involving Sonogashira coupling and deprotection. Their CD spectra in chloroform exhibited large differences between the oligomers with less than seven helicenes and their higher homologues, which indicated the formation of helical structures for the latter and random coil structures for the former. The helical heptamer gradually unfolded to a random coil structure in chloroform at room temperature. The unfolding rate was examined by CD in several aromatic solvents as well, and the rate constant k was found to be highly dependent on the type of aromatic substituent: k differed by seven orders of magnitude between iodobenzene and trifluoromethylbenzene. Several features of the rates are notable: The reaction rates in halobenzenes were in the order of iodobenzene > bromobenzene > chlorobenzene > benzene > fluorobenzene > m-difluorobenzene, those in alkylbenzenes were styrene > phenylacetylene > ethylbenzene > toluene > benzene, and those in heteroatom-substituted arenes were thioanisole > benzonitrile > anisole > ethyl benzoate > benzene > trifluoromethylbenzene. The log k values exhibited good correlation with the absolute hardness, eta, of the arenes, and higher unfolding rates were observed in the soft arenes. Vapor pressure osmometry studies indicated that the helical structure of the heptamer is dimeric in benzene, fluorobenzene, and trifluoromethylbenzene, while the random coil structure of the heptamer is monomeric in chloroform and toluene. When a chloroform solution of the random coil structure was concentrated to a small volume, the helical structure could be regenerated. 相似文献
6.
Naohiro Terasawa Nobutaka Tanigaki Kenji Kiyohara 《Journal of fluorine chemistry》2006,127(8):1096-1104
The alignment behavior of the triphenylene compounds possessing fluoroalkylated side chains was investigated for the hexagonal columnar (Colh) mesophase on the polyimide-, cetyltrimethylammonium bromide (CTAB)-, and indium-SnO2 (ITO)-coated glass substrates by polarizing optical microscopy. It was found that 2,3,6,7,10,11-hexakis(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)- and 2,3,6,7,10,11-hexakis(1H,1H,2H,2H,3H,3H-perfluorononyloxy)-triphenylenes exhibit a spontaneous homeotropic alignment on these substrates, in contrast to the non-uniformity of alignment of Colh phase in the corresponding hydrocarbon mesogens. On the other hand, it was also found that 4,4,4-trifluorobutyloxy, 4,4,5,5,5-pentafluoropentyloxy and 4,4,5,5,6,6,6-heptafluorohexyloxy derivatives do not show such a spontaneous homeotropic alignment on these substrates. These results indicate that the spontaneous homeotropic alignment of the Colh phase could be easily attained by the introduction of an appropriate number and length of the fluoromethylene chains in the peripheral parts of discogens. 相似文献
7.
Koji YamamotoHiroki Sugiura Ryo AmemiyaHaruo Aikawa Zengjian AnMasahiko Yamaguchi Masashi Mizukami Kazue Kurihara 《Tetrahedron》2011,67(33):5972-5978
Optically active ethynylhelicene pentamers and hexamers linked by disulfide bonds were synthesized. They formed self-assembled monolayers (SAMs) with double helix structure on gold surfaces, which were analyzed by infrared reflection-absorption spectroscopy (IR-RAS), quartz crystal microbalance (QCM), surface plasmon resonance (SPR), and circular dichroism (CD). Double helix SAMs could be formed on gold surfaces either from double helices or random coils in solution. The double helices on the surface were more stable than in solution. This result suggested the presence of strong intercomplex interactions between double helix complexes on the surface. 相似文献
8.
The alignment behaviour of triphenylene‐based compounds possessing fluoroalkylated and alkyl side chains was investigated for the hexagonal columnar (Colh) mesophase on polyimide‐, cetyltrimethylammonium bromide (CTAB)‐, and indium tin oxide‐coated glass substrates by polarizing optical microscopy. It was found that 2,6,10‐trinonyloxy‐3,7,11‐tris(1H,1H,2H,2H,3H,3H‐perfluorononyloxy)triphenylene and 2,6,11‐trinonyloxy‐3,7,10‐tris(1H,1H,2H,2H,3H,3H‐perfluorononyloxy)triphenylene exhibit spontaneous homeotropic alignment on these substrates. On the other hand, it was found that 2,6,10‐triheptyloxy‐3,7,11‐tris(1H,1H,2H,2H,3H,3H‐perfluoroheptyloxy)triphenylene, 2,6,11‐triheptyloxy‐3,7,10‐tris(1H,1H,2H,2H,3H,3H‐perfluoroheptyloxy)triphenylene, 2,6,10‐trihexyloxy‐3,7,11‐tris(1H,1H,2H,2H,3H,3H‐perfluorohexyloxy)triphenylene, 2,6,11‐trihexyloxy‐3,7,10‐tris(1H,1H,2H,2H,3H,3H‐perfluorohexyloxy)triphenylene, 2,6,10‐tributyloxy‐3,7,11‐tris(1H,1H,2H,2H,3H,3H‐perfluorobutyloxy)triphenylene and 2,6,11‐tributyloxy‐3,7,10‐tris(1H,1H,2H,2H,3H,3H‐perfluorobutyloxy)triphenylene do not show such spontaneous homeotropic alignment on these substrates. These results indicate that the spontaneous homeotropic alignment of the Colh phase could be easily attained by the introduction of an appropriate length of the fluoromethylene chains in the peripheral parts of discogens. Therefore, it is suggested that the balance between the hydrocarbon part including the triphenylene core and the fluoroalkyl part determines the alignment control behaviour. Furthermore, it was found that alignment behaviour is independent of the rotation symmetry of the chemical structure but is dependent on the number of fluoromethylene chains in the chemical structure. 相似文献
9.
The alignment behaviour of triphenylene-based compounds possessing fluoroalkylated and alkyl side chains was investigated for the hexagonal columnar (Colh) mesophase on polyimide-, cetyltrimethylammonium bromide (CTAB)-, and indium tin oxide-coated glass substrates by polarizing optical microscopy. It was found that 2,6,10-trinonyloxy-3,7,11-tris(1H,1H,2H,2H,3H,3H-perfluorononyloxy)triphenylene and 2,6,11-trinonyloxy-3,7,10-tris(1H,1H,2H,2H,3H,3H-perfluorononyloxy)triphenylene exhibit spontaneous homeotropic alignment on these substrates. On the other hand, it was found that 2,6,10-triheptyloxy-3,7,11-tris(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)triphenylene, 2,6,11-triheptyloxy-3,7,10-tris(1H,1H,2H,2H,3H,3H-perfluoroheptyloxy)triphenylene, 2,6,10-trihexyloxy-3,7,11-tris(1H,1H,2H,2H,3H,3H-perfluorohexyloxy)triphenylene, 2,6,11-trihexyloxy-3,7,10-tris(1H,1H,2H,2H,3H,3H-perfluorohexyloxy)triphenylene, 2,6,10-tributyloxy-3,7,11-tris(1H,1H,2H,2H,3H,3H-perfluorobutyloxy)triphenylene and 2,6,11-tributyloxy-3,7,10-tris(1H,1H,2H,2H,3H,3H-perfluorobutyloxy)triphenylene do not show such spontaneous homeotropic alignment on these substrates. These results indicate that the spontaneous homeotropic alignment of the Colh phase could be easily attained by the introduction of an appropriate length of the fluoromethylene chains in the peripheral parts of discogens. Therefore, it is suggested that the balance between the hydrocarbon part including the triphenylene core and the fluoroalkyl part determines the alignment control behaviour. Furthermore, it was found that alignment behaviour is independent of the rotation symmetry of the chemical structure but is dependent on the number of fluoromethylene chains in the chemical structure. 相似文献
10.
A guanine-rich PNA dodecamer having the sequence H-G4T4G4-Lys-NH2 (G-PNA) hybridizes with a DNA dodecamer of homologous sequence to form a four-stranded quadruplex (Datta, B.; Schmitt, C.; Armitage, B. A. J. Am. Chem. Soc. 2003, 125, 4111-4118). This report describes quadruplex formation by the PNA alone. UV melting curves and fluorescence resonance energy transfer experiments reveal formation of a multistranded structure stabilized by guanine tetrads. The ion dependency of these structures is analogous to that reported for DNA quadruplexes. Electrospray ionization mass spectrometry indicates that both dimeric and tetrameric quadruplexes are formed by G4-PNA, with the dimeric form being preferred. These results have implications for the use of G-rich PNA for homologous hybridization to G-rich targets in chromosomal DNA and suggest additional applications in assembling quadruplex structures within lipid bilayer environments. 相似文献
11.
Maltoheptaonamide modified polydimethylsiloxane was prepared applying a simplified synthetic pathway in the derivatization sequence of the carbohydrate. The products were characterized by 13C NMR and FT-IR spectroscopy. The glucan side chains of these “sweet siloxanes” were elongated by enzymatic catalysis with potato phosphorylase. 相似文献
12.
Akihito Sakakibara Maki Itoh Itaru Mita 《Journal of polymer science. Part A, Polymer chemistry》1995,33(8):1293-1303
Aromatic polybenzobisoxazoles, having polydimethylsiloxane side chains (SCPBOs), were prepared using terephthaloyl chloride-terminated polydimethylsiloxane macromonomers and 3,3′-bis(trimethylsiloxy)-4,4′-bis(trimethylsilylamino)biphenyl for the purpose of dispersing rigid-rod molecules in silicone matrices for molecular reinforcement. The degree of polymerization of the side chain was varied from 7.8 to 45.4, and a small amount of (3-butenyloxy)terephthaloyl chloride was copolymerized to give the polymers a functionality that can be linked to the matrices. For all the SCPBOs, the WAXD pattern showed only diffuse reflections, suggesting limited structural regularity, although the polymers were optically anisotropic. No melting transition was observed below the side chain decomposition temperature, 350°C. A polydimethylsiloxane/polybenzobisoxazole composite elastomer was obtained first curing the polysiloxane matrix containing the prepolymer of the SCPBO, followed by in situ thermal ring closure of the prepolymer. Some reinforcement was observed, but the presence of plasticizing effect by the unbound SCPBO was suggested at the same time. © 1995 John Wiley & Sons, Inc. 相似文献
13.
Mollerup JM 《Journal of chromatography. A》2011,1218(49):8869-8873
Oligomer forms of proteins are formed by self and cross association or complex formation with ligands. Modelling studies using an ion-exchange adsorbent have demonstrated that the formation of an oligomer form of a target protein can improve a chromatographic separation because the oligomer form displaces the impurities. The results of the investigation show that the process is very robust, that the purity, the yield, and the productivity increase with increasing load and increasing salt concentration in the eluant. An impurity level less than 1 ppm is easy to achieve having a yield of 98%. A universal model for the adsorption equilibria of mono and oligomer forms of proteins on ion-exchange, hydrophobic, and bimodal adsorbents has been developed. 相似文献
14.
Modeling studies were performed for a rigid-rod polyester with hexadecyloxy side chains (n=16) in order to simulate x-ray scattering curves in the medium angle scattering region (s=4 sin / from 0.2 Å–1 to 2.2 Å=t–1). The experimental ones were taken from a material obtained by cooling to room temeperature from the smectic mesophase at 150°C. The wide-angle x-ray diffractograms were calculated for given conformations and molecular arrangements using Debye's equation. The theoretical result thus obtained for a great variety of possible packing models and structures was compared to the experimental result. The size of the effective scattering region is found to be 61×18×52=6×104 Å3 and consists of approximately five layers, each of which is composed of two rigid rods and 20 side chains. The planes form by the rigid rods, together with the side chains, have a distance of 3.6 Å, the distance between the rods being 26 Å. As the main result, it was found that the side chains form regions with a denser ordering (clustering). The interchain distance for side chains decreases in the regions from 5.3 Å to 4.8 Å. 相似文献
15.
Sixteen new side chain liquid polysiloxanes, either homopolymers derived from poly(hydrogenmethyl)siloxane or copolymers derived from poly(hydrogenmethyl-dimethylsiloxane), are reported with side chains carrying fluoro-substituents. The known effects of fluoro-substitution in low molar mass liquid crystals are strongly echoed in the polymeric analogues and interesting comparisons are made between homo- and co-polymers carrying the same fluorinated side chains. 相似文献
16.
The in vivo formation of beta-pleated protein aggregates underlies a number of fatal neurodegenerative disorders, such as Alzheimer disease. Since molecular mechanisms of protein misfolding and aggregation remain poorly understood, this has been calling for many diverse biophysical tools capable of addressing different dynamic and conformational aspects of the phenomenon. The two model polypeptides used in this study are poly(l-tyrosine) and insulin. According to FT-IR spectra, poly(l-tyrosine) produced two distinct types of films with dominant either disordered or antiparallel beta-sheet conformations depending on carrier solvent used for film's deposition. Electrochemical analysis of both the types of polypeptide films by the means of cyclic voltammetry and differential pulse voltammetry proved that different electrochemical behaviour of the tyrosine residues is determined by the conformation of polypeptide chains. We have rationalized this difference in terms of varying electrochemical accessibility of Tyr residues in each structure. We have also carried out spectral and electrochemical characterization of insulin beta-sheet-rich amyloid fibrils. It appears that the detectable electrochemical response of the protein stems from the presence of four tyrosine residues per insulin monomer. Since hydrophobic residues, among them tyrosines play an important role in the formation of protein amyloid fibrils, but, on a molecular level, may be also critical in explaining neurotoxic properties of aggregates, their electrochemical properties may become a very valuable complementary tool in biophysical studies on protein misfolding. 相似文献
17.
Ab initio study of hydrogen-bond formation between cyclic ethers and selected amino acid side chains
Binding energies for hydrogen-bonded complexes of six cyclic ethers with five hydrogen-bond donor molecules that mimic selected amino acid side chains have been calculated at the MP2/6-31G*, MP2/6-31+G*, MP2/6-311++G**(single point), and MP2/aug-cc-pvtz levels, using geometries obtained with or without counterpoise corrections throughout the geometry optimization. The calculated basis set superposition error (BSSE) amounts to 10-20% and 5-10% of the uncorrected binding energies for the neutral and ionic species, respectively, at the MP2/aug-cc-pvtz level. The authors conclude that the O...H distances in the hydrogen bonds and binding energies for the studied systems may be determined with uncertainties of up to 0.08 A and 1-2 kcal/mol, respectively, in comparison with the MP2/aug-cc-pvtz values at a reasonable computational cost by performing standard geometry optimization at the MP2/6-31+G* level. Hydrogen-bond formation energies are more negative for cyclic ethers compared to their counterparts with a C=C double bond in the ring next to the oxygen atom. The less negative hydrogen-bonding energy and the increased O...H separation have been attributed to the reduced basicity of the ether oxygen when the lone pairs can enter conjugation with the pi-electrons of the Calpha=Cbeta double bond. The present study is the first step toward the development of an affordable computational level for estimating the binding energies of natural product, fused ring ether systems to the human estrogen receptor. 相似文献
18.
Rubbing-induced molecular reorientation on an alignment surface of an aromatic polyimide containing cyanobiphenyl side chains 总被引:3,自引:0,他引:3
Ge JJ Li CY Xue G Mann IK Zhang D Wang SY Harris FW Cheng SZ Hong SC Zhuang X Shen YR 《Journal of the American Chemical Society》2001,123(24):5768-5776
Surface lamellar decoration (SLD), surface enhanced Raman scattering (SERS) and optical second harmonic generation (SHG) experiments have been utilized to study the molecular orientation and conformation changes at a rubbed polyimide alignment-layer surface. This aromatic polyimide containing pendent cyanobiphenyl mesogens was synthesized via a polycondensation of 2,2'-bis(3,4-dicarboxy-phenyl)hexafluoropropane dianhydride (6FDA) with bis[omega-[4-(4-cyanophenyl)phenoxy]hexyl] 4,4'-diamino-2,2'-biphenyldicarboxylate (nCBBP, n = 6), abbreviated as 6FDA--6CBBP. Uniform alignment layers, possessing high pretilt angles ranging from 39 degrees to 43 degrees, have been achieved after mechanical rubbing of the polyimide thin film surface at room temperature and subsequent annealing. This is the first time that high pretilt angles have been detected to possess a negative angle (-theta(c)) with respect to the rubbing direction (i.e., opposite to the rubbing direction), considerably different from the conventional pretilt angle (theta(c)) observed along the rubbing direction. This observation is confirmed using magnetic null and SHG methods. Combined polyethylene (PE) SLD and atomic force microscopy experiments reveal that the azimuthal orientation distribution of the long axis of the edge-on PE lamellar crystals is oriented normal to the rubbing direction, indicating that the PE chains are aligned parallel to the rubbing direction. This SLD technique probes the anisotropic surface orientation of the outermost molecules of the rubbed polyimide layer. The SERS results show that prior to rubbing the surface, both the pendent cyanobiphenyls in the side chains and backbones possess nearly planar chain conformations at the polyimide surface. Mechanical rubbing causes not only tilting of the backbone moieties, such as imide-phenylene structure, but also significant conformational rearrangements of the pendent side chains at the surfaces. The molecular mechanism of this unusual alignment is due to the fact that the pendent cyanobiphenyls forms a uniformly tilted conformation on the rubbed surface, and the polar cyano groups point down toward the layer surface deduced from SHG phase measurements. This conformational rearrangement of the side chains results in the formation of fold-like bent structures on the surface, which directly leads to the long axis of cyanobiphenyls having the -theta(c) pretilt angle with respect to the rubbing direction. 相似文献
19.
20.
N-Substituted glycine peptoid oligomers were synthesized to incorporate a photoresponsive azobenzene side chain. The ability of this side chain to undergo reversible photoisomerization was established, and the cis- to trans-azobenzene thermal isomerization of this side chain was investigated. Circular dichroism studies indicated that trans- to cis-azobenzene isomerization does not significantly alter the backbone conformation in a series of peptoids thought to have well-defined structures. 相似文献