Novel organogelators based on amine-derived hexaazatrinaphthylene

Novel C(3)-symmetrical heteroaromatic hexaazatrinaphthylene (HATNA) gelators symmetrically end-substituted with pendant aromatic and aliphatic amines were synthesized. Some of these π-conjugated structures induce self-assembly, forming fibers able to gelate solvents of different polarity at low wt% as demonstrated by spectroscopic and microscopic techniques.     

Novel organogelators based on pyrazine-2,5-dicarboxylic acid derivatives and their mesomorphic behaviors

A series of new low molecular organogelators (LMOGs) with thermotropic mesophase were synthesized via the reaction of 3,6-dimethyl-pyrazine-2,5-dicarboxylic acid with p-alkoxyl anilines. These compounds readily formed stable gels in a variety of organic solvents and their self-assembly behavior, structure–property relationship were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), ¹H nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectroscopy (FTIR) and ultra-violet–visible spectroscopy (UV). The results showed a combination of intra-hydrogen bonding, π–π stacking and van der Waals interaction resulted in the aggregation of the organogelators to form three-dimension fibrous networks. The gels formed were multi-responsive to environmental stimuli, such as temperature, fluorinion, and shear stress. More importantly, all the organogelators exhibited thermotropic hexagonal column mesophase as revealed by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable temperature XRD studies. A control compound was synthesized and its gelling ability was also checked.     

Novel thymidine-based organogelators and their gelation behaviours

We report on a synthesis of novel thymidine based organogelators and a study of their gelation types in relation to structure and solvent, using various data acquired through FT-IR, SEM images and differential scanning calorimetry.     

某些胆酸及去氧胆酸肟类化合物的合成

从胆酸和去氧胆酸出发,经过不同反应,将甾核以及支链上的取代基分别转化为羰基及酯基,然后和盐酸羟胺反应引进肟基,合成了六个新的甾体肟类化合物:7-羟基-12-氧代-3-肟基胆酸甲酯(5)、7,12-二氧代-3-肟基胆酸甲酯(6)、12-氧代-3,7-二肟基胆酸甲酯(7)、3,7,12-三肟基胆酸甲酯(8)、12-氧代-3-肟基去氧胆酸甲酯(12)、3,12-二肟基去氧胆酸甲酯(13)。通过NMR和IR对合成物5~10的结构进行了表征。     

Inclusion polymerization of isoprene in deoxycholic acid

The radiation-induced polymerization of isoprene was made on its inclusion (or clathrate) complex with deoxycholic acid (DOCA) at 150 and 300 kGy. The microstructure of the resulting polyisoprene (PIP) was studied by FTIR spectroscopy and found fully comparable to that of PIP prepared by emulsion polymerization by a free radical initiator. Thus, the 1,4-trans content was found to be 48% and that of 1,4-cis units was 28% of the polymer structure; the remaining are being 1,2 and 3,4 units. The PIP irregular microstructure was justified in terms of monomer dynamics inside the DOCA channels. PIP from inclusion polymerization is fully amorphous as studied by differential thermal analysis (DTA) in comparison to an authentic sample of trans-1,4-polyisoprene, which instead has a crystalline melting point of 71.5 °C. The inclusion complex of PIP with DOCA (PIP@DOCA) shows a DTA melting point of 194.4 °C, 12.4 °C higher than the melting point of pure DOCA. PIP isolated from inclusion polymerization from DOCA and its complex PIP@DOCA was studied also by thermogravimetry (TGA) and differential thermogravimetry (DTG).Isoprene does not form inclusion complexes with urea and thiourea. When irradiated with these two compounds it produces an oily PIP oligomer whose microstructure was found by FTIR spectroscopy analogous to that of PIP prepared by emulsion polymerization by a free radical initiator.     

A synthesis of bufalin from deoxycholic acid

Bufalin acetate (14) has been prepared from deoxycholic acid (1) in 12 steps.     

Thixotropic twin-dendritic organogelators

Twin-dendritic organogelators have been prepared through selective functionalization of N-(3-aminopropyl)-1,3-propanediamine (APPDA) with self-assembling dendrons by using 1,1'-carbonyldiimidazole (CDI). Subsequent modification of the APPDA linker provided an additional degree of structural diversity by which to tailor the gelator self-assembly in bulk or in the gel state. These compounds are able to gel cyclohexane, toluene, n-butyl acetate, ethyl acetate, dichloromethane, and tetrahydrofuran. 3,4-Disubstituted apical branching units provided the most efficient organogelators and show a propensity to form thixotropic gels, wherein the gel recovers its elasticity after being subjected to shear. Structural and retrostructural analysis of the twin-dendritic organogelators reveals the bulk structural characteristics to be indicative of the subsequent gel properties. Diverse self-organized arrays were identified in bulk and all are able to form gels, thus indicating the role of quasiequivalence in mediating self-assembly in the gel state. Furthermore, we have found that porous columnar mesophases provide a strategy by which to prepare thixotropic gels. We demonstrate the importance of weak lateral hydrogen bonding within a column stratum versus hydrogen bonding along the length of the column for forming porous columnar mesophases and, by extension, thixotropic gels.     

Oxidative polymerization of hydroquinone using deoxycholic acid supramolecular template

Polyhydroquinone (PHQ) is a redox-active polymer with quinone/hydroquinone redox active units in the main chain and may have potential applications as a mediator in biosensors and biofuel cells. By the oxidative polymerization of hydroquinone (HQ), PHQ can be easily synthesized, but the reaction lacks control over the structure of the product. Deoxycholic acid (DCA) was introduced as a supramolecular template to control the reaction. The reaction rate is 14 times of that in deionized water and twice of that in buffer. The DCA template increases not only the reaction rate, but also the molecular weight of the polymer obtained. The template effect of DCA was attributed to the supramolecular assemblies of DCA formed in the solution. Cyclic voltammetry study indicated the resulting PHQ was redox-active. While the supramolecular assemblies of DCA provided a template for the oxidative polymerization of HQ, the protons released as a by-product of the oxidative polymerization of HQ in turn enhanced the self-assembly of DCA. As a result, DCA microfibers form and separate out of the solution.     

Inclusion polymerization of 1-chlorobutadiene in a deoxycholic acid canal

Inclusion polymerization of 1-chlorobutadiene was studied using 3α,12α-dihydroxy-5β-cholan-24-oic acid (deoxycholic acid, DCA) as host molecules. It was found that the poly(1-chlorobutadiene) had almost 100% of head to tail, trans-1,4-structure on the basis of ¹³C-NMR and IR spectroscopies. This was the first example of preparing the highly regulated poly(1-chlorobutadiene) by using the inclusion polymerization technique. The polymers obtained were optically active and the maximum value of specific rotation was [α]_D-41.9°. Both the rate constants and the value of activation energy of the elementary reactions of inclusion polymerization of 1-chlorobutadiene were determined by graphical evaluation. The activation energy of propagation and termination was 11.7 and 11.1 kcal/mol, respectively.     

Synthesis of polyphenylacetylene by radiation-induced polymerization in deoxycholic acid clathrate

Phenylacetylene was polymerized as inclusion compound (clathrate) inside deoxycholic acid (DOCA) crystals. The polymerization was initiated by γ radiation and a total dose of 320 kGy was employed. The resulting polyphenylacetylene (PPA) was isolated by dissolution of deoxycholic acid in boiling ethanol. PPA high polymer was accompanied by a series of phenylacetylene oligomers, which were detected by liquid chromatographic analysis (HPLC). PPA was characterized by electronic absorption spectroscopy and by FT-IR spectroscopy in comparison to a reference PPA prepared by a stereospecific catalyst. The microstructure of PPA from inclusion polymerization was highly trans type, similar to that observed on PPA prepared by bulk radiolysis. No optical activity was detected by polarimetry on PPA prepared by inclusion polymerization.The host–guest complex PPA/DOCA was studied by differential thermal analysis (DTA) and by thermogravimetry (TGA). DTA provided evidences of the host–guest complex formation from the shift of the melting point of DOCA while the TGA confirmed the identity – in terms of thermal behaviour – of the PPA from inclusion polymerization with that from stereospecific polymerization.     

Isomerization processes in inclusion compounds: Xylenes in deoxycholic acid

The isomerization processes induced by UV photons in inclusion compounds of the host-guest type are examined, with special attention to the photophysics of the energy transfer process between the host and the guest, as well as to the influence of the host molecular cavity symmetry and the guest molecular symmetry. In particular, the experimental study has been carried out on the isomerization processes ofp-,m-, ando-xylene inside the molecular cavities of deoxycholic acid. The results have been compared with those obtained by irradiating the xylenes in an inert solution of hexane. The main difference is the elimination of by-products when the photochemical process is carried out in the solid state inclusion compound; however, the high purity of the isomerization product corresponds to a decrease in its yield with respect to the reaction in solution, due to the energy transfer process from the host to the guest moiety.     

Phosphorescent platinum acetylide organogelators

The series of platinum acetylide oligomers (PAOs) with the general structure trans,trans-[(RO)3Ph-C[triple bond]C-Pt(PMe3)2-C[triple bond]C-(Ar)-C[triple bond]C-Pt(PMe3)2-C[triple bond]C-Ph(OR)3], where Ar = 1,4-phenylene, 2,5-thienylene, or bis-2,5-(S-2-methylbutoxy)-1,4-phenylene and R = n-C12H25 gel hydrocarbon solvents at concentrations above 1 mM. Gelation is thermally reversible (T(gel-sol) approximately 40-50 degrees C), and it occurs due to aggregation of the PAOs resulting in the formation of a fibrous network that is observed for dried gels imaged by TEM. The influence of aggregation/gelation on the photophysical properties of the PAOs is explored in detail. Aggregation induces a significant blue shift in the oligomers' absorption spectra, and the shift is attributed to exciton interactions arising from H-aggregation of the chromophores. Strong circular dichroism (CD) is observed for gelled solutions of a PAO substituted with homochiral S-2-methylbutoxy side chains on the central phenylene unit. The CD is attributed to formation of a chiral supramolecular aggregate structure. The PAOs are phosphorescent at ambient temperature in solution and in the aggregate/gel state. The phosphorescence band is blue-shifted ca. 20 nm in the aggregate/gel, and the shift is assigned to emission from an unrelaxed conformation of the triplet excited state. Phosphorescence spectroscopy of mixed aggregate/gels consisting of a triplet donor/host oligomer (Ar = 1,4-phenylene) doped with low concentrations of an acceptor/trap oligomer (Ar = 2,5-thienylene) indicates that energy transfer occurs efficiently in the aggregates. Triplet energy transfer involves exciton diffusion among the host chromophores followed by Dexter exchange energy transfer to the trap chromophore.     

Novel odd/even effect of alkylene chain length on the photopolymerizability of organogelators

[reaction: see text] Starting from diactylene diacarboxylic acids, we have synthesized a series of photopolymerizable organogelators that possess simple amide structures, different alkylene chain lengths, and either optically active or racemic 3,7-dimethyl-1-octylamine units. The alkylene chain length of these compounds exhibits a prominent odd/even effect with respect to the photopolymerization in the gel state and is accompanied by a stereostructural effect on the gelation ability.     

Radiation-induced polymerization of 2,3-dimethyl-1,3-butadiene clathrate in deoxycholic acid

Poly(dimethylbutadiene) (PDMB) was synthesized through the inclusion polymerization technique, by γ-irradiation of a clathrate of 2,3-dimethyl-1,3-butadiene in deoxycholic acid (DOCA) at 75, 150, 320 and 430 kGy. The resulting inclusion complexes PDMB@DOCA were studied by FTIR spectroscopy and by thermal analysis (DTA, TGA and DTG). Pure PDMB was isolated by extracting the complex PDMB@DOCA with ethanol. The best sample in terms of purity was that prepared at 75 kGy, while the other samples prepared at higher doses suffered of DOCA grafting on PDMB chains. Pure PDMB isolated from PDMB@DOCA complex was studied by FT-IR spectroscopy and by thermal analysis in comparison to a reference highly crystalline and ≈=100% trans-1,4-PDMB prepared by inclusion polymerization in thiourea and in comparison to PDMB prepared by emulsion polymerization. A lower degree of regularity and crystallinity has been found on the PDMB sample prepared as inclusion compound in DOCA in comparison to the reference PDMB obtained by inclusion polymerization in thiourea.     

Novel self-assembling organogelators by combination of a double chain-alkylated L-glutamide and a polymeric head group

This communication introduces a new class of self-assembling organogelators composed of a double chain-alkylated L-glutamide with a polymeric head group.     

氨基甲酸酯型脱氧胆酸分子钳对氨基酸甲酯的手性识别 研究

以脱氧胆酸为spacer,通过三光气桥连各种芳胺,合成了新的氨基甲酸酯型分子钳受体1～4,这些化合物的结构经IR,^1HNMR和元素分析所证实。利用差光谱滴定法考察了其与D/L氨基酸甲酯的对映选择性识别性能。结果表明,分子钳1～4对所考察的氨基酸甲酯均具有识别能力,其对D-氨基酸甲酯的识别优于对L-氨基酸甲酯的识别。从主客体间的大小形状匹配及几何互补关系等方面对这些受体的识别能力及对映选择性进行了讨论。     

Hydrolysis of ionized deoxycholic acid in the aqueous phase and rate analysis for transfer of neutralized deoxycholic acid into the benzene phase across the benzene/water interface

Sodium deoxycholate in water dissociates into sodium cation and deoxycholate anion in the aqueous phase, and then, the latter anions partially hydrolyze to form deionized deoxycholic acids. The acids move into the benzene phase, when liquid benzene is placed upon the aqueous phase, and finally the partition equilibrium is reached. The above processes were traced by pH change in the aqueous phase by a pH meter or the change in [OH-] with time, from which the rate for transfer of neutralized acid to the organic phase was analyzed. From the trace, the rate constants for hydrolysis of acid anion ( kf), neutralization of acid ( kb), transfer of neutralized acid from the aqueous phase to the organic phase ( kin*), and its back-transfer from the organic phase to the aqueous phase ( kut*) were evaluated; kf = 2.18 x 10 (-4) mol (-1) dm (3) min (-1), kb = 1.24 x 10 (5) mol (-1) dm (3) min (-1), kin* = 4.06 x 10 (-1) min (-1) cm (-2), and kout*) = 8.00 x 10 (-2) min (-1) cm (-2). The above values are supported by the partition constant of deoxycholic acid between the benzene phase and the aqueous phase.     

Degradation of deoxycholic acid by Pseudomonas Sp. NCIB 10590

The microbial degradation of deoxycholic acid 1 by Pseudomonas NCIB 10590 has been studied and two major products have been isolated and identified as 12β-hydroxyandrosta-1,4-dien-3,17-dione 2 and 12α-hydroxypregna-1,4-dien-3-one-20-carboxylic acid 9. Three minor products were isolated and evidence is given for the following structures: 12α-hydroxyandrosta-1,4-dien-3,17-dione 4, 12β-hydroxyandrosta-4-en-3,17-dione 7 and 12?, 17?-dihydroxyandrosta-1,4-dien-3-one 8.