Gel Sculpture: Moldable, Load-Bearing and Self-Healing Non-Polymeric Supramolecular Gel Derived from a Simple Organic Salt

An easy access to a library of simple organic salts derived from tert-butoxycarbonyl (Boc)-protected L-amino acids and two secondary amines (dicyclohexyl- and dibenzyl amine) are synthesized following a supramolecular synthon rationale to generate a new series of low molecular weight gelators (LMWGs). Out of the 12 salts that we prepared, the nitrobenzene gel of dicyclohexylammonium Boc-glycinate (GLY.1) displayed remarkable load-bearing, moldable and self-healing properties. These remarkable properties displayed by GLY.1 and the inability to display such properties by its dibenzylammonium counterpart (GLY.2) were explained using microscopic and rheological data. Single crystal structures of eight salts displayed the presence of a 1D hydrogen-bonded network (HBN) that is believed to be important in gelation. Powder X-ray diffraction in combination with the single crystal X-ray structure of GLY.1 clearly established the presence of a 1D hydrogen-bonded network in the xerogel of the nitrobenzene gel of GLY.1. The fact that such remarkable properties arising from an easily accessible (salt formation) small molecule are due to supramolecular (non-covalent) interactions is quite intriguing and such easily synthesizable materials may be useful in stress-bearing and other applications.

Phase behavior of concentrated aqueous solutions of cetyltrimethylammonium bromide (CTAB) and sodium hydroxy naphthoate (SHN)

We have characterized the phase behavior of mixtures of the cationic surfactant cetyltrimethylammonium bromide (CTAB) and the organic salt 3-sodium-2-hydroxy naphthoate (SHN) over a wide range of surfactant concentrations using polarizing optical microscopy and X-ray diffraction. A variety of liquid crystalline phases, such as hexagonal, lamellar with and without curvature defects, and nematic, are observed in these mixtures. At high temperatures the curvature defects in the lamellar phase are annealed gradually on decreasing the water content. However, at lower temperatures these two lamellar structures are separated by an intermediate phase, where the bilayer defects appear to order into a lattice. The ternary phase diagram shows a high degree of symmetry about the line corresponding to equimolar CTAB/SHN composition, as in the case of mixtures of cationic and anionic surfactants.

Novel organic porous solids with channel and layered structures from 1,3,5-triazine-2,4,6-triaminehexaacetic acid and its calcium salt

Single crystals of a symmetrically substituted molecule, 1,3,5-triazine-2,4,6-triaminehexaacetic acid, (TTHA) and its Ca2+ salt have been synthesized, the analysis of which reveals the existence of novel channel type cavities and helical packing organizations in the crystals.

Structure and properties of two component hydrogels comprising lithocholic acid and organic amines

We demonstrate the aptitude of supramolecular hydrogel formation using simple bile acid such as lithocholic acid in aqueous solution in the presence of various dimeric or oligomeric amines. By variation of the choice of the amines in such mixtures the gelation properties could be modulated. However, the replacement of lithocholic acid (LCA) by cholic acid or deoxycholic acid resulted in no hydrogel formation. FT-IR studies confirm that the carboxylate and ammonium residues of the two components are involved in the salt (ion-pair) formation. This promotes further assembly of the components reinforced by a continuous hydrogen bonded network leading to gelation. Electron microscopy shows the morphology of the internal organization of gels of two component systems which also depends significantly on the amine part. Variation of the amine component from the simple 1,2-ethanediamine (EDA) to oligomeric amines in such gels of lithocholic acid changes the morphology of the assembly from long one-dimensional nanotubes to three-dimensional complex structures. Single crystal X-ray diffraction analysis with one of the amine-LCA complexes suggested the motif of fiber formation where the amines interact with the carboxylate and hydroxyl moieties through electrostatic forces and hydrogen bonding. From small angle neutron scattering study, it becomes clear that the weak gel from LCA-EDA shows scattering oscillation due to the presence of non-interacting nanotubules while for gels of LCA with oligomeric amines the individual fibers come together to form complex three-dimensional organizations of higher length scale. The rheological properties of this class of two component system provide clear evidence that the flow behavior can be modulated varying the acid-amine ratio.

Oxonium salt intermediates from half ester acid chlorides

Isomeric half eater acid chlorides derived from 1,2-and 1-3-carboxylic acids give rise to the same oxonium salt with Lewis acids.

Neutron-diffraction study of structure and conformation of nucleotide uridine-5 phosphate (disodium salt)

Acta Crystallographica Section A: Foundations of Crystallography covers theoretical and fundamental aspects of the structure of matter. The journal is the prime forum for research in diffraction physics and the theory of crystallographic structure determination by diffraction methods using X-rays, neutrons and electrons. The structures include periodic and aperiodic crystals, and non-periodic disordered materials, and the corresponding Bragg, satellite and diffuse scattering, thermal motion and symmetry aspects. Spatial resolutions range from the subatomic domain in charge-density studies to nanodimensional imperfections such as dislocations and twin walls. The chemistry encompasses metals, alloys, and inorganic, organic and biological materials. Structure prediction and properties such as the theory of phase transformations are also covered.

Large molecular motions are tolerated in crystals of diamine double salt of trans-chlorocinnamic acids with trans-1,2-diaminocyclohexane

Contrary to the general assumption that photoreactions in crystals may not proceed with large molecular motions, a pedal-like motion prompted by electronic excitation is believed to be involved during the β-dimer formation from the crystals of the diamine double salt of trans-2,4-dichlorocinnamic acid and trans-1,2-diaminocyclohexane.

Dynamics of bound dyes in a nonpolymeric aqueous gel derived from a tripodal bile salt

Rotational dynamics of polarity sensitive fluorescent dyes (ANS and DPH) in a nonpolymertic aqueous gel derived from tripodal cholamide I was studied using ultrafast time-resolved fluorescence technique. Results were compared with that of naturally occurring di- and trihydroxy bile salts. ANS in the gel showed two rotational correlation time (phi) components, 13.2 ns (bound to the hydrophobic region of the gel) and 1.0 ns (free aqueous ANS), whereas DPH showed only one component (4.8 ns). In the sol state, faster rotational motion was observed, both for ANS and DPH. Our data revealed that dyes get encapsulated more tightly in the gel network when compared to the micellar aggregates. ANS has more restrained rotation compared to DPH. This was attributed to the interaction of the sulfonate group of ANS with water molecules and hydrophilic parts of the gelator molecule. No restricted rotation was observed for DPH in the gel state unlike when it is in the gel phase of lipid bilayer.

Ionic conductivity of bis(2-cyanoethyl) ether-lithium salt and poly(propylether imine)-lithium salt liquid electrolytes

We report here a multiple-nitrile based lithium-salt liquid electrolyte. The ionic conductivity of poly (propyl ether imine) (abbreviated as PETIM) lithium salt dendrimer liquid electrolyte was observed to be a function of dendrimer generation number, n=0 (monomer)-3. While the highest room temperature ionic conductivity value (similar to 10(-1) Sm-1) was recorded for the bis-2cyanoethyl ether monomer (i.e. zeroth generation; G(0)-CN), conductivity decreased progressively to lower values (similar to 10(-3) Sm-1) with increase in generation number (G(1)-CN -> G(3)-CN). The G(0)-CN and higher dendrimer generations showed high thermal stability (approximate to 150 to 200 degrees C), low moisture sensitivity and tunable viscosity (similar to 10(-2) (G(0)-CN) to 3 (G(3)-CN) Pa s). The linker ether group was found to be crucial for ion transport and also eliminated a large number of detrimental features, chiefly moisture sensitivity, chemical instability associated typically with prevalent molecular liquid solvents. Based on the combination of several beneficial physicochemical properties, we presently envisage that the PETIM dendrimers especially the G(0)-CN electrolytes hold promise as electrolytes in electrochemical devices such as lithium-ion batteries.

Unusual Salt-Induced Color Modulation through Aggregation-Induced Emission Switching of a Bis-cationic Phenylenedivinylene-Based pi Hydrogelator

The synthesis, hydrogelation, and aggregation-induced emission switching of the phenylenedivinylene bis-N-octyl pyridinium salt is described. Hydrogelation occurs as a consequence of pi-stacking, van der Waals, and electrostatic interactions that lead to a high gel melting temperature and significant mechanical properties at a very low weight percentage of the gelator. A morphology transition from fiber-to-coil-to-tube was observed depending on the concentration of the gelator. Variation in the added salt type, salt concentrations, or temperature profoundly influenced the order of aggregation of the gelator molecules in aqueous solution. Formation of a novel chromophore assembly in this way leads to an aggregation-induced switch of the emission colors. The emission color switches from sky blue to white to orange depending upon the extent of aggregation through mere addition of external inorganic salts. Remarkably, the salt effect on the assembly of such cationic phenylenedivinylenes in water follow the behavior predicted from the well-known Hofmeister effects. Mechanistic insights for these aggregation processes were obtained through the counterion exchange studies. The aggregation-induced emission switching that leads to a room-temperature white-light emission from a single chromophore in a single solvent (water) is highly promising for optoelectronic applications.

Time-Temperature Scaling of Conductivity Spectra of Organic Plastic Crystalline Conductors

Organic plastic crystalline soft matter ion conductors are interesting alternatives to liquid electrolytes in electrochemical storage devices such as Lithium-ion batteries. The solvent dynamics plays a major role in determining the ion transport in plastic crystalline ion conductors. We present here an analysis of the frequency-dependent ionic conductivity of succinonitrile-based plastic crystalline ion conductors at varying salt composition (0.005 to 1 M) and temperature (-20 to 60 degrees C) using time-temperature superposition principle (TTSP). The main motivation of the work has been to establish comprehensive insight into the ion transport mechanism from a single method viz, impedance spectroscopy rather than employing cluster of different characterization methods probing various length and time scales. The TTSP remarkably aids in explicit identification of the extent of the roles of solvent dynamics and ion-ion interactions on the effective conductivity of the orientationally disordered plastic crystalline ion conductors.

Solute induced liquid crystalline behaviour of a quaternary ammonium salt and its application to structure determination

A new liquid crystalline phase, induced by the addition of small amounts of a non-mesogenic solute (such as dimethyl sulphoxide or methyl iodide) to a quaternary ammonium salt, N-methyl-N,N,N-trioctadecylammonium iodide (MTAI), has been detected by NMR and optical microscopic studies. In some cases, there is a coexistence of nematic and smectic phases. Information on the ordering of the phases in the magnetic field of the spectrometer has been derived from NMR spectra of a dissolved molecule, C-13-enriched methyl iodide. The low order parameter of the pure thermotropic nematic phase of the salt provides first-order spectra of the dissolved oriented molecules. Analyses of spectra of cis,cis-mucononitrile exemplifies the utility of the MTAI nematic phase in the determination of structural parameters of the solute.

Electron spin resonance absorption in organic metal polyaniline and its blend with PMMA

The electron spin resonance absorption in the synthetic metal polyaniline (PANI) doped with PTSA and its blend with poly(methylmethacrylate) (PMMA) is investigated in the temperature range between 4.2 and 300 K. The observed line shape follows Dyson's theory for a thick metallic plate with slowly diffusing magnetic dipoles. At low temperatures the line shape become symmetric and Lorentzian when the sample dimensions are small in comparison with the skin depth. The temperature dependence of electron spin relaxation time is discussed. (C) 1999 Elsevier Science Ltd. All rights reserved.

Gossypol-induced hypokalemia and role of exogenous potassium salt supplementation when used as an antispermatogenic agent in male langur monkey

In our earlier study, we have observed that hypokalemia in langur monkeys, following gossypol acetic acid (GAA) treatment (5 mg dose level) when used as an antispermatogenic agent, and potassium salt supplementation partially maintained body potassium level of the animals. The aims of the present investigation was to confirm further occurrence of hypokalemia in the monkey (comparatively at two higher dose levels) and the role of potassium salt in preventing occurrence of gossypol-induced hypokalemia. Highly purified gossypol acetic acid alone at two dose levels (7.5 and 10 mg/animal/day; oral) and in combination with potassium chloride (0.50 and 0.75 mg/animal/day; oral) was given for 180 days. Treatment with gossypol alone as well as with the supplementation of potassium salt resulted in severe oligospermia and azoospermia. Animals receiving gossypol alone showed significant potassium deficiency with signs of fatigue at both dose levels. Enhanced potassium loss through urine was found in potassium-deficient animals, whereas animals receiving gossypol acetic acid plus potassium salt showed normal serum potassium with a less significant increase in urine potassium level during treatment phases. Other parameters of the body remained within normal range except gradual and significant elevation in serum transaminases activity. The animals gradually returned to normalcy following 150 and 180 days of termination of the treatment.

First donor-acceptor interaction promoted gelation of organic fluids

In recent years there has been considerable interest in developing new types of gelators of organic solvents.1 Despite the recent advances, a priori design of a gelator for gelling a given solvent has remained a challenging task. Various noncovalent interactions like hydrogen-bonding,2 metal coordination3 etc. have been used as the driving force for the gelation process. A special class of cholesterol-based gelators were reported by Weiss,4 and by Shinkai.5 Gels derived from these molecules have been used for chiral recognition/sensing,6 for studying photo- and metal-responsive functions,7 and as templates to make hollow fiber silica.8 Other types of organogels have been used for designing polymerized 9 and reverse aerogels,10 and in molecular imprinting.11 Hanabusa’s group has recently reported organogels with a bile acid derivative.12 This has prompted us to disclose our results on a novel electron donor–acceptor (EDA) interaction mediated two-component13 gelator system based on the bile acid14 backbone.