Fiber formation in water by a mono-urea dicarboxylic acid

Fibers formed by a mono-urea dicarboxylic acid derivative in water were analyzed by SEM, IR and XRD. The resulting data were used to develop a model of the molecular aggregation leading to fiber formation.     

Lipid nanotubes and microtubes: experimental evidence for unsymmetrical monolayer membrane formation from unsymmetrical bolaamphiphiles

Unsymmetrical bolaamphiphiles, omega- [N-beta-D-glucopyranosylcarbamoyl] alkanoic acids, with even-numbered oligomethylene chains (12, 14, 16, 18, and 20 carbons) self-assembled in water to form lipid nano- and microtubes. The tubular assemblies were separated by centrifugation and examined by transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy to study the molecular packing within the tubular membranes. The nanotubes encapsulated the staining reagent phosphotungstate, which revealed them to be hollow cylinders up to several hundred micrometers long with 30-43-nm outer diameters and 14-29-nm inner diameters. By comparing the membrane stacking periodicity obtained from powder X-ray diffraction analysis of the dehydrated tubes with the molecular packing within single crystals, we found that the nanotubes consist of an unsymmetrical monolayer lipid membrane (MLM) in which the molecules are packed in a parallel fashion. This suggests that the inner surface of the nanotubes is covered with carboxy headgroups and the outer surface with 1-glucosamide headgroups. The inner diameters of the lipid nanotubes could be controlled in the range 17.7-22.2 nm in steps of approximately 1.5 nm/two carbons by varying the oligomethylene spacer length. The microtubes had three types of molecular arrangements. The first type was a symmetrical MLM in which the molecules were packed in an antiparallel fashion. The other two types had unsymmetrical MLM stacking with head-to-head and head-to-tail motifs. Increasing the number of oligomethylene spacers stabilized the unsymmetrical MLM structure in both nano- and microtubes.     

Extraction of mono- and dicarboxylic acids from a curative water

A method for the analysis of mono- and dicarboxylic acids from water is presented. For this purpose two techniques, a C(18) solid phase extraction (SPE) and a combination method of liquid-liquid extraction (LLE) and aminopropyl SPE, were tested. With the combination method all analytes, short-chain mono- and long-chain dicarboxylic acids, could be analysed in one approach. The C(18) SPE was not suitable for short-chain mono- but for dicarboxylic acids. Concentrations in the investigated water ranged from 315 mg/l (butanoic acid) to 2.9 mg/l (octanoic acid). Dicarboxylic acids were found from 5 mg/l (octanedioic acid) to 0.5 mg/l (dodecanedioic acid).     

Extraction of mono- and dicarboxylic acids from a curative water

A method for the analysis of mono- and dicarboxylic acids from water is presented. For this purpose two techniques, a C₁₈ solid phase extraction (SPE) and a combination method of liquid-liquid extraction (LLE) and aminopropyl SPE, were tested. With the combination method all analytes, short-chain mono- and long-chain dicarboxylic acids, could be analysed in one approach. The C₁₈ SPE was not suitable for short-chain mono- but for dicarboxylic acids. Concentrations in the investigated water ranged from 315 mg/l (butanoic acid) to 2.9 mg/l (octanoic acid). Dicarboxylic acids were found from 5 mg/l (octanedioic acid) to 0.5 mg/l (dodecanedioic acid).     

The ionization of aliphatic dicarboxylic acids in water

Potentiometric, calorimetric, and dilatometric data on the ionization of several saturated dicarboxylic acids in water at 25°C are reported. A correlation is attempted between structure and thermodynamic evidences for the two dissociation stages of the diacids considered, in particular in terms of the propensity toward intramolecular hydrogen bond formation of some singly ionized species.     

Supramolecular assemblies from single-chain hydrocarbon fluorocarbon hybrid bolaamphiphiles

Three types of single-chain hydrocarbon fluorocarbon hybrid bolaamphiphiles were synthesized.They readily formed different kinds of organized supramolecular assemblies,including vesicles,tapes,and micellar fibers,in aqueous solution.The aggregates morphology was characterized by transmission electron microscopy (TEM) after negative staining.The superstructures of these aggregates seemed to be determined by the geometry and the head group's properties of the corresponding amphiphiles.     

Binary adduct formation of desipramine with dicarboxylic acids

This paper presents the results obtained in a screening study for binary adduct formation of desipramine with three dicarboxylic acids—namely succinic, malonic and glutaric acids. Adduct formation is important because most tricyclic antidepressants show limited water solubility as free bases. Three binary adducts were prepared using a wet kneading method in non-homogenous media in presence of ethanol. Investigations of the solid state (ATR-FTIR, PXRD) and thermal analysis (TG/DTG/HF) were used for characterization of the prepared samples. The corroboration of data from employed instrumental techniques suggests that binary adducts in molar ratio 1:1 were obtained under the used experimental conditions.     

Monolayer lipid membrane-forming dissymmetrical bolaamphiphiles derived from alginate oligosaccharides

New dissymmetrical neutral-cationic or anionic-cationic alpha,omega-diamido bolaamphiphiles have been synthesized in which the polar headgroups are derived from alginate and glycine betaine and which exhibit monolayer lipid membrane vesicles, large lamellae and rods.     

The formation of polyethylene terephthalate in the presence of dicarboxylic acids

The process of polyethylene terephthalate (PET) formation in the presence of dicarboxylic acids has been studied. Certain amounts of terephthalic acid (TPA) have two- to threefold accelerating efficiency in the polycondensation process. To elucidate the causes of the acceleration the main reactions leading to PET formation in the presence of dicarboxylic acids have been investigated by the use of models. The evaluation of kinetic and equilibrium parameters obtained for model reactions made it possible to conclude that the influence of carboxyl-containing additives on the apparent rate of polycondensation manifests itself in accelerating direct reactions and facilitating the liberation of the eliminated by-product; that is, ethylene glycol (EG) from the polymer melt. Carboxylic acid acts as a catalyst on the ester interchange of 2-hydroxyethyl ester end groups and thus increases the rate of polymer formation in this reaction 10–40 times. The parallel interaction between the 2-hydroxyethyl ester end group and the carboxyl group of the added acid is also catalyzed by the acid and its rate constant is four times larger than that of the catalytic polycondensation of 2-hydroxyethyl ester end groups. Unlike EG, the reaction water formed in the process is more readily removed from the reaction system and thus promotes the intensification of the process. In addition, the carboxyl groups react with the eliminated EG to decrease its amount and shift the equilibrium toward polymer formation. The investigation of the consequent parallel reactions on models made it possible to draw a conclusion about the higher reactivity of 2-hydroxyethyl esters in the esterification processes. This fact has been explained by strengthening the nucleophilicity of the oxygen atom in the hydroxyl of a 2-hydroxyethyl ester group compared with that of EG; for example, by the formation of an intramolecular cycle involving a hydrogen bond. Simultaneously, it has been found that in the system simulating PET polycondensation in the presence of dicarboxylic acids the reaction mechanism involves the catalysis by a proton formed during the carboxyl group dissociation and accepted by the 2-hydroxyethyl ester group.     

Photochemical free radical formation from aliphatic dicarboxylic acids in solution as studied by electron spin resonance spectroscopy

Various free radicals formed during UV.-irradiation of aliphatic dicarboxylic acids in aqueous and methanolic solution are identified by ESR.-spectroscopy. Their structures point to α-cleavage and photoreduction as the dominant primary photochemical decay processes. The relative contributions of these reactions to the overall photodecomposition depend on solvent and degree of α-alkylation of the acid. Emission ESR.-spectra are found for radicals formed by C, CO-bond cleavage of α-dimethyl substituted acids. The polarization is referred to the triplet mechanism of CIDEP. and indicates this cleavage reaction occurs from a triplet molecular state.     

Intramolecular formation of excimers in model compounds for polyesters obtained from 2,6-naphthalene dicarboxylic acid and cyclohexanediols

The fluorescence in dilute solution has been measured as a function of solvent viscosity for four bichromophoric models for polyesters with naphthalene in the rigid aromatic unit and diols derived from cyclohexane as the flexible spacer. The spacers are 1,2-cis-cyclohexanediol, 1,2-trans-cyclohexanediol, a 1:2 mixture of 1,3-cis- and 1,3-trans-cyclohexanediols, and a 1:2 mixture of 1,4-cis- and 1,4-trans-cyclohexanediols. The shape of the emission spectra for the molecules in this series is less sensitive to the viscosity of the medium than was the case for an analogous series in which a methylene or oxyethylene spacer replaces the cyclohexanediol spacer. The dependence of the excimer emission on the type of spacer is different also in the series in which the rigid units contain naphthalene or benzene. When the rigid units contain naphthalene, excimer formation is maximal if the spacer contains 1,2-trans-cyclohexanediol, but this spacer produces a molecule with a very small tendency for excimer formation in its polymers with terephthalate. A conformational analysis correctly concludes that the spacer most conducive to excimer formation should be 1,2-trans-cyclohexanediol, but it does not identify the correct order of the remaining three bichromophoric model compounds. The problem may reside in the method for taking into account the finite width of the torsional well associated with each rotational isomer. © 1994 John Wiley & Sons, Inc.     

Electrostatic effects on nanofiber formation of self-assembling peptide amphiphiles

Self-assembling peptide amphiphile molecules have been of interest to various tissue engineering studies. These molecules self-assemble into nanofibers which organize into three-dimensional networks to form hydrocolloid systems mimicking the extracellular matrix. The formation of nanofibers is affected by the electrostatic interactions among the peptides. In this work, we studied the effect of charged groups on the peptides on nanofiber formation. The self-assembly process was studied by pH and zeta potential measurements, FT-IR, circular dichroism, rheology, atomic force microscopy, scanning electron microscopy and transmission electron microscopy. The aggregation of the peptides was triggered upon neutralization of the charged residues by pH change or addition of electrolyte or biomacromolecules. Understanding the controlled formation of the hydrocolloid gels composed of peptide amphiphile nanofibers can lead us to develop in situ gel forming bioactive collagen mimetic nanofibers for various tissue engineering studies including bioactive surface coatings.     

功能大分子金属轮烷和索烃的研究进展

金属轮烷和金属索烃是通过在轮烷和索烃中引入金属离子或金属配合物而制得的,它们不仅结构特殊,而且具有许多特殊的性质,因此受到化学家们的广泛关注。本文综述了近几年来金属轮烷和金属索烃在分子机器、分子开关、仿生物质、分子材料等方面的应用及研究进展,并对该领域的前景进行了展望。     

Self-sorting in rodlike micelles of chiral bisurea bolaamphiphiles

We have demonstrated the formation of segregated enantiomeric dynamic rods in water, from the self-sorting of chiral trans-1,2-bisureido cyclohexane-based bolaamphiphiles. Fluorescence probes have been used to investigate the self-sorting through forming exciplex and FRET.     

Effect of ion-exchange nanofiber fabrics on water splitting in bipolar membrane

In the present study, the effect of ion-exchange fiber fabric made by electrospray deposition (ESD) on water splitting in a composite bipolar membrane (CBM) was investigated. Cation- and anion-exchange fiber (CEF and AEF) fabrics, which were composed of very thin fibers, were prepared by ESD and postdeposition chemical modification and then used as the intermediate layer of a CBM. The current-voltage characteristics under reverse bias conditions showed that the AEF fabrics enhanced water splitting. The water dissociation is accelerated by the AEF fabric, which contains both tertiary pyridyl groups and quaternary pyridinium groups and has a high specific surface area. On the other hand, the CEF fabric, which contains sulfonic acid groups and has an insufficient specific surface area, reduced water splitting. These results indicate that fiber fabric with catalytic activity and a high surface area obtained by ESD can improve the performance of a CBM.     

Internucleobase-interaction-directed self-assembly of nanofibers from homo- and heteroditopic 1,omega-nucleobase bolaamphiphiles.

The complementary 1,omega-thymine, 1,omega-adenine, and 1,omega-(thymine, adenine) bolaamphiphiles, [N,N'-bis[3-(2,4-dihydroxy-5-methylpyrimidine-1-yl)propionyl]1,n-diaminoalkane [T-n-T (n = 10, 11, 12)], N, N'-bis[3-(6-aminopurine-9-yl)propionyl]1,n-diaminoalkane [A-n-A (n = 10, 11, 12)], and N-[3-(2,4-dihydroxy-5-methylpyrimidine-1-yl)propionyl], N'-[3-(6-aminopurine-9-yl)propionyl]1,n-diaminoalkane [T-n-A (n = 10, 11, 12)], respectively] have been synthesized. The spontaneous homo- and heteroassembly of these nucleobase-based bolaamphiphiles has been studied by light microscopy, energy-filtering transmission electron microscopy, FT-IR, and powder X-ray diffraction analyses. The achiral T-10-T bolaamphiphile produced in 10% ethanolic/aqueous solutions unprecedented double-helical ropes of 1-2 microm in widths and several hundred micrometers in length, whereas the complementary homologue A-10-A gave only microcrystalline solids of 1-10 microm in size. In contrast, an equimolar mixture of T-10-T and A-10-A yielded supramolecular fibers of 15-30 nm in width. (1)H NMR, CD, and UV studies of solution photoreactions of T-10-T suggested that under natural light the chiral rope formation is triggered by photodimerization of trace amounts of the thymine moieties in the T-10-T assemblies. Complementary hydrogen bond formation between the thymine-adenine heterobase pairs was found to prevent such a photoreaction and resulted in no chiral rope formation. The heteroditopic T-12-A bolaamphiphile self-assembled to form supramolecular fibers. Multilamellar organization was proposed for the homo- and heteroassemblies made of T-n-T and A-n-A.     

Electrospun nanofiber based colorimetric probe for rapid detection of Fe in water

An imidazole derivative, 2-(2′-pyridyl)imidazole (PIMH), was developed as a colorimetric probe for the qualitative analysis of Fe²⁺ in aqueous solution. PIMH was then used to post-functionalize poly(vinylbenzyl chloride) (PVBC) nanofibers after electrospinning so as to afford a solid state colorimetric probe. Upon treatment with Fe²⁺ the probe displayed a distinctive color change both in liquid and solid platforms. The linear dynamic range for the colorimetric determination of Fe²⁺ was 0.0988–3.5 μg mL⁻¹. The ligand showed a high chromogenic selectivity for Fe²⁺ over other cations with a detection limit of 0.102 μg mL⁻¹ in solution (lower than the WHO drinking water guideline limit of 2 mg L⁻¹), and 2 μg mL⁻¹ in the solid state. The concentration of Fe²⁺ in a certified reference material (Iron, Ferrous, 1072) was found to be 2.39 ± 0.01 mg L⁻¹, which was comparable with the certified value of 2.44 ± 0.12 mg L⁻¹. Application of the probe to real samples spiked with Fe²⁺ achieved recoveries of over 97% confirming accuracy of the method and its potential for on-site monitoring.     

Improving titanium dioxide dispersion in water through surface functionalization by a dicarboxylic acid

In this work, we show evidence of improving the dispersion of titanium dioxide particles in water. This is observed in the titanium dioxide-water colloid by the shear-thinning flow behavior in rheological measurements induced by the functionalization of a glutaric acid layer on the surface of titanium dioxide particles. The characterization of the layer was achieved by using infrared spectroscopy and ^13?C nuclear magnetic resonance. Rheological measurements corroborated that functionalization of TiO₂ particles decreases the rheological properties such as viscosity measurements at a constant shear rate in two orders of magnitude compared with the pure TiO₂ in suspensions. We present the results as a novel strategy to limit the formation of agglomerates in these colloidal suspensions, and this will be of great use in applications in the paints field and printing technologies.     

The role of rheology of polymer solutions in predicting nanofiber formation by electrospinning

Electrospun polymer nanofibers are gaining increasing importance in tissue engineering, wound dressing and drug delivery. Here, we present a thorough rheological study of polymer solutions in the bulk and at the interface to find correlations between those properties and the electrospinnability of the solutions and the morphology of the resultant nanofibers. Our results indicate that blended solutions of chitosan or alginate with poly(ethylene oxide) (PEO) are appropriate for electrospinning when they form conductive, unstructured fluids displaying plasticity, rather than elasticity, in the bulk and at the interface. The interfacial rheological parameters are three orders of magnitude lower than those in the bulk. We demonstrate for the first time that interfacial, rather than bulk, rheological parameters show improved correlation and can be used to predict the success of the electrospinning process. Using the interfacial parameters of samples with homologous compositions, different groups of solutions can be identified that form smooth nanofibers. However, rheological parameters of the bulk and at the interface provide complimentary information. The bulk parameters are determined by polymer concentration and directly affect jet initiation, while the interfacial behaviour determines the continuation of the jet and fibre formation. We propose that interfacial parameters are indispensible tools for the design of electrospinning experiments.