New gemini organogelators linked by oxalyl amide: organogel formation and their thermal stabilities

New gemini organogelators linked by an oxalyl amide that can be easily, effectively, and cheaply synthesized have good organogelation abilities and their cyclohexane gels have superior thermal stabilities; especially 7 possessing the branched alkyl ester can gel at 0.7 wt% cyclohexane even at 70°C.     

Modular synthesis of formamidines and their formation of stable organogels

An improvement in the practical aspects of formamidine synthesis has resulted in the discovery of a class of compounds which produce organogels in protic solvents, presumably through intermolecular hydrogen bonding and pi-pi stacking interactions.     

Novel thermally stable polyimides based on flexible diamine: synthesis, characterization, and properties

A novel diamine with built-in sulfone, ether, and amide structure was prepared via three-step reactions. Nucleophilic reaction of 4-aminophenol with 4-nitrobenzoyl chloride in the presence of propylene oxide led to preparation of N-(4-hydroxy phenyl)-4-nitrobenzamide (HPNB). The nitro group of this compound was reduced with hydrazine and Pd/C to afford 4-amino-N-(4-hydroxy phenyl)benzamide (AHPB). Two moles of AHPB were reacted with bis-(4-chloro phenyl)sulfone to provide a novel sulfone ether amide diamine (SEAD). All the prepared compounds were characterized by common spectroscopic methods. The prepared diamine (SEAD) used to prepare related polyimides by reaction with different aromatic dianhydrides. The obtained poly(sulfone ether amide imide)s were characterized and their properties were studied.     

Nanofibers of asymmetrically substituted bisphenazine through organogelation and their acid sensing properties

This paper reports the formation of an organogel of an asymmetric bisphenazine through the growth of one-dimensional nanofibers via a coopertive interplay of pi-pi interaction, hydrogen bonding, and van der Waals interaction and the colorimetric acid sensing property of the nanofibers.     

A family of low-molecular-weight organogelators based on N,N-diacyl-l-lysine: effect of alkyl chains on their organogelation behaviour

A family of low-molecular-weight organogelators based on N^α,N^?-diacyl-l-lysine was synthesized by acylation of N^?-dodecyl-l-lysine with acyl chlorides through the one-pot synthetic procedure and their organogelation properties were examined. These compounds functioned as an organogelator; especially, l-lysine derivatives possessing the branched alkyl groups are a better organogelation property. The NMR and IR studies demonstrate that the organogelation occurred through hydrogen bonding interactions between the amide groups and between the carboxy groups.     

Synthesis and ion-exchange properties of thermally stable stannic selenite

Stannic selenites have been synthesized under a variety of conditions. The most stable sample is prepared by mixing 0-0.5M solutions of stannic chloride and sodium selenite in the ratio of 1:1 at pH 1. It is a bifunctional amorphous material. A tentative structure has been proposed on the basis of chemical composition, pH titrations, infrared and thermogravimetric analyses. Its ion-exchange capacity is 0.75 and 0.73 meq g after drying at 50 degrees and 500 degrees respectively. Its analytical importance has been established by the following quantitative separations: Cu(2+) from Ni(2+), Co(2+), Fe(3+), Ga(3+) and In(3+), Fe(3+) from Pb(2+) and Sc(3+), and Sc(3+) from VO(2+).     

Self-assembling and photophysical properties of the organogelators based on cyanostyryl-substituted carbazoles

Four cyanostyryl-substituted carbazole derivatives (CN-ODEC1, CN-ODEC2, CN-DDEC1, and CN-DDEC) were synthesized and their self-assembly properties have been studied. It was found that they could form organogels especially in aromatic solvents. Scanning electron microscopy and light microscopy images show that the xerogels formed from monosubstituted derivatives (CN-O/DDEC1) gave well-organized tapes, and those from disubstituted derivatives (CN-O/DDEC2) exhibited heavy entangled three-dimensional structures. The UV–vis absorption and fluorescence emission spectra, as well as X-ray diffraction patterns, suggest that carbazole derivatives underwent J-type π-stacking. Meanwhile, we suggested that strong H-bonding and moderate π–π interactions were the key driving force for the gelation of the monosubstituted derivatives, and head-to-tail “ladder-type” J-aggregates were formed in the gel state. On the other hand, strong π–π interaction might be considered as the main driving force for the gelation of disubstituted derivatives, and J-aggregates with no well-organized packing mode of molecules were obtained in the gel phase. It should be noticed that aggregation-induced emission was observed during the gelation processes.     

Synthesis and properties of coumarin-derived organogelators

A new family of coumarin derivatives containing amide group with different alkyl chain lengths was synthesized and their properties as organogelators were evaluated. It was found that the organogelation abilities were not obviously affected by the alkyl spacer length of amide group. Helical morphologies formed either in nonpolar or high polar solvents by most of the gelators. Occurrence of reversible and stereoselective photodimerization of the gel formed by 4-(7′-coumarinoxy)-N-octadecylbutanamide (3a) in cyclohexane was confirmed by ¹H NMR, UV absorption, and fluorescence spectra. The photoreaction of the gel proceeded without any dissolution, but the drastic microscopic changes of gel morphologies accompanied with the irradiation were identified using SEM and AFM investigations.     

Synthesis of transparent and thermally stable polycyanurates and their thermal rearrangement

Transparent and thermally stable polycyanurates, whose solubility can be changed by thermal rearrangement, have been synthesized as functional films used in the multilayer coating process. Before the synthesis of polycyanurates, the model compound, 2,6‐bis(4‐methoxyphenyl)?6‐methoxy‐1,3,5‐triazine as a cyanurate is prepared and rearranged to an isocyanurate, 1,3‐bis(4‐methoxyphenyl)?5‐methyl‐1,3,5‐triazinane‐2,4,6‐trione in an excellent yield by thermal treatment. Based on this result, polycyanurates are prepared by the phase‐transfer‐catalyzed polycondensation of 2,4‐dichloro‐6‐methoxy‐1,3,5‐triazine with bisphenol monomers in the presence of quaternary ammonium salts. The polycyanurate obtained from 9,9‐bis(hydroxyphenyl)fluorene exhibits a high glass transition temperature at 251 °C. The solubility of polycyanurate films containing 1 wt % of tetrabutylammonium bromide can be changed by thermal rearrangement. The partially rearranged films keep high transparency and low birefringence. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3950–3955     

Thixotropic organogels based on a simple N-hydroxyalkyl amide: rheological and aging properties

The thixotropic properties ofthermoreversible organogels composed ofN-3-hydroxypropyl dodecanamide and various apolar fluids have been investigated by X-ray scattering, light microscopy, and rheo-optics experiments. This revealed that gel formation occurs via a precipitation process. Depending upon the cooling rate, large interconnected aggregates are formed and induce an elastic behavior. When submitted to a shear flow, these aggregates disentangled and became aligned in the direction of the velocity. Nevertheless, shear does not alter the structure of the individual aggregate and connections between the aggregates are quickly rebuilt due to gravity and thermal fluctuations when the applied flow is stopped. The alignment under flow and the reformation of the connections after the cessation of the shear induces the thixotropic behavior.     

Studies on hydroquinone based maleate bolaamphiphile organogels and their drug formulations

Now a day’s there is an upsurge in topical gel formulations, they can be prepared by varying physico-chemical methods and provide better localized action. A maleate based symmetric bolaamphiphile was synthesized by using cost-effective starting materials under mild reaction condition. The gelation ability of bolaamphiphile in aqueous medium was examined for a series of organic solvents. In hexane, the gelator showed better gelation ability with relatively higher critical strain (54 Pa) values. Further, the microscopic images of the gel revealed flakes like morphology, both the XRD and DFT studies revealed the presence of non covalent interactions. These gels showed a high internal-phase mole ratio of the topical drugs in the order of curcumin < salicylic acid < Ibuprofen. Formation of aqueous and organic gel-phase formulation may facilitate the topical medications for various applications related to ophthalmic and skin infections.     

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.     

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.     

Synthesis and self-assembling properties of polymerizable organogelators

In this paper we report the development of a family of polymerizable urea derivatives that are gelators for organic solvents. The design involves amino-acid-based urea derivatives containing methacrylate functional groups. Several of the bis-ureas show excellent gelation properties in a variety of organic solvents at very low concentrations (1.5 mM). The self-assembling properties of these compounds were studied by X-ray powder diffraction, optical microscopy, and electronic microscopy. The molecules self-assemble into fibrous aggregates as indicated by scanning electron microscopy. Depending on the nature of the monomeric unit, the structure of the aggregates ranges from small to large fibers and planar sheets. In polar solvents, the molecules exhibit multilamellar packing modes. The organogels can be polymerized by photoirradiation leading to significant increases in stability as indicated by changes in phase-transition temperature. The morphology of the aggregates was seen to maintain a similar structure both before and after irradiation. This method provides a novel type of polymer with designed self-assembling architecture and also affords to a route to stabilized polymer gels.     

Synthesis and properties of thermally stable polyimides bearing pendent fluorene moieties

A new diamine monomer containing fluorene unit, 3,5‐diamino‐N‐(9H‐fluoren‐2‐yl)benzamide was successfully synthesized via the condensation of 2‐aminofluorene and 3,5‐dinitrobenzoyl chloride and subsequent reduction of the dinitro compound. A series of novel aromatic polyimides having pendent fluorenamide moieties were prepared from the reaction of the diamine monomer and various tetracarboxylic dianhydrides by a conventional two‐step polymerization process. The polyimides were obtained in quantitative yields with inherent viscosities of 0.33–0.44 dl/g. The resulting polymers dissolved in N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfoxide. The glass transition temperature of these polymers was in the range of 261–289°C. They were fairly stable up to a temperature around 450°C and lost 10% weight in the range of 498–556°C in nitrogen. The UV–vis absorption spectra showed that all of the polymers had absorption maxima around 320 nm. Cyclic voltammograms of the polyimides revealed an oxidation wave with a peak around 1.3 V. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface activity and micellar properties of anionic gemini surfactants and their analogues

The properties of didodecyldiphenylether disulfonate gemini-type surfactants have been studied and compared to mono-alkylated and monosulfonated analogous surfactants. Dynamic and equilibrium surface tension measurements indicate that the gemini surfactants have a higher surface activity compared to that of the monoalkyl analogues. The gemini-type surfactants have much larger surface area per molecule, opposite effect of carbon number on CMC and considerable swelling of the micelles upon increasing surfactant concentration. Determination of aggregation numbers by fluorescence measurements reveals that the longer chain gemini surfactants form micelles having less than 10 molecules per micelle.     

Adsorption properties of thermally stable and biologically active polyurea: its synthesis and spectral aspects

Novel polymer metal complexes were prepared by the condensation polymerization of a polymeric ligand with transition metal ions of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). The polymeric ligand was prepared by the addition polymerization of urea with toluene 2,4‐diisocyanate in 1:1 molar ratio. The polymeric ligand and its polymer metal complexes were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹³C‐NMR, and¹H‐NMR (nuclear magnetic resonance). The geometry was determined by electronic spectra and magnetic moment measurement. Thermogravimetric analysis (TGA) was utilized to find out the degradation process of the polyurea ligand and the polymer metal complexes. The TGA data revealed that all the metal‐containing polyureas are much more thermally stable than the corresponding polyurea ligand. The surface morphology of the polyurea ligand and cobalt(II)‐containing polyureas was determined by scanning electron micrographs. The antibacterial and antifungal activities of all the synthesized polymers were investigated against Staphylococcus aureus, Escherichia coli, and Bacillus subtilis (bacteria) and Aspergillus niger, Candida albicans, and Aspergillus flavus (fungi). These compounds show remarkably good biocidal activities, which were enhanced after complexation with the metal. Batch adsorption studies of the ligand were carried out for malachite green dye, and the polyurea ligand was found to be a good adsorbent for this dye. Copyright © 2011 John Wiley & Sons, Ltd.     

Solubilizing and catalytic properties of supramolecular systems based on gemini surfactants

Quantitative parameters characterizing the aggregation behavior of dicationic surfactants of the 12-s-12 type in aqueous solutions were determined: critical micelle concentrations, aggregation numbers, and surface potentials. The effects of the spacer length of the surfactants on their solubilizing effect with respect to hydrophobic (dye Orange OT) and water-soluble (p-nitrophenol) spectral probes and on their ability to shift acid-base equilibria were studied. The kinetics of alkaline hydrolysis of p-nitrophenyl acetate and p-nitrophenyl caprinate in 12-s-12 solutions was studied by spectrophotometry. A correlation between the micellar catalytic effect and the surface potential of micelles was established. The pronounced substrate specificity was revealed: the maximum acceleration of hydrolysis is observed in solutions of 12-6-12, attaining 1760 times for p-nitrophenyl caprinate.     

Epoxide composites with thermally reduced graphite oxide and their properties

The properties of epoxide composites modified by thermal reduced graphite oxide are studied. The dielectric permittivities of epoxide composites with additives of up to 1.5 wt % of reduced graphite oxide are studied at a frequency of 9.8 GHz. It is shown that despite its low electrical conductivity, the large specific surface area of reduced graphite oxide allows us to create epoxide composites with high complex dielectric permittivities and dielectric loss tangents.