External and internal gelation of pectin solutions: microscopic dynamics versus macroscopic rheology

NASA Astrophysics Data System (ADS)

Secchi, E.; Munarin, F.; Alaimo, M. D.; Bosisio, S.; Buzzaccaro, S.; Ciccarella, G.; Vergaro, V.; Petrini, P.; Piazza, R.

2014-11-01

Pectin is a natural biopolymer that forms, in the presence of divalent cations, ionic-bound gels typifying a large class of biological gels stabilized by non-covalent cross-links. We investigate and compare the kinetics of formation and aging of pectin gels obtained either through external gelation via perfusion of free Ca2+ ions, or by internal gelation due to the supply of the same ions from the dissolution of CaCO3 nanoparticles. The microscopic dynamics obtained with photon correlation imaging, a novel optical technique that allows obtaining the microscopic dynamics of the sample while retaining the spatial resolution of imaging techniques, is contrasted with macroscopic rheological measurements at constant strain. Pectin gelation is found to display peculiar two-stage kinetics, highlighted by non-monotonic growth in time of both microscopic correlations and gel mechanical strength. These results are compared to those found for alginate, another biopolymer extensively used in food formulation.

Fast Response and Spontaneous Alignment in Liquid Crystals Doped with 12-Hydroxystearic Acid Gelators.

PubMed

Lin, Hui-Chi; Wang, Chih-Hung; Wang, Jyun-Kai; Tsai, Sheng-Feng

2018-05-07

The spontaneous vertical alignment of liquid crystals (LCs) in gelator (12-hydroxystearic acid)-doped LC cells was studied. Gelator-induced alignment can be used in both positive and negative LC cells. The electro-optical characteristics of the gelator-doped negative LC cell were similar to those of an LC cell that contained a vertically aligned (VA) host. The rise time of the gelator-doped LC cell was two orders of magnitude shorter than that of the VA host LC cell. The experimental results indicate that the gelator-induced vertical alignment of LC molecules occurred not only on the surface of the indium tin oxide (ITO) but also on the homogeneous alignment layer. Various LC alignments (planar, hybrid, multistable hybrid, and vertical alignments) were achieved by modulating the doped gelator concentrations. The multistable characteristic of LCs doped with the gelator is also presented. The alignment by doping with a gelator reduces the manufacturing costs and provides a means of fabricating fast-responding, flexible LC displays using a low-temperature process.

Low-molecular-weight gelators: elucidating the principles of gelation based on gelator solubility and a cooperative self-assembly model.

PubMed

Hirst, Andrew R; Coates, Ian A; Boucheteau, Thomas R; Miravet, Juan F; Escuder, Beatriu; Castelletto, Valeria; Hamley, Ian W; Smith, David K

2008-07-16

This paper highlights the key role played by solubility in influencing gelation and demonstrates that many facets of the gelation process depend on this vital parameter. In particular, we relate thermal stability ( T gel) and minimum gelation concentration (MGC) values of small-molecule gelation in terms of the solubility and cooperative self-assembly of gelator building blocks. By employing a van't Hoff analysis of solubility data, determined from simple NMR measurements, we are able to generate T calc values that reflect the calculated temperature for complete solubilization of the networked gelator. The concentration dependence of T calc allows the previously difficult to rationalize "plateau-region" thermal stability values to be elucidated in terms of gelator molecular design. This is demonstrated for a family of four gelators with lysine units attached to each end of an aliphatic diamine, with different peripheral groups (Z or Boc) in different locations on the periphery of the molecule. By tuning the peripheral protecting groups of the gelators, the solubility of the system is modified, which in turn controls the saturation point of the system and hence controls the concentration at which network formation takes place. We report that the critical concentration ( C crit) of gelator incorporated into the solid-phase sample-spanning network within the gel is invariant of gelator structural design. However, because some systems have higher solubilities, they are less effective gelators and require the application of higher total concentrations to achieve gelation, hence shedding light on the role of the MGC parameter in gelation. Furthermore, gelator structural design also modulates the level of cooperative self-assembly through solubility effects, as determined by applying a cooperative binding model to NMR data. Finally, the effect of gelator chemical design on the spatial organization of the networked gelator was probed by small-angle neutron and X-ray scattering (SANS/SAXS) on the native gel, and a tentative self-assembly model was proposed.

Effect of Sol Concentration, Aging and Drying Process on Cerium Stabilization Zirconium Gel Produced by External Gelation

NASA Astrophysics Data System (ADS)

Sukarsono, R.; Rachmawati, M.; Susilowati, S. R.; Husnurrofiq, D.; Nurwidyaningrum, K.; Dewi, A. K.

2018-02-01

Cerium Stabilized Zirconium gel has been prepared using external gelation process. As the raw materials was used ZrO(NO3)2 and Ce(NO3)4 nitrate salt which was dissolved with water into Zr-Ce nitrate mixture. The concentration of the nitrate salt mixture in the sol solution was varied by varying the concentration of zirconium and cerium nitrate in the sol solution and the addition of PVA and THFA to produce a sol with a viscosity of 40-60 cP. The viscosity range of 40-60cP is the viscosity of the sol solution that was easy to produce a good gel in the gelation apparatus. Sol solution was casted in a gelation column equipped with following tools: a 1 mm diameter drip nozzle which was vibrated to adjust the best frequency and amplitude of vibration, a flow meter to measure the flow rate of sol, flowing of NH3 gas to presolidification process. Gelation column was contained NH4OH solution as gelation medium and gel container to collect gel product. Gel obtained from the gelation process than processed with ageing, washing, drying and calcinations to get round gel and not broken at calcinations up to 500°C. The parameters observed in this research are variation of Zr nitrate concentration, Ce nitrate concentration, ratio of Zr and Ce in the sol and ageing and drying process method which was appropriate to get a good gel. From the gelation processes that has been done, it can be seen that with the presolidification process can be obtained a round gel and without presolidification process, produce not round gel. In the process of ageing to get not broken gel, ageing was done on the rotary flask so that during the ageing, gels rotate in gelation media. Gels, then be washed by dilute ammonium nitrate, demireralized water and iso prophyl alcohol. The washed gel was then dried by vacuum drying to form pores on the gel which become the path for the gases resulting from decomposition of the gel to exit the gel. Vacuum drying can prevent cracking because the pores allow the gel to release the decomposition of the material during heating. Larger the concentration of nitric metal in sol solution, yields a gel with a larger diameter of gels. This research allows us to plan the diameter of the sintered particles to be made.

Modifying a known gelator scaffold for nitrite detection.

PubMed

Zurcher, Danielle M; Adhia, Yash J; Romero, Julián Díaz; McNeil, Anne J

2014-07-25

The process of selecting and modifying a known gelator scaffold to develop a new nitrite-based sensor is described. Five new azo-sulfonate gelators were discovered and characterized. The most promising scaffold exhibits a stable diazonium intermediate, proceeds in a high yield, and gels nitrite-spiked tap, river, and pond water.

Fast Response and Spontaneous Alignment in Liquid Crystals Doped with 12-Hydroxystearic Acid Gelators

PubMed Central

Lin, Hui-Chi; Wang, Chih-Hung; Wang, Jyun-Kai; Tsai, Sheng-Feng

2018-01-01

The spontaneous vertical alignment of liquid crystals (LCs) in gelator (12-hydroxystearic acid)-doped LC cells was studied. Gelator-induced alignment can be used in both positive and negative LC cells. The electro-optical characteristics of the gelator-doped negative LC cell were similar to those of an LC cell that contained a vertically aligned (VA) host. The rise time of the gelator-doped LC cell was two orders of magnitude shorter than that of the VA host LC cell. The experimental results indicate that the gelator-induced vertical alignment of LC molecules occurred not only on the surface of the indium tin oxide (ITO) but also on the homogeneous alignment layer. Various LC alignments (planar, hybrid, multistable hybrid, and vertical alignments) were achieved by modulating the doped gelator concentrations. The multistable characteristic of LCs doped with the gelator is also presented. The alignment by doping with a gelator reduces the manufacturing costs and provides a means of fabricating fast-responding, flexible LC displays using a low-temperature process. PMID:29735937

Rational Design of Molecular Gelator - Solvent Systems Guided by Solubility Parameters

NASA Astrophysics Data System (ADS)

Lan, Yaqi

Self-assembled architectures, such as molecular gels, have attracted wide interest among chemists, physicists and engineers during the past decade. However, the mechanism behind self-assembly remains largely unknown and no capability exists to predict a priori whether a small molecule will gelate a specific solvent or not. The process of self-assembly, in molecular gels, is intricate and must balance parameters influencing solubility and those contrasting forces that govern epitaxial growth into axially symmetric elongated aggregates. Although the gelator-gelator interactions are of paramount importance in understanding gelation, the solvent-gelator specific (i.e., H-bonding) and nonspecific (dipole-dipole, dipole-induced and instantaneous dipole induced forces) intermolecular interactions are equally important. Solvent properties mediate the self-assembly of molecular gelators into their self-assembled fibrillar networks. Herein, solubility parameters of solvents, ranging from partition coefficients (logP), to Henry's law constants (HLC), to solvatochromic ET(30) parameters, to Kamlet-Taft parameters (beta, alpha and pi), to Hansen solubility parameters (deltap, deltad, deltah), etc., are correlated with the gelation ability of numerous classes of molecular gelators. Advanced solvent clustering techniques have led to the development of a priori tools that can identify the solvents that will be gelled and not gelled by molecular gelators. These tools will greatly aid in the development of novel gelators without solely relying on serendipitous discoveries.

Photothermal characterization of the gelation process in Gelidium robustum Agar

NASA Astrophysics Data System (ADS)

Freile-Pelegrín, Y.; Bante, J.; Alvarado-Gil, J. J.; Yánez-Limón, J. M.

2005-06-01

Agar is a hydrophilic colloid formed by polysaccharides, whose ability to form reversible gels simply by cooling hot aqueous solutions is the most important property and can be regarded as the prototype and model for all gelling systems. In this paper the evolution of the gelation process of agar obtained from algae of the species Gelidium robustum, using the photopyroelectric technique is reported. It is shown that thermal effusivity increase when the agar is cooled, reaching a maximum value around 37°C. The increase in thermal effusivity can be related to the increasing of the bondings in the gel as temperature decreases, reaching the maximum at the gelation point. The decrease of the thermal effusivity at lower temperature could be due to the syneresis process involving a gradual release of water after gelation.

Synthesis-Free Phase-Selective Gelator for Oil-Spill Remediation.

PubMed

Cui, Yaowen; Li, Mei-Chun; Wu, Qinglin; Pojman, John A; Kuroda, Daniel G

2017-10-04

A new deep eutectic solvent (DES) was developed as a phase-selective gelator for oil-spill remediation. The newly designed nonionic DES is based on a combination of an amide (N-methylacetamide) and a long chain carboxylic acid (lauric acid) and does not require any synthetic procedure besides mixing. Our studies show that the DES works as gelator by forming a gel between lauric acid and the hydrocarbon, whereas the amide serves to form the DES and dissolves in water during the gelation process. In addition, the DES material has gelation properties comparable to those considered as state-of-the-art. Overall, the newly developed material shows a promising future in oil recovery methodologies.

Tools for identifying gelator scaffolds and solvents.

PubMed

Zurcher, Danielle M; McNeil, Anne J

2015-03-06

Small molecule gelators are serendipitously discovered more often than they are designed. As a consequence, it has been challenging to develop applications based on the limited set of known materials. This synopsis highlights recent strategies to streamline the process of gelator discovery, with a focus on the role of unidirectional intermolecular interactions and solvation. We present these strategies as a series of tools that can be employed to help identify gelator scaffolds and solvents for gel formation. Overall, we suggest that this guided approach is more efficient than random derivatization and screening.

Exploring Orthogonal Hydrogen Bonding towards Designing Organic-Salt-Based Supramolecular Gelators: Synthesis, Structures, and Anticancer Properties.

PubMed

Chakraborty, Poulami; Dastidar, Parthasarathi

2018-05-18

A series of primary ammonium monocarboxylate (PAM) salts derived from β-alanine derivatives of pyrene and naphthalene acetic acid, along with the parent acids, were explored to probe the plausible role of orthogonal hydrogen bonding resulting from amide⋅⋅⋅amide and PAM synthons on gelation. Single-crystal X-ray diffraction (SXRD) studies were performed on two parent acids and five PAM salts in the series. The data revealed that orthogonal hydrogen bonding played an important role in gelation. Structure-property correlation based on SXRD and powder X-ray diffraction data also supported the working hypothesis upon which these gelators were designed. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and cell migration assay on a highly aggressive human breast cancer cell line, MDA-MB-231, revealed that one of the PAM salts in the series, namely, PAA.B2, displayed anticancer properties, and internalization of the gelator salt in the same cell line was confirmed by cell imaging. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gelation induced supramolecular chirality: chirality transfer, amplification and application.

PubMed

Duan, Pengfei; Cao, Hai; Zhang, Li; Liu, Minghua

2014-08-14

Supramolecular chirality defines chirality at the supramolecular level, and is generated from the spatial arrangement of component molecules assembling through non-covalent interactions such as hydrogen bonding, van der Waals interactions, π-π stacking, hydrophobic interactions and so on. During the formation of low molecular weight gels (LMWGs), one kind of fascinating soft material, one frequently encounters the phenomenon of chirality as well as chiral nanostructures, either from chiral gelators or even achiral gelators. A view of gelation-induced supramolecular chirality will be very helpful to understand the self-assembly process of the gelator molecules as well as the chiral structures, the regulation of the chirality in the gels and the development of the "smart" chiral materials such as chiroptical devices, catalysts and chiral sensors. It necessitates fundamental understanding of chirality transfer and amplification in these supramolecular systems. In this review, recent progress in gelation-induced supramolecular chirality is discussed.

Genuine non-self-averaging and ultraslow convergence in gelation.

PubMed

Cho, Y S; Mazza, M G; Kahng, B; Nagler, J

2016-08-01

In irreversible aggregation processes droplets or polymers of microscopic size successively coalesce until a large cluster of macroscopic scale forms. This gelation transition is widely believed to be self-averaging, meaning that the order parameter (the relative size of the largest connected cluster) attains well-defined values upon ensemble averaging with no sample-to-sample fluctuations in the thermodynamic limit. Here, we report on anomalous gelation transition types. Depending on the growth rate of the largest clusters, the gelation transition can show very diverse patterns as a function of the control parameter, which includes multiple stochastic discontinuous transitions, genuine non-self-averaging and ultraslow convergence of the transition point. Our framework may be helpful in understanding and controlling gelation.

Characterization of the fluid and solid components of cyanogel systems during the gelation process

NASA Astrophysics Data System (ADS)

Fortmeyer, Ivy Camille

The work in this thesis concerns the sol-gel transformation in cyanogel systems comprised of d8 square planar chlorometalates (M=Pd(II), Pt(II)) and d6 octahedral hexacyanometalates (M=Fe(II), Co(III), Ru(II)). The body of this thesis is split into two chapters. The first chapter examines the physical changes in the solvent phase of the sol-gel network, and the second focuses on the polymer backbone of the gel. Studies on the water component of cyanogel systems during the gelation process were carried out with a variety of in situ spectroscopic techniques. The use of high resolution-magic angle spinning nuclear magnetic resonance (HR-MAS NMR) to identify and characterize different water environments was explored, but was ultimately found to disrupt gelation. Standard solution-phase 1H NMR proved sufficient for calculation and qualitative modeling of spin-spin and spin-lattice relaxations, providing distinct spectral markers of the gelation point and subsequent aging process. Vibrational spectroscopy was used to explore the hydrogen bonding environment of the water during gelation. The kinetics of polymerization of the cyanogel backbone was explored using both in situ and ex situ techniques. Data collected by 13C NMR and 195Pt NMR primarily demonstrated first order kinetics, implying a dissociative substitution mechanism at the chlorometalate center. Rate constants for gelation in the presence of various added monopotassium and nitrate salts were calculated. Added chloride was found to significantly slow gelation and was further explored using NMR and vibrational spectroscopy. A mechanism was proposed for the polymerization taking into account the dissociative substitution and the bridging geometries implied by 13C NMR.

Topology evolution and gelation mechanism of agarose gel.

PubMed

Xiong, Jun-Ying; Narayanan, Janaky; Liu, Xiang-Yang; Chong, Tan Kok; Chen, Shing Bor; Chung, Tai-Shung

2005-03-31

Kinetics as well as the evolution of the agarose gel topology is discussed, and the agarose gelation mechanism is identified. Aqueous high melting (HM) agarose solution (0.5% w/v) is used as the model system. It is found that the gelation process can be clearly divided into three stages: induction stage, gelation stage, and pseudoequilibrium stage. The induction stage of the gelation mechanism is identified using an advanced rheological expansion system (ARES, Rheometric Scientific). When a quench rate as large as 30 deg C/min is applied, gelation seems to occur through a nucleation and growth mechanism with a well-defined induction time (time required for the formation of the critical nuclei which enable further growth). The relationship between the induction time and the driving force which is determined by the final setting temperature follows the 3D nucleation model. A schematic representation of the three stages of the gelation mechanism is given based on turbidity and rheological measurements. Aggregation of agarose chains is promoted in the polymer-rich phase and this effect is evident from the increasing mass/length ratio of the fiber bundles upon gelation. Continuously increasing pore size during gelation may be attributed to the coagulation of the local polymer-rich phase in order to achieve the global minimum of the free energy of the gelling system. The gel pore size determined using turbidity measurements has been verified by electrophoretic mobility measurements.

Importance of casein micelle size and milk composition for milk gelation.

PubMed

Glantz, M; Devold, T G; Vegarud, G E; Lindmark Månsson, H; Stålhammar, H; Paulsson, M

2010-04-01

The economic output of the dairy industry is to a great extent dependent on the processing of milk into other milk-based products such as cheese. The yield and quality of cheese are dependent on both the composition and technological properties of milk. The objective of this study was to evaluate the importance and effects of casein (CN) micelle size and milk composition on milk gelation characteristics in order to evaluate the possibilities for enhancing gelation properties through breeding. Milk was collected on 4 sampling occasions at the farm level in winter and summer from dairy cows with high genetic merit, classified as elite dairy cows, of the Swedish Red and Swedish Holstein breeds. Comparisons were made with milk from a Swedish Red herd, a Swedish Holstein herd, and a Swedish dairy processor. Properties of CN micelles, such as their native and rennet-induced CN micelle size and their zeta-potential, were analyzed by photon correlation spectroscopy, and rennet-induced gelation characteristics, including gel strength, gelation time, and frequency sweeps, were determined. Milk parameters of the protein, lipid, and carbohydrate profiles as well as minerals were used to obtain correlations with native CN micelle size and gelation characteristics. Milk pH and protein, CN, and lactose contents were found to affect milk gelation. Smaller native CN micelles were shown to form stronger gels when poorly coagulating milk was excluded from the correlation analysis. In addition, milk pH correlated positively, whereas Mg and K correlated negatively with native CN micellar size. The milk from the elite dairy cows was shown to have good gelation characteristics. Furthermore, genetic progress in relation to CN micelle size was found for these cows as a correlated response to selection for the Swedish breeding objective if optimizing for milk gelation characteristics. The results indicate that selection for smaller native CN micelles and lower milk pH through breeding would enhance gelation properties and may thus improve the initial step in the processing of cheese. Copyright (c) 2010 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Towards a fully synthetic substitute of alginate: optimization of a thermal gelation/chemical cross-linking scheme ("tandem" gelation) for the production of beads and liquid-core capsules.

PubMed

Cellesi, F; Weber, W; Fussenegger, M; Hubbell, J A; Tirelli, N

2004-12-20

Fully synthetic polymers were used for the preparation of hydrogel beads and capsules, in a processing scheme that, originally designed for calcium alginate, was adapted to a "tandem" process, that is the combination a physical gelation with a chemical cross-linking. The polymers feature a Tetronic backbone (tetra armed Pluronics), which exhibits a reverse thermal gelation in water solutions within a physiological range of temperatures and pHs. The polymers bear terminal reactive groups that allow for a mild, but effective chemical cross-linking. Given an appropriate temperature jump, the thermal gelation provides a hardening kinetics similar to that of alginate. With slower kinetics, the chemical cross-linking then develops an irreversible and elastic gel structure, and determines its transport properties. In the present article this process has been optimized for the production of monodisperse, high elastic, hydrogel microbeads, and liquid-core microcapsules. We also show the feasibility of the use of liquid-core microcapsules in cell encapsulation. In preliminary experiments, CHO cells have been successfully encapsulated preserving their viability during the process and after incubation. The advantages of this process are mainly in the use of synthetic polymers, which provide great flexibility in the molecular design. This, in principle, allows for a precise tailoring of mechanical and transport properties and of bioactivity of the hydrogels, and also for a precise control in material purification.

The formation of helical mesoporous silica nanotubes

NASA Astrophysics Data System (ADS)

Wan, Xiaobing; Pei, Xianfeng; Zhao, Huanyu; Chen, Yuanli; Guo, Yongmin; Li, Baozong; Hanabusa, Kenji; Yang, Yonggang

2008-08-01

Three chiral cationic gelators were synthesized. They can form translucent hydrogels in pure water. These hydrogels become highly viscous liquids under strong stirring. Mesoporous silica nanotubes with coiled pore channels in the walls were prepared using the self-assemblies of these gelators as templates. The mechanism of the formation of this hierarchical nanostructure was studied using transmission electron microscopy at different reaction times. The results indicated that there are some interactions between the silica source and the gelator. The morphologies of the self-assemblies of gelators changed gradually during the sol-gel transcription process. It seems that the silica source directed the organic self-assemblies into helical nanostructures.

Cooperative Assembly of a Peptide Gelator and Silk Fibroin Afford an Injectable Hydrogel for Tissue Engineering.

PubMed

Cheng, Baochang; Yan, Yufei; Qi, Jingjing; Deng, Lianfu; Shao, Zeng-Wu; Zhang, Ke-Qin; Li, Bin; Sun, Ziling; Li, Xinming

2018-04-18

Silk fibroin (SF) from Bombyx mori has received increasing interest in biomedical fields, because of its slow biodegradability, good biocompatibility, and low immunogenicity. Although SF-based hydrogels have been studied intensively as a potential matrix for tissue engineering, weak gelation performance and low mechanical strength are major limitations that hamper their widespread applicability. Therefore, searching for new strategies to improve the SF gelation property is highly desirable in tissue engineering research. Herein, we report a facile approach to induce rapid gelation of SF by a small peptide gelator (e.g., NapFF). Following the simple mixing of SF and NapFF in water, a stable hydrogel of SF was obtained in a short time period at physiological pH, and the minimum gelation concentration of SF can reach as low as 0.1%. In this process of gelation, NapFF not only can behave itself as a gelator for supramolecular self-assembly, but also can trigger the conformational transition of the SF molecule from random coil to β-sheet structure via hydrophobic and hydrogen-bonding interactions. More importantly, for the generation of a scaffold with favorable cell-surface interactions, a new peptide gelator (NapFFRGD) with Arg-Gly-Asp (RGD) domain was applied to functionalize SF hydrogel with improved bioactivity for cell adhesion and growth. Following encapsulating the vascular endothelial growth factor (VEGF), the SF gel was subcutaneously injected in mice, and served as an effective matrix to trigger the generation of new blood capillaries in vivo.

Molecular gels in the gas phase? Gelator-gelator and gelator-solvent interactions probed by vibrational spectroscopy.

PubMed

Lozada-Garcia, Rolando; Mu, Dan; Plazanet, Marie; Çarçabal, Pierre

2016-08-10

Benzylidene glucose (BzGlc) is a member of the benzylidene glycoside family. These molecules have the ability to form molecular physical gels. These materials are formed when gelator molecules create a non-covalently bound frame where solvent molecules are trapped. Since the gel formation process and its properties are determined by the subtle balance between non-covalent forces, it is difficult to anticipate them. Quantitative and qualitative understanding of the gelator-gelator and gelator-solvent interactions is needed to better control these materials for important potential applications. We have used gas phase vibrational spectroscopy and theoretical chemistry to study the conformational choices of BzGlc, its dimer and the complexes it forms with water or toluene. To interpret the vibrational spectra we have used the dispersion corrected functional B97D which we have calibrated for the calculation of OH stretching frequencies. Even at the most basic molecular level, it is possible to interrogate a large range of non-covalent interactions ranging from OH → OH hydrogen bonding, to OH → π, and CH → π, all being at the center of gel properties at the macroscopic level.

Stable dye-sensitized solar cells based on a gel electrolyte with ethyl cellulose as the gelator

NASA Astrophysics Data System (ADS)

Vasei, Maryam; Tajabadi, Fariba; Jabbari, Ali; Taghavinia, Nima

2015-09-01

A simple gelating process is developed for the conventional acetonitrile-based electrolyte of dye solar cells, based on ethyl cellulose as the gelator. The electrolyte becomes quasi-solid-state upon addition of an ethanolic solution of ethyl cellulose to the conventional acetonitrile-based liquid electrolyte. The photovoltaic conversion efficiency with the new gel electrolyte is only slightly lower than with the liquid electrolyte, e.g., 6.5 % for liquid electrolyte versus 5.9 % for gel electrolyte with 5.8 wt% added ethyl cellulose. Electrolyte gelation has small effect on the ionic diffusion coefficient of iodide, and the devices are remarkably stable for at least 550 h under irradiation at 55 °C.

Computational Modeling and High Performance Computing in Advanced Materials Processing, Synthesis, and Design

DTIC Science & Technology

2014-12-07

parameters of resin viscosity and preform permeability prior to resin gelation. However, there could be significant variations in these two parameters...during actual manufacturing due to differences in the resin batches, mixes, temperature, ambient conditions for viscosity ; in the preform rolls...optimal injection time and locations for given process parameters of resin viscosity and preform permeability prior to resin gelation. However, there

Supramolecular Phase-Selective Gelation by Peptides Bearing Side-Chain Azobenzenes: Effect of Ultrasound and Potential for Dye Removal and Oil Spill Remediation

PubMed Central

Bachl, Jürgen; Oehm, Stefan; Mayr, Judith; Cativiela, Carlos; Marrero-Tellado, José Juan; Díaz Díaz, David

2015-01-01

Phase selective gelation (PSG) of organic phases from their non-miscible mixtures with water was achieved using tetrapeptides bearing a side-chain azobenzene moiety. The presence of the chromophore allowed PSG at the same concentration as the minimum gelation concentration (MGC) necessary to obtain the gels in pure organic phases. Remarkably, the presence of the water phase during PSG did not impact the thermal, mechanical, and morphological properties of the corresponding organogels. In the case of miscible oil/water mixtures, the entire mixture was gelled, resulting in the formation of quasi-hydrogels. Importantly, PSG could be triggered at room temperature by ultrasound treatment of the mixture or by adding ultrasound-aided concentrated solution of the peptide in an oil-phase to a mixture of the same oil and water. Moreover, the PSG was not affected by the presence of salts or impurities existing in water from natural sources. The process could be scaled-up, and the oil phases (e.g., aromatic solvents, gasoline, diesel fuel) recovered almost quantitatively after a simple distillation process, which also allowed the recovery and reuse of the gelator. Finally, these peptidic gelators could be used to quantitatively remove toxic dyes from aqueous solutions. PMID:26006247

Status report on GELNG (gelled LNG)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudnicki, M.; Hoffman, L.C.; Vander Wall, E.M.

1980-01-01

Over the past 2 years, Aerojet's research on characterizing the process, flow, and use properties of gelled LNG has covered (1) its safety-enhancement potential, (2) the economics and preliminary design of an industrial-scale gelation system, and (3) the design of a portable gelator for larger scale (40 m/sup 3/) spill tests. The technical results thus far continue to support the conclusion that GELNG would substantially reduce spill hazards. Operating parameters would not be significantly changed by gelation, and the cost impact on delivered LNG appears to be small (about 5%).

Sodium oleate induced rapid gelation of silk fibroin.

PubMed

Yang, Yuejiao; Chen, Jie; Bonani, Walter; Chen, Bin; Eccheli, Sabrina; Maniglio, Devid; Migliaresi, Claudio; Motta, Antonella

2018-07-01

Silk fibroin has acquired increasing interest in the last years for application in medicine and namely in tissue engineering. Several methods have been developed to process fibroin and for the fabrication of nets, sponges, films and gels. This paper deals with the fabrication and characterization of fibroin hydrogels obtained by using sodium oleate as gelation agent. Gels have been prepared by mixing Silk fibroin (SF) and Sodium oleate (SO) water solutions in different concentrations, and a quite wide frame of compositions have been explored. Rheological tests have been performed to determine the gelation times, scanning electron microscopies have been made to evaluate morphologies, FTIR analysis has been done to determine the conformation of the starting materials and of the resulting gels, water content has been measured and cytotoxicity tests have been performed to validate the potential biomedical use of the hydrogels. Depending on the SF and SO different gelation times have been obtained thanks to the formation of intermolecular bonds between the fibroin chains. The obtained fastest gelation of about 80 s could make this specific formulation compatible with in situ gelation. By changing composition, gels with different morphologies, rheological properties and water contents have been prepared.

Structure formation in pH-sensitive hydrogels composed of sodium caseinate and N,O-carboxymethyl chitosan.

PubMed

Wei, Yanxia; Xie, Rui; Lin, Yanbin; Xu, Yunfei; Wang, Fengxia; Liang, Wanfu; Zhang, Ji

2016-08-01

The pH-sensitive hydrogels composed of sodium caseinate (SC) and N,O-carboxymethyl chitosan (NOCC) were prepared and a new method to characterize the gelation process was presented in this work. Reological tests suggested that RSC/NOCC=3/7 (the weight ratio of SC and NOCC) was the best ratio of hydrogel. The well-developed three-dimensional network structures in the hydrogel were confirmed by AFM. Two structural parameters, tIS and tCS, denoted as the initial and critical structure formation time, respectively, were used to provide an exact determination of the start of structure formation and description of gelation process. The gelation process strongly depended on temperature changes, a high temperature resulted in an early start of gelation. The non-kinetic model suggested the higher activation energy in the higher temperatures was disadvantageous to structure formation, and vice versa. Due to the smart gel reported here was very stable at room temperature, we believed that the gel is required for applications in drug delivery or could be exploited in the development of potential application as molecular switches in the future. Copyright © 2016 Elsevier B.V. All rights reserved.

Eco-friendly Synthesis of Ceria Foam via Carboxymethylcellulose Gelation: Application for the Epoxidation of Chalcone

EPA Science Inventory

A simple and innovative process is described for the eco-friendly preparation of ceria foams via the carboxymethylcellulose gelation by Ce4+ cations; heat treatment of the ensuing xerogels produces ceria foams. The influence of the concentration of cerium and of the calcination t...

L-cysteine-derived ambidextrous gelators of aromatic solvents and ethanol/water mixtures.

PubMed

Pal, Amrita; Dey, Joykrishna

2013-02-19

A series of L-cysteine-derived double hydrocarbon chain amphiphilic gelators L-(3-alkyl-carbamoylsulfanyl)-2-(3-alkylurido)propionic acid with different hydrocarbon chain lengths (C6-C16) was designed and synthesized. These gelators efficiently gelate only aromatic solvents. The gelation ability increased with the increase of chain length up to C14, but then it dropped with further increase of chain length. The C12 and C14 derivatives also gelled ethanol/water mixtures. The gels were characterized by a number of methods, including FT-IR, NMR, and XRD spectroscopy, electron microscopy, and rheology. The amphiphiles were observed to form either flat lamellar or ribbonlike aggregates in aromatic solvents as well as in ethanol/water mixtures. The gelation in all the solvents employed was observed to be thermoreversible. The gel-to-sol transition temperature as well as mechanical strength of the organogels were observed to increase with the hydrocarbon chain length. Both types of gels of C8-C16 amphiphiles have gel-to-sol transition temperatures above the physiological temperature (310 K). FT-IR and variable temperature (1)H NMR measurements suggested that van der Waals interactions have major contribution in the gelation process. The gel-to-sol transition temperature and mechanical strength of the organogels in ethanol/water mixtures was observed to be higher than those of benzene organogel.

Delivery and Establishing Slow Release Carbon Source to the Hanford Vadose Zone Using Colloidal Silica Suspension Injection and Subsequent Gelation - Laboratory Study

NASA Astrophysics Data System (ADS)

Zhong, L.; Lee, M. H.; Lee, B.; Yang, S.

2016-12-01

Delivery of nutrient to and establish a slow release carbon source in the vadose zone and capillary fringe zone is essential for setting up of a long-lasting bioremediation of contaminations in those zones. Conventional solution-based injection and infiltration approaches are facing challenges to achieve the delivery and remedial goals. Aqueous silica suspensions undergo a delayed gelation process under favorite geochemical conditions. The delay in gelation provides a time window for the injection of the suspension into the subsurface; and the gelation of the amendment-silica suspension enables the amendment-laden gel to stay in the target zone and slowly release the constituents for contaminant remediation. This approach can potentially be applied to deliver bio-nutrients to the vadose zone and capillary fringe zone for enhanced bioremediation and achieve remedial goals. This research was conducted to demonstrate delayed gelation of colloidal silica suspensions when carbon sources were added and to prove the gelation occurs in sediments under vadose conditions. Sodium lactate, vegetable oil, ethanol, and molasses were tested as the examples of carbon source (or nutrient) amendments. The rheological properties of the silica suspensions during the gelation were characterized. The influence of silica, salinity, nutrient concentrations, and the type of nutrients was studied. The kinetics of nutrient release from silica-nutrient gel was quantified using molasses as the example, and the influence of suspension gelation time was evaluated. The injection behavior of the suspensions was investigated by monitoring their viscosity changes and the injection pressures when the suspensions were delivered into sediment columns.

Probing insulin bioactivity in oral nanoparticles produced by ultrasonication-assisted emulsification/internal gelation

PubMed Central

Lopes, Marlene A; Abrahim-Vieira, Bárbara; Oliveira, Claudia; Fonte, Pedro; Souza, Alessandra M T; Lira, Tammy; Sequeira, Joana A D; Rodrigues, Carlos R; Cabral, Lúcio M; Sarmento, Bruno; Seiça, Raquel; Veiga, Francisco; Ribeiro, António J

2015-01-01

Alginate–dextran sulfate-based particles obtained by emulsification/internal gelation technology can be considered suitable carriers for oral insulin delivery. A rational study focused on the emulsification and particle recovery steps was developed in order to reduce particles to the nanosize range while keeping insulin bioactivity. There was a decrease in size when ultrasonication was used during emulsification, which was more pronounced when a cosurfactant was added. Ultrasonication add-on after particle recovery decreased aggregation and led to a narrower nanoscale particle-size distribution. Insulin encapsulation efficiency was 99.3%±0.5%, attributed to the strong pH-stabilizing electrostatic effect between insulin and nanoparticle matrix polymers. Interactions between these polymers and insulin were predicted using molecular modeling studies through quantum mechanics calculations that allowed for prediction of the interaction model. In vitro release studies indicated well-preserved integrity of nanoparticles in simulated gastric fluid. Circular dichroism spectroscopy proved conformational stability of insulin and Fourier transform infrared spectroscopy technique showed rearrangements of insulin structure during processing. Moreover, in vivo biological activity in diabetic rats revealed no statistical difference when compared to nonencapsulated insulin, demonstrating retention of insulin activity. Our results demonstrate that alginate–dextran sulfate-based nanoparticles efficiently stabilize the loaded protein structure, presenting good physical properties for oral delivery of insulin. PMID:26425087

Shock Wave-Stimulated Periosteum for Cartilage Repair

DTIC Science & Technology

2013-12-01

were added to the Gtn-HPA prior to the gelation 6 process, at a cell density of 1×105 cells/ml. In the control groups, cells received no treatment...Mesenchymal Stem Cell Viability Viability test was performed 24 hours post- gelation using the Live/Dead assay. Viability/cytotoxicity kit was used (Molecular

The interplay of aggregation, fibrillization and gelation of an unexpected low molecular weight gelator: glycylalanylglycine in ethanol/water.

PubMed

Farrell, Stefanie; DiGuiseppi, David; Alvarez, Nicolas; Schweitzer-Stenner, Reinhard

2016-07-13

Hydrogels formed by polypeptides could be much-favored tools for drug delivery because their main ingredients are generally biodegradable. However, the gelation of peptides in aqueous solution generally requires a minimal length of the peptide as well as distinct sequences of hydrophilic and hydrophobic residues. The aggregation of short peptides like tripeptides, which are relatively cheap and offer a high degree of biodegradability, are generally thought to require a high hydrophobicity of their residues. We found that contrary to this expectation cationic glycylalanylglycine in 55 mol% ethanol/45 mol% water forms a gel below a melting temperature of ca. 36 °C. A pure hydrogel state can be obtained after allowing the ethanol component to evaporate. The gel phase consists of crystalline fibrils of several 100 μm, which form a sample-spanning network. Rheological data reveal a soft elastic solid gel. We investigated the kinetics of the various processes that lead to the final gel state of the ternary mixture by a unique combination of UV circular dichroism, infrared, vibrational circular dichroism (VCD) and rheological measurements. A mathematical analysis of our data show that gelation is preceded by the formation of peptide β-sheet like tapes or ribbons, which give rise to a significant enhancement of the amide I' VCD signal, and the subsequent formation of rather thick and long fibrils. The VCD signals indicate that the tapes exhibit a right-handed helicity at temperatures above 16 °C and a left-handed helicity below. The tapes'/ribbons' helicity change occurs at a temperature where the UVCD data reflect a relatively long nucleation process. The kinetics of gel formation probed by the storage and loss moduli are composed of a fast process that follows tape/ribbon/fibril formation and is clearly identifiable in a movie that shows the gelation process and a slow process that causes an additional gel stabilization. The rheological data indicate that left-handed fibrils observed at low temperatures form a more solid-like structure than their right-handed counterparts formed at higher temperatures. Taken together our data reveal GAG as an unexpected gelator, the formation of which is underlied by a set of distinguishable kinetic processes.

The Metal Effect on Self-Assembling of Oxalamide Gelators Explored by Mass Spectrometry and DFT Calculations.

PubMed

Dabić, Dario; Brkljačić, Lidija; Tandarić, Tana; Žinić, Mladen; Vianello, Robert; Frkanec, Leo; Kobetić, Renata

2018-01-01

Gels formed by self-assembly of small organic molecules are of wide interest as dynamic soft materials with numerous possible applications, especially in terms of nanotechnology for functional and responsive biomaterials, biosensors, and nanowires. Four bis-oxalamides were chosen to show if electrospray ionization mass spectrometry (ESI-MS) could be used as a prediction of a good gelator and also to shed light on the gelation processes. By inspecting the gelation of several solvent, we showed that bis(amino acid)oxalamide 1 proved to be the most efficient, also being able of forming the largest observable assemblies in the gas phase. The formation of singly charged assemblies holding from one up to six monomer units is the outcome of the strong intermolecular H-bonds, particularly among terminal carboxyl groups. The variation of solvents from polar aprotic towards polar protic did not have any significant effects on the size of the assemblies. The addition of a salt such as NaOAc or Mg(OAc) 2 , depending on the concentration, altered the assembling. Computational analysis at the DFT level aided in the interpretation of the observed trends and revealed that individual gelator molecules spontaneously assemble to higher aggregates, but the presence of the Na + cation disrupts any gelator organization since it becomes significantly more favorable for gelator molecules to bind Na + cations up to the 3:1 ratio than to self-assemble, being fully in line with experimental observations reported here. Graphical Abstract ᅟ.

The Metal Effect on Self-Assembling of Oxalamide Gelators Explored by Mass Spectrometry and DFT Calculations

NASA Astrophysics Data System (ADS)

Dabić, Dario; Brkljačić, Lidija; Tandarić, Tana; Žinić, Mladen; Vianello, Robert; Frkanec, Leo; Kobetić, Renata

2018-01-01

Gels formed by self-assembly of small organic molecules are of wide interest as dynamic soft materials with numerous possible applications, especially in terms of nanotechnology for functional and responsive biomaterials, biosensors, and nanowires. Four bis-oxalamides were chosen to show if electrospray ionization mass spectrometry (ESI-MS) could be used as a prediction of a good gelator and also to shed light on the gelation processes. By inspecting the gelation of several solvent, we showed that bis(amino acid)oxalamide 1 proved to be the most efficient, also being able of forming the largest observable assemblies in the gas phase. The formation of singly charged assemblies holding from one up to six monomer units is the outcome of the strong intermolecular H-bonds, particularly among terminal carboxyl groups. The variation of solvents from polar aprotic towards polar protic did not have any significant effects on the size of the assemblies. The addition of a salt such as NaOAc or Mg(OAc)2, depending on the concentration, altered the assembling. Computational analysis at the DFT level aided in the interpretation of the observed trends and revealed that individual gelator molecules spontaneously assemble to higher aggregates, but the presence of the Na+ cation disrupts any gelator organization since it becomes significantly more favorable for gelator molecules to bind Na+ cations up to the 3:1 ratio than to self-assemble, being fully in line with experimental observations reported here. [Figure not available: see fulltext.

Chitosan Nanoparticles Prepared by Ionotropic Gelation: An Overview of Recent Advances.

PubMed

Desai, Kashappa Goud

2016-01-01

The objective of this review is to summarize recent advances in chitosan nanoparticles prepared by ionotropic gelation. Significant progress has occurred in this area since the method was first reported. The gelation technique has been improved through a number of creative methodological modifications. Ionotropic gelation via electrospraying and spinning disc processing produces nanoparticles with a more uniform size distribution. Large-scale manufacturing of the nanoparticles can be achieved with the latter approach. Hydrophobic and hydrophilic drugs can be simultaneously encapsulated with high efficiency by emulsification followed by ionic gelation. The turbulent mixing approach facilitates nanoparticle formation at a relatively high polymer concentration (5 mg/mL). The technique can be easily tuned to achieve the desired polymer/surface modifications (e.g., blending, coating, and surface conjugation). Using factorial-design-based approaches, optimal conditions for nanoparticle formation can be determined with a minimum number of experiments. New insights have been gained into the mechanism of chitosan-tripolyphosphate nanoparticle formation. Chitosan nanoparticles prepared by ionotropic gelation tend to aggregate/agglomerate in unfavorable environments. Factors influencing this phenomenon and strategies that can be adopted to minimize the instability are discussed. Ionically cross-linked nanoparticles based on native chitosan and modified chitosan have shown excellent efficacy for controlled and targeted drug-delivery applications.

Fabrication of chiroptically switchable films via co-gelation of a small chiral gelator with an achiral azobenzene-containing polymer.

PubMed

Yang, Dong; Zhang, Li; Yin, Lu; Zhao, Yin; Zhang, Wei; Liu, Minghua

2017-09-20

Helical polymers are widely found in nature and synthetic functional materials. Although a number of elaborate strategies have been developed to endow polymers with helicity through either covalent bonds or supramolecular techniques, it still remains a challenge to get the desired helical polymers with controlled handedness in an easy but effective manner. In this study, we report an easily accessible gelation-guided self-assembly system where the chirality of a gelator can be easily transferred to an achiral azobenzene-containing polymer during gelation. It is found that during the process of chiral induction, the induced chirality of the polymer was entirely dominated by the molecular chirality of the gelator. Experimentally, achiral azobenzene-containing polymers with different side-chain lengths were doped into a supramolecular gel system formed with amphiphilic N,N'-bis-(octadecyl)-l(d)-Boc-glutamic (LBG-18 or DBG-18 for short). CD spectra and SEM observation confirmed that the co-assembly of polymer/LBG-18 or polymer/DBG-18 in the xerogel state exhibited supramolecular chirality. More importantly, alternate UV and visible light irradiation on the xerogel film caused the induced CD signal to switch between on and off states. Thus a chiroptical switch was fabricated based on the isomerization of the azo-polymer in xerogel films.

Effect of the molecular weight of a neutral polysaccharide on soy protein gelation.

PubMed

Monteiro, Sónia R; Lopes-da-Silva, José A

2017-12-01

The effects of galactomannans with different molecular weights on the heat-induced gelation characteristics of soybean protein were investigated using dynamic small-strain rheometry, under conditions where the proteins carry a net negative charge (pH7). Microstructure of the resulting gels was investigated by confocal laser scanning microscopy. Phase-separated systems were obtained with different morphologies and degree of phase separation, depending on both biopolymer concentrations and polysaccharide molecular weight. In general, a gelling enhancing effect on soy proteins was verified, despite extensive phase-separation processes observed at the higher polysaccharide molecular weight. This effect was demonstrated by an increase of the gelation rate, a decrease in the temperature at the onset of gelation, and an increase of gel stiffness and elastic character, with the length of polysaccharide chains. Overall, the results obtained established that the judicious selection of the galactomannan molecular weight may be used to modify the structure and gelation properties of soy proteins, originating a diversity of rheological characteristics and microstructures that will impact on the design of novel food formulations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Photoinduced gelation by stilbene oxalyl amide compounds.

PubMed

Miljanić, Snezana; Frkanec, Leo; Meić, Zlatko; Zinić, Mladen

2005-03-29

Oxalyl amide derivatives bearing 4-dodecyloxy-stilbene as a cis-trans photoisomerizing unit were synthesized. The trans derivative acted as a versatile gelator of various organic solvents, whereas the corresponding cis derivative showed a poor gelation ability or none at all. In diluted solution (c = 2.0 x10(-5) mol dm(-3), ethanol), the cis isomer was photochemically converted into the trans isomer within 4 min. Depending on the radiation wavelength, the trans isomer was stable or liable to photodecomposition. When exposed to irradiation, a concentrated solution of the cis isomer (c = 2.0 x 10(-2) mol dm(-3), ethanol) turned into a gel. The FT-Raman, FT-IR, and 1H NMR spectra demonstrated that the gelation process occurred because of a rapid cis --> trans photoisomerization followed by a self-assembly of the trans molecules. Apart from the formation of hydrogen bonding between the oxalyl amide parts of the molecules, confirmed by FT-IR spectroscopy, it was assumed that the pi-pi stacking between the trans-stilbene units of the molecule and a lipophilic interaction between long alkyl chains were the interactions responsible for gelation.

Optimized spray drying process for preparation of one-step calcium-alginate gel microspheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Popeski-Dimovski, Riste

Calcium-alginate micro particles have been used extensively in drug delivery systems. Therefore we establish a one-step method for preparation of internally gelated micro particles with spherical shape and narrow size distribution. We use four types of alginate with different G/M ratio and molar weight. The size of the particles is measured using light diffraction and scanning electron microscopy. Measurements showed that with this method, micro particles with size distribution around 4 micrometers can be prepared, and SEM imaging showed that those particles are spherical in shape.

Gelation kinetics of gelatin using particle tracking microrheology

NASA Astrophysics Data System (ADS)

Hardcastle, Joseph; Bansil, Rama

2012-02-01

Previous studies with gelatin have observed four distinct stages during the physical gelation process [Normand et al. Macromolecules, 2000, 33, 1063]. In this presentation we report measurements of microrheology in an effort to examine the time evolution of the gel on short length scales and time scales. By tracking latex particles in gelatin solution at different temperatures we can follow the microrheological changes and kinetics of the gelation process. Using the generalized Stokes-Einstein relation viscoelastic properties of these quasi-static gel states the evolution of the storage and loss moduli, G' and G'', are examined as functions of both time and temperature. The data show that both G' and G'' exhibit power law scaling versus frequency with the same exponent. The temperature and concentration dependence of the frequency at which the system crosses over from viscous to elastic behavior will be presented.

Gelation-driven component selection in the generation of constitutional dynamic hydrogels based on guanine-quartet formation

PubMed Central

Sreenivasachary, Nampally; Lehn, Jean-Marie

2005-01-01

The guanosine hydrazide 1 yields a stable supramolecular hydrogel based on the formation of a guanine quartet (G-quartet) in presence of metal cations. The effect of various parameters (concentration, nature of metal ion, and temperature) on the properties of this gel has been studied. Proton NMR spectroscopy is shown to allow a molecular characterization of the gelation process. Hydrazide 1 and its assemblies can be reversibly decorated by acylhydrazone formation with various aldehydes, resulting in formation of highly viscous dynamic hydrogels. When a mixture of aldehydes is used, the dynamic system selects the aldehyde that leads to the most stable gel. Mixing hydrazides 1, 9 and aldehydes 6, 8 in 1:1:1:1 ratio generated a constitutional dynamic library containing the four acylhydrazone derivatives A, B, C, and D. The library constitution displayed preferential formation of the acylhydrazone B that yields the strongest gel. Thus, gelation redirects the acylhydrazone distribution in the dynamic library as guanosine hydrazide 1 scavenges preferentially aldehyde 8, under the pressure of gelation because of the collective interactions in the assemblies of G-quartets B, despite the strong preference of the competing hydrazide 9 for 8. Gel formation and component selection are thermoreversible. The process amounts to gelation-driven self-organization with component selection and amplification in constitutional dynamic hydrogels based on G-quartet formation and reversible covalent connections. The observed self-organization and component selection occur by means of a multilevel self-assembly involving three dynamic processes, two of supramolecular and one of reversible covalent nature. They extend constitutional dynamic chemistry to phase-organization and phase-transition events. PMID:15840720

Gelation-driven component selection in the generation of constitutional dynamic hydrogels based on guanine-quartet formation.

PubMed

Sreenivasachary, Nampally; Lehn, Jean-Marie

2005-04-26

The guanosine hydrazide 1 yields a stable supramolecular hydrogel based on the formation of a guanine quartet (G-quartet) in presence of metal cations. The effect of various parameters (concentration, nature of metal ion, and temperature) on the properties of this gel has been studied. Proton NMR spectroscopy is shown to allow a molecular characterization of the gelation process. Hydrazide 1 and its assemblies can be reversibly decorated by acylhydrazone formation with various aldehydes, resulting in formation of highly viscous dynamic hydrogels. When a mixture of aldehydes is used, the dynamic system selects the aldehyde that leads to the most stable gel. Mixing hydrazides 1, 9 and aldehydes 6, 8 in 1:1:1:1 ratio generated a constitutional dynamic library containing the four acylhydrazone derivatives A, B, C, and D. The library constitution displayed preferential formation of the acylhydrazone B that yields the strongest gel. Thus, gelation redirects the acylhydrazone distribution in the dynamic library as guanosine hydrazide 1 scavenges preferentially aldehyde 8, under the pressure of gelation because of the collective interactions in the assemblies of G-quartets B, despite the strong preference of the competing hydrazide 9 for 8. Gel formation and component selection are thermoreversible. The process amounts to gelation-driven self-organization with component selection and amplification in constitutional dynamic hydrogels based on G-quartet formation and reversible covalent connections. The observed self-organization and component selection occur by means of a multilevel self-assembly involving three dynamic processes, two of supramolecular and one of reversible covalent nature. They extend constitutional dynamic chemistry to phase-organization and phase-transition events.

NMR study of the gelation of a designed gelator.

PubMed

Brand, Torsten; Nolis, Pau; Richter, Sven; Berger, Stefan

2008-06-01

The gelation of a designed gelator was investigated by different NMR methods, which showed a clear thermal hysteresis. Two very simple approaches for the NMR determination of the gelation point are suggested. One involves the observation of the NMR integral, and the other records the ratio of the diffusion coefficients between the gelator and the solvent. Differential behavior of the gelator protons are interpreted as a hint that a part of the gelator molecule might still be flexible as in the dissolved state. Copyright (c) 2008 John Wiley & Sons, Ltd

New Alternatives in Seafood Restructured Products.

PubMed

Moreno, Helena M; Herranz, Beatriz; Pérez-Mateos, Miriam; Sánchez-Alonso, Isabel; Borderías, Javier A

2016-01-01

A general overview, focusing on new trends in the different techniques used in restructured seafood product processing has been described in this work. Heat-induced gelation has been more widely studied in scientific literature than cold gelation technology. This latter technology includes the use of hydrocolloids (alginates and glucomannan) or enzymes (microbial transglutaminase) for making both raw and cooked restructured products. In restructuration processes, fortification processing with some functional ingredients is studied, giving as a result extra value to the products as well as increasing the variety of new seafood products. The process of alleviating heavy metals and organic pollutants from the raw material used has also been reviewed in the present paper.

Mobile LNG (liquified natural gas) gelator. Final report, July 1980-September 1981

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudnicki, M.I.; Hoffman, L.C.; Newton, R.A.

1981-12-01

Gelled liquified natural gas (GELNG) offers potential safety advantages over LNG in the case of an accidental spill. GELNG has shown reduced spread area, lower vaporization rate, and crack sealing capability relative to the ungelled material. The purpose of this contract was to develop a mobile, continuous gelator which would produce a minimum of one cubic meter per hour of GELNG; previously, GELNG had been produced in small quantities by batch processes. Major achievements under the contract were the design and construction of the mobile gelator, checkout of the system with liquid nitrogen, and testing of the system on LNG.more » GELNG was not produced in the test series.« less

Description and Verification of a Novel Flow and Transport Model for Silicate-Gel Emplacement

NASA Astrophysics Data System (ADS)

Walther, M.; Solpuker, U.; Böttcher, N.; Kolditz, O.; Liedl, R.; Schwartz, F. W.

2013-12-01

Remediation of contamination is one of the basic tasks associated with groundwater management. While many different methods exist to reduce contaminant mass in situ, there is still a need for research on new approaches to significantly speed-up decontamination and to lower costs. Solpuker et al. (2012) describe flow-tank experiments that utilize dense, viscous silicate solutions to aid in the remediation process. The unique silicate solutions exhibit density-dependent flow and rapid gelation after some time that can be altered by adjusting the solute's composition. Based on the experiments, a novel approach was developed to simulate the behaviour of the rapidly gelating solute. The approach was implenented in the open-source software package OpenGeoSys (Kolditz et al. 2012). Specifically, the method involves simulating two mass transport processes: one is related to the density-dependent flow, while the other does not alter the fluid density but is designed to provide a first order decay process. While both concentrations are subject to standard mass transport processes (i.e. advection, dispersion, diffusion), the difference in the two concentrations yields information on the residence time of the injected solute. This information can be used to calculate the fluid viscosity and the appropriate change in fluid properties when gelation takes place. As with all models that involve the implementation of ';new' physics, it is crucial to verify the ability of the code to rigorously reproduce the vital processes that describe the movement of fluids and solutes. This step is particularly important here because such a density-dependent, viscosity-changing flow and transport process poses unique requirements in terms of stability for the numerical code. Therefore, our theoretical approach was verified successfully against the experimental data for three different gelation behaviors. Comparison of both, laboratory and numerical results, show that the key processes can be reproduced correctly, including e.g. persistence of solute in regions of gelation due to high viscosity, or concentration-dependent gelation. Further research is needed to relate the empirical parameters describing the viscosity-change function to measurable laboratory data, or to study field-scale implementations. Literature SOLPUKER, U., HAWKINS, J., SCHINCARIOL, R., IBARAKI, M., & SCHWARTZ, F. W. (2012). HARNESSING THE COMPLEX BEHAVIOR OF ULTRA-DENSE AND VISCOUS TREATMENT FLUIDS AS A STRATEGY FOR AQUIFER REMEDIATION. MODELS - REPOSITORIES OF KNOWLEDGE. MODELCARE2011, LEIPZIG, GERMANY. KOLDITZ, O., BAUER, S., BILKE, L., BÖTTCHER, N., DELFS, J. O., FISCHER, T., GÖRKE, U. J., ET AL. (2012). OPENGEOSYS: AN OPEN-SOURCE INITIATIVE FOR NUMERICAL SIMULATION OF THERMO-HYDRO-MECHANICAL/CHEMICAL (THM/C) PROCESSES IN POROUS MEDIA. ENVIRONMENTAL EARTH SCIENCES, 67(2), 589-599. DOI:10.1007/S12665-012-1546-X

Inhibition and Promotion of Heat-Induced Gelation of Whey Proteins in the Presence of Calcium by Addition of Sodium Caseinate.

PubMed

Nguyen, Bach T; Balakrishnan, Gireeshkumar; Jacquette, Boris; Nicolai, Taco; Chassenieux, Christophe; Schmitt, Christophe; Bovetto, Lionel

2016-11-14

Heat-induced aggregation and gelation of aqueous solutions of whey protein isolate (WPI) in the presence of sodium caseinate (SC) and CaCl 2 was studied at pH 6.6. The effect of adding SC (0-100 g/L) on the structure of the aggregates and the gels was investigated by light scattering and confocal laser scanning microscopy at different CaCl 2 concentration ([CaCl 2 ] = 0-30 mM). The gelation process was studied by oscillatory shear rheology. At the whey protein concentrations studied here (34 and 60 g/L), no gels were formed in the absence of CaCl 2 and SC. However, WPI solutions gelled above a critical CaCl 2 concentration that increased with increasing SC concentration. In the absence of CaCl 2 , WPI gels were formed only above a critical SC concentration. The critical SC concentration needed to induce WPI gelation decreased weakly when CaCl 2 was added. In an intermediate range of CaCl 2 concentrations, gels were formed both at low and high SC concentrations, but not at intermediate SC concentrations. Finally, at high CaCl 2 concentrations gels were formed at all SC concentrations. The gelation rate and the gel structure of the gels formed at low and high casein concentrations were very different. The effect of SC on the thermal gelation of WPI was interpreted by competition for Ca 2+ , a chaperon effect, and microphase separation.

A Peptide Amphiphile Organogelator of Polar Organic Solvents.

PubMed

Rouse, Charlotte K; Martin, Adam D; Easton, Christopher J; Thordarson, Pall

2017-03-03

A peptide amphiphile is reported, that gelates a range of polar organic solvents including acetonitrile/water, N,N-dimethylformamide and acetone, in a process dictated by β-sheet interactions and facilitated by the presence of an alkyl chain. Similarities with previously reported peptide amphiphile hydrogelators indicate analogous underlying mechanisms of gelation and structure-property relationships, suggesting that peptide amphiphile organogel design may be predictably based on hydrogel precedents.

A Peptide Amphiphile Organogelator of Polar Organic Solvents

PubMed Central

Rouse, Charlotte K.; Martin, Adam D.; Easton, Christopher J.; Thordarson, Pall

2017-01-01

A peptide amphiphile is reported, that gelates a range of polar organic solvents including acetonitrile/water, N,N-dimethylformamide and acetone, in a process dictated by β-sheet interactions and facilitated by the presence of an alkyl chain. Similarities with previously reported peptide amphiphile hydrogelators indicate analogous underlying mechanisms of gelation and structure-property relationships, suggesting that peptide amphiphile organogel design may be predictably based on hydrogel precedents. PMID:28255169

Positionally isomeric organic gelators: structure-gelation study, racemic versus enantiomeric gelators, and solvation effects.

PubMed

Caplar, Vesna; Frkanec, Leo; Sijaković Vujicić, Natasa; Zinić, Mladen

2010-03-08

Low molecular weight gelator molecules consisting of aliphatic acid, amino acid (phenylglycine), and omega-aminoaliphatic acid units have been designed. By varying the number of methylene units in the aliphatic and omega-aminoaliphatic acid chains, as defined by descriptors m and n, respectively, a series of positionally isomeric gelators having different positions of the peptidic hydrogen-bonding unit within the gelator molecule has been obtained. The gelation properties of the positional isomers have been determined in relation to a defined set of twenty solvents of different structure and polarity and analyzed in terms of gelator versatility (G(ver)) and effectiveness (G(eff)). The results of gelation tests have shown that simple synthetic optimizations of a "lead gelator molecule" by variation of m and n, end-group polarity (carboxylic acid versus sodium carboxylate), and stereochemistry (racemate versus optically pure form) allowed the identification of gelators with tremendously improved versatility (G(ver)) and effectiveness (G(eff)). Dramatic differences in G(eff) values of up to 70 times could be observed between pure racemate/enantiomer pairs of some gelators, which were manifested even in the gelation of very similar solvents such as isomeric xylenes. The combined results of spectroscopic ((1)H NMR, FTIR), electron microscopy (TEM), and X-ray diffraction studies suggest similar organization of the positionally isomeric gelators at the molecular level, comprising parallel beta-sheet hydrogen-bonded primary assemblies that form inversed bilayers at a higher organizational level. Differential scanning calorimetry (DSC) studies of selected enantiomer/racemate gelator pairs and their o- and p-xylene gels revealed the simultaneous presence of different polymorphs in the racemate gels. The increased gelation effectiveness of the racemate compared to that of the single enantiomer is most likely a consequence of its spontaneous resolution into enantiomeric bilayers and their subsequent organization into polymorphic aggregates of different energy. The latter determine the gel fiber thickness and solvent immobilization capacity of the formed gel network.

Multiple stimulus reversible hydrogels

DOEpatents

Gutowska, Anna; Krzyminski, Karol J.

2003-12-09

A polymeric solution capable of gelling upon exposure to a critical minimum value of a plurality of environmental stimuli is disclosed. The polymeric solution may be an aqueous solution utilized in vivo and capable of having the gelation reversed if at least one of the stimuli fall below, or outside the range of, the critical minimum value. The aqueous polymeric solution can be used either in industrial or pharmaceutical environments. In the medical environment, the aqueous polymeric solution is provided with either a chemical or radioisotopic therapeutic agent for delivery to a specific body part. The primary advantage of the process is that exposure to one environmental stimuli alone will not cause gelation, thereby enabling the therapeutic agent to be conducted through the body for relatively long distances without gelation occurring.

Multiple stimulus reversible hydrogels

DOEpatents

Gutowska, Anna; Krzyminski, Karol J.

2006-04-25

A polymeric solution capable of gelling upon exposure to a critical minimum value of a plurality of environmental stimuli is disclosed. The polymeric solution may be an aqueous solution utilized in vivo and capable of having the gelation reversed if at least one of the stimuli fall below, or outside the range of, the critical minimum value. The aqueous polymeric solution can be used either in industrial or pharmaceutical environments. In the medical environment, the aqueous polymeric solution is provided with either a chemical or radioisotopic therapeutic agent for delivery to a specific body part. The primary advantage of the process is that exposure to one environmental stimuli alone will not cause gelation, thereby enabling the therapeutic agent to be conducted through the body for relatively long distances without gelation occurring.

Heat stability and acid gelation properties of calcium-enriched reconstituted skim milk affected by ultrasonication.

PubMed

Chandrapala, Jayani; Bui, Don; Kentish, Sandra; Ashokkumar, Muthupandian

2014-05-01

The aggregation of proteins after heating of calcium-fortified milks has been an ongoing problem in the dairy industry. This undesirable effect restricts the manufacture of calcium rich dairy products. To overcome this problem, a completely new approach in controlling the heat stability of dairy protein solutions, developed in our lab, has been employed. In this approach, high intensity, low frequency ultrasound is applied for a very short duration after a pre-heating step at ⩾70 °C. The ultrasound breaks apart whey/whey and whey/casein aggregates through the process of acoustic cavitation. Protein aggregates do not reform on subsequent post-heating, thereby making the systems heat stable. In this paper, the acid gelation properties of ultrasonicated calcium-enriched skim milks have also been investigated. It is shown that ultrasonication alone does not change the gelation properties significantly whereas a sequence of preheating (72 °C/1 min) followed by ultrasonication leads to decreased gelation times, decreased gel syneresis and increased skim milk viscosity in comparison to heating alone. Overall, ultrasonication has the potential to provide calcium-fortified dairy products with increased heat stability. However, enhanced gelation properties can only be achieved when ultrasonication is completed in conjunction with heating.

Different additives to enhance the gelation of surimi gel with reduced sodium content.

PubMed

Cando, Deysi; Herranz, Beatriz; Borderías, A Javier; Moreno, Helena M

2016-04-01

This study tested the effect of adding tetra-sodium pyrophosphate, cystine and lysine as surimi gelation enhancers (Alaska Pollock) in order to reduce the sodium content of gels up to 0.3%. These gels were compared with others that contained 3% NaCl content (the amount typically used for surimi processing). To induce protein gelation, gels were first heated and then set at 5 °C/24 h. Once the physicochemical and rheological properties of the gels were determined, cystine and lysine were found to be the most effective additives improving the characteristics of low NaCl surimi gels. The action of these additives is mainly based on the induction of myofibrillar protein unfolding thus facilitating the formation of the types of bonds needed to establish an appropriate network. It was found that a setting period was needed for gel processing to maximize the effect of the additives. Copyright © 2015 Elsevier Ltd. All rights reserved.

Chiral bis(amino acid)- and bis(amino alcohol)-oxalamide gelators. Gelation properties, self-assembly motifs and chirality effects.

PubMed

Frkanec, Leo; Zinić, Mladen

2010-01-28

Bis(amino acid)- and bis(amino alcohol)oxalamide gelators represent the class of versatile gelators whose gelation ability is a consequence of strong and directional intermolecular hydrogen bonding provided by oxalamide units and lack of molecular symmetry due to the presence of two chiral centres. Bis(amino acid)oxalamides exhibit ambidextrous gelation properties, being capable to form gels with apolar and also highly polar solvent systems and tend to organise into bilayers or inverse bilayers in hydrogel or organic solvent gel assemblies, respectively. (1)H NMR and FTIR studies of gels revealed the importance of the equilibrium between the assembled network and smaller dissolved gelator assemblies. The organisation in gel assemblies deduced from spectroscopic structural studies are in certain cases closely related to organisations found in the crystal structures of selected gelators, confirming similar organisations in gel assemblies and in the solid state. The pure enantiomer/racemate gelation controversy is addressed and the evidence provided that rac-16 forms a stable toluene gel due to resolution into enantiomeric bilayers, which then interact giving gel fibres and a network of different morphology compared to its (S,S)-enantiomer gel. The TEM investigation of both gels confirmed distinctly different gel morphologies, which allowed the relationship between the stereochemical form of the gelator, the fibre and the network morphology and the network solvent immobilisation capacity to be proposed. Mixing of the constitutionally different bis(amino acid) and bis(amino alcohol)oxalamide gelators resulted in some cases in highly improved gelation efficiency denoted as synergic gelation effect (SGE), being highly dependent also on the stereochemistry of the component gelators. Examples of photo-induced gelation based on closely related bis(amino acid)-maleic acid amide and -fumaramide and stilbene derived oxalamides where gels form by irradiation of the solution of a non-gelling isomer and its photo-isomerisation into gelling isomer are provided, as well as examples of luminescent gels, gel-based fluoride sensors, LC-gels and nanoparticle-hydrogel composites.

Mammalian Cell Encapsulation in Alginate Beads Using a Simple Stirred Vessel.

PubMed

Hoesli, Corinne A; Kiang, Roger L J; Raghuram, Kamini; Pedroza, René G; Markwick, Karen E; Colantuoni, Antonio M R; Piret, James M

2017-06-29

Cell encapsulation in alginate beads has been used for immobilized cell culture in vitro as well as for immunoisolation in vivo. Pancreatic islet encapsulation has been studied extensively as a means to increase islet survival in allogeneic or xenogeneic transplants. Alginate encapsulation is commonly achieved by nozzle extrusion and external gelation. Using this method, cell-containing alginate droplets formed at the tip of nozzles fall into a solution containing divalent cations that cause ionotropic alginate gelation as they diffuse into the droplets. The requirement for droplet formation at the nozzle tip limits the volumetric throughput and alginate concentration that can be achieved. This video describes a scalable emulsification method to encapsulate mammalian cells in 0.5% to 10% alginate with 70% to 90% cell survival. By this alternative method, alginate droplets containing cells and calcium carbonate are emulsified in mineral oil, followed by a decrease in pH leading to internal calcium release and ionotropic alginate gelation. The current method allows the production of alginate beads within 20 min of emulsification. The equipment required for the encapsulation step consists in simple stirred vessels available to most laboratories.

Periodic Grating-like Patterns Induced by Self-Assembly of Gelator Fibres in Nematic Gels.

PubMed

Topnani, Neha B; Prutha, N; Pratibha, R

2018-03-15

Periodic orientation patterns occurring in nematic gels, revealed by optical and scanning electron microscopy, are found to be formed by spontaneous self-assembly of fibrous aggregates of a low-molecular-weight organogelator in an aligned thermotropic liquid crystal (LC). Self-organization into periodic structures is also reflected in a calorimetric study, which shows the occurrence of three thermoreversible states, namely, isotropic liquid, nematic and nematic gel. The segregation and self-assembly of the fibrous aggregates leading to pattern formation are attributed to the highly polar LC and to hydrogen bonding between gelator molecules, as shown by X-ray diffraction and vibrational spectroscopy. This study aims to investigate in detail the effect of the chemical nature and alignment of an anisotropic solvent on the morphology of the gelator fibres and the resulting gelation process. The periodic organization of LC-rich and fibre-rich regions can also provide a way to obtain templates for positioning nanoparticle arrays in an LC matrix, which can lead to novel devices. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nozzleless Fabrication of Oil-Core Biopolymeric Microcapsules by the Interfacial Gelation of Pickering Emulsion Templates.

PubMed

Leong, Jun-Yee; Tey, Beng-Ti; Tan, Chin-Ping; Chan, Eng-Seng

2015-08-05

Ionotropic gelation has been an attractive method for the fabrication of biopolymeric oil-core microcapsules due to its safe and mild processing conditions. However, the mandatory use of a nozzle system to form the microcapsules restricts the process scalability and the production of small microcapsules (<100 μm). We report, for the first time, a nozzleless and surfactant-free approach to fabricate oil-core biopolymeric microcapsules through ionotropic gelation at the interface of an O/W Pickering emulsion. This approach involves the self-assembly of calcium carbonate (CaCO3) nanoparticles at the interface of O/W emulsion droplets followed by the addition of a polyanionic biopolymer into the aqueous phase. Subsequently, CaCO3 nanoparticles are dissolved by pH reduction, thus liberating Ca(2+) ions to cross-link the surrounding polyanionic biopolymer to form a shell that encapsulates the oil droplet. We demonstrate the versatility of this method by fabricating microcapsules from different types of polyanionic biopolymers (i.e., alginate, pectin, and gellan gum) and water-immiscible liquid cores (i.e., palm olein, cyclohexane, dichloromethane, and toluene). In addition, small microcapsules with a mean size smaller than 100 μm can be produced by selecting the appropriate conventional emulsification methods available to prepare the Pickering emulsion. The simplicity and versatility of this method allows biopolymeric microcapsules to be fabricated with ease by ionotropic gelation for numerous applications.

Pyrenyl-linker-glucono gelators. Correlations of gel properties with gelator structures and characterization of solvent effects.

PubMed

Yan, Ni; Xu, Zhiyan; Diehn, Kevin K; Raghavan, Srinivasa R; Fang, Yu; Weiss, Richard G

2013-01-15

A series of glucono-appended 1-pyrenesulfonyl derivatives containing α,ω-diaminoalkane spacers (Pn, where n, the number of methylene units separating the amino groups, is 2, 3, 4, 6, 7, and 8) have been prepared. Careful analyses of correlations between the structures of these molecules and their gels have provided important insights into the factors responsible for one-dimensional aggregation of small molecules containing both lipophilic and hydrophilic parts. The gelation behavior has been examined in 30 liquids of diverse structure and polarity, and the properties of their gels and the gelation mechanisms have been investigated using a variety of techniques. Possible reasons are discussed regarding why the Pn are better gelators than the corresponding naphthyl analogues (Nn) which had been investigated previously. P2 and P3 are ambidextrous gelators (i.e., they gelate both water and some organic liquids), and P4-P8 gelate some organic liquids which are protic and aprotic, but not water. In at least one of the liquids examined, P3, P4, P6, P7, and P8 form gels at less than 1 w/v % concentrations, and some of the gels in 1-decanol are thixotropic. Analyses of the gelation abilities using Hansen solubility parameters yield both qualitative and quantitative insights into the role of liquid-gelator interactions. For example, the critical gelation concentrations increase generally with increasing polar and hydrogen bonding interactions between the gelators and their liquid components. As revealed by FT-IR, (1)H NMR, UV-vis, and fluorescence spectra, hydrogen-bonding between glucono units and π-π stacking between pyrenyl groups are important in the formation and maintenance of the gel networks. The results from this study, especially those relating the aggregation modes and liquid properties, offer insights for the design of new surfactant-containing low-molecular-mass gelators with predefined gelating abilities.

Hydrogen-bonding A(LS)2-type low-molecular-mass gelator and its thermotropic mesomorphic behavior.

PubMed

Hou, Qiufei; Wang, Shichao; Zang, Libin; Wang, Xiaoliang; Jiang, Shimei

2009-10-15

A unique cholesterol-based A(LS)2-type gelator, which is a hydrogen-bonding complex based on an ALS-type non-gelator molecule 3-cholesteryl 4-(trans-2-(4-pyridinyl)vinyl)phenyl succinate and a counterpart 3-cholesteryloxycarbonylpropanoic acid, shows strong gelation ability in alcohol and aromatic solvents. The formed gel has a high Tg at low gelation concentration, and its xerogel shows fibrillar microstructure revealed by scanning electron microscopy (SEM). FTIR confirms the existence of intermolecular hydrogen bond in the gelator, and X-ray diffraction (XRD) analysis reveals that the gelator possesses a folded conformation in gel and self-assembles into the fibrillar structure mainly by van der Waals interaction between cholesteryl moieties of the gelator. Further more, the thermotropic behavior of the xerogel is studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM), which shows typical optical textures of liquid crystals.

Effect of food additives on egg yolk gelation induced by freezing.

PubMed

Primacella, Monica; Fei, Tao; Acevedo, Nuria; Wang, Tong

2018-10-15

This study demonstrates technological advances in preventing yolk gelation during freezing and thawing. Gelation negatively affects yolk functionality in food formulation. Preventing gelation using 10% salt or sugar limits the application of the yolk. Novel food additives were tested to prevent gelation induced by freezing. Significant reduction (p < 0.05) in gel hardness of frozen-thawed yolk (45 h freezing at -20 °C) indicates that hydrolyzed carboxymethyl cellulose (HCMC), proline, and hydrolyzed egg white and yolk (HEW and HEY) are effective gelation inhibitors. The mechanisms in which these additives prevented gelation were further studied through measuring the changes in the amount of freezable water, lipoprotein particle size, and protein surface hydrophobicity. Overall, this study provides several alternatives of gelation inhibitor that have great potentials in replacing the use of salt or sugar in commercial operation of freezing egg yolk for shelf-life extension. Copyright © 2018 Elsevier Ltd. All rights reserved.

In Situ Observations of Thermoreversible Gelation and Phase Separation of Agarose and Methylcellulose Solutions under High Pressure.

PubMed

Kometani, Noritsugu; Tanabe, Masahiro; Su, Lei; Yang, Kun; Nishinari, Katsuyoshi

2015-06-04

Thermoreversible sol-gel transitions of agarose and methylcellulose (MC) aqueous solutions on isobaric cooling or heating under high pressure up to 400 MPa have been investigated by in situ observations of optical transmittance and falling-ball experiments. For agarose, which undergoes the gelation on cooling, the application of pressure caused a gradual rise in the cloud-point temperature over the whole pressure range examined, which is almost consistent with the pressure dependence of gelling temperature estimated by falling-ball experiments, suggesting that agarose gel is stabilized by compression and that the gelation occurs nearly in parallel with phase separation under ambient and high-pressure conditions. For MC, which undergoes the gelation on heating, the cloud-point temperature showed a slight rise with an initial elevation of pressure up to ∼150 MPa, whereas it showed a marked depression above 200 MPa. In contrast, the gelling temperature of MC, which is nearly identical to the cloud-point temperature at ambient pressure, showed a monotonous rise with increasing pressure up to 350 MPa, which means that MC undergoes phase separation prior to gelation on heating under high pressure above 200 MPa. Similar results were obtained for the melting process of MC gel on cooling. The unique behavior of the sol-gel transition of MC under high pressure has been interpreted in terms of the destruction of hydrophobic hydration by compression.

Towards a fragment-based approach in gelator design: halogen effects leading to thixotropic, mouldable and self-healing systems in aryl-triazolyl amino acid-based gelators!

PubMed

Srivastava, Bhartendu K; Manheri, Muraleedharan K

2017-04-18

A simple replacement of a H atom by Br transformed non-gelating aryl triazolyl amino acid benzyl ester into a versatile gelator, which formed shape-persistent, self-healing and mouldable gels. The 'bromo-aryl benzyl ester' fragment was then transplanted into another framework, which resulted in similar solvent preference and gelation efficiency.

A novel aggregation-induced emission enhancement triggered by the assembly of a chiral gelator: from non-emissive nanofibers to emissive micro-loops.

PubMed

Chen, Wenrui; Qing, Guangyan; Sun, Taolei

2016-12-22

In this study, a novel aggregation-induced emission (AIE) enhancement triggered by the self-assembly of chiral gelator is described. Tuning of molecular chirality in situ triggers different assemblies of superstructures exhibiting fluorescence. This novel AIE material can constitute an emerging library of chiral supramolecules for turn-on fluorescent sensors. It will also help in better understanding the effects of chiral factors on the photophysical process.

Light driven mesoscale assembly of a coordination polymeric gelator into flowers and stars with distinct properties.

PubMed

Mukhopadhyay, Rahul Dev; Praveen, Vakayil K; Hazra, Arpan; Maji, Tapas Kumar; Ajayaghosh, Ayyappanpillai

2015-11-13

Control over the self-assembly process of porous organic-inorganic hybrids often leads to unprecedented polymorphism and properties. Herein we demonstrate how light can be a powerful tool to intervene in the kinetically controlled mesoscale self-assembly of a coordination polymeric gelator. Ultraviolet light induced coordination modulation via photoisomerisation of an azobenzene based dicarboxylate linker followed by aggregation mediated crystal growth resulted in two distinct morphological forms (flowers and stars), which show subtle differences in their physical properties.

Blending Gelators to Tune Gel Structure and Probe Anion-Induced Disassembly

PubMed Central

Foster, Jonathan A; Edkins, Robert M; Cameron, Gary J; Colgin, Neil; Fucke, Katharina; Ridgeway, Sam; Crawford, Andrew G; Marder, Todd B; Beeby, Andrew; Cobb, Steven L; Steed, Jonathan W

2014-01-01

Blending different low molecular weight gelators (LMWGs) provides a convenient route to tune the properties of a gel and incorporate functionalities such as fluorescence. Blending a series of gelators having a common bis-urea motif, and functionalised with different amino acid-derived end-groups and differing length alkylene spacers is reported. Fluorescent gelators incorporating 1-and 2-pyrenyl moieties provide a probe of the mixed systems alongside structural and morphological data from powder diffraction and electron microscopy. Characterisation of the individual gelators reveals that although the expected α-urea tape motif is preserved, there is considerable variation in the gelation properties, molecular packing, fibre morphology and rheological behaviour. Mixing of the gelators revealed examples in which: 1) the gels formed separate, orthogonal networks maintaining their own packing and morphology, 2) the gels blended together into a single network, either adopting the packing and morphology of one gelator, or 3) a new structure not seen for either of the gelators individually was created. The strong binding of the urea functionalities to anions was exploited as a means of breaking down the gel structure, and the use of fluorescent gel blends provides new insights into anion-mediated gel dissolution. PMID:24302604

Enhancing gelation ability of a dendritic gelator through complexation with a polyelectrolyte.

PubMed

Zhang, Zijian; Yang, Miao; Zhang, Xinjun; Zhang, Lichu; Liu, Bo; Zheng, Ping; Wang, Wei

2009-01-01

A poly(urethane amide) (PUA) dendron with long alkyl chains on its periphery was synthesized and then attached to the backbone of a polyelectrolyte, in which each unit contained a positive charge, by ionizing the carboxyl groups on the apexes of the dendrons to form a dendronized polymer. We found that both the PUA dendron and the dendronized polymer could form organogels in toluene. Interestingly, both the minimum gelation concentration and the gelation time of the dendronized polymer gelator were greatly reduced compared with the dendron alone. Our investigations showed that in the gel phase the intermolecular hydrogen bonding between adjacent dendrons creates similar supramolecular structures in both the dendron and the dendronized polymer gelator, which immobilize solvent molecules by means of interactions between dendrons and solvent molecules. Further studies on the gelation kinetics indicated that the polyelectrolyte backbone plays an important role in prearranging the attached dendritic gelators orderly and quickly into the supramolecular structures through a nucleation-elongation mechanism. Therefore, the gel-forming ability of the dendritic PUA gelator is enhanced by being complexed with the polyelectrolyte. In this work, this positive macromolecular effect is discussed in detail.

Pyridyl-Amides as a Multimode Self-Assembly Driver for the Design of a Stimuli-Responsive π-Gelator.

PubMed

Kartha, Kalathil K; Praveen, Vakayil K; Babu, Sukumaran Santhosh; Cherumukkil, Sandeep; Ajayaghosh, Ayyappanpillai

2015-10-01

An oligo(p-phenylenevinylene) (OPV) derivative connected to pyridyl end groups through an amide linkage (OPV-Py) resulted in a multistimuli-responsive π-gelator. When compared to the corresponding OPV π-gelator terminated by a phenyl-amide (OPV-Ph), the aggregation properties of OPV-Py were found to be significantly different, leading to multistimuli gelation and other morphological properties. The pyridyl moiety in OPV-Py initially interferes with the amide H-bonded assembly and gelation, however, protonation of the pyridyl moiety with trifluoroacetic acid (TFA) facilitated the formation of amide H-bonded assembly leading to gelation, which is reversible by the addition of N,N-diisopropyethylamine (DiPEA). Interestingly, addition of Ag(+) ions to a solution of OPV-Py facilitated the formation of a metallo-supramolecular assembly leading to gelation. Surprisingly, ultrasound-induced gelation was observed when OPV-Py was mixed with a dicarboxylic acid (A1). A detailed study using different spectroscopic and microscopic experimental techniques revealed the difference in the mode of assembly in the two molecules and the multistimuli-responsive nature of the OPV-Py gelation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlled Gelation of Particle Suspensions Using Controlled Solvent Removal in Picoliter Droplets

NASA Astrophysics Data System (ADS)

Vuong, Sharon; Walker, Lynn; Anna, Shelley

2013-11-01

Droplets in microfluidic devices have proven useful as uniform picoliter reactors for nanoparticle synthesis and as components in tunable emulsions. However, there can be significant transport between the component phases depending on solubility and other factors. In the present talk, we show that water droplets trapped within a microfluidic device for tens of hours slowly dehydrate, concentrating the contents encapsulated within. We use this slow dehydration along with control of the initial droplet composition to monitor gelation of aqueous suspensions of spherical silica particles (Ludox) and disk-shaped clay particles (Laponite). Droplets are generated in a microfluidic device containing small wells that trap the droplets. We monitor the concentration process through size and shape changes of these droplets as a function of time in tens of droplets and use the large number of individual reactors to generate statistics regarding the gelation process. We also examine changes in suspension viscosity through fluorescent particle tracking as a function of dehydration rate, initial suspension concentration and initial droplet volume, and added salt, and compare the results with the Krieger-Dougherty model in which viscosity increases dramatically with particle volume fraction.

Chaperone gelator for the chiral self-assembly of all proteinogenic amino acids and their enantiomers.

PubMed

Chen, Jie; Wang, Tianyu; Liu, Minghua

2016-05-04

A concept of a chaperone gelator that can assist non-gelator molecules to form gels is proposed. Such a new gelator was developed and found to tune all the proteinogenic l-amino acids, as well as their enantiomers into supramolecular gels.

A new insight into the physiological role of bile salt hydrolase among intestinal bacteria from the genus Bifidobacterium.

PubMed

Jarocki, Piotr; Podleśny, Marcin; Glibowski, Paweł; Targoński, Zdzisław

2014-01-01

This study analyzes the occurrence of bile salt hydrolase in fourteen strains belonging to the genus Bifidobacterium. Deconjugation activity was detected using a plate test, two-step enzymatic reaction and activity staining on a native polyacrylamide gel. Subsequently, bile salt hydrolases from B. pseudocatenulatum and B. longum subsp. suis were purified using a two-step chromatographic procedure. Biochemical characterization of the bile salt hydrolases showed that the purified enzymes hydrolyzed all of the six major human bile salts under the pH and temperature conditions commonly found in the human gastrointestinal tract. Next, the dynamic rheometry was applied to monitor the gelation process of deoxycholic acid under different conditions. The results showed that bile acids displayed aqueous media gelating properties. Finally, gel-forming abilities of bifidobacteria exhibiting bile salt hydrolase activity were analyzed. Our investigations have demonstrated that the release of deconjugated bile acids led to the gelation phenomenon of the enzymatic reaction solution containing purified BSH. The presented results suggest that bile salt hydrolase activity commonly found among intestinal microbiota increases hydrogel-forming abilities of certain bile salts. To our knowledge, this is the first report showing that bile salt hydrolase activity among Bifidobacterium is directly connected with the gelation process of bile salts. In our opinion, if such a phenomenon occurs in physiological conditions of human gut, it may improve bacterial ability to colonize the gastrointestinal tract and their survival in this specific ecological niche.

A crown ether appended super gelator with multiple stimulus responsiveness.

PubMed

Dong, Shengyi; Zheng, Bo; Xu, Donghua; Yan, Xuzhou; Zhang, Mingming; Huang, Feihe

2012-06-26

A crown ether appended super gelator is designed and synthesized. It can gel a variety of organic solvents and shows excellent gelation properties with both low critical gelation concentration and short gelation time. Due to the introduction of the crown ether moiety and a secondary ammonium unit, the supramolecular gels show reversible gel-sol transitions. The supramolecular gels can also be molded into shape-persistent and free-standing objects. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Viscoelastic properties, gelation behavior and percolation theory model for the temperature induced forming (TIF) ceramic slurries

NASA Astrophysics Data System (ADS)

Yang, Yunpeng

Controlled ceramic processing is required to produce ceramic parts with few strength-limiting defects and the economic forming of near net shape components. Temperature induced forming (TIF) is a novel ceramic forming process that uses colloidal processing to form ceramic green bodies by physical gelation. The dissertation research shows that TIF alumina suspensions (>40vol%) can be successfully fabricated by using 0.4wt% of ammonium citrate powder and <0.1wt% poly (acrylic acid) (PAA). It is found that increasing the volume fraction of alumina or the molecular weight of polymer will increase the shear viscosity and shear modulus. Larger molecular weight PAA tends to decrease the volume fraction gelation threshold of the alumina suspensions. The author is the first in this field to utilize the continuous percolation theory to interpret the evolution of the storage modulus with temperature for the TIF alumina suspensions. A model that relates the storage modulus with temperature and the volume fraction of solids is proposed. Calculated results using this percolation model show that the storage modulus of the suspensions can be affected by the volume fraction of solids, temperature, volume fraction gelation threshold and the percolation nature. The parameters in this model have been derived from the experimental data. The calculated results fit the measured data well. For the PAA-free TIF alumina suspensions, it is found that the ionization reaction of the magnesium citrate, which is induced by the pH or temperature of the suspensions, controls the flocculation of the suspensions. The percolation theory model was successfully applied to this type of suspension. Compared with the PAA addition TIF suspensions, these suspensions reflect a higher degree of percolation nature, as indicated by a larger value of percolation exponent. These results show that the percolation model proposed in this dissertation can be used to predict the gelation degree of the TIF suspensions. Complex-shape engineering ceramic parts have been successfully fabricated by direct casting using the TIF alumina suspensions, which has a relative density of ˜65%. The sintered sample at 1550°C for 2h is translucent and has a uniform grain size.

Method of controlling crystallite size in nuclear-reactor fuels

DOEpatents

Lloyd, Milton H.; Collins, Jack L.; Shell, Sam E.

1985-01-01

Improved spherules for making enhanced forms of nuclear-reactor fuels are prepared by internal gelation procedures within a sol-gel operation and are accomplished by first boiling the concentrated HMTA-urea feed solution before engaging in the spherule-forming operation thereby effectively controlling crystallite size in the product spherules.

Method of controlling crystallite size in nuclear-reactor fuels

DOEpatents

Lloyd, M.H.; Collins, J.L.; Shell, S.E.

Improved spherules for making enhanced forms of nuclear-reactor fuels are prepared by internal gelation procedures within a sol-gel operation and are accomplished by first boiling the concentrated HMTA-urea feed solution before engaging in the spherule-forming operation thereby effectively controlling crystallite size in the product spherules.

Actin assembly factors regulate the gelation kinetics and architecture of F-actin networks.

PubMed

Falzone, Tobias T; Oakes, Patrick W; Sees, Jennifer; Kovar, David R; Gardel, Margaret L

2013-04-16

Dynamic regulation of the actin cytoskeleton is required for diverse cellular processes. Proteins regulating the assembly kinetics of the cytoskeletal biopolymer F-actin are known to impact the architecture of actin cytoskeletal networks in vivo, but the underlying mechanisms are not well understood. Here, we demonstrate that changes to actin assembly kinetics with physiologically relevant proteins profilin and formin (mDia1 and Cdc12) have dramatic consequences on the architecture and gelation kinetics of otherwise biochemically identical cross-linked F-actin networks. Reduced F-actin nucleation rates promote the formation of a sparse network of thick bundles, whereas increased nucleation rates result in a denser network of thinner bundles. Changes to F-actin elongation rates also have marked consequences. At low elongation rates, gelation ceases and a solution of rigid bundles is formed. By contrast, rapid filament elongation accelerates dynamic arrest and promotes gelation with minimal F-actin density. These results are consistent with a recently developed model of how kinetic constraints regulate network architecture and underscore how molecular control of polymer assembly is exploited to modulate cytoskeletal architecture and material properties. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Actin Assembly Factors Regulate the Gelation Kinetics and Architecture of F-actin Networks

PubMed Central

Falzone, Tobias T.; Oakes, Patrick W.; Sees, Jennifer; Kovar, David R.; Gardel, Margaret L.

2013-01-01

Dynamic regulation of the actin cytoskeleton is required for diverse cellular processes. Proteins regulating the assembly kinetics of the cytoskeletal biopolymer F-actin are known to impact the architecture of actin cytoskeletal networks in vivo, but the underlying mechanisms are not well understood. Here, we demonstrate that changes to actin assembly kinetics with physiologically relevant proteins profilin and formin (mDia1 and Cdc12) have dramatic consequences on the architecture and gelation kinetics of otherwise biochemically identical cross-linked F-actin networks. Reduced F-actin nucleation rates promote the formation of a sparse network of thick bundles, whereas increased nucleation rates result in a denser network of thinner bundles. Changes to F-actin elongation rates also have marked consequences. At low elongation rates, gelation ceases and a solution of rigid bundles is formed. By contrast, rapid filament elongation accelerates dynamic arrest and promotes gelation with minimal F-actin density. These results are consistent with a recently developed model of how kinetic constraints regulate network architecture and underscore how molecular control of polymer assembly is exploited to modulate cytoskeletal architecture and material properties. PMID:23601318

Description of recovery method used for curdlan produced by Agrobacterium sp. IFO 13140 and its relation to the morphology and physicochemical and technological properties of the polysaccharide

PubMed Central

Mangolim, Camila Sampaio; da Silva, Thamara Thaiane; Fenelon, Vanderson Carvalho; Koga, Luciana Numata; Ferreira, Sabrina Barbosa de Souza; Bruschi, Marcos Luciano; Matioli, Graciette

2017-01-01

Curdlan is a linear polysaccharide considered a dietary fiber and with gelation properties. This study evaluated the structure, morphology and the physicochemical and technological properties of curdlan produced by Agrobacterium sp. IFO 13140 recovered by pre-gelation and precipitation methods. Commercial curdlan submitted or otherwise to the pre-gelation process was also evaluated. The data obtained from structural analysis revealed a similarity between the curdlan produced by Agrobacterium sp. IFO 13140 (recovered by both methods) and the commercial curdlans. The results showed that the curdlans evaluated differed significantly in terms of dispersibility and gelation, and only the pre-gelled ones had significant potential for food application, because this method influence on the size of the particles and in the presence of NaCl. In terms of technological properties, the curdlan produced by Agrobacterium sp. IFO 13140 (pre-gelation method) had a greater water and oil holding capacity (64% and 98% greater, respectively) and a greater thickening capacity than the pre-gelled commercial curdlan. The pre-gelled commercial curdlan displayed a greater gelling capacity at 95°C than the others. When applied to food, only the pre-gelled curdlans improved the texture parameters of yogurts and reduced syneresis. The curdlan gels, which are rigid and stable in structure, demonstrated potential for improving the texture of food products, with potential industrial use. PMID:28245244

Self-Assembly of a Strong Polyhedral Oligomeric Silsesquioxane Core-Based Aspartate Derivative Dendrimer Supramolecular Gelator in Different Polarity Solvents.

PubMed

He, Huiwen; Chen, Si; Tong, Xiaoqian; An, Zhihang; Ma, Meng; Wang, Xiaosong; Wang, Xu

2017-11-21

Aromatic groups are introduced into the end peripherals of polyhedral oligomeric silsesquioxane (POSS) core-based organic/inorganic hybrid supramolecules to get a novel dendrimer gelator POSS-Z-Asp(OBzl) (POSS-ASP), which have eight aspartate derivative arms to make full use of strong π-π stacking forces to get strong supramolecular gels in addition to multiple hydrogen bindings and van der Waals interactions. POSS-ASP can self-assemble into three-dimensional nanoscale gel networks to provide hybrid physical gels especially with strong mechanical properties and fast-recovery behaviors. Two totally different morphologies of the connected spherical particle structures and banded ultralong fibers are observed owing to the polarity of solvents confirmed by the scanning electron microscopy, polarized optical microscopy, and transmission electron microscopy techniques, expecting the existing various self-assembly models and illustrating the peripherals of the dendrimer and the polarity of solvents having huge influences in the supramolecular self-assembly mechanism. What is more, the thermal stability, rheological properties, and network architecture information have also been investigated via tube-inversion, rotational rheometer, and powder X-ray diffraction methods, the results of which confirm the two different gel formation mechanisms that make POSS-ASP to exhibit two totally different thermal and mechanical properties. Such a study reports a new gelation system in organic or organic/aqueous mixed solvents, which can be helpful for investigating the relationship of dendritic supramolecular gelation and different polarity solvents during the supramolecular self-assembly process of gelators.

Description of recovery method used for curdlan produced by Agrobacterium sp. IFO 13140 and its relation to the morphology and physicochemical and technological properties of the polysaccharide.

PubMed

Mangolim, Camila Sampaio; Silva, Thamara Thaiane da; Fenelon, Vanderson Carvalho; Koga, Luciana Numata; Ferreira, Sabrina Barbosa de Souza; Bruschi, Marcos Luciano; Matioli, Graciette

2017-01-01

Curdlan is a linear polysaccharide considered a dietary fiber and with gelation properties. This study evaluated the structure, morphology and the physicochemical and technological properties of curdlan produced by Agrobacterium sp. IFO 13140 recovered by pre-gelation and precipitation methods. Commercial curdlan submitted or otherwise to the pre-gelation process was also evaluated. The data obtained from structural analysis revealed a similarity between the curdlan produced by Agrobacterium sp. IFO 13140 (recovered by both methods) and the commercial curdlans. The results showed that the curdlans evaluated differed significantly in terms of dispersibility and gelation, and only the pre-gelled ones had significant potential for food application, because this method influence on the size of the particles and in the presence of NaCl. In terms of technological properties, the curdlan produced by Agrobacterium sp. IFO 13140 (pre-gelation method) had a greater water and oil holding capacity (64% and 98% greater, respectively) and a greater thickening capacity than the pre-gelled commercial curdlan. The pre-gelled commercial curdlan displayed a greater gelling capacity at 95°C than the others. When applied to food, only the pre-gelled curdlans improved the texture parameters of yogurts and reduced syneresis. The curdlan gels, which are rigid and stable in structure, demonstrated potential for improving the texture of food products, with potential industrial use.

Regulation of substituent groups on morphologies and self-assembly of organogels based on some azobenzene imide derivatives

NASA Astrophysics Data System (ADS)

Jiao, Tifeng; Wang, Yujin; Zhang, Qingrui; Zhou, Jingxin; Gao, Faming

2013-04-01

In this paper, new azobenzene imide derivatives with different substituent groups were designed and synthesized. Their gelation behaviors in 21 solvents were tested as novel low-molecular-mass organic gelators. It was shown that the alkyl substituent chains and headgroups of azobenzene residues in gelators played a crucial role in the gelation behavior of all compounds in various organic solvents. More alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Scanning electron microscopy and atomic force microscopy observations revealed that the gelator molecules self-assemble into different aggregates, from wrinkle, lamella, and belt to fiber with the change of solvents. Spectral studies indicated that there existed different H-bond formations between amide groups and conformations of methyl chains. The present work may give some insight to the design and character of new organogelators and soft materials with special molecular structures.

Regulation of substituent groups on morphologies and self-assembly of organogels based on some azobenzene imide derivatives

PubMed Central

2013-01-01

In this paper, new azobenzene imide derivatives with different substituent groups were designed and synthesized. Their gelation behaviors in 21 solvents were tested as novel low-molecular-mass organic gelators. It was shown that the alkyl substituent chains and headgroups of azobenzene residues in gelators played a crucial role in the gelation behavior of all compounds in various organic solvents. More alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Scanning electron microscopy and atomic force microscopy observations revealed that the gelator molecules self-assemble into different aggregates, from wrinkle, lamella, and belt to fiber with the change of solvents. Spectral studies indicated that there existed different H-bond formations between amide groups and conformations of methyl chains. The present work may give some insight to the design and character of new organogelators and soft materials with special molecular structures. PMID:23566628

Toluene diisocyanate based phase-selective supramolecular oil gelator for effective removal of oil spills from polluted water.

PubMed

Wang, Yongzhen; Wang, Youshan; Yan, Xingru; Wu, Songquan; Shao, Lu; Liu, Yuyan; Guo, Zhanhu

2016-06-01

Due to tremendous resource wastes and great harm to ecological environment caused by the accidental oil spills, an alkyl bicarbamate supramolecular oil gelator was synthesized and applied to selectively gelate oils from oil/water mixtures. Interestingly, the oil gelator could be self-assembled in a series of organic solvents, i.e., edible oils and fuel oils to form 3D networks and then turned into thermally reversible organogels, allowing easy separation and removal of oil spills from oil/water mixtures. The possible self-assembly mode for the formation of organogels was proposed. What's more, the optimal conditions for using the oil gelator to recover oils were experimentally determined. Inspiringly, taking gasoline as the co-congealed solvent, a complete gelation of oil phase was achieved within 15 min with high oil removal rate and oil retention rate after convenient salvage and cleanup of oil gels from oil/water mixtures. The oil gelator had some advantages in solidifying oil spills on water surface, exhibiting fast oil gelation, convenient and thorough oil removal and easy recovery. This work illustrates the significant role of oil gelators in the potential cleanup of spilled oils for water purification. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evidence of solvent-gelator interaction in sugar-based organogel studied by field-cycling NMR relaxometry.

PubMed

Bielejewski, Michal; Tritt-Goc, Jadwiga

2010-11-16

The dynamics of bulk toluene and toluene confined in the 1,2-O-(1-ethylpropylidene)-α-D-glucofuranose gel was studied using (1)H field-cycling nuclear magnetic resonance relaxometry. The proton spin-lattice relaxation time T(1) was measured as a function of the magnetic field strength and temperature. The observed dispersion in the frequency range 10(4)-10(6) Hz for the relaxation rate of toluene in the gel system give evidence of the interaction between the toluene and the gelator aggregates. The data were interpreted in terms of the two-fraction fast-exchange model. Additionally it was also shown that a cooling rate during gel preparation process influences the gel microstructure and leads to different gelator-solvent interactions as reflected in a different behavior of the proton spin-lattice relaxation rate of toluene within the gel observed at the low frequency range.

Exchange-driven growth.

PubMed

Ben-Naim, E; Krapivsky, P L

2003-09-01

We study a class of growth processes in which clusters evolve via exchange of particles. We show that depending on the rate of exchange there are three possibilities: (I) Growth-clusters grow indefinitely, (II) gelation-all mass is transformed into an infinite gel in a finite time, and (III) instant gelation. In regimes I and II, the cluster size distribution attains a self-similar form. The large size tail of the scaling distribution is Phi(x) approximately exp(-x(2-nu)), where nu is a homogeneity degree of the rate of exchange. At the borderline case nu=2, the distribution exhibits a generic algebraic tail, Phi(x) approximately x(-5). In regime III, the gel nucleates immediately and consumes the entire system. For finite systems, the gelation time vanishes logarithmically, T approximately [lnN](-(nu-2)), in the large system size limit N--> infinity. The theory is applied to coarsening in the infinite range Ising-Kawasaki model and in electrostatically driven granular layers.

Rheological Properties of Gels from Pyrene Based Low Molecular Weight Gelators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leivo, Kimmo T.; Hahma, Arno P.

2008-07-07

Gels of pyrene derived low molecular weight organogelators (LMOGs) in primary alcohols have been characterized by rheometry and scanning electron microscopy. Total gelator concentration was 1-2.7 % w/w depending on the solvent and the gelator, including equimolar amounts of the gelator and 2,4,7-trinitrofluorenone (TNF), which is necessary for gelation. Thermoreversible and strongly shear thinning gels were achieved as the two components interact non-covalently to form a gel network. A qualitative correlation between the rheological properties and the nanoscale gel structure were found.

Rheological Properties of Gels from Pyrene Based Low Molecular Weight Gelators

NASA Astrophysics Data System (ADS)

Leivo, Kimmo T.; Hahma, Arno P.

2008-07-01

Gels of pyrene derived low molecular weight organogelators (LMOGs) in primary alcohols have been characterized by rheometry and scanning electron microscopy. Total gelator concentration was 1-2.7 % w/w depending on the solvent and the gelator, including equimolar amounts of the gelator and 2,4,7-trinitrofluorenone (TNF), which is necessary for gelation. Thermoreversible and strongly shear thinning gels were achieved as the two components interact non-covalently to form a gel network. A qualitative correlation between the rheological properties and the nanoscale gel structure were found.

Molecular insights into early stage aggregation of di-Fmoc-L-lysine in binary mixture of organic solvent and water

NASA Astrophysics Data System (ADS)

Huda, Md Masrul; Rai, Neeraj

Molecular gels are relatively new class of soft materials, which are formed by the supramolecular aggregation of low molecular weight gelators (LMWGs) in organic solvents and/or water. Hierarchical self-assembly of small gelator molecules lead to three-dimensional complex fibrillar networks, which restricts the flow of solvents and results in viscous solid like materials or gels. These gels have drawn significant attentions for their potential applications for drug delivery, tissue engineering, materials for sensors etc. As of now, self-assembly of gelator molecules into one-dimensional fibers is not well understood, although that is very important to design new gelators for desired applications. Here, we present molecular dynamics study that provides molecular level insight into early stage aggregation of selected gelator, di-Fmoc-L-lysine in binary mixture of organic solvent and water. We will present the role of different functional groups of gelator molecule such as aromatic ring, amide, and carboxylic group on aggregation. We will also present the effect of concentrations of gelator and solvent on self-assembly of gelators. This study has captured helical fiber growth and branching of fiber, which is in good agreement with experimental observations.

Robust multi-responsive supramolecular hydrogel based on a mono-component host-guest gelator.

PubMed

Cheng, Weinan; Zhao, Dongxu; Qiu, Yuan; Hu, Haisi; Wang, Hong; Wang, Qin; Liao, Yonggui; Peng, Haiyan; Xie, Xiaolin

2018-05-29

Supramolecular hydrogels have been widely investigated, but the construction of stimuli-responsive mono-component host-guest hydrogels remains a challenge in that it is still hard to balance the solubility and gelation ability of the gelator. In this work, three azobenzene-modified β-cyclodextrin derivatives with different alkyl lengths (β-CD-Azo-Cn) have been synthesized. The length of the alkyl chain dramatically influences the solubility and gelation ability of β-CD derivatives in water. Among these derivatives, β-CD-Azo-C8 possesses the lowest minimum gelation concentration (MGC). Based on the host-guest interaction between β-CD and azobenzene units in aqueous solution, which is confirmed by UV-visible and ROESY NMR spectra, the gelators self-assemble and further interwine into networks through the hydrogen bonds on the surface of β-CD cavities. Hydrogels formed by mono-component gelators can collapse under external stimuli such as heating, competition guests and hosts, and UV irradiation. When the concentration of the gelator is more than 8 wt%, the hydrogel exhibits good self-supporting ability with a storage modulus higher than 104 Pa. The gel-sol transition temperature of the hydrogel is near body temperature, indicating its potential applications in biological materials.

Stoichiometric sensing to opt between gelation and crystallization.

PubMed

Vidyasagar, Adiyala; Sureshan, Kana M

2015-10-05

A new class of organogelators having a cyclohexane-1a,3a-diol motif capable of congealing non-polar liquids was developed. These gelators underwent crystallization at low concentration and gelation above the critical gelation concentration (CGC) in the same solvent. The crystals and gel fibers were analyzed by single crystal XRD and PXRD respectively, which revealed their different modes of assembly. The XRD studies and thermogravimetric analysis (TGA) confirmed that the crystals contain a water of crystallization whereas the gel fibers do not. A systematic study revealed that when the concentration of the gelator exceeds that of adventitious water in the solvent, it congeals the solvent and when the concentration of the gelator is less than water, it undergoes crystallization. This unprecedented stoichiometric sensing behavior in deciding the mode of self-assembly offers a handle to opt between mutually competing gelation and crystallization. We have confirmed that the system can be biased to congeal or crystallize by varying the amount of water. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stabilization Mechanism of Roxithromycin Tablets under Gastric pH Conditions.

PubMed

Inukai, Koki; Noguchi, Shuji; Kimura, Shin-Ichiro; Itai, Shigeru; Iwao, Yasunori

2018-05-31

Macrolide antibiotics are widely used at clinical sites. Clarithromycin (CAM), a 14-membered macrolide antibiotic, was reported to gelate under acidic conditions. Gelation allows oral administration of acid-sensitive CAM without enteric coating by hindering the penetration of gastric fluid into CAM tablets. However, it is unknown whether this phenomenon occurs in other macrolide antibiotics. In this study, we examined the gelation ability of three widely used macrolide antibiotics, roxithromycin (RXM), erythromycin A (EM), and azithromycin (AZM). The results indicated that not only CAM but also RXM gelated under acidic conditions. EM and AZM did not gelate under the same conditions. Gelation of RXM delayed the disintegration of the tablet and release of RXM from the tablet. Disintegration and release were also delayed in commercial RXM tablets containing disintegrants. This study showed that two of the four macrolides gelated, which affects tablet disintegration and dissolution and suggests that this phenomenon might also occur in other macrolides. Copyright © 2018. Published by Elsevier Inc.

Interlocked Photo-degradable Macrocycles Allow One-Off Photo-triggerable Gelation of Organo- and Hydrogelators.

PubMed

Tung, Shun-Te; Cheng, Hung-Te; Inthasot, Alex; Hsueh, Fang-Che; Gu, Ting-Jia; Yan, Pei-Cong; Lai, Chien-Chen; Chiu, Sheng-Hsien

2018-02-01

[2]Rotaxanes displaying one-off photo-triggerable gelation properties have been synthesized through the "clipping" of photo-degradable macrocycles around the amide or urea functionalities of organo- and hydrogelators. Irradiation with UV-light cleaved the photo-labile macrocyclic components from the [2]rotaxanes, resulting in the free gelators being released into solution and, thereafter, forming gels. When the rate of gelation was sufficiently rapid, selective gelation of specific regions of the solution-and, indeed, photo-patterning of the solution-was possible. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational investigation of intense short-wavelength laser interaction with rare gas clusters

NASA Astrophysics Data System (ADS)

Bigaouette, Nicolas

Current Very High Temperature Reactor designs incorporate TRi-structural ISOtropic (TRISO) particle fuel, which consists of a spherical fissile fuel kernel surrounded by layers of pyrolytic carbon and silicon carbide. An internal sol-gel process forms the fuel kernel by dropping a cold precursor solution into a column of hot trichloroethylene (TCE). The temperature difference drives the liquid precursor solution to precipitate the metal solution into gel spheres before reaching the bottom of a production column. Over time, gelation byproducts inhibit complete gelation and the TCE must be purified or discarded. The resulting mixed-waste stream is expensive to dispose of or recycle, and changing the forming fluid to a non-hazardous alternative could greatly improve the economics of kernel production. Selection criteria for a replacement forming fluid narrowed a list of ~10,800 chemicals to yield ten potential replacements. The physical properties of the alternatives were measured as a function of temperature between 25 °C and 80 °C. Calculated terminal velocities and heat transfer rates provided an overall column height approximation. 1-bromotetradecane, 1-chlorooctadecane, and 1-iodododecane were selected for further testing, and surrogate yttria-stabilized zirconia (YSZ) kernels were produced using these selected fluids. The kernels were characterized for density, geometry, composition, and crystallinity and compared to a control group of kernels produced in silicone oil. Production in 1-bromotetradecane showed positive results, producing dense (93.8 %TD) and spherical (1.03 aspect ratio) kernels, but proper gelation did not occur in the other alternative forming fluids. With many of the YSZ kernels not properly gelling within the length of the column, this project further investigated the heat transfer properties of the forming fluids and precursor solution. A sensitivity study revealed that the heat transfer properties of the precursor solution have the strongest impact on gelation time. A COMSOL heat transfer model estimated an effective thermal diffusivity range for the YSZ precursor solution as 1.13x10 -8 m2/s to 3.35x10-8 m 2/s, which is an order of magnitude smaller than the value used in previous studies. 1-bromotetradecane is recommended for further investigation with the production of uranium-based kernels.

Formation of artificial granules for proving gelation as the main mechanism of aerobic granulation in biological wastewater treatment.

PubMed

Li, Yun; Yang, Shu-Fang; Zhang, Jian-Jun; Li, Xiao-Yan

2014-01-01

In this study, gelation-facilitated biofilm formation as a new mechanism is proposed for the phenomenon of aerobic granulation in biological wastewater treatment. To obtain an experimental proof for the gelation-based theory, the granulation process was simulated in a chemical system using latex particles for bacterial cells and organic polymers (alginate and peptone) for extracellular polymeric substances (EPS) in a solution with the addition of cations (Ca²⁺, Mg²⁺ and Fe³⁺). The results showed that at a low alginate content (70 mg g⁻¹ mixed liquid suspended solids (MLSS)) flocculation was observed in the suspension with loose flocs. At a higher alginate content (180 mg g⁻¹ MLSS), together with discharge of small flocs, formation of artificial gel granules was successfully achieved leading to granulation. The artificial granules show a morphological property similar to that of actual microbial granules. However, if the protein content increased, granulation became difficult with little gel formation. The experimental work demonstrates the importance of the bonding interactions between EPS functional groups and cations in gel formation and granulation. The laboratory results on the formation of artificial granules provide a sound proof for the theory of gelation-facilitated biofilm formation as the main mechanism for aerobic granulation in sludge suspensions.

Cancer cell death induced by the intracellular self-assembly of an enzyme-responsive supramolecular gelator.

PubMed

Tanaka, Akiko; Fukuoka, Yuki; Morimoto, Yuka; Honjo, Takafumi; Koda, Daisuke; Goto, Masahiro; Maruyama, Tatsuo

2015-01-21

We report cancer cell death initiated by the intracellular molecular self-assembly of a peptide lipid, which was derived from a gelator precursor. The gelator precursor was designed to form nanofibers via molecular self-assembly, after cleavage by a cancer-related enzyme (matrix metalloproteinase-7, MMP-7), leading to hydrogelation. The gelator precursor exhibited remarkable cytotoxicity to five different cancer cell lines, while the precursor exhibited low cytotoxicity to normal cells. Cancer cells secrete excessive amounts of MMP-7, which converted the precursor into a supramolecular gelator prior to its uptake by the cells. Once inside the cells, the supramolecular gelator formed a gel via molecular self-assembly, exerting vital stress on the cancer cells. The present study thus describes a new drug where molecular self-assembly acts as the mechanism of cytotoxicity.

Controlling Mechanical Properties of Bis-leucine Oxalyl Amide Gels

NASA Astrophysics Data System (ADS)

Chang, William; Carvajal, Daniel; Shull, Kenneth

2011-03-01

is-leucine oxalyl amide is a low molecular weight gelator capable of gelling polar and organic solvents. A fundamental understanding of self-assembled systems can lead to new methods in drug delivery and the design of new soft material systems. An important feature of self-assembled systems are the intermolecular forces between solvent and gelator molecule; by changing the environment the gel is in, the mechanical properties also change. In this project two variables were considered: the degree of neutralization present for the gelator molecule from neutral to completely ionized, and the concentration of the gelator molecule, from 1 weight percent to 8 weight percent in 1-butanol. Mechanical properties were studied using displacement controlled indentation techniques and temperature sweep rheometry. It has been found that properties such as the storage modulus, gelation temperature and maximum stress allowed increase with bis-leucine oxalyl amide concentration. The results from this study establish a 3-d contour map between the gelator concentration, the gelator degree of ionization and mechanical properties such as storage modulus and maximum stress allowed. The intermolecular forces between the bis-leucine low molecular weight gelator and 1-butanol govern the mechanical properties of the gel system, and understanding these interactions will be key to rationally designed self-assembled systems.

Organogel formation rationalized by Hansen solubility parameters: influence of gelator structure.

PubMed

Bonnet, Julien; Suissa, Gad; Raynal, Matthieu; Bouteiller, Laurent

2015-03-21

Some organic compounds form gels in liquids by forming a network of anisotropic fibres. Based on extensive solubility tests of four gelators of similar structures, and on Hansen solubility parameter formalism, we have probed the quantitative effect of a structural variation of the gelator structure on its gel formation ability. Increasing the length of an alkyl group of the gelator obviously reduces its polarity, which leads to a gradual shift of its solubility sphere towards lower δp and δh values. At the same time, its gelation sphere is shifted - to a much stronger extent - towards larger δp and δh values.

Self-assembly of organogels via new luminol imide derivatives: diverse nanostructures and substituent chain effect

PubMed Central

2013-01-01

Luminol is considered as an efficient sycpstem in electrochemiluminescence (ECL) measurements for the detection of hydrogen peroxide. In this paper, new luminol imide derivatives with different alkyl substituent chains were designed and synthesized. Their gelation behaviors in 26 solvents were tested as novel low molecular mass organic gelators. It was shown that the length and number of alkyl substituent chains linked to a benzene ring in gelators played a crucial role in the gelation behavior of all compounds in various organic solvents. Longer alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Scanning electron microscope and atomic force microscope observations revealed that the gelator molecules self-assemble into different micro/nanoscale aggregates from a dot, flower, belt, rod, and lamella to wrinkle with change of solvents. Spectral studies indicated that there existed different H-bond formations and hydrophobic forces, depending on the alkyl substituent chains in molecular skeletons. The present work may give some insight to the design and characteristic of new versatile soft materials and potential ECL biosensors with special molecular structures. PMID:23758979

Self-assembly of organogels via new luminol imide derivatives: diverse nanostructures and substituent chain effect

NASA Astrophysics Data System (ADS)

Jiao, Tifeng; Huang, Qinqin; Zhang, Qingrui; Xiao, Debao; Zhou, Jingxin; Gao, Faming

2013-06-01

Luminol is considered as an efficient sycpstem in electrochemiluminescence (ECL) measurements for the detection of hydrogen peroxide. In this paper, new luminol imide derivatives with different alkyl substituent chains were designed and synthesized. Their gelation behaviors in 26 solvents were tested as novel low molecular mass organic gelators. It was shown that the length and number of alkyl substituent chains linked to a benzene ring in gelators played a crucial role in the gelation behavior of all compounds in various organic solvents. Longer alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Scanning electron microscope and atomic force microscope observations revealed that the gelator molecules self-assemble into different micro/nanoscale aggregates from a dot, flower, belt, rod, and lamella to wrinkle with change of solvents. Spectral studies indicated that there existed different H-bond formations and hydrophobic forces, depending on the alkyl substituent chains in molecular skeletons. The present work may give some insight to the design and characteristic of new versatile soft materials and potential ECL biosensors with special molecular structures.

Highly Conductive Ionic-Liquid Gels Prepared with Orthogonal Double Networks of a Low-Molecular-Weight Gelator and Cross-Linked Polymer.

PubMed

Kataoka, Toshikazu; Ishioka, Yumi; Mizuhata, Minoru; Minami, Hideto; Maruyama, Tatsuo

2015-10-21

We prepared a heterogeneous double-network (DN) ionogel containing a low-molecular-weight gelator network and a polymer network that can exhibit high ionic conductivity and high mechanical strength. An imidazolium-based ionic liquid was first gelated by the molecular self-assembly of a low-molecular-weight gelator (benzenetricarboxamide derivative), and methyl methacrylate was polymerized with a cross-linker to form a cross-linked poly(methyl methacrylate) (PMMA) network within the ionogel. Microscopic observation and calorimetric measurement revealed that the fibrous network of the low-molecular-weight gelator was maintained in the DN ionogel. The PMMA network strengthened the ionogel of the low-molecular-weight gelator and allowed us to handle the ionogel using tweezers. The orthogonal DNs produced ionogels with a broad range of storage elastic moduli. DN ionogels with low PMMA concentrations exhibited high ionic conductivity that was comparable to that of a neat ionic liquid. The present study demonstrates that the ionic conductivities of the DN and single-network, low-molecular-weight gelator or polymer ionogels strongly depended on their storage elastic moduli.

Self-assemblies, helical ribbons and gelation tuned by solvent-gelator interaction in a bi-1,3,4-oxadiazole gelator

NASA Astrophysics Data System (ADS)

Zhao, Chengxiao; Bai, Binglian; Wang, Haitao; Qu, Songnan; Xiao, Guanjun; Tian, Taiji; Li, Min

2013-04-01

A bi-1,3,4-oxadiazole derivative (BOXDH-T12) showed intramolecular charge transition at concentrations lower than 1 × 10-5 mol/L. The self-assembling behaviors of BOXDH-T12 depended on solvents that it self-assembled into H-aggregates in alcohols and slipped packing aggregates in DMSO. FTIR, 1H NMR and TGA results revealed that strong gelator-gelator hydrogen bonding interaction induced H-aggregation of BOXDH-T12 in alcohols and the interactions between DMSO and BOXDH-T12 molecules caused a slipped stacking. BOXDH-T12 can gel the mixtures of DMSO and ethanol through a cooperative effect of the hydrogen bonding, van der Waals interaction and π-π stacking forces, furthermore, helical ribbons could be observed in DMSO/ethanol due to DMSO molecule interacting. In alcohols, solvophobic/solvophilic effect plays a critical role in gelation behaviors.

Control of fibroin conformation: Toward the development of a biomimetic spinning process for silk fibers

NASA Astrophysics Data System (ADS)

Carlson, Kimberly Ann Trabbic

1999-09-01

Nature has shown that silks are sophisticated structural materials with remarkable mechanical properties; however, they are produced using far milder conditions than high-performance synthetic polymer fibers. While recent advances in molecular biotechnology have taken great strides toward the production of proteinaceous biopolymers, little is known about the processing conditions needed to spin fibers with the correct microstructures and mechanical properties. It is the purpose of this research to gain a fundamental understanding about how processing conditions affect the molecular structure of a model protein biopolymer, Bombyx mori silkworm fibroin, the structural protein of cocoon silk. Fibers of B. mori fibroin were wet spun from 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) into a methanol coagulation bath. X-ray fiber diffraction and quantitative Raman spectroscopy were used to determine that both naturally- and synthetically-spun fibers contain a high degree of beta-sheet (~50%). Fibers subjected to a post-spinning draw exhibited a preferential molecular alignment parallel to the fiber axis resulting in increased strength, stiffness, and extensibility. Fibers with microstructures and mechanical properties most similar to those of naturally-spun fibers were reproduced in synthetically-spun fibers with a draw ratio of 3.5. The transformation of helical fibroin in HFIP to beta-sheet sheet fibroin in synthetically-spun fibers was determined to be caused by the methanol coagulation bath. The kinetics beta-sheet fibroin crystallization from aqueous solution was investigated by monitoring the sigmoidal progression of gel formation using turbidity and Raman spectroscopy. Gelation kinetics were evaluated by measuring lag time, maximum gelation rate, and optical density to determine the effects of protein concentration, detergent concentration (nucleating agent), headgroup chemistry, ionic strength, pH, and temperature. An optimal molar ratio between SDS and fibroin (100:1) was found to produce gels with minimum lag times and maximum gelation rates. Fluorescence spectroscopy and a two-step denaturation and aggregation model for gelation were used to explore the mechanism of fibroin gelation. Conditions that lead to fibroin expansion (dilute fibroin, low ionic strength, highly charged fibroin, or increased temperature) result in decreased lag times. The results presented in this dissertation should aid in developing biomimetic spinning techniques for proteinaceous, biopolymers through the use of amphiphilic sheet nucleating agents.

Impact of preacidification of milk and fermentation time on the properties of yogurt.

PubMed

Peng, Y; Horne, D S; Lucey, J A

2009-07-01

Casein interactions play an important role in the textural properties of yogurt. The objective of this study was to investigate how the concentration of insoluble calcium phosphate (CCP) that is associated with casein particles and the length of fermentation time influence properties of yogurt gels. A central composite experimental design was used. The initial milk pH was varied by preacidification with glucono-delta-lactone (GDL), and fermentation time (time to reach pH 4.6 from the initial pH) was altered by varying the inoculum level. We hypothesized that by varying the initial milk pH value, the amount of CCP would be modified and that by varying the length of the fermentation time we would influence the rate and extent of solubilization of CCP during any subsequent gelation process. We believe that both of these factors could influence casein interactions and thereby alter gel properties. Milks were preacidified to pH values from 6.55 to 5.65 at 40 degrees C using GDL and equilibrated for 4 h before inoculation. Fermentation time was varied from 250 to 500 min by adding various amounts of culture at 40 degrees C. Gelation properties were monitored using dynamic oscillatory rheology, and microstructure was studied using fluorescence microscopy. Whey separation and permeability were analyzed at pH 4.6. The preacidification pH value significantly affected the solubilization of CCP. Storage modulus values at pH 4.6 were positively influenced by the preacidification pH value and negatively affected by fermentation time. The value for the loss tangent maximum during gelation was positively affected by the preacidification pH value. Fermentation time positively affected whey separation and significantly influenced the rate of CCP dissolution during fermentation, as CCP dissolution was a slow process. Longer fermentation times resulted in greater loss of CCP at the pH of gelation. At the end of fermentation (pH approximately 4.6), virtually all CCP was dissolved. Preacidification of milk increased the solubilization of CCP, increased the early loss of CCP crosslinks, and produced weak gels. Long fermentation times allowed more time for solubilization of CCP during the critical gelation stage of the process and increased the possibility of greater casein rearrangements; both could have contributed to the increase in whey separation.

Chemical Changes in Proteins Produced by Thermal Processing.

ERIC Educational Resources Information Center

Dutson, T. R.; Orcutt, M. W.

1984-01-01

Discusses effects of thermal processing on proteins, focusing on (1) the Maillard reaction; (2) heat denaturation of proteins; (3) aggregation, precipitation, gelation, and degradation; and (4) other thermally induced protein reactions. Also discusses effects of thermal processing on muscle foods, egg proteins, fruits and vegetables, and cereal…

Pectin gelation with chlorhexidine: Physico-chemical studies in dilute solutions.

PubMed

Lascol, Manon; Bourgeois, Sandrine; Guillière, Florence; Hangouët, Marie; Raffin, Guy; Marote, Pedro; Lantéri, Pierre; Bordes, Claire

2016-10-05

Low methoxyl pectin is known to gel with divalent cations (e.g. Ca(2+), Zn(2+)). In this study, a new way of pectin gelation in the presence of an active pharmaceutical ingredient, chlorhexidine (CX), was highlighted. Thus chlorhexidine interactions with pectin were investigated and compared with the well-known pectin/Ca(2+) binding model. Gelation mechanisms were studied by several physico-chemical methods such as zeta potential, viscosity, size measurements and binding isotherm was determined by Proton Nuclear Magnetic Resonance Spectroscopy ((1)H NMR). The binding process exhibited similar first two steps for both divalent ions: a stoichiometric monocomplexation of the polymer followed by a dimerization step. However, stronger interactions were observed between pectin and chlorhexidine. Moreover, the dimerization step occurred under stoichiometric conditions with chlorhexidine whereas non-stoichiometric conditions were involved with calcium ions. In the case of chlorhexidine, an additional intermolecular binding occurred in a third step. Copyright © 2016 Elsevier Ltd. All rights reserved.

Supramolecular gels with high strength by tuning of calix[4]arene-derived networks

NASA Astrophysics Data System (ADS)

Lee, Ji Ha; Park, Jaehyeon; Park, Jin-Woo; Ahn, Hyo-Jun; Jaworski, Justyn; Jung, Jong Hwa

2015-03-01

Supramolecular gels comprised of low-molecular-weight gelators are generally regarded as mechanically weak and unable to support formation of free-standing structures, hence, their practical use with applied loads has been limited. Here, we reveal a technique for in situ generation of high tensile strength supramolecular hydrogels derived from low-molecular-weight gelators. By controlling the concentration of hydrochloric acid during hydrazone formation between calix-[4]arene-based gelator precursors, we tune the mechanical and ductile properties of the resulting gel. Organogels formed without hydrochloric acid exhibit impressive tensile strengths, higher than 40 MPa, which is the strongest among self-assembled gels. Hydrogels, prepared by solvent exchange of organogels in water, show 7,000- to 10,000-fold enhanced mechanical properties because of further hydrazone formation. This method of molding also allows the gels to retain shape after processing, and furthermore, we find organogels when prepared as gel electrolytes for lithium battery applications to have good ionic conductivity.

Supramolecular gels with high strength by tuning of calix[4]arene-derived networks

PubMed Central

Lee, Ji Ha; Park, Jaehyeon; Park, Jin-Woo; Ahn, Hyo-Jun; Jaworski, Justyn; Jung, Jong Hwa

2015-01-01

Supramolecular gels comprised of low-molecular-weight gelators are generally regarded as mechanically weak and unable to support formation of free-standing structures, hence, their practical use with applied loads has been limited. Here, we reveal a technique for in situ generation of high tensile strength supramolecular hydrogels derived from low-molecular-weight gelators. By controlling the concentration of hydrochloric acid during hydrazone formation between calix-[4]arene-based gelator precursors, we tune the mechanical and ductile properties of the resulting gel. Organogels formed without hydrochloric acid exhibit impressive tensile strengths, higher than 40 MPa, which is the strongest among self-assembled gels. Hydrogels, prepared by solvent exchange of organogels in water, show 7,000- to 10,000-fold enhanced mechanical properties because of further hydrazone formation. This method of molding also allows the gels to retain shape after processing, and furthermore, we find organogels when prepared as gel electrolytes for lithium battery applications to have good ionic conductivity. PMID:25799459

Synthesis and Properties of Gelators Derived from Tetraphenylethylene and Gallic Acid with Aggregation-Induced Emission

NASA Astrophysics Data System (ADS)

Luo, Miao; Zhou, Xie; Chi, Zhenguo; Ma, Chunping; Zhang, Yi; Liu, Siwei; Xu, Jiarui

2013-09-01

Two novel organogelators (TEG and TAG) based on tetraphenylethylene and 3,4,5-tris(dodecyloxy) benzoic acid were synthesized through ester bond and amido bond linkages, respectively. Compounds TEG and TAG were able to induce gelation in ethanol. Aggregation-induced enhanced emission was observed in these organogelator molecules, with increased fluorescence intensity from the solutions to the gels. The completely thermoreversible gelation occurred due to the aggregation of the organogelators. In the process, a fibrous network was formed by a combination of intermolecular hydrogen bonding, π-π stacking and van der Waals interactions. These phenomena were observed in the xerogels by field-emission scanning electron microscopy and Fourier-transform infrared spectroscopy. The results of differential scanning calorimetry and polarized optical microscopy indicated that compound TAG exhibited stable liquid crystalline phases over a wide temperature range. The linking groups have severe influence on the properties of the organogelators, which was mainly attributed to the hydrogen bonding interaction in compound TAG.

A novel low-molecular-mass gelator with a redox active ferrocenyl group: tuning gel formation by oxidation.

PubMed

Liu, Jing; Yan, Junlin; Yuan, Xuanwei; Liu, Kaiqiang; Peng, Junxia; Fang, Yu

2008-02-15

A novel low-molecular-mass gelator containing a redox-active ferrocenyl group, cholesteryl glycinate ferrocenoylamide (CGF), was intentionally designed and prepared. It was demonstrated that the gelator gels 13 out of the 45 solvents tested. Scanning electron microscopy (SEM) measurements revealed that the gelator self-assembled into different supramolecular network structures in different gels. Chemical oxidation of the ferrocenyl residue resulted in phase transition of the gel from gel state to solution state. FTIR and (1)H NMR spectroscopy studies revealed that hydrogen bonding between the gelator molecules in the gel was one of the main driving forces for the formation of the gels.

Mechanochemical Strengthening of a Synthetic Polymer in Response to Typically Destructive Shear Forces

DTIC Science & Technology

2013-08-04

were at or below the limit of detection of our rhe- ometer, whereas the stress-responsive gelation resulted in a modulus increase of greater than two...in a wide variety of organic solvents. The absence of gelation in nucleophilically inactive 2 provides good evidence that gelation does, indeed...did not lead to precipitation, gelation or changes in the carbonyl region of the infrared spectrum. The same result was obtained with a polymer that

Self-assembly of a chiral lipid gelator controlled by solvent and speed of gelation.

PubMed

Xue, Pengchong; Lu, Ran; Yang, Xinchun; Zhao, Li; Xu, Defang; Liu, Yan; Zhang, Hanzhuang; Nomoto, Hiroyuki; Takafuji, Makoto; Ihara, Hirotaka

2009-09-28

Glutamine derivative 1 with two-photon absorbing units has been synthesized and was found to show gelation ability in some solvents. Its self-assembly in the gel phase could be controlled by the solvent and speed of gelation. For example, in DMSO the organogelator self-assembled into H-aggregates with weak exciton coupling between the aromatic moieties. On the other hand, in DMSO/diphenyl ether (1:9, v/v) the molecules formed 1D aggregates, but with strong exciton coupling due to the small distance between the chromophores. Moreover, the formation of these two kinds of aggregates could be adjusted by the ratio of DMSO to diphenyl ether. In DMSO/toluene, DMSO/butanol, DMSO/butyl acetate, and DMSO/acetic acid systems similar results were observed. Therefore, conversion of the packing model occurs irrespective of the nature of the solvent. Notably, a unique sign inversion in the CD spectra could be realized by controlling the speed of gelation in the DMSO/diphenyl ether (1:9, v/v) system. It was found that a low speed of gelation induces the gelator to adopt a packing model with strong pi-pi interactions between the aromatic units. Moreover, the gels, when excited at 800 nm, emit strong green fluorescence and the quantum chemical calculations suggest that intramolecular charge transfer leads to two-photon absorption of the gelator molecule.

Rheology of tissue conditioners.

PubMed

Murata, H; Hamada, T; Djulaeha, E; Nikawa, H

1998-02-01

Tissue conditioners can be used to condition abused tissues, record functional impressions, make temporary relinings, and for other clinical applications, mainly because of their specific viscoelasticity. However, little information is available on the rheology of the materials, manipulation, and suitability for various clinical applications. This study evaluated the gelation times, the viscoelastic properties after gelation of tissue conditioners, and the influence of the powder/liquid (P/L) ratio. Ten tissue conditioners were used and gelation times were obtained with an oscillating rheometer. A series of stress relaxation tests were also conducted to evaluate the viscoelastic properties after gelation and the changes with the passage of time by means of Maxwell model analogies. Significant differences were found in the gelation times and flow properties after gelation among the materials mixed with the P/L ratios recommended by the manufacturers. The flow properties tended to increase with time of storage. Large differences in the limits of the clinically acceptable P/L ratios and the adjustable limits of elasticity and viscosity by altering P/L ratios were found among the materials. The results suggested that each material should be selected according to each clinical purpose because of the wide ranges of viscoelastic properties and changes in viscoelasticity with time among the materials. Furthermore, gelation times and the viscoelastic properties after gelation can be controlled to improve handling and suit various applications by altering the P/L ratios within the acceptable limits.

Hydroxyl radical and ferryl-generating systems promote gel network formation of myofibrillar protein.

PubMed

Xiong, Youling L; Blanchard, Suzanne P; Ooizumi, Tooru; Ma, Yuanyuan

2010-03-01

The objective of the study was to examine how oxidatively induced protein cross-linking would influence the gelation properties of myofibrillar protein (MP) under meat processing conditions. MP suspensions in 0.6 M NaCl at pH 6 were treated with an iron-catalyzed oxidizing system (IOS: 10 microM FeCl(3), 0.1 mM ascorbic acid, 0.05 to 5 mM H(2)O(2)) or a H(2)O(2)-activated metmyoglobin oxidizing system (MOS: 0.01 to 0.1 mM metmyoglobin/H(2)O(2)) that produced hydroxyl radical and ferryl species, respectively. Both oxidizing systems promoted MP thermal gelation, which was evidenced by rapid protein-protein interaction and the enhancement in storage modulus (elasticity) of the gel network as revealed by dynamic rheological testing in the 20 to 74 degrees C temperature range. This gelation-enhancing effect was attributed to the shift of myosin aggregation in the early stage of heating from predominantly head-head association (nonoxidized control samples) to prevalently tail-tail cross-linking through disulfide bonds. However, both hardness and water-holding capacity of chilled gels tended to decline when MP was exposed to >or=1 mM H(2)O(2) in IOS and to all concentrations of metmyoglobin in MOS. Microscopic examination confirmed a more porous structure in oxidized gels when compared with nonoxidized protein gels. The results demonstrated that mild oxidation altered the mode of myosin aggregation in favor of an elastic gel network formation, but it did not improve or had a negative effect on water-binding properties of MP gels. Mild oxidation promotes protein network formation and enhances gelation of myofibrillar protein under normal salt and pH conditions used in meat processing. This oxidative effect, which involves disulfide linkages, is somewhat similar to that in bakery product processing where oxidants are used to improve dough performance through gluten protein interaction.

Peptide-based ambidextrous bifunctional gelator: applications in oil spill recovery and removal of toxic organic dyes for waste water management.

PubMed

Basu, Kingshuk; Nandi, Nibedita; Mondal, Biplab; Dehsorkhi, Ashkan; Hamley, Ian W; Banerjee, Arindam

2017-12-06

A low molecular weight peptide-based ambidextrous gelator molecule has been discovered for efficient control of water pollution. The gelator molecules can gel various organic solvents with diverse polarity, e.g. n -hexane, n -octane, petroleum ether, petrol, diesel, aromatic solvents like chlorobenzene, toluene, benzene, o -xylene and even aqueous phosphate buffer of pH 7.5. These gels have been thoroughly characterized using various techniques including field emission scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray powder diffraction analysis, small angle X-ray scattering and rheological experiments. Interestingly, hydrogel obtained from the gelator molecule has been found to absorb toxic organic dyes (both cationic and anionic dyes) from dye-contaminated water. The gelator molecule can be reused for several cycles, indicating its possible future use in waste water management. Moreover, this gelator can selectively gel petrol, diesel, pump oil from an oil-water mixture in the presence of a carrier solvent, ethyl acetate, suggesting its efficient application for oil spill recovery. These results indicate that the peptide-based ambidextrous gelator produces soft materials (gels) with dual function: (i) removal of toxic organic dyes in waste water treatment and (ii) oil spill recovery.

Selection and properties of alternative forming fluids for TRISO fuel kernel production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, M. P.; King, J. C.; Gorman, B. P.

2013-01-01

Current Very High Temperature Reactor (VHTR) designs incorporate TRi-structural ISOtropic (TRISO) fuel, which consists of a spherical fissile fuel kernel surrounded by layers of pyrolytic carbon and silicon carbide. An internal sol-gel process forms the fuel kernel using wet chemistry to produce uranium oxyhydroxide gel spheres by dropping a cold precursor solution into a hot column of trichloroethylene (TCE). Over time, gelation byproducts inhibit complete gelation, and the TCE must be purified or discarded. The resulting TCE waste stream contains both radioactive and hazardous materials and is thus considered a mixed hazardous waste. Changing the forming fluid to a non-hazardousmore » alternative could greatly improve the economics of TRISO fuel kernel production. Selection criteria for a replacement forming fluid narrowed a list of ~10,800 chemicals to yield ten potential replacement forming fluids: 1-bromododecane, 1- bromotetradecane, 1-bromoundecane, 1-chlorooctadecane, 1-chlorotetradecane, 1-iododecane, 1-iodododecane, 1-iodohexadecane, 1-iodooctadecane, and squalane. The density, viscosity, and surface tension for each potential replacement forming fluid were measured as a function of temperature between 25 °C and 80 °C. Calculated settling velocities and heat transfer rates give an overall column height approximation. 1-bromotetradecane, 1-chlorooctadecane, and 1-iodododecane show the greatest promise as replacements, and future tests will verify their ability to form satisfactory fuel kernels.« less

Selection and properties of alternative forming fluids for TRISO fuel kernel production

NASA Astrophysics Data System (ADS)

Baker, M. P.; King, J. C.; Gorman, B. P.; Marshall, D. W.

2013-01-01

Current Very High Temperature Reactor (VHTR) designs incorporate TRi-structural ISOtropic (TRISO) fuel, which consists of a spherical fissile fuel kernel surrounded by layers of pyrolytic carbon and silicon carbide. An internal sol-gel process forms the fuel kernel using wet chemistry to produce uranium oxyhydroxide gel spheres by dropping a cold precursor solution into a hot column of trichloroethylene (TCE). Over time, gelation byproducts inhibit complete gelation, and the TCE must be purified or discarded. The resulting TCE waste stream contains both radioactive and hazardous materials and is thus considered a mixed hazardous waste. Changing the forming fluid to a non-hazardous alternative could greatly improve the economics of TRISO fuel kernel production. Selection criteria for a replacement forming fluid narrowed a list of ˜10,800 chemicals to yield ten potential replacement forming fluids: 1-bromododecane, 1-bromotetradecane, 1-bromoundecane, 1-chlorooctadecane, 1-chlorotetradecane, 1-iododecane, 1-iodododecane, 1-iodohexadecane, 1-iodooctadecane, and squalane. The density, viscosity, and surface tension for each potential replacement forming fluid were measured as a function of temperature between 25 °C and 80 °C. Calculated settling velocities and heat transfer rates give an overall column height approximation. 1-bromotetradecane, 1-chlorooctadecane, and 1-iodododecane show the greatest promise as replacements, and future tests will verify their ability to form satisfactory fuel kernels.

Studies on a new class of organogelator containing 2-anthracenecarboxylic acid: influence of gelator and solvent on stereochemistry of the photodimers.

PubMed

Dawn, Arnab; Fujita, Norifumi; Haraguchi, Shuichi; Sada, Kazuki; Tamaru, Shun-ichi; Shinkai, Seiji

2009-11-07

A new class of binary organogelator (G1, G2 and G3) based on 2-anthracenecarboxylic acid (2Ac), attached noncovalently with the gelator counterpart containing a 3,4,5-tris(n-dodecyloxy)benzoylamide backbone has been developed. Among the three gelators, two (G2 and G3) are chiral containing D-alanine or L-2-phenylglycine moieties, respectively. They can act as efficient gelators of organic solvents with varying polarity depending upon the gelator systems. Gelator G1 even gelates chiral solvents. The photoirradiation of the gel samples produces photocyclodimers having different degrees of stereoselectivity for different systems. Gels with G1 and G2 produce head-to-head (h-h) photodimers as major products, whereas the stereoselectivity is reversed for the gels with G3 producing head-to-tail (h-t) photodimers as major products. Among those, G2/cyclohexane gel shows the highest degree of stereoselectivity, producing only h-h photodimers with some significant amount of chiral induction. Other chiral systems exhibit low to moderate chiral inductions. The gelator G1 can differentiate between the racemic and enantiomerically pure varieties of a solvent by exhibiting different gel melting temperatures (T(gel)). For different gel systems, T(gel) increases in all the cases as a consequence of photoreaction, except for the G2/cyclohexane gel, where a prominent gel-to-sol phase transition can be observed during the photoreaction. Hydrogen-bonding and pi-pi stacking interactions play the principal roles in constructing the gel structure. The morphologies of the gel systems vary between one-dimensional fibrils and a fibrillar network structure. In addition, the influences of the gelator and solvent polarity on the rate of photoreactions, photoproduct distributions as well as gel structures are investigated.

Supramolecular Assembly of Tripodal Trisamides

NASA Astrophysics Data System (ADS)

Feng, Li

2010-03-01

A series of tripodal trisamide compounds have been synthesized from tris(2-aminoethyl)amine (TREN) by condensation with different acid chlorides. Gelation of organic solvents with these compounds was investigated as a function of concentration and solvent solubility parameter. Compounds made with linear acid chlorides were poor gelators. A gelator made with 2-ethylbutyryl chloride (TREN-EB) was an excellent gelator for many organic solvents. It was found that the minimum gelation concentration of TREN-EB increased with increasing solubility parameter of the solvent. Thin films samples were prepared by spin-coating mixtures of TREN-EB and a poly(acrylate). Scanning force microscopy measurements showed that TREN-EB formed nanofibrillar network structures. In addition a dependence of the network morphology on the casting solvent was found.

A novel chiral separation material: polymerized organogel formed by chiral gelators for the separation of D- and L-phenylalanine.

PubMed

Fu, Xinjian; Yang, Yang; Wang, Ningxia; Wang, Hong; Yang, Yajiang

2007-01-01

N-Stearine-N'-stearyl-L-phenylalanine, a chiral compound, was synthesized and used as a gelator for the gelation of polymerizable solvents, such as ss-hydroxyethyl methacrylate (HEMA), styrene, etc. The scanning electron microscope (SEM) images of the gelator aggregates show fibril-like helices, typical chiral aggregates with diameters of 100-200 nm. The solvent molecules were immobilized by capillary forces in the three-dimensional network structures of the organogels. The HEMA organogels containing crosslinker polyethylene glycol dimethacrylates (PEG200DMA) were subsequently polymerized by in situ UV irradiation. A porous polymerized organogels were obtained after removal of gelator aggregates through ethanol extraction. The chiral separation of D- and L-phenylalanine was carried out by the adsorption of the polymerized organogels. The adsorption efficiency of L-phenylalanine on the polymerized organogels was found to be dependent on the concentration of the gelator and crosslinker. (c) 2007 John Wiley & Sons, Ltd.

Helical Inversion of Gel Fibrils by Elongation of Perfluoroalkyl Chains as Studied by Vibrational Circular Dichroism.

PubMed

Sato, Hisako; Yajima, Tomoko; Yamagishi, Akihiko

2016-05-01

Vibrational circular dichroism (VCD) spectroscopy was applied to gelation by a chiral low-molecular mass weight gelator, N,N'-diperfluoroalkanoyl-1,2-trans-diaminocyclohexane. Attention was focused on the winding effects of (-CF2 )n chains on the gelating ability. For this purpose, a series of gelators were synthesized with perfluoroalkyl chains of different length (n = 6-8). When gelation was studied using acetonitrile as a solvent, the fibrils took different morphologies, depending on the chain length: twisted saddle-like ribbon or helical ribbon from fibril (n = 6) and a helical ribbon from platelet (n = 8). The signs of VCD peaks assigned to the couplet of C=O stretching and to the C-F stretching were also dependent on n, indicating that a gelator molecule changed conformation on elongating perfluoroalkyl chains. A model is proposed for the aggregation modes in fibrils. Chirality 28:361-364, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Gelation of Na-alginate aqueous solution: A study of sodium ion dynamics via NMR relaxometry.

PubMed

Zhao, Congxian; Zhang, Chao; Kang, Hongliang; Xia, Yanzhi; Sui, Kunyan; Liu, Ruigang

2017-08-01

Sodium alginate (SA) hydrogels have a wide range of applications including tissue engineering, drug delivery and formulations for preventing gastric reflux. The dynamics of sodium ions during the gelation process of SA solution is critical for clarification of the gelation procedure. In this work, nuclear magnetic resonance (NMR) relaxometry and pulsed-field-gradient (PFG) NMR diffusometry were used to investigate the dynamics of the sodium ions during the gelation of SA alginate. We find that sodium ions are in two different states with the addition of divalent calcium ions, corresponding to Ca 2+ crosslinked and un-crosslinked regions in the hydrogels. The sodium ions within the un-crosslinked regions are those released from the alginate chains without Ca 2+ crosslinking. The relative content of sodium ions within the Ca 2+ crosslinked regions decreased with the increase in the content of calcium ions in the system. The relaxation time T 2 of sodium ions within the Ca 2+ crosslinked and un-crosslinked regions shift to shorter and longer relaxation time with the increase in concentration of calcium ion, which indicates the closer package of SA chains and the larger space for the diffusion of free sodium ions. This work clarifies the dynamics of 23 Na + in a calcium alginate gel at the equilibrium state. Copyright © 2017 Elsevier Ltd. All rights reserved.

Functionalized core-shell hydrogel microsprings by anisotropic gelation with bevel-tip capillary

PubMed Central

Yoshida, Koki; Onoe, Hiroaki

2017-01-01

This study describes a novel microfluidic-based method for the synthesis of hydrogel microsprings that are capable of encapsulating various functional materials. A continuous flow of alginate pre-gel solution can spontaneously form a hydrogel microspring by anisotropic gelation around the bevel-tip of the capillary. This technique allows fabrication of hydrogel microsprings using only simple capillaries and syringe pumps, while their complex compartmentalization characterized by a laminar flow inside the capillary can contribute to the optimization of the microspring internal structure and functionality. Encapsulation of several functional materials including magnetic-responsive nanoparticles or cell dispersed collagen for tissue scaffold was demonstrated to functionalize the microsprings. Our core-shell hydrogel microsprings have immense potential for application in a number of fields, including biological/chemical microsensors, biocompatible soft robots/microactuators, drug release, self-assembly of 3D structures and tissue engineering. PMID:28378803

Order and gelation of cellulose nanocrystal suspensions: an overview of some issues

NASA Astrophysics Data System (ADS)

Gray, Derek G.

2017-12-01

Cellulose nanocrystals (CNCs) are polydisperse rod-shaped particles of crystalline cellulose I, typically prepared by sulfuric acid hydrolysis of natural cellulose fibres to give aqueous colloidal suspensions stabilized by sulfate half-ester groups. Sufficiently dilute suspensions are isotropic fluids, but as the concentration of CNC in water is increased, a critical concentration is reached where a spontaneously ordered phase is observed. The (equilibrium) phase separation of the ordered chiral nematic phase is in competition with a tendency of the CNC suspension to form a gel. Qualitatively, factors that reduce the stability of the CNC suspension favour the onset of gelation. The chiral nematic structure is preserved, at least partially, when the suspension dries. Solid chiral nematic films of cellulose are of interest for their optical and templating properties, but the preparation of the films requires improvement. The processes that govern the formation of solid chiral nematic films from CNC suspensions include phase separation, gelation and also the effects of shear on CNC orientation during evaporation. Some insight into these processes is provided by polarized light microscopy, which indicates that the relaxation of shear-induced orientation to give a chiral nematic structure may occur via an intermediate twist-bend state. This article is part of a discussion meeting issue `New horizons for cellulose nanotechnology'.

Gelation or molecular recognition; is the bis-(α,β-dihydroxy ester)s motif an omnigelator?

PubMed

Griffiths, Peter C; Knight, David W; Morgan, Ian R; Ford, Amy; Brown, James; Davies, Ben; Heenan, Richard K; King, Stephen M; Dalgliesh, Robert M; Tomkinson, John; Prescott, Stuart; Schweins, Ralf; Paul, Alison

2010-11-18

Understanding the gelation of liquids by low molecular weight solutes at low concentrations gives an insight into many molecular recognition phenomena and also offers a simple route to modifying the physical properties of the liquid. Bis-(α,β-dihydroxy ester)s are shown here to gel thermoreversibly a wide range of solvents, raising interesting questions as to the mechanism of gelation. At gelator concentrations of 5-50 mg ml⁻¹, gels were successfully formed in acetone, ethanol/water mixtures, toluene, cyclohexane and chloroform (the latter, albeit at a higher gelator concentration). A range of neutron techniques - in particular small-angle neutron scattering (SANS) - have been employed to probe the structure of a selection of these gels. The universality of gelation in a range of solvent types suggests the gelation mechanism is a feature of the bis-(α,β-dihydroxy ester) motif, with SANS demonstrating the presence of regular structures in the 30-40 Å range. A correlation between the apparent rodlike character of the structures formed and the polarity of the solvent is evident. Preliminary spin-echo neutron scattering studies (SESANS) indicated the absence of any larger scale structures. Inelastic neutron spectroscopy (INS) studies demonstrated that the solvent is largely unaffected by gelation, but does reveal insights into the thermal history of the samples. Further neutron studies of this kind (particularly SESANS and INS) are warranted, and it is hoped that this work will stimulate others to pursue this line of research.

Fluorescent 'two-faced' polymer wafers with embedded pyrene-functionalised gelator nanofibres.

PubMed

Moffat, Jamie R; Smith, David K

2011-11-21

Pyrene-functionalised gelators self-assemble into nano-fibrillar organogels in DMSO/styrene/divinylbenzene mixtures, which when polymerised yield polymer wafers with two distinct faces, only one of which is fluorescent and has embedded gelator nanofibres. This journal is © The Royal Society of Chemistry 2011

Fine-Tuning of Saponification-Triggered Gelation by Strategic Modification of Peripheral Substituents: Gelation Regulators.

PubMed

Kumar, Ashish; Singh, Roop Shikha; Kumar, Amit; Ali, Afsar; Biswas, Arnab; Pandey, Daya Shankar

2016-09-19

A pioneering approach towards controlling the efficiency of saponification assisted gelation in ethyl ester based Zn II -complexes have been described. Using four new ester containing bis-salen Zn II complexes (C1-C4) involving different para-azo phenyl substituted ligands it has been clearly shown that gelation efficiency is greatly influenced by the electronic effects of the substituents (-H (C1), -CH 3 (C2), -NO 2 (C3), and -OCH 3 (C4)). Morphological, photophysical, and rheological investigations corroborated the experimental observations well and established that gelation efficiency was enhanced with electron-withdrawing characteristics of substituents (C4

Origin of Toughness in Dispersion-Cast Nafion Membranes

DOE PAGES

Kim, Yu Seung; Welch, Cynthia F.; Hjelm, Rex Paul; ...

2015-03-23

In this study, the gelation behavior of Nafion dispersions was investigated using small-angle neutron scattering to better understand the mechanical toughness of dispersion-cast Nafion membranes. Three types of gelation were observed, depending on dispersing fluids: (i) homogeneous, thermally reversible gelation that was present in most aprotic polar dispersing fluids; (ii) inhomogeneous, thermally irreversible gelation as films, found in alcohols; and (iii) inhomogeneous, thermally irreversible gelation which precipitates in water/monohydric alcohol mixtures. The mechanical toughness of dispersion-cast Nafion membranes depends on the dispersing fluid, varying by more than 4 orders of magnitude. Excellent correlation between the critical gelation concentration and mechanicalmore » toughness was demonstrated with the Nafion membranes cast at 140 °C. Additional thermal effects among Nafion membranes cast at 190 °C were qualitatively related to the boiling point of dispersing fluids. Little correlation between mechanical toughness and percent crystalline area of Nafion was observed, suggesting that the origin of mechanical toughness of dispersion-cast Nafion membranes is due to chain entanglements rather than crystallinity. Finally, the correlation between critical gelation concentration and mechanical toughness is a new way of predicting mechanical behavior in dispersion-cast polymer systems in which both polymer-dispersing fluid and polymer–polymer interactions play a significant role in the formation of polymer chain entanglements.« less

Oxalyl retro-peptide gelators. Synthesis, gelation properties and stereochemical effects

PubMed Central

Makarević, Janja; Jokić, Milan; Frkanec, Leo; Čaplar, Vesna; Šijaković Vujičić, Nataša

2010-01-01

Summary In this work we report on gelation properties, self-assembly motifs, chirality effects and morphological characteristics of gels formed by chiral retro-dipeptidic gelators in the form of terminal diacids (1a–5a) and their dimethyl ester (1b–5b) and dicarboxamide (1c–5c) derivatives. Terminal free acid retro-dipeptides (S,S)-bis(LeuLeu) 1a, (S,S)-bis(PhgPhg) 3a and (S,S)-bis(PhePhe) 5a showed moderate to excellent gelation of highly polar water/DMSO and water/DMF solvent mixtures. Retro-peptides incorporating different amino acids (S,S)-(LeuPhg) 2a and (S,S)-(PhgLeu) 4a showed no or very weak gelation. Different gelation effectiveness was found for racemic and single enantiomer gelators. The heterochiral (S,R)-1c diastereoisomer is capable of immobilizing up to 10 and 4 times larger volumes of dichloromethane/DMSO and toluene/DMSO solvent mixtures compared to homochiral (S,S)-1c. Based on the results of 1H NMR, FTIR, CD investigations, molecular modeling and XRPD studies of diasteroisomeric diesters (S,S)-1b/(S,R)-1b and diacids (S,S)-1b/(S,R)-1a, a basic packing model in their gel aggregates is proposed. The intermolecular hydrogen bonding between extended gelator molecules utilizing both, the oxalamide and peptidic units and layered organization were identified as the most likely motifs appearing in the gel aggregates. Molecular modeling studies of (S,S)- 1a/(S,R)-1a and (S,S)-1b/(S,R)- 1b diasteroisomeric pairs revealed a decisive stereochemical influence yielding distinctly different low energy conformations: those of (S,R)-diastereoisomers with lipophilic i-Bu groups and polar carboxylic acid or ester groups located on the opposite sides of the oxalamide plane resembling bola amphiphilic structures and those of (S,S)-diasteroisomers possessing the same groups located at both sides of the oxalamide plane. Such conformational characteristics were found to strongly influence both, gelator effectiveness and morphological characteristics of gel aggregates. PMID:21085503

Oxalyl retro-peptide gelators. Synthesis, gelation properties and stereochemical effects.

PubMed

Makarević, Janja; Jokić, Milan; Frkanec, Leo; Caplar, Vesna; Sijaković Vujičić, Nataša; Zinić, Mladen

2010-10-04

In this work we report on gelation properties, self-assembly motifs, chirality effects and morphological characteristics of gels formed by chiral retro-dipeptidic gelators in the form of terminal diacids (1a-5a) and their dimethyl ester (1b-5b) and dicarboxamide (1c-5c) derivatives. Terminal free acid retro-dipeptides (S,S)-bis(LeuLeu) 1a, (S,S)-bis(PhgPhg) 3a and (S,S)-bis(PhePhe) 5a showed moderate to excellent gelation of highly polar water/DMSO and water/DMF solvent mixtures. Retro-peptides incorporating different amino acids (S,S)-(LeuPhg) 2a and (S,S)-(PhgLeu) 4a showed no or very weak gelation. Different gelation effectiveness was found for racemic and single enantiomer gelators. The heterochiral (S,R)-1c diastereoisomer is capable of immobilizing up to 10 and 4 times larger volumes of dichloromethane/DMSO and toluene/DMSO solvent mixtures compared to homochiral (S,S)-1c. Based on the results of (1)H NMR, FTIR, CD investigations, molecular modeling and XRPD studies of diasteroisomeric diesters (S,S)-1b/(S,R)-1b and diacids (S,S)-1b/(S,R)-1a, a basic packing model in their gel aggregates is proposed. The intermolecular hydrogen bonding between extended gelator molecules utilizing both, the oxalamide and peptidic units and layered organization were identified as the most likely motifs appearing in the gel aggregates. Molecular modeling studies of (S,S)-1a/(S,R)-1a and (S,S)-1b/(S,R)-1b diasteroisomeric pairs revealed a decisive stereochemical influence yielding distinctly different low energy conformations: those of (S,R)-diastereoisomers with lipophilic i-Bu groups and polar carboxylic acid or ester groups located on the opposite sides of the oxalamide plane resembling bola amphiphilic structures and those of (S,S)-diasteroisomers possessing the same groups located at both sides of the oxalamide plane. Such conformational characteristics were found to strongly influence both, gelator effectiveness and morphological characteristics of gel aggregates.

Specialist gelator for ionic liquids.

PubMed

Hanabusa, Kenji; Fukui, Hiroaki; Suzuki, Masahiro; Shirai, Hirofusa

2005-11-08

Cyclo(l-beta-3,7-dimethyloctylasparaginyl-L-phenylalanyl) (1) and cyclo(L-beta-2-ethylhexylasparaginyl-L-phenylalanyl) (2), prepared from L-asparaginyl-L-phenylalanine methyl ester, have been found to be specialist gelators for ionic liquids. They can gel a wide variety of ionic liquids, including imizazolium, pyridinium, pyrazolidinium, piperidinium, morpholinium, and ammonium salts. The mean minimum gel concentrations (MGCs) necessary to make gels at 25 degrees C were determined for ionic liquids. The gel strength increased at a rate nearly proportional to the concentration of added gelator. The strength of the transparent gel of 1-butylpyridinium tetrafluoroborate ([C(4)py]BF(4)), prepared at a concentration of 60 g L(-1) (gelator 1/[C(4)py]BF(4)), was ca. 1500 g cm(-2). FT-IR spectroscopy indicated that a driving force for gelation was intermolecular hydrogen bonding between amides and that the phase transition from gel to liquid upon heating was brought about by the collapse of hydrogen bonding. The gels formed from ionic liquids were very thermally stable; no melting occurs up to 140 degrees C when the gels were prepared at a concentration of 70 g L(-1) (gelator/ionic liquid). The ionic conductivities of the gels were nearly the same as those of pure ionic liquids. The gelator had electrochemical stability and a wide electrochemical window. When the gels were prepared from ionic liquids containing propylene carbonate, the ionic conductivities of the resulting gels increased to levels rather higher than those of pure ionic liquids. The gelators also gelled ionic liquids containing supporting electrolytes.

Gelation or molecular recognition; is the bis-(α,β-dihydroxy ester)s motif an omnigelator?

PubMed Central

Knight, David W; Morgan, Ian R; Ford, Amy; Brown, James; Davies, Ben; Heenan, Richard K; King, Stephen M; Dalgliesh, Robert M; Tomkinson, John; Prescott, Stuart; Schweins, Ralf; Paul, Alison

2010-01-01

Summary Understanding the gelation of liquids by low molecular weight solutes at low concentrations gives an insight into many molecular recognition phenomena and also offers a simple route to modifying the physical properties of the liquid. Bis-(α,β-dihydroxy ester)s are shown here to gel thermoreversibly a wide range of solvents, raising interesting questions as to the mechanism of gelation. At gelator concentrations of 5–50 mg ml−1, gels were successfully formed in acetone, ethanol/water mixtures, toluene, cyclohexane and chloroform (the latter, albeit at a higher gelator concentration). A range of neutron techniques – in particular small-angle neutron scattering (SANS) – have been employed to probe the structure of a selection of these gels. The universality of gelation in a range of solvent types suggests the gelation mechanism is a feature of the bis-(α,β-dihydroxy ester) motif, with SANS demonstrating the presence of regular structures in the 30–40 Å range. A correlation between the apparent rodlike character of the structures formed and the polarity of the solvent is evident. Preliminary spin-echo neutron scattering studies (SESANS) indicated the absence of any larger scale structures. Inelastic neutron spectroscopy (INS) studies demonstrated that the solvent is largely unaffected by gelation, but does reveal insights into the thermal history of the samples. Further neutron studies of this kind (particularly SESANS and INS) are warranted, and it is hoped that this work will stimulate others to pursue this line of research. PMID:21160568

CO2 as a smart gelator for Pluronic aqueous solutions.

PubMed

Liu, Chengcheng; Mei, Qingqing; Zhang, Jianling; Kang, Xinchen; Peng, Li; Han, Buxing; Xue, Zhimin; Sang, Xinxin; Yang, Xiaogan; Wu, Zhonghua; Li, Zhihong; Mo, Guang

2014-11-25

It was found that CO2 could induce the gelation of Pluronic aqueous solutions, during which the microstructure of the solution transforms from randomly dispersed spherical micelles to cubic close packed micelles. The gelation switched by compressed CO2 has many advantages and can be applied in the synthesis of porous materials.

Synergistic enhancement in the co-gelation of salt-soluble pea proteins and whey proteins.

PubMed

Wong, Douglas; Vasanthan, Thava; Ozimek, Lech

2013-12-15

This paper investigated the enhancement of thermal gelation properties when salt-soluble pea proteins were co-gelated with whey proteins in NaCl solutions, using different blend ratios, total protein concentrations, pH, and salt concentrations. Results showed that the thermal co-gelation of pea/whey proteins blended in ratio of 2:8 in NaCl solutions showed synergistic enhancement in storage modulus, gel hardness, paste viscosity and minimum gelation concentrations. The highest synergistic enhancement was observed at pH 6.0 as compared with pH 4.0 and 8.0, and at the lower total protein concentration of 10% as compared with 16% and 22% (w/v), as well as in lower NaCl concentrations of 0.5% and 1.0% as compared with 1.5%, 2.0%, 2.5%, and 3.0% (w/v). The least gelation concentrations were also lower in the different pea/whey protein blend ratios than in pure pea or whey proteins, when dissolved in 1.0% or 2.5% (w/v) NaCl aqueous solutions. Copyright © 2013 Elsevier Ltd. All rights reserved.

An efficient phase-selective gelator for aromatic solvents recovery based on a cyanostilbene amide derivative.

PubMed

Zhang, Yuping; Ma, Yao; Deng, Mengyu; Shang, Hongxing; Liang, Chunshuang; Jiang, Shimei

2015-07-07

Two novel low molecular weight organogelators (LMOGs) 1 and 2 composed of a cholesteryl group, an amide group and various terminal cyanostilbene moieties were synthesized. They could form stable gels in p-xylene. In particular, 2 with more extended π-conjugation length showed remarkable gelation ability in many aromatic solvents, chloroform and chloroform-containing mixed solvents at a relatively low concentration. FT-IR and XRD spectra indicated that the difference between 1 and 2 in the gelation properties may result from the deviation of the intermolecular hydrogen bonding and π–π stacking as driving forces for the formation of the gels. Significantly, 2 can function as an efficient room-temperature phase-selective gelator (PSG) for potential application in the separation and recovery of various aromatic solvents from its mixture with water. Meanwhile, the gelator can be easily recovered and reused several times. Furthermore, the phase-selective gelation properties of 2 can provide a simple and feasible approach for the removal of the rhodamine B (RhB) dye from water.

Ultrasonication-enhanced gelation properties of a versatile amphiphilic formamidine-based gelator exhibiting both organogelation and hydrogelation abilities.

PubMed

Bachl, Jürgen; Sampedro, Diego; Mayr, Judith; Díaz Díaz, David

2017-08-30

We describe the preparation of a novel amphiphilic gelator built from a formamidine core, which is able to form a variety of physical organogels and hydrogels at concentrations ranging from 15 to 150 mg mL -1 . Interestingly, ultrasound treatment of isotropic solutions (i.e., gel-precursor) resulted in a remarkable enhancement of the gelation kinetics as well as the gelation scope and characteristic gel properties (e.g., critical gelation concentration, gel-to-sol transition temperature, viscoelastic moduli) in comparison to the heating-cooling protocol typically used to obtain supramolecular gels. Thermoreversibility, thixotropy, injectability and multistimuli responsiveness are some of the most relevant functionalities of these gels. Electron microscopy imaging revealed the formation of entangled networks made of fibers of nanometer diameters and micrometer lengths, with different morphological features depending on the solvent. Insights into the driving forces for molecular aggregations were obtained from FTIR, NMR, PXRD and computational studies. The results suggest a major stabilization of the fibers through additive N-HO hydrogen bonds, in combination with hydrophobic interactions, over π-π stacking interactions.

Investigating cold gelation properties of recombined highly concentrated micellar casein concentrate and cream for use in cheese making.

PubMed

Lu, Y; McMahon, D J; Vollmer, A H

2016-07-01

Highly concentrated micellar casein concentrate (HC-MCC), a potential ingredient for cheese making, contains ~20% casein with ~70% of serum proteins removed by microfiltration and diafiltration of skim milk, followed by vacuum evaporation. Our objective was to investigate cold gelation properties of recombined concentrated milk (RCM) by mixing thawed frozen HC-MCC and cream under different casein levels, pH, and protein-to-fat ratios, and with addition of sodium citrate or calcium. The HC-MCC was recombined with cream using low shear at 50°C for 30 min, and rheological measurements were conducted. Cold-gelling temperature [the temperature at which storage modulus (G')=loss modulus (G″)] was linearly correlated with casein levels from 8.6 to 11.5% (R(2)=0.71), pH from 6.6 to 7.0 (R(2)=0.96), and addition of sodium citrate from 0 to 0.36mmol/g of casein (R(2)=0.80). At pH 7.0, gelation occurred at 12, 26, and 38°C with 9, 10, and 11% casein, respectively. At pH 6.6, 6.8, and 7.0, RCM with 12% casein gelled at a mean temperature of 12, 26, and 37°C, respectively. Adding calcium chloride at 0.17mmol/g of casein significantly increased cold-gelling temperature from 18 to ≥50°C, whereas no significant change was observed at levels up to 0.12mmol/g of casein. Different protein to fat ratios ranging from 0.8 to 1.2 did not significantly influence gelling temperature. In transmission electron micrographs of RCM with 12% casein, casein micelles were nonspherical and partially dissociated into small protein strands. Upon addition of calcium chloride at 0.21mmol/g of casein, casein micelles were more spherical and retained colloidal structure with the presence of aggregated casein micelles. These gelation processes of RCM with or without addition of trisodium citrate were both reversible. We propose that cold gelation of RCM occurs when protein strands that have been partially released from the casein micelles entangle, restrict their mobility, and form a fine-stranded gel network. Upon addition of high levels of calcium, cold gelation was promoted presumably through direct aggregation of casein micelles. Understanding cold gelation properties can facilitate potential use of RCM in cheese making. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Development and characterization of colloidal silica-based slow-release permanganate gel (SRP-G): laboratory investigations.

PubMed

Lee, Eung Seok; Gupta, Neha

2014-08-01

Slow-release permanganate (MnO4(-)) gel (SRP-G) is a hyper-saline KMnO4 solution that can be used for treating large, dilute, or deep plumes of chlorinated solvents in groundwater. Ideally, the SRP-G injected into aquifers will slowly gelate to form MnO4(-) gel in situ, and the gel will slowly releases MnO4(-). Objectives of this study were to develop SRP-G using colloidal silica as gelling solution, characterize its gelation and release kinetics, and delineate its dynamics in a saturated sandy media. The SRP-G exhibited a two-phase increase in viscosity: a lag phase characterized by little increase in viscosity followed by a short gelation phase. Gelation lag times of SRP-G solutions increased (from 0.5h to 13d) with decreasing KMnO4 concentrations (from 25 to 8 g L(-1)). Permanganate release from gelated SRP-G increased with increasing KMnO4 concentrations, and was characterized as asymptotic release with initial peak (0.9-2.2 mg min(-1)) followed by more attenuated release. Gelation lag times of SRP-G flowing in sands (linear velocity=2.1md(-1)) increased (1, 3, and 6h) with decreasing KMnO4 concentrations (25.0, 23.0, and 22.9 g L(-1)). Permanganate release from gelated SRP-Gs continued for up to 3d and was characterized as asymptotic release with an initial peak release (∼1.2 g min(-1)) followed by more attenuated release over 70h. Dilution of SRP-G by dispersion in porous media affects gelation and release kinetics. Increasing the silica concentration in the SRP-G may facilitate gelation and extend the duration of MnO4(-) release from emplaced SRP-G in porous media. Copyright © 2014. Published by Elsevier Ltd.

Role of Heavy Meromyosin in Heat-Induced Gelation in Low Ionic Strength Solution Containing L-Histidine.

PubMed

Hayakawa, Toru; Yoshida, Yuri; Yasui, Masanori; Ito, Toshiaki; Wakamatsu, Jun-ichi; Hattori, Akihito; Nishimura, Takanori

2015-08-01

The gelation of myosin has a very important role in meat products. We have already shown that myosin in low ionic strength solution containing L-histidine forms a transparent gel after heating. To clarify the mechanism of this unique gelation, we investigated the changes in the nature of myosin subfragments during heating in solutions with low and high ionic strengths with and without L-histidine. The hydrophobicity of myosin and heavy meromyosin (HMM) in low ionic strength solution containing L-histidine was lower than in high ionic strength solution. The SH contents of myosin and HMM in low ionic strength solution containing l-histidine did not change during the heating process, whereas in high ionic strength solution they decreased slightly. The heat-induced globular masses of HMM in low ionic strength solution containing L-histidine were smaller than those in high ionic strength solution. These findings suggested that the polymerization of HMM molecules by heating was suppressed in low ionic strength solution containing L-histidine, resulting in formation of the unique gel. © 2015 Institute of Food Technologists®

New composite thixotropic hydrogel composed of a polymer hydrogelator and a nanosheet

NASA Astrophysics Data System (ADS)

Ohsedo, Yutaka; Oono, Masashi; Saruhashi, Kowichiro; Watanabe, Hisayuki; Miyamoto, Nobuyoshi

2017-12-01

A composite gel composed of a water-soluble aromatic polyamide hydrogelator and the nanosheet Laponite®, a synthetic layered silicate, was produced and found to exhibit thixotropic behaviour. Whereas the composite gel contains the gelator at the same concentration as the molecular gel made by the gelator only, the composite gel becomes a softer thixotropic gel compared to the molecular gel made by the gelator only. The reason for this could be that bundles of polymer gelator may be loosened and the density of the polymer network increased in the presence of Laponite.

New composite thixotropic hydrogel composed of a polymer hydrogelator and a nanosheet

PubMed Central

Oono, Masashi; Saruhashi, Kowichiro; Watanabe, Hisayuki; Miyamoto, Nobuyoshi

2017-01-01

A composite gel composed of a water-soluble aromatic polyamide hydrogelator and the nanosheet Laponite®, a synthetic layered silicate, was produced and found to exhibit thixotropic behaviour. Whereas the composite gel contains the gelator at the same concentration as the molecular gel made by the gelator only, the composite gel becomes a softer thixotropic gel compared to the molecular gel made by the gelator only. The reason for this could be that bundles of polymer gelator may be loosened and the density of the polymer network increased in the presence of Laponite. PMID:29308249

Investigation of the relationships between the thermodynamic phase behavior and gelation behavior of a series of tripodal trisamide compounds

NASA Astrophysics Data System (ADS)

Feng, Li

Low molecular weight organic gelators(LMOGs) are important due to potential applications in many fields. Currently, most of the major studies focus on the empirical explanation of the crystallization for gelator assembly formation and morphologies, few efforts have been devoted to the thermodynamic phase behaviors and the effect of the non-ideal solution behavior on the structure of the resultant gels. In this research, tripodal trisamide compounds, synthesized from tris(2-aminoethyl)amine (TREN) by condensation with different acid chlorides, were studied as model LMOGs due to the simple one-step reaction and the commercially available chemical reactants. Gelation of organic solvents was investigated as a function of concentration and solvent solubility parameter.It has been found that the introduction of branches or cyclic units have dramatically improves the gelation ability compared to linear alkyl peripheral units. Fitting the liquidus lines using the regular solution model and calculation of the trisamide solubility parameter using solubility parameter theory gave good agreement with the trisamide solubility parameter calculated by group contribution methods. These results demonstrate that non-ideal solution behavior is an important factor in the gelation behavior of low molecular mass organic gelators. Understanding and controlling the thermodynamics and phase behaviors of the gel systems will provide effective ways to produce new efficient LMOGs in the future.

Process of forming a sol-gel/metal hydride composite

DOEpatents

Congdon, James W [Aiken, SC

2009-03-17

An external gelation process is described which produces granules of metal hydride particles contained within a sol-gel matrix. The resulting granules are dimensionally stable and are useful for applications such as hydrogen separation and hydrogen purification. An additional coating technique for strengthening the granules is also provided.

Kinetics of microstructure formation of high-pressure induced gel from a whey protein isolate

NASA Astrophysics Data System (ADS)

He, Jin-Song; Yang, Hongwei; Zhu, Wanpeng; Mu, Tai-Hua

2010-03-01

The kinetic process of pressure-induced gelation of whey protein isolate (WPI) solutions was studied using in situ light scattering. The relationship of the logarithm of scattered light intensity (I) versus time (t) was linear after the induced time and could be described by the Cahn-Hilliard linear theory. With increasing time, the scattered intensity deviated from the exponential relationship, and the time evolution of the scattered light intensity maximum Im and the corresponding wavenumber qm could be described in terms of the power-law relationship as Im~fβ and qm~f-α, respectively. These results indicated that phase separation occurred during the gelation of WPI solutions under high pressure.

Self-assembly of gelator molecules in liquid crystals studied by ESR

NASA Astrophysics Data System (ADS)

Andreis, Mladen; Carić, Dejana; Vujičić, Nataša Šijaković; Jokić, Milan; Žinić, Mladen; Kveder, Marina

2012-07-01

Thermotropic liquid crystal trans-4-heptylcyclohexanecarboxylic acid (HCCA) doped with 4-oxo-2,2,6,6,-tetramethyl-1-piperidinyloxy spin probe (Tempone) is investigated by electron spin resonance (ESR) spectroscopy in the presence of chiral bisoxalamide gelator 1 during both cooling and heating cycles. In the temperature range 295-383 K, where HCCA displays isotropic, nematic, smectic B and crystalline phases, the impact of 1 self-organization was detected via (non) homogeneous partitioning of the spin probe in the environments varying in the polarity, an effect dependent on the gelator concentration. In particular, the evidence of the onset of the gelator network self-assembly in the nematic phase was detected by ESR at higher temperatures than the ones reported so far by other experimental techniques. Additionally, the spectral analysis points to the switching of the polarity in the vicinity of the spin probe when the transfer of chirality from 1 to HCCA upon cooling of the sample from isotropic to chiral nematic phase appears and when the event of LC gelation results in the achiral nematic phase during chiral gel fibers formation. When the gelation proceeds in the smectic phase, the melting of the gelator network is studied in the nematic phase during the heating cycle. Furthermore, the event of HCCA crystallization is shown to be strongly affected by the presence of 1 as well. The experimental evidence is provided that gelator network confines the HCCA into the domains within the bulk crystalline matrix where the local molecular dynamics are still not frozen. Therefore, we propose that non-homogeneous polarity profile of molecular organization/packing within LC gels could be determinable for the physical properties of various LC gel phases.

Enzyme-triggered self-assembly of a small molecule: a supramolecular hydrogel with leaf-like structures and an ultra-low minimum gelation concentration

NASA Astrophysics Data System (ADS)

Wang, Huaimin; Ren, Chunhua; Song, Zhijian; Wang, Ling; Chen, Xuemei; Yang, Zhimou

2010-06-01

We report on the use of a phosphatase to assist the formation of leaf-like structures and a supramolecular hydrogel with an ultra-low minimum gelation concentration. The compound can gel water at a minimum gelation concentration of 0.01 wt%, which is the lowest gelation concentration reported up to now. The images obtained by transmission electron microscopy (TEM) reveal the existence of leaf-like structures serving as the matrix of the hydrogels. The stability of the hydrogels was studied and emission spectra were used to get information about the molecular packing in the leaf-like structures. Since lowering the concentration of the gelator decreases the toxicity of the resulting hydrogels, ultra-low concentration gels have potential uses as biocompatible biomaterials for, e.g., cell cultures, tissue engineering, and drug delivery.

Aligned 1-D nanorods of a π-gelator exhibit molecular orientation and excitation energy transport different from entangled fiber networks.

PubMed

Sakakibara, Keita; Chithra, Parayalil; Das, Bidisa; Mori, Taizo; Akada, Misaho; Labuta, Jan; Tsuruoka, Tohru; Maji, Subrata; Furumi, Seiichi; Shrestha, Lok Kumar; Hill, Jonathan P; Acharya, Somobrata; Ariga, Katsuhiko; Ajayaghosh, Ayyappanpillai

2014-06-18

Linear π-gelators self-assemble into entangled fibers in which the molecules are arranged perpendicular to the fiber long axis. However, orientation of gelator molecules in a direction parallel to the long axes of the one-dimensional (1-D) structures remains challenging. Herein we demonstrate that, at the air-water interface, an oligo(p-phenylenevinylene)-derived π-gelator forms aligned nanorods of 340 ± 120 nm length and 34 ± 5 nm width, in which the gelator molecules are reoriented parallel to the long axis of the rods. The orientation change of the molecules results in distinct excited-state properties upon local photoexcitation, as evidenced by near-field scanning optical microscopy. A detailed understanding of the mechanism by which excitation energy migrates through these 1-D molecular assemblies might help in the design of supramolecular structures with improved charge-transport properties.

Counteranion Driven Homochiral Assembly of a Cationic C3-Symmetric Gelator through Ion-Pair Assisted Hydrogen Bond.

PubMed

Maity, Arunava; Gangopadhyay, Monalisa; Basu, Arghya; Aute, Sunil; Babu, Sukumaran Santhosh; Das, Amitava

2016-09-07

The helical handedness in achiral self-assemblies is mostly complex due to spontaneous symmetry breaking or kinetically controlled random assembly formation. Here an attempt has been made to address this issue through chiral anion exchange. A new class of cationic achiral C3-symmetric gelator devoid of any conventional gelation assisting functional units is found to form both right- and left-handed helical structures. A chiral counteranion exchange-assisted approach is successfully introduced to control the chirality sign and thereby to obtain preferred homochiral assemblies. Formation of anion-assisted chiral assembly was confirmed by circular dichroism (CD) spectroscopy, microscopic images, and crystal structure. The X-ray crystal structure reveals the construction of helical assemblies with opposite handedness for (+)- and (-)-chiral anion reformed gelators. The appropriate counteranion driven ion-pair-assisted hydrogen-bonding interactions are found responsible for the helical bias control in this C3-symmetric gelator.

Mesoporous organohydrogels from thermogelling photocrosslinkable nanoemulsions

NASA Astrophysics Data System (ADS)

Helgeson, Matthew E.; Moran, Shannon E.; An, Harry Z.; Doyle, Patrick S.

2012-04-01

We report the formation of mesoporous organohydrogels from oil-in-water nanoemulsions containing an end-functionalized oligomeric gelator in the aqueous phase. The nanoemulsions exhibit an abrupt thermoreversible transition from a low-viscosity liquid to a fractal-like colloidal gel of droplets with mesoscale porosity and solid-like viscoelasticity with moduli approaching 100 kPa, possibly the highest reported for an emulsion-based system. We hypothesize that gelation is brought about by temperature-induced interdroplet bridging of the gelator, as shown by its dependence on the gelator chemistry. The use of photocrosslinkable gelators enables the freezing of the nanoemulsion’s microstructure into a soft hydrogel nanocomposite containing a large fraction of dispersed liquid hydrophobic compartments, and we show its use in the encapsulation and release of lipophilic biomolecules. The tunable structural, mechanical and optical properties of these organohydrogels make them a robust material platform suitable for a wide range of applications.

Catalytic activity of acid and base with different concentration on sol-gel kinetics of silica by ultrasonic method.

PubMed

Das, R K; Das, M

2015-09-01

The effects of both acid (acetic acid) and base (ammonia) catalysts in varying on the sol-gel synthesis of SiO2 nanoparticles using tetra ethyl ortho silicate (TEOS) as a precursor was determined by ultrasonic method. The ultrasonic velocity was received by pulsar receiver. The ultrasonic velocity in the sol and the parameter ΔT (time difference between the original pulse and first back wall echo of the sol) was varied with time of gelation. The graphs of ln[ln1/ΔT] vs ln(t), indicate two region - nonlinear region and a linear region. The time corresponds to the point at which the non-linear region change to linear region is considered as gel time for the respective solutions. Gelation time is found to be dependent on the concentration and types of catalyst and is found from the graphs based on Avrami equation. The rate of condensation is found to be faster for base catalyst. The gelation process was also characterized by viscosity measurement. Normal sol-gel process was also carried out along with the ultrasonic one to compare the effectiveness of ultrasonic. The silica gel was calcined and the powdered sample was characterized with scanning electron microscopy, energy dispersive spectra, X-ray diffractogram, and FTIR spectroscopy. Copyright © 2014 Elsevier B.V. All rights reserved.

Preparation of Chitosan-based Injectable Hydrogels and Its Application in 3D Cell Culture.

PubMed

Li, Yongsan; Zhang, Yaling; Wei, Yen; Tao, Lei

2017-09-29

The protocol presents a facile, efficient, and versatile method to prepare chitosan-based hydrogels using dynamic imine chemistry. The hydrogel is prepared by mixing solutions of glycol chitosan with a synthesized benzaldehyde terminated polymer gelator, and hydrogels are efficiently obtained in several minutes at room temperature. By varying ratios between glycol chitosan, polymer gelator, and water contents, versatile hydrogels with different gelation times and stiffness are obtained. When damaged, the hydrogel can recover its appearances and modulus, due to the reversibility of the dynamic imine bonds as crosslinkages. This self-healable property enables the hydrogel to be injectable since it can be self-healed from squeezed pieces to an integral bulk hydrogel after the injection process. The hydrogel is also multi-responsive to many bio-active stimuli due to different equilibration statuses of the dynamic imine bonds. This hydrogel was confirmed as bio-compatible, and L929 mouse fibroblast cells were embedded following standard procedures and the cell proliferation was easily assessed by a 3D cell cultivation process. The hydrogel can offer an adjustable platform for different research where a physiological mimic of a 3D environment for cells is profited. Along with its multi-responsive, self-healable, and injectable properties, the hydrogels can potentially be applied as multiple carriers for drugs and cells in future bio-medical applications.

Exploring the kinetics of gelation and final architecture of enzymatically cross-linked chitosan/gelatin gels.

PubMed

da Silva, Marcelo A; Bode, Franziska; Grillo, Isabelle; Dreiss, Cécile A

2015-04-13

Small-angle neutron scattering (SANS) was used to characterize the nanoscale structure of enzymatically cross-linked chitosan/gelatin hydrogels obtained from two protocols: a pure chemical cross-linking process (C), which uses the natural enzyme microbial transglutaminase, and a physical-co-chemical (PC) hybrid process, where covalent cross-linking is combined with the temperature-triggered gelation of gelatin, occurring through the formation of triple-helices. SANS measurements on the final and evolving networks provide a correlation length (ξ), which reflects the average size of expanding clusters. Their growth in PC gels is restricted by the triple-helices (ξ ∼ 10s of Å), while ξ in pure chemical gels increases with cross-linker concentration (∼100s of Å). In addition, the shear elastic modulus in PC gels is higher than in pure C gels. Our results thus demonstrate that gelatin triple helices provide a template to guide the cross-linking process; overall, this work provides important structural insight to improve the design of biopolymer-based gels.

Thiolated chitosan nanoparticles as an oral delivery system for Amikacin: in vitro and ex vivo evaluations.

PubMed

Atyabi, F; Talaie, F; Dinarvand, R

2009-08-01

The purpose of this study was the synthesis of two thiol conjugated Chitosan polymers, and evaluation of the potential of Thiomer nanoparticle formulation as a carrier for oral delivery system. Mediated by EDAC (Ethylene-3-(3-di-methylaminopropyl)-carbodiimide), either N-acetyl Cysteine (NAC) or N-acetyl D-penicillamine (NAP) were covalently attached to Chitosan. The success of the synthesis was demonstrated by comparing FTIR spectra. Iodometric titration demonstrated that depending on the pH value of the synthesis medium, the Thiomers display 250 +/- 30 microMol and 300 +/- 20 microMol thiol groups per gram of polymer respectively. The interaction between mucin and Thiomers, compared to mucin and Chitosan was studied for assessment of mucoadhesion properties of synthesized polymers. This interaction was determined by the measurement of the amount of mucin adsorbed on Chitosan and the conjugated polymers. Rotating cylinder method demonstrated an average of 20 times improvement in mucoadhesion of Thiomers compared to the unmodified polymer. Chitosan and Thiomer nanoparticles were formulated by two methods; TPP and Sodium Sulfate gelation. SEM micrographs and data achieved by a Malvern nano/zetasizer show nanoparticles formed by TPP gelation have a mean size of 150 +/- 15 nm compared to 300 +/- 25 nm sized nanoparticles obtained by Sodium sulfate gelation. TPP gelation yields smaller, more spherical shaped nanoparticles with a smaller range of size distribution. Amikacin loaded nanoparticles with an average size of 280 nm were prepared by TPP gelation in which disulfide bond formation was achieved by a time dependent oxidation process. In vitro studies were carried out; a recovery rate of 33% and a drug entrapment of 25% were achieved. The amount of release was determined during 18 hr in a carefully prepared media. The permeation time across a biological membrane was observed to be about 150 minutes. Microbiological tests were carried out on two microorganisms; Pseudomona aeruginosa and Staphylococcus aureus to further confirm the amount of Amikacin inside drug loaded nanoparticles.

Capillary break-up, gelation and extensional rheology of hydrophobically modified cellulose ethers

NASA Astrophysics Data System (ADS)

Sharma, Vivek; Haward, Simon; Pessinet, Olivia; Soderlund, Asa; Threlfall-Holmes, Phil; McKinley, Gareth

2012-02-01

Cellulose derivatives containing associating hydrophobic groups along their hydrophilic polysaccharide backbone are used extensively in the formulations for inks, water-borne paints, food, nasal sprays, cosmetics, insecticides, fertilizers and bio-assays to control the rheology and processing behavior of multi-component dispersions. These complex dispersions are processed and used over a broad range of shear and extensional rates. The presence of hydrophobic stickers influences the linear and nonlinear rheology of cellulose ether solutions. In this talk, we systematically contrast the difference in the shear and extensional rheology of a cellulose ether: ethy-hydroxyethyl-cellulose (EHEC) and its hydrophobically-modified analog (HMEHEC) using microfluidic shear rheometry at deformation rates up to 10^6 inverse seconds, cross-slot flow extensional rheometry and capillary break-up during jetting as a rheometric technique. Additionally, we provide a constitutive model based on fractional calculus to describe the physical gelation in HMEHEC solutions.

Effects of process variables on the encapsulation of oil in ca-alginate capsules using an inverse gelation technique.

PubMed

Abang, Sariah; Chan, Eng-Seng; Poncelet, Denis

2012-01-01

The objective of this study was to investigate the effects of process variables on the encapsulation of oil in a calcium alginate membrane using an inverse gelation technique. A dispersion of calcium chloride solution in sunflower oil (water-in-oil emulsion) was added dropwise to the alginate solution. The migration of calcium ions to the alginate solution initiates the formation of a ca-alginate membrane around the emulsion droplets. The membrane thickness of wet capsules and the elastic modulus of dry capsules increased following first-order kinetics with an increasing curing time. An increase in the calcium chloride concentration increased the membrane thickness of wet capsules and the elastic modulus of dry capsules. An increase in the alginate concentration decreased the mean diameter of wet capsules but increased the elastic modulus of dry capsules.

Comparing and Correlating Solubility Parameters Governing the Self-Assembly of Molecular Gels Using 1,3:2,4-Dibenzylidene Sorbitol as the Gelator

PubMed Central

2014-01-01

Solvent properties play a central role in mediating the aggregation and self-assembly of molecular gelators and their growth into fibers. Numerous attempts have been made to correlate the solubility parameters of solvents and gelation abilities of molecular gelators, but a comprehensive comparison of the most important parameters has yet to appear. Here, the degree to which partition coefficients (log P), Henry’s law constants (HLC), dipole moments, static relative permittivities (εr), solvatochromic ET(30) parameters, Kamlet–Taft parameters (β, α, and π), Catalan’s solvatochromic parameters (SPP, SB, and SA), Hildebrand solubility parameters (δi), and Hansen solubility parameters (δp, δd, δh) and the associated Hansen distance (Rij) of 62 solvents (covering a wide range of properties) can be correlated with the self-assembly and gelation of 1,3:2,4-dibenzylidene sorbitol (DBS) gelation, a classic molecular gelator, is assessed systematically. The approach presented describes the basis for each of the parameters and how it can be applied. As such, it is an instructional blueprint for how to assess the appropriate type of solvent parameter for use with other molecular gelators as well as with molecules forming other types of self-assembled materials. The results also reveal several important insights into the factors favoring the gelation of solvents by DBS. The ability of a solvent to accept or donate a hydrogen bond is much more important than solvent polarity in determining whether mixtures with DBS become solutions, clear gels, or opaque gels. Thermodynamically derived parameters could not be correlated to the physical properties of the molecular gels unless they were dissected into their individual HSPs. The DBS solvent phases tend to cluster in regions of Hansen space and are highly influenced by the hydrogen-bonding HSP, δh. It is also found that the fate of this molecular gelator, unlike that of polymers, is influenced not only by the magnitude of the distance between the HSPs for DBS and the HSPs of the solvent, Rij, but also by the directionality of Rij: if the solvent has a larger hydrogen-bonding HSP (indicating stronger H-bonding) than that of the DBS, then clear gels are formed; opaque gels form when the solvent has a lower δh than does DBS. PMID:24849281

Comparing and correlating solubility parameters governing the self-assembly of molecular gels using 1,3:2,4-dibenzylidene sorbitol as the gelator.

PubMed

Lan, Yaqi; Corradini, Maria G; Liu, Xia; May, Tim E; Borondics, Ferenc; Weiss, Richard G; Rogers, Michael A

2014-12-02

Solvent properties play a central role in mediating the aggregation and self-assembly of molecular gelators and their growth into fibers. Numerous attempts have been made to correlate the solubility parameters of solvents and gelation abilities of molecular gelators, but a comprehensive comparison of the most important parameters has yet to appear. Here, the degree to which partition coefficients (log P), Henry's law constants (HLC), dipole moments, static relative permittivities (ε(r)), solvatochromic E(T)(30) parameters, Kamlet-Taft parameters (β, α, and π), Catalan's solvatochromic parameters (SPP, SB, and SA), Hildebrand solubility parameters (δ(i)), and Hansen solubility parameters (δ(p), δ(d), δ(h)) and the associated Hansen distance (R(ij)) of 62 solvents (covering a wide range of properties) can be correlated with the self-assembly and gelation of 1,3:2,4-dibenzylidene sorbitol (DBS) gelation, a classic molecular gelator, is assessed systematically. The approach presented describes the basis for each of the parameters and how it can be applied. As such, it is an instructional blueprint for how to assess the appropriate type of solvent parameter for use with other molecular gelators as well as with molecules forming other types of self-assembled materials. The results also reveal several important insights into the factors favoring the gelation of solvents by DBS. The ability of a solvent to accept or donate a hydrogen bond is much more important than solvent polarity in determining whether mixtures with DBS become solutions, clear gels, or opaque gels. Thermodynamically derived parameters could not be correlated to the physical properties of the molecular gels unless they were dissected into their individual HSPs. The DBS solvent phases tend to cluster in regions of Hansen space and are highly influenced by the hydrogen-bonding HSP, δ(h). It is also found that the fate of this molecular gelator, unlike that of polymers, is influenced not only by the magnitude of the distance between the HSPs for DBS and the HSPs of the solvent, R(ij), but also by the directionality of R(ij): if the solvent has a larger hydrogen-bonding HSP (indicating stronger H-bonding) than that of the DBS, then clear gels are formed; opaque gels form when the solvent has a lower δ(h) than does DBS.

Transdermal thiol-acrylate polyethylene glycol hydrogel synthesis using near infrared light

NASA Astrophysics Data System (ADS)

Chung, Solchan; Lee, Hwangjae; Kim, Hyung-Seok; Kim, Min-Gon; Lee, Luke P.; Lee, Jae Young

2016-07-01

Light-induced polymerization has been widely applied for hydrogel synthesis, which conventionally involves the use of ultraviolet or visible light to activate a photoinitiator for polymerization. However, with these light sources, transdermal gelation is not efficient and feasible due to their substantial interactions with biological systems, and thus a high power is required. In this study, we used biocompatible and tissue-penetrating near infrared (NIR) light to remotely trigger a thiol-acrylate reaction for efficient in vivo gelation with good controllability. Our gelation system includes gold nanorods as a photothermal agent, a thermal initiator, diacrylate polyethylene glycol (PEG), and thiolated PEG. Irradiation with a low-power NIR laser (0.3 W cm-2) could induce gelation via a mixed-mode reaction with a small increase in temperature (~5 °C) under the optimized conditions. We also achieved successful transdermal gelation via the NIR-assisted photothermal thiol-acryl reactions. This new type of NIR-assisted thiol-acrylate polymerization provides new opportunities for in situ hydrogel formation for injectable hydrogels and delivery of drugs/cells for various biomedical applications.Light-induced polymerization has been widely applied for hydrogel synthesis, which conventionally involves the use of ultraviolet or visible light to activate a photoinitiator for polymerization. However, with these light sources, transdermal gelation is not efficient and feasible due to their substantial interactions with biological systems, and thus a high power is required. In this study, we used biocompatible and tissue-penetrating near infrared (NIR) light to remotely trigger a thiol-acrylate reaction for efficient in vivo gelation with good controllability. Our gelation system includes gold nanorods as a photothermal agent, a thermal initiator, diacrylate polyethylene glycol (PEG), and thiolated PEG. Irradiation with a low-power NIR laser (0.3 W cm-2) could induce gelation via a mixed-mode reaction with a small increase in temperature (~5 °C) under the optimized conditions. We also achieved successful transdermal gelation via the NIR-assisted photothermal thiol-acryl reactions. This new type of NIR-assisted thiol-acrylate polymerization provides new opportunities for in situ hydrogel formation for injectable hydrogels and delivery of drugs/cells for various biomedical applications. Electronic supplementary information (ESI) available: FE-SEM image of thiol-acrylate hydrogels; UV/Vis spectra of Ellman's assay; the temperature increase during transdermal photothermal hydrogelation. See DOI: 10.1039/c6nr01956k

Thermoreversible gelation of poly(vinylidene fluoride) in phthalates: the influence of aliphatic chain length of solvents.

PubMed

Yadav, P Jaya Prakash; Ghosh, Goutam; Maiti, Biswajit; Aswal, Vinod K; Goyal, P S; Maiti, Pralay

2008-04-17

Thermoreversible gelation of poly(vinylidene fluoride) (PVDF) has been studied in a new series of solvents (phthalates), for example, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), and dihexyl phthalate (DHP) as a function of temperature and polymer concentration, both by test tube tilting and dynamic light scattering (DLS) method. The effect of aliphatic chain length (n) of diesters on the gelation kinetics, structure/microstructure and morphology of PVDF gels has been examined. Gelation rate was found to increase with increasing aliphatic chain length of diester. DLS results indicate that the sol-gel transformation proceeds via two-steps: first, microgel domains were formed, and then the infinite three-dimensional (3D) network is established by connecting microgels through polymer chains. The crystallites are responsible for 3D network for gelation in phthalates, and alpha-polymorph is formed during gelation producing higher amount of crystallinity with increasing aliphatic chain length of diester. Morphology of the networks of dried gels in different phthalates showed that fibril thickness and lateral dimensions decrease with higher homologues of phthalates. The scattering intensity is fitted with Debye-Bueche model in small-angle neutron scattering and suggested that both the correlation length and interlamellar spacing increases with n. A model has been proposed, based on electronic structure calculations, to explain the conformation of PVDF chain in presence of various phthalates and their complexes, which offer the cause of higher gelation rate for longer aliphatic chain length.

Chemical Processing and Characterization of Fiber Reinforced Nanocomposite Silica Materials

NASA Astrophysics Data System (ADS)

Burnett, Steven Shannon

Ultrasound techniques, acoustic and electroacoustic spectroscopy, are used to investigate and characterize concentrated fluid phase nanocomposites. In particular, the data obtained from ultrasound methods are used as tools to improve the understanding of the fundamental process chemistry of concentrated, multicomponent, nanomaterial dispersions. Silicon nitride nanofibers embedded in silica are particularly interesting for lightweight nanocomposites, because silicon nitride is isostructural to carbon nitride, a super hard material. However, the major challenge with processing these composites is retarding particle-particle aggregation, to maintain highly dispersed systems. Therefore, a systematic approach was developed to evaluate the affect of process parameters on particle-particle aggregation, and improving the chemical kinetics for gelation. From the acoustic analysis of the nanofibers, this thesis was able to deduce that changes in aspect ratio affects the ultrasound propagation. In particular, higher aspect ratio fibers attenuate the ultrasound wave greater than lower aspect fibers of the same material. Furthermore, our results confirm that changes in attenuation depend on the hydrodynamical interactions between particles, the aspect ratio, and the morphology of the dispersant. The results indicate that the attenuation is greater for fumed silica due to its elastic nature and its size, when compared to silica Ludox. Namely, the larger the size, the greater the attenuation. This attenuation is mostly the result of scattering loss in the higher frequency range. In addition, the silica nanofibers exhibit greater attenuation than their nanoparticle counterparts because of their aspect ratio influences their interaction with the ultrasound wave. In addition, this study observed how 3M NH 4 Cl's acoustic properties changes during the gelation process, and during that change, the frequency dependency deviates from the expected squared of the frequency, until the system becomes fully dense and turns into a pure gel. Moreover, our results demonstrated the use of ultrasound to determine the critical coagulation concentration, and a double logarithm plot of the CVI indicated a possible power law dependency for NH4 Cl concentrations. Lastly, the mechanism of the gelation reaction of colloidal silica, Si(OH) 4(aq) + Si(OH)3(O) --(aq) → Si2O8H5--( aq) + H2O, by an anionic pathway was investigated using density functional theory (DFT). Using transition state theory, the rate constants were obtained by analyzing the potential energy surface at the reactants, saddle point, and the products. In addition, reaction rate constants were investigated in the presence of ammonium chloride (NH 4 Cl) and sodium chloride (NaCl). These salts act as catalysis to induce gelation due to their ability to destabilize the double layer of the colloid. Furthermore, it was observed that ammonium chloride plays an important role by initiating a hydride transfer allowing the reaction to proceed from the second transition state to the final product, and was predicted to be spontaneous for all temperatures. In summary, this thesis provides a comprehensive approach on examining the parameters required for the chemical processing of nanofiber dispersions, thus improving the understanding of the physio-chemical interactions, the gelation mechanism, and their influence on obtaining highly dispersed fluid phase composite systems.

Structure of starch aerogel as affected by crosslinking and feasibility assessment of the aerogel for an anti-fungal volatile release.

PubMed

Abhari, Negar; Madadlou, Ashkan; Dini, Ali

2017-04-15

Starch suspensions were crosslinked with trisodium citrate for either 0 or 17h, gelled and then freeze-dried to corresponding aerogels. The aerogel from the 17h-crosslinked suspension was loaded with the antifungal compound, trans-2-hexenal, and coated with the surfactant, sorbitan monooleate. Aerogel hardness was increased by the citrate-mediated crosslinking, whereas its adhesiveness decreased. Starch gelation decreased the crystallinity index (CrI) from 59% to ≈23%; however, the pre-gelation crosslinking resulted in a higher CrI value (i.e. ≈38%) for the aerogel. The voids at the internal microstructure of the 17h-crosslinked aerogel were more uniform and coating with surfactant closed the surface openings. The latter accordingly resulted in a more sustained release of the volatile, trans-2-hexenal, from the crosslinked starch aerogel and led to slower lethality of Aspergillus parasiticus cells inoculated on pistachio nuts compared with the non-coated condition. Copyright © 2016 Elsevier Ltd. All rights reserved.

Self-assembly into soft materials of molecules derived from naturallyoccurring fatty-acids

NASA Astrophysics Data System (ADS)

Zhang, Mohan

The self-assembly of molecular gelators has provided an attractive route for the construction of nanostructured materials with desired functionalities. A well-defined paradigm for the design of molecular gels is needed, but none has yet been established. One of the important challenges to defining this paradigm is the creation of structure-property correlations for gelators at different distance scales. This dissertation centers on gaining additional insights in the relationship between small changes in gelator structures derived from long-chain, naturally-occurring fatty acids and the properties of the corresponding gels. This approach offers a reasonable method to probe the rational design of molecular gelators. (Abstract shortened by ProQuest.).

Biobased Fat Mimicking Molecular Structuring Agents for Medium-Chain Triglycerides (MCTs) and Other Edible Oils.

PubMed

Silverman, Julian R; John, George

2015-12-09

To develop sustainable value-added materials from biomass, novel small-molecule sugar ester gelators were synthesized using biocatalysis. The facile one-step regiospecific coupling of the pro-antioxidant raspberry ketone glucoside and unsaturated or saturated long- and medium-chain fatty acids provides a simple approach to tailor the structure and self-assembly of the amphiphilic product. These low molecular weight molecules demonstrated the ability to self-assemble in a variety of solvents and exhibited supergelation, with a minimum gelation concentration of 0.25 wt %, in numerous organic solvents, as well as in a range of natural edible oils, specifically a relatively unstudied group of liquids: natural medium-chain triglyceride oils, notably coconut oil. Spectroscopic analysis details the gelator structure as well as the intermolecular noncovalent interactions, which allow for gelation. X-ray diffraction studies indicate fatty acid chain packing of gelators is similar to that of natural fats, signifying the crystalline nature may lead to desirable textural properties and mouthfeel.

Gelation of Oil upon Contact with Water: A Bioinspired Scheme for the Self-Repair of Oil Leaks from Underwater Tubes.

PubMed

Oh, Hyuntaek; Yaraghi, Nicholas; Raghavan, Srinivasa R

2015-05-19

Molecular organogelators convert oils into gels by forming self-assembled fibrous networks. Here, we demonstrate that such gelation can be activated by contacting the oil with an immiscible solvent (water). Our gelator is dibenzylidene sorbitol (DBS), which forms a low-viscosity sol when added to toluene containing a small amount of dimethyl sulfoxide (DMSO). Upon contact with water, DMSO partitions into the water, activating gelation of DBS in the toluene. The gel grows from the oil/water interface and slowly envelops the oil phase. We have exploited this effect for the self-repair of oil leaks from underwater tubes. When a DBS/toluene/DMSO solution flows through the tube, it forms a gel selectively at the leak point, thereby plugging the leak and restoring flow. Our approach is reminiscent of wound-sealing via blood-clotting: there also, inactive gelators in blood are activated at the wound site into a fibrous network, thereby plugging the wound and restoring blood flow.

Effects of single-walled carbon nanotubes on lysozyme gelation.

PubMed

Tardani, Franco; La Mesa, Camillo

2014-09-01

The possibility to disperse carbon nanotubes in biocompatible matrices has got substantial interest from the scientific community. Along this research line, the inclusion of single walled carbon nanotubes in lysozyme-based hydrogels was investigated. Experiments were performed at different nanotube/lysozyme weight ratios. Carbon nanotubes were dispersed in protein solutions, in conditions suitable for thermal gelation. The state of the dispersions was determined before and after thermal treatment. Rheology, dynamic light scattering and different microscopies investigated the effect that carbon nanotubes exert on gelation. The gelation kinetics and changes in gelation temperature were determined. The effect of carbon and lysozyme content on the gel properties was, therefore, determined. At fixed lysozyme content, moderate amounts of carbon nanotubes do not disturb the properties of hydrogel composites. At moderately high volume fractions in carbon nanotubes, the gels become continuous in both lysozyme and nanotubes. This is because percolating networks are presumably formed. Support to the above statements comes by rheology. Copyright © 2014 Elsevier B.V. All rights reserved.

Spacer effect on nanostructures and self-assembly in organogels via some bolaform cholesteryl imide derivatives with different spacers

PubMed Central

2013-01-01

In this paper, new bolaform cholesteryl imide derivatives with different spacers were designed and synthesized. Their gelation behaviors in 23 solvents were investigated, and some of them were found to be low molecular mass organic gelators. The experimental results indicated that these as-formed organogels can be regulated by changing the flexible/rigid segments in spacers and organic solvents. Suitable combination of flexible/rigid segments in molecular spacers in the present cholesteryl gelators is favorable for the gelation of organic solvents. Scanning electron microscopy and atomic force microscopy observations revealed that the gelator molecules self-assemble into different aggregates, from wrinkle and belt to fiber with the change of spacers and solvents. Spectral studies indicated that there existed different H-bond formations between imide groups and assembly modes, depending on the substituent spacers in molecular skeletons. The present work may give some insight into the design and character of new organogelators and soft materials with special molecular structures. PMID:24083361

Spacer effect on nanostructures and self-assembly in organogels via some bolaform cholesteryl imide derivatives with different spacers

NASA Astrophysics Data System (ADS)

Jiao, Tifeng; Gao, Fengqing; Zhang, Qingrui; Zhou, Jingxin; Gao, Faming

2013-10-01

In this paper, new bolaform cholesteryl imide derivatives with different spacers were designed and synthesized. Their gelation behaviors in 23 solvents were investigated, and some of them were found to be low molecular mass organic gelators. The experimental results indicated that these as-formed organogels can be regulated by changing the flexible/rigid segments in spacers and organic solvents. Suitable combination of flexible/rigid segments in molecular spacers in the present cholesteryl gelators is favorable for the gelation of organic solvents. Scanning electron microscopy and atomic force microscopy observations revealed that the gelator molecules self-assemble into different aggregates, from wrinkle and belt to fiber with the change of spacers and solvents. Spectral studies indicated that there existed different H-bond formations between imide groups and assembly modes, depending on the substituent spacers in molecular skeletons. The present work may give some insight into the design and character of new organogelators and soft materials with special molecular structures.

The gelation influence on diffusion and conductivity enhancement effect in renewable ionic gels based on a LMWG.

PubMed

Bielejewski, M; Rachocki, A; Kaszyńska, J; Tritt-Goc, J

2018-02-21

This paper reports the interdisciplinary study on molecular dynamics, ionic interactions and electrical conductivity in a quaternary ammonium salt (TMABr) ionogel based on a low molecular weight gelator (LMWG) in a wide range of electrolyte molar concentrations. The thermal scanning conductometry (TSC) was used to investigate the electric properties of the ionogels. The prepared TMABr/H 2 O/LMWG ionogel exhibits better ion transport properties than the dissociated TMA + cation in solution. The enhanced ionic conductivity effect (EICE) was observed in the concentration range of the TMABr salt up to 1 M. To investigate the transport properties of the TMA + cation and solvent molecules in the gel and sol phase, the NMR diffusiometry method was used. The field-cycling relaxometry method (FFC NMR) was applied to study the local motions of the electrolyte at the surface of the gelator matrix. On the basis of the obtained data, the higher ionic conductivity observed in the gel phase has been related to the microstructure of the gel matrix. The possible explanation for the origin of this effect has been given. The investigated system is a thermally reversible physical gel, all registered data were reproducible upon transforming the sample from gel to sol and back to the gel state, confirming the enhancement effect as a permanent property of the investigated ionogels. Therefore, the EICE has been proposed to be used as an internal sensor to monitor the condition of the ionogel phase, thus making them smart materials.

Structural and evaporative evolutions in desiccating sessile drops of blood

NASA Astrophysics Data System (ADS)

Sobac, B.; Brutin, D.

2011-07-01

We report an experimental investigation of the drying of a deposited drop of whole blood. Flow motion, adhesion, gelation, and fracturation all occur during the evaporation of this complex matter, leading to a final typical pattern. Two distinct regimes of evaporation are highlighted: the first is driven by convection, diffusion, and gelation in a liquid phase, whereas the second, with a much slower rate of evaporation, is characterized by the mass transport of the liquid left over in the gellified biocomponent matter. A diffusion model of the drying process allows a prediction of the transition between these two regimes of evaporation. Moreover, the formation of cracks and other events occurring during the drying are examined and shown to be driven by critical solid mass concentrations.

Structural and mechanical properties of organogels: Role of oil and gelator molecular structure.

PubMed

Cerqueira, Miguel A; Fasolin, Luiz H; Picone, Carolina S F; Pastrana, Lorenzo M; Cunha, Rosiane L; Vicente, António A

2017-06-01

This work aims at evaluating the influence of oil and gelator structure on organogels' properties through rheological measurements, polarized microscopy and small-angle X-ray scattering (SAXS). Four different food-grade gelators (glyceryl tristearate - GT; sorbitan tristearate - ST; sorbitan monostearate - SM and glyceryl monostearate - GM) were tested in medium-chain triglyceride and high oleic sunflower (MCT and LCT, respectively) oil phases. Organogels were prepared by mixing the oil phase and gelator at different concentrations (5, 10, 15, 20 and 25%) at 80°C during 30min. All organogels presented birefringence confirming the formation of a crystalline structure that changed with the increase of the gelator concentration. Through the evaluation of SAXS peaks it has been confirmed that all structures were organized as lamellas but with different d-spacing values. These particularities at micro- and nanoscale level lead to differences in rheological properties of organogels. Results showed that the oil type (i.e. medium- and long-chain triglyceride) and hydrophilic head of gelators (i.e. sorbitan versus glyceryl) exert influence on the organogels physical properties, but the presence of monostearate leads to the formation of stronger organogels. Moreover, gels produced with LCT were stronger and gelled at lower organogelator concentration than MCT. Copyright © 2017 Elsevier Ltd. All rights reserved.

In situ synthesis-gelation at room temperature vs. heating-cooling procedure. Fine tuning of molecular gels derived from succinic acid and L-valine.

PubMed

Fontanillo, Miriam; Angulo-Pachón, César A; Escuder, Beatriu; Miravet, Juan F

2013-12-15

The reaction between succinic anhydride and a diamine derived from L-valine should afford efficiently a molecular gelator. Based on this reaction, it should be feasible to prepare molecular gels at room temperature, avoiding the conventional thermal treatment required for the solubilization of the gelator, by in situ, simultaneous, synthesis and gelation. The gels prepared by in situ and conventional heating-cooling protocols could present important differences relevant for potential practical applications of these materials. The gelator was synthesized by reaction of succinic anhydride and a diamine derived from L-valine, affording two new amide bonds. The molecular gels were studied by IR, NMR, electron microscopy, X-ray diffraction and DSC. The results indicate that different polymorphic fibrillar networks are formed depending on the gel preparation method, highlighting how the properties of molecular gels can be tuned in this way. Significant differences between thermal and in situ gels were found in properties such as thermal stability, thixotropic behavior or release of an entrapped dye. In situ synthesis-gelation has also been shown to provide gels in media such as oleic acid which cannot be jellified by conventional heating-cooling procedures. Copyright © 2013 Elsevier Inc. All rights reserved.

In situ gel-to-crystal transition and synthesis of metal nanoparticles obtained by fluorination of a cyclic β-aminoalcohol gelator.

PubMed

Xu, Yang; Kang, Chuanqing; Chen, Yu; Bian, Zheng; Qiu, Xuepeng; Gao, Lianxun; Meng, Qingxin

2012-12-21

A new fluorinated version of a cyclic β-aminoalcohol gelator derived from 1,2,3,4-tetrahydroisoquinoline is presented. The gelator is able to gel various nonprotic solvents through OH⋅⋅⋅N hydrogen bonds and additional CH⋅⋅⋅F interactions due to the introduction of fluorine. A bimolecular lamellar structure is formed in the gel phase, which partly preserves the pattern of molecular organization in the single crystal. The racemate of the chiral gelator shows lower gelation ability than its enantiomer because of a higher tendency to form microcrystals, as shown by X-ray diffraction analysis. The influence of fluorination on the self-assembly of the gelator and the properties of the gel was investigated in comparison to the original fluorine-free gel system. The introduction of fluorine brings two new features. The first is good recognition of o-xylene by the gelator, which induces an in situ transition from gels of o-xylene and of an o-xylene/toluene mixture to identical single crystals with unique tubular architecture. The second is the enhanced stability of the toluene gel towards ions, including quaternary ammonium salts, which enables the preparation of a stable toluene gel in the presence of chloroaurate or chloroplatinate. The gel system can be used as a template for the synthesis of spherical gold nanoparticles with a diameter of 5 to 9 nm and wormlike platinum nanostructures with a diameter of 2 to 3 nm and a length of 5 to 12 nm. This is the first example of a synthesis of platinum nanoparticles in an organogel medium. Therefore, the appropriate introduction of a fluorine atom and corresponding nonbonding interactions into a known gelator to tune the properties and functions of a gel is a simple and effective tactic for design of a gel system with specific targets. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of storage and drying temperature on the gelation behavior and structural characteristics of sericin.

PubMed

Jo, Yoon Nam; Park, Byung-Dae; Um, In Chul

2015-11-01

Owing to unique properties, including the wound healing effect, sericin gel and films have attracted significant attention in the biomedical and cosmetic fields. The structural characteristics and properties of sericin gels and films are especially important owing to their effect on the performance of sericin in biomedical and cosmetic applications. In the present study, the effect of temperature on the gelation behavior, gel disruption, and sol-gel transition of sericin was examined using rheometry. In addition, the effect of the drying temperature on the structural characteristics of the sericin film was determined via Fourier transform infrared (FTIR) spectroscopy. The strength of the sericin gel increased and the gelation process was prolonged with decreasing storage temperatures. FTIR and differential scanning calorimetry (DSC) results also revealed that the crystallinity and the thermal decomposition temperature of the sericin film increased with decreasing drying temperature. The sericin gels were disrupted at a storage time of 40min when they were stored at temperatures higher than 50°C, and the corresponding gel strength decreased with increasing temperature. Furthermore, the thermo-reversible nature of gel-sol transition of sericin was confirmed by rheological and FTIR measurements. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecular interactions in high conductive gel electrolytes based on low molecular weight gelator.

PubMed

Bielejewski, Michał; Łapiński, Andrzej; Demchuk, Oleg

2017-03-15

Organic ionic gel (OIG) electrolytes, also known as gel electrolytes or ionogels are one example of modern functional materials with the potential to use in wide range of electrochemical applications. The functionality of OIGs arises from the thermally reversible solidification of electrolytes or ionic liquids and their superior ionic conductivity. To understand and to predict the properties of these systems it is important to get the knowledge about the interactions on molecular level between the solid gelator matrix and the electrolyte solution. This paper reports the spectroscopic studies (FT-IR, UV-Vis and Raman) of the gel electrolyte based on low molecular weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside and solution of quaternary ammonium salt, tetramethylammonium bromide. The solidification process was based on sol-gel technique. Below characteristic temperature, defined as gel to sol phase transition temperature, T gs , the samples were solid-like and showed high conductivity values of the same order as observed for pure liquid electrolytes. The investigations were performed for a OIGs in a wide range of molar concentrations of the electrolyte solution. Copyright © 2016 Elsevier Inc. All rights reserved.

Aggregation and Gelation of Aromatic Polyamides with Parallel and Anti-parallel Alignment of Molecular Dipole Along the Backbone

NASA Astrophysics Data System (ADS)

Zhu, Dan; Shang, Jing; Ye, Xiaodong; Shen, Jian

2016-12-01

The understanding of macromolecular structures and interactions is important but difficult, due to the facts that a macromolecules are of versatile conformations and aggregate states, which vary with environmental conditions and histories. In this work two polyamides with parallel or anti-parallel dipoles along the linear backbone, named as ABAB (parallel) and AABB (anti-parallel) have been studied. By using a combination of methods, the phase behaviors of the polymers during the aggregate and gelation, i.e., the forming or dissociation processes of nuclei and fibril, cluster of fibrils, and cluster-cluster aggregation have been revealed. Such abundant phase behaviors are dominated by the inter-chain interactions, including dispersion, polarity and hydrogen bonding, and correlatd with the solubility parameters of solvents, the temperature, and the polymer concentration. The results of X-ray diffraction and fast-mode dielectric relaxation indicate that AABB possesses more rigid conformation than ABAB, and because of that AABB aggregates are of long fibers while ABAB is of hairy fibril clusters, the gelation concentration in toluene is 1 w/v% for AABB, lower than the 3 w/v% for ABAB.

A Capped Dipeptide Which Simultaneously Exhibits Gelation and Crystallization Behavior.

PubMed

Martin, Adam D; Wojciechowski, Jonathan P; Bhadbhade, Mohan M; Thordarson, Pall

2016-03-08

Short peptides capped at their N-terminus are often highly efficient gelators, yet notoriously difficult to crystallize. This is due to strong unidirectional interactions within fibers, resulting in structure propagation only along one direction. Here, we synthesize the N-capped dipeptide, benzimidazole-diphenylalanine, which forms both hydrogels and single crystals. Even more remarkably, we show using atomic force microscopy the coexistence of these two distinct phases. We then use powder X-ray diffraction to investigate whether the single crystal structure can be extrapolated to the molecular arrangement within the hydrogel. The results suggest parallel β-sheet arrangement as the dominant structural motif, challenging existing models for gelation of short peptides, and providing new directions for the future rational design of short peptide gelators.

Sol-gel transition behavior of aqueous peptide-amphiphile (C16-W3K) solutions: effects of alkyl-tail length, mechanical shear, temperature, and salt

NASA Astrophysics Data System (ADS)

Yamamoto, Masashi; Otsuka, Takahiro; Orimo, Yoshinori; Maeda, Tomoki; Hotta, Atsushi

Peptide amphiphiles (PA) possess nanoscale micelle structures and excellent biocompatibility. In aqueous PA solution, PA molecules can self-assemble through various configurations into spherical and wormlike micelles, which can occasionally form hydrogels. C16-W3K is one of the unique PA, whose micelle configurations can transfer from spherical to wormlike structures in its aqueous solution over time, while the wormlike micelles could also lead to gelation. In our recent research, the effects of the length of the hydrophobic alkyl tail and other external factors of C16-W3K on the gelation behavior of the C16-W3K solution have been discussed. It has been revealed that longer alkyl-tails could facilitate the gelation of the C16-W3K solution, and that the external stimuli, such as mechanical shear and heat, could promote faster gelation of the C16-W3K solution. It was also found that salt could adjust the pH of the C16-W3K solution, having profound influence on the gelation behavior of the C16-W3K solution. In fact, the gelation of the C16-W3K with a higher storage modulus could be obtained from relatively acidic solutions, while the gelation of the C16-W3K solution was firmly suppressed in highly basic solutions. This work was supported by a Grant-in-Aid for Scientific Research (A) (No. 15H02298 to A.H.) and a Grant-in-Aid for Research Activity Start-up (No.15H06586 to T.M.) from JSPS: KAKENHI.

Mechano-switchable, luminescent gels derived from salts of a long-chained, fatty-acid gelator.

PubMed

Zhang, Mohan; Weiss, Richard G

2016-07-27

Stimulus-responsive molecular gel systems, based on metal salts of a luminescent gelator, 9,10-dioxooctadecanoic acid (DODA), are reported. These salts are structurally the simplest metallo-gelators of which we are aware that exhibit controllable mechano-responsive and luminescent properties. Aggregation is more favored by the metal salts than for DODA itself. However, gelation ability differs dramatically depending on the metal ion: whereas the salts with zinc(ii) and calcium(ii) are inefficient gelators, those with nickel(ii) and copper(ii) can gelate various aromatic liquids, alkanes, and long-chained alcohols. Unlike the DODA gels, no aggregation-induced shift in the positions of the emission spectra of the metal salts could be observed as the sols were transformed to their gel phases. Gels of both nickel(ii) and copper(ii) salts in benzonitrile are among the few known examples with crystalline networks and exhibiting thixotropic behavior. However, there are significant differences in their abilities to recover the initial viscoelastic properties. Structural data for the solid and gel states lead us to conclude that differences among the gelating abilities can be attributed principally to the specific nature of interactions of the salts at their head groups. They appear to control the mechanical and emissive properties of the gels as well as whether the initial aggregation of the salts in the sol phases will support the growth of 1D objects that are capable of maintaining strong contacts, leading to 3D networks and gel formation. Overall, the results provide a facile strategy for the design of luminescent materials with controllable mechano-responsiveness by modifying the metal ions within fibrillar assemblies.

Granular gel support-enabled extrusion of three-dimensional alginate and cellular structures.

PubMed

Jin, Yifei; Compaan, Ashley; Bhattacharjee, Tapomoy; Huang, Yong

2016-06-03

Freeform fabrication of soft structures has been of great interest in recent years. In particular, it is viewed as a critical step toward the grand vision of organ printing--the on-demand design and fabrication of three-dimensional (3D) human organ constructs for implantation and regenerative medicine. The objective of this study is to develop a novel granular gel support material-enabled, two-step gelation-based 'printing-then-gelation' approach to fabricate 3D alginate structures using filament extrusion. Specifically, a granular Carbopol microgel bath holds the ungelled alginate structure being extruded, avoiding the instantaneous gelation of each printed layer as well as resultant surface tension-induced nozzle clogging. Since Carbopol microgels react with multivalent cations, which are needed for alginate crosslinking, gelatin is introduced as a sacrificial material to make an alginate and gelatin bioink for extrusion, which gels thermally (step-one gelation) to initially stabilize the printed structure for removal from Carbopol. Then gelatin is melted and diffused away while alginate is ionically crosslinked in a 37 °C calcium chloride bath (step-two gelation), resulting in an alginate structure. The proposed 'printing-then-gelation' approach works for alginate structure fabrication, and it is also applicable for the printing of cellular constructs and other similar homogeneous soft structures using a two-step or even multi-step approach. The main conclusions are: (1) 0.8% (w/v) Carbopol bath with a neutral pH value may be most suitable for soft structure printing; (2) it is most effective to use a 0.9% (w/v) NaCl solution to facilitate the removal of residual Carbopol; and (3) alginate structures fabricated using the proposed approach demonstrate better mechanical properties than those fabricated using the conventional 'gelation-while-printing' approach.

Thermal properties of the gel made by low molecular weight gelator 1,2-O-(1-ethylpropylidene)-alpha-D-glucofuranose with toluene and molecular dynamics of solvent.

PubMed

Tritt-Goc, Jadwiga; Bielejewski, Michał; Luboradzki, Roman; Lapiński, Andrzej

2008-01-15

The studies of the gel-to-sol phase transition by the Raman, FT-IR, and 1H NMR methods of the gel made by low molecular weight organogelator 1,2-O-(1-ethylpropylidene)-alpha-D-glucofuranose with toluene as the solvent are reported. The FT-IR spectra revealed the existence of a hydrogen bond network formed by gelator molecules in the crystalline and gel phase. In both phases, the network formation is dominated by the gelator self-interaction. Upon gelation, only one stretching band of infrared absorption modes nualpha, assigned to the O(6)H hydroxyl protons of gelator, is shifted by Deltaupsilonalpha = 25 cm-1, which indicates the involvement of this proton in the interaction with the solvent molecules. The phase transition measurements performed as a function of gelator concentration allowed the calculation of the energy correlated with the transition from gel to solution phase. The obtained value of 72 kJ/mol is the largest one reported up until now for monosaccharide-based gels. The analysis of the temperature measurements of the toluene 1H NMR spectra provides evidence for a different chemical environment of toluene molecules in the gel. The toluene spin-lattice relaxation in bulk and gel indicate that the viscosity is most likely the main factor that influences the dynamics of toluene.

Light driven mesoscale assembly of a coordination polymeric gelator into flowers and stars with distinct properties† †Electronic supplementary information (ESI) available: Text, figures, and tables depicting different synthetic procedures, detailed experimental procedures, characterisation data including FT-IR, microscopic analyses, TGA, EDAX and SAED analyses, pore size distribution. See DOI: 10.1039/c5sc02233a Click here for additional data file.

PubMed Central

Mukhopadhyay, Rahul Dev; Praveen, Vakayil K.; Hazra, Arpan; Maji, Tapas Kumar

2015-01-01

Control over the self-assembly process of porous organic–inorganic hybrids often leads to unprecedented polymorphism and properties. Herein we demonstrate how light can be a powerful tool to intervene in the kinetically controlled mesoscale self-assembly of a coordination polymeric gelator. Ultraviolet light induced coordination modulation via photoisomerisation of an azobenzene based dicarboxylate linker followed by aggregation mediated crystal growth resulted in two distinct morphological forms (flowers and stars), which show subtle differences in their physical properties. PMID:28757961

Supramolecular gelation of a polymeric prodrug for its encapsulation and sustained release.

PubMed

Ma, Dong; Zhang, Li-Ming

2011-09-12

A polymeric prodrug, PEGylated indomethacin (MPEG-indo), was prepared and then used to interact with α-cyclodextrin (α-CD) in their aqueous mixed system. This process could lead to the formation of supramolecular hydrogel under mild conditions and simultaneous encapsulation of MPEG-indo in the hydrogel matrix. For the formed supramolecular hydrogel, its gelation kinetics, mechanical strength, shear-thinning behavior and thixotropic response were investigated with respect to the effects of MPEG-indo and α-CD amounts by dynamic and steady rheological tests. Meanwhile, the possibility of using this hydrogel matrix as injectable drug delivery system was also explored. By in vitro release and cell viability tests, it was found that the encapsulated MPEG-indo could exhibit a controlled and sustained release behavior as well as maintain its biological activity.

Interactions between tea catechins and casein micelles and their impact on renneting functionality.

PubMed

Haratifar, Sanaz; Corredig, Milena

2014-01-15

Many studies have shown that tea catechins bind to milk proteins. This research focused on the association of tea polyphenols with casein micelles, and the consequences of the interactions on the renneting behaviour of skim milk. It was hypothesized that epigallocatechin-gallate (EGCG), the main catechin present in green tea, forms complexes with the casein micelles and that the association modifies the processing functionality of casein micelles. The binding of EGCG to casein micelles was quantified using HPLC. The formation of catechin-casein micelles complexes affected the rennet induced gelation of milk, and the effect was concentration dependent. Both the primary as well as the secondary stage of gelation were affected. These experiments clearly identify the need for a better understanding of the effect of tea polyphenols on the processing functionality of casein micelles, before milk products can be used as an appropriate platform for delivery of bioactive compounds. Copyright © 2013 Elsevier Ltd. All rights reserved.

Self-assembling electroactive hydrogels for flexible display technology

NASA Astrophysics Data System (ADS)

Jones, Scott L.; Hou Wong, Kok; Thordarson, Pall; Ladouceur, François

2010-12-01

We have assessed the potential of self-assembling hydrogels for use in conformal displays. The self-assembling process can be used to alter the transparency of the material to all visible light due to scattering by fibres. The reversible transition is shown to be of low energy by differential scanning calorimetry. For use in technology it is imperative that this transition is controlled electrically. We have thus synthesized novel self-assembling hydrogelator molecules which contain an electroactive group. The well-known redox couple of anthraquinone/anthrahydroquinone has been used as the hydrophobic component for a series of small molecule gelators. They are further functionalized with peptide combinations of L-phenylalanine and glycine to provide the hydrophilic group to complete 'head-tail' models of self-assembling gels. The gelation and electroactive characteristics of the series were assessed. Cyclic voltammetry shows the reversible redox cycle to be only superficially altered by functionalization. Additionally, spectroelectrochemical measurements show a reversible transparency and colour change induced by the redox process.

Encapsulation of biomaterials in porous glass-like matrices prepared via an aqueous colloidal sol-gel process

DOEpatents

Liu, Dean-Mo; Chen, I-Wei

2001-01-01

The present invention provides a process for the encapsulation of biologically important proteins into transparent, porous silica matrices by an alcohol-free, aqueous, colloidal sol-gel process, and to the biological materials encapsulated thereby. The process is exemplified by studies involving encapsulated cytochrome c, catalase, myoglobin, and hemoglobin, although non-proteinaceous biomaterials, such as active DNA or RNA fragments, cells or even tissues, may also be encapsulated in accordance with the present methods. Conformation, and hence activity of the biomaterial, is successfully retained after encapsulation as demonstrated by optical characterization of the molecules, even after long-term storage. The retained conformation of the biomaterial is strongly correlated to both the rate of gelation and the subsequent drying speed of the encapsulatng matrix. Moreover, in accordance with this process, gelation is accelerated by the use of a higher colloidal solid concentration and a lower synthesis pH than conventional methods, thereby enhancing structural stability and retained conformation of the biomaterials. Thus, the invention also provides a remarkable improvement in retaining the biological activity of the encapsulated biomaterial, as compared with those involved in conventional alkoxide-based processes. It further provides new methods for the quantitative and qualitative detection of test substances that are reactive to, or catalyzed by, the active, encapsulated biological materials.

Tuning of multiple luminescence outputs and white-light emission from a single gelator molecule through an ESIPT coupled AIEE process.

PubMed

Maity, Arunava; Ali, Firoj; Agarwalla, Hridesh; Anothumakkool, Bihag; Das, Amitava

2015-02-07

A unique example of an ESIPT coupled AIEE process, associated with a single molecule (1), is utilized for generating multiple luminescent colors (blue-green-white-yellow). The J-aggregated state of 1 forms a luminescent gel in THF and this luminescent property is retained even in the solid state.

The self-crosslinking smart hyaluronic acid hydrogels as injectable three-dimensional scaffolds for cells culture.

PubMed

Bian, Shaoquan; He, Mengmeng; Sui, Junhui; Cai, Hanxu; Sun, Yong; Liang, Jie; Fan, Yujiang; Zhang, Xingdong

2016-04-01

Although the disulfide bond crosslinked hyaluronic acid hydrogels have been reported by many research groups, the major researches were focused on effectively forming hydrogels. However, few researchers paid attention to the potential significance of controlling the hydrogel formation and degradation, improving biocompatibility, reducing the toxicity of exogenous and providing convenience to the clinical operations later on. In this research, the novel controllable self-crosslinking smart hydrogels with in-situ gelation property was prepared by a single component, the thiolated hyaluronic acid derivative (HA-SH), and applied as a three-dimensional scaffold to mimic native extracellular matrix (ECM) for the culture of fibroblasts cells (L929) and chondrocytes. A series of HA-SH hydrogels were prepared depending on different degrees of thiol substitution (ranging from 10 to 60%) and molecule weights of HA (0.1, 0.3 and 1.0 MDa). The gelation time, swelling property and smart degradation behavior of HA-SH hydrogel were evaluated. The results showed that the gelation and degradation time of hydrogels could be controlled by adjusting the component of HA-SH polymers. The storage modulus of HA-SH hydrogels obtained by dynamic modulus analysis (DMA) could be up to 44.6 kPa. In addition, HA-SH hydrogels were investigated as a three-dimensional scaffold for the culture of fibroblasts cells (L929) and chondrocytes cells in vitro and as an injectable hydrogel for delivering chondrocytes cells in vivo. These results illustrated that HA-SH hydrogels with controllable gelation process, intelligent degradation behavior, excellent biocompatibility and convenient operational characteristics supplied potential clinical application capacity for tissue engineering and regenerative medicine. Copyright © 2016 Elsevier B.V. All rights reserved.

Microfluidic production of single micrometer-sized hydrogel beads utilizing droplet dissolution in a polar solvent

PubMed Central

Sugaya, Sari; Yamada, Masumi; Hori, Ayaka; Seki, Minoru

2013-01-01

In this study, a microfluidic process is proposed for preparing monodisperse micrometer-sized hydrogel beads. This process utilizes non-equilibrium aqueous droplets formed in a polar organic solvent. The water-in-oil droplets of the hydrogel precursor rapidly shrunk owing to the dissolution of water molecules into the continuous phase. The shrunken and condensed droplets were then gelled, resulting in the formation of hydrogel microbeads with sizes significantly smaller than the initial droplet size. This study employed methyl acetate as the polar organic solvent, which can dissolve water at 8%. Two types of monodisperse hydrogel beads—Ca-alginate and chitosan—with sizes of 6–10 μm (coefficient of variation < 6%) were successfully produced. In addition, we obtained hydrogel beads with non-spherical morphologies by controlling the degree of droplet shrinkage at the time of gelation and by adjusting the concentration of the gelation agent. Furthermore, the encapsulation and concentration of DNA molecules within the hydrogel beads were demonstrated. The process presented in this study has great potential to produce small and highly concentrated hydrogel beads that are difficult to obtain by using conventional microfluidic processes. PMID:24396529

Microfluidic production of single micrometer-sized hydrogel beads utilizing droplet dissolution in a polar solvent.

PubMed

Sugaya, Sari; Yamada, Masumi; Hori, Ayaka; Seki, Minoru

2013-01-01

In this study, a microfluidic process is proposed for preparing monodisperse micrometer-sized hydrogel beads. This process utilizes non-equilibrium aqueous droplets formed in a polar organic solvent. The water-in-oil droplets of the hydrogel precursor rapidly shrunk owing to the dissolution of water molecules into the continuous phase. The shrunken and condensed droplets were then gelled, resulting in the formation of hydrogel microbeads with sizes significantly smaller than the initial droplet size. This study employed methyl acetate as the polar organic solvent, which can dissolve water at 8%. Two types of monodisperse hydrogel beads-Ca-alginate and chitosan-with sizes of 6-10 μm (coefficient of variation < 6%) were successfully produced. In addition, we obtained hydrogel beads with non-spherical morphologies by controlling the degree of droplet shrinkage at the time of gelation and by adjusting the concentration of the gelation agent. Furthermore, the encapsulation and concentration of DNA molecules within the hydrogel beads were demonstrated. The process presented in this study has great potential to produce small and highly concentrated hydrogel beads that are difficult to obtain by using conventional microfluidic processes.

An Internal Gelation Method for Forming Multilayer Microspheres and Product Thereof.

DTIC Science & Technology

1995-12-26

lyophilization bottle and 18 plunged into liquid nitrogen for 10 min before pumping down in the 19 freeze drying unit. For samples where trehalose was present...the 20 supernatant was replaced with a trehalose solution at a final 21 concentration of 50 mM. In cases where glycerol was used for 22...interesting to note that the addition of trehalose , a synthetic 24 sugar, to the supernatant prior to lyophilization has a protective 25 effect on

Coprocessed nuclear fuels containing (U, Pu) values as oxides, carbides or carbonitrides

DOEpatents

Lloyd, M.H.

1981-01-09

Method for direct coprocessing of nuclear fuels derived from a product stream of fuels reprocessing facility containing uranium, plutonium, and fission product values comprising nitrate stabilization of said stream vacuum concentration to remove water and nitrates, neutralization to form an acid deficient feed solution for the internal gelation mode of sol-gel technology, green spherule formation, recovery and treatment for loading into a fuel element by vibra packed or pellet formation technologies.

Coprocessed nuclear fuels containing (U, Pu) values as oxides, carbides or carbonitrides

DOEpatents

Lloyd, Milton H.

1983-01-01

Method for direct coprocessing of nuclear fuels derived from a product stream of a fuels reprocessing facility containing uranium, plutonium, and fission product values comprising nitrate stabilization of said stream vacuum concentration to remove water and nitrates, neutralization to form an acid deficient feed solution for the internal gelation mode of sol-gel technology, green spherule formation, recovery and treatment for loading into a fuel element by vibra packed or pellet formation technologies.

Precipitation and ultimate pH effect on chemical and gelation properties of protein prepared by isoelectric solubilization/precipitation process from pale, soft, exudative (PSE)-like chicken breast meat1.

PubMed

Zhao, X; Xing, T; Chen, X; Han, M-Y; Li, X; Xu, X-L; Zhou, G-H

2017-05-01

Pale, soft, exudative (PSE)-like chicken breast is considered deteriorated raw material in the poultry meat industry that has inferior processing ability. The chemical and gelation properties of PSE-like chicken breast meat paste were studied. These pastes were prepared by the pH adjustment method and protein isolation using the isoelectric solubilization/precipitation (ISP) process from PSE-like chicken meat. The ISP-isolated samples were solubilized at pH 11.0 and recovered at pH 5.5 and 6.2. The ultimate pH of the ISP-isolated protein and meat paste was adjusted to 6.2 and 7.0. The ultimate pH in this article referred to the final pH of the extracted protein and meat paste. Higher reactive sulfhydryl content and surface hydrophobicity were found in the precipitation at pH 6.2 than at pH 5.5. However, various ultimate pH values showed no significant influence on the surface hydrophobicity. The hardness of gel, as measured by textural profile analysis, was improved using 6.2 as the precipitation pH compared with pH 5.5. The viscoelastic modulus (G΄) of gel pastes prior to the thermal gelation was higher with ISP treatment. However, lower G΄ was seen after thermal gelation compared with the control. Dynamic rheological measurement demonstrated a different gel-forming mechanism for protein precipitated at pH values of 5.5 and 6.2 compared with the meat paste. The cooking loss showed that the recovered protein failed to form a gel with good water-retention capacity unless the ultimate pH was adjusted to 7.0. Gels made from protein extracted by the ISP method had higher yellowness and lower redness values, probably due to protein denaturation. Precipitation at pH 6.2 formed a harder gel with lower water-retention ability than that at pH 5.5, and this result was possibly due to higher surface hydrophobicity and S-S bridge formation. Overall, network characteristics of ISP-treated protein gels were strongly dependent on precipitation pH and ultimate pH. © 2016 Poultry Science Association Inc.

Thermosensitive and mucoadhesive in situ gel based on poloxamer as new carrier for rectal administration of nimesulide.

PubMed

Yuan, Yuan; Cui, Ying; Zhang, Li; Zhu, Hui-Ping; Guo, Yi-Sha; Zhong, Bo; Hu, Xia; Zhang, Ling; Wang, Xiao-Hui; Chen, Li

2012-07-01

Poloxamer 407 has excellent thermo-sensitive gelling properties. Nevertheless, these gels possess inadequate poor bioadhesiveness and high permeability to water, which limited its' application as a thermoresponsive matrix. The main aim of the present investigation was to develop thermosensitive and mucoadhesive rectal in situ gel of nimesulide (NM) by using mucoadhesive polymers such as sodium alginate (Alg-Na) and HPMC. These gels were prepared by addition of mucoadhesive polymers (0.5%) to the formulations of thermosensitive gelling solution containing poloxamer 407 (18%) and nimesulide (2.0%). Polyethylene glycol (PEG) was used to modify gelation temperature and drug release properties. The gelation temperature and drug release rate of the prepared in situ gels were evaluated. Gelation temperature was significantly increased with incorporation of nimesulide (2.0%) in the poloxamer solution, while the addition of the mucoadhesive polymers played a reverse role on gelation temperature. The addition of PEG polymers increased the gelation temperature and the drug release rate. Among the formulations examined, the poloxamer 407/nimesulide/sodium alginate/PEG 4000 (18/2.0/0.5/1.2%) exhibited the appropriate gelation temperature, acceptable drug release rate and rectal retention at the administration site. Furthermore, the micrographic results showed that in situ gel, given at the dose of 20mg/kg, was safe for no mucosa irritation. In addition, it resulted in significantly higher initial serum concentrations, C(max) and AUC of NM compared to the solid suppository. Copyright © 2012 Elsevier B.V. All rights reserved.

Influence of pre-cooking protein paste gelation conditions and post-cooking gel storage conditions on gel texture.

PubMed

Paker, Ilgin; Matak, Kristen E

2016-01-15

Gelation conditions affect the setting of myofibrillar fish protein gels. Therefore the impact of widely applied pre-cooking gelation time/temperature strategies and post-cooking period on the texture and color of final protein gels was determined. Four pre-cooking gelation strategies (no setting time, 30 min at 25 °C, 1 h at 40 °C or 24 h at 4 °C) were applied to protein pastes (fish protein concentrate and standard functional additives). After cooking, texture and color were analyzed either directly or after 24 h at 4 °C on gels adjusted to 25 °C. No-set gels were harder, gummier and chewier (P < 0.05) when analyzed immediately after cooling; however, gel chewiness, cohesiveness and firmness indicated by Kramer force benefited from 24 h at 4 °C gel setting when stored post-cooking. Gel-setting conditions had a greater (P < 0.05) effect on texture when directly analyzed and most changes occurred in no-set gels. There were significant (P < 0.05) changes between directly analyzed and post-cooking stored gels in texture and color, depending on the pre-cooking gelation strategy. Pre-cooking gelation conditions will affect final protein gel texture and color, with gel stability benefiting from a gel-setting period. However, post-cooking storage may have a greater impact on final gels, with textural attributes becoming more consistent between all samples. © 2015 Society of Chemical Industry.

Supra-dendron Gelator Based on Azobenzene-Cyclodextrin Host-Guest Interactions: Photoswitched Optical and Chiroptical Reversibility.

PubMed

Xie, Fan; Ouyang, Guanghui; Qin, Long; Liu, Minghua

2016-12-12

A novel amphiphilic dendron (AZOC 8 GAc) with three l-glutamic acid units and an azobenzene moiety covalently linked by an alkyl spacer has been designed. The compound formed hydrogels with water at very low concentration and self-assembled into chiral-twist structures. The gel showed a reversible macroscopic volume phase transition in response to pH variations and photo-irradiation. During the photo-triggered changes, although the gel showed complete reversibility in its optical absorptions, only an incomplete chiroptical property change was achieved. On the other hand, the dendron could form a 1:1 inclusion complex through a host-guest interaction with α-cyclodextrin (α-CD), designated as supra-dendron gelator AZOC 8 GAc/α-CD. The supra-dendron showed similar gelation behavior to that of AZOC 8 GAc, but with enhanced photoisomerization-transition efficiency and chiroptical switching capacity, which was completely reversible in terms of both optical and chiroptical performances. The self-assembly of the supra-dendron is a hierarchical or multi-supramolecular self-assembling process. This work has clearly illustrated that the hierarchical and multi-supramolecular self-assembling system endows the supramolecular nanostructures or materials with superior reversible optical and chiroptical switching. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

In Situ Gelation-Induced Death of Cancer Cells Based on Proteinosomes.

PubMed

Zhou, Yuting; Song, Jianmin; Wang, Lei; Xue, Xuting; Liu, Xiaoman; Xie, Hui; Huang, Xin

2017-08-14

Hydrogels are an excellent type of material that can be utilized as a platform for cell culture. However, when a bulky hydrogel forms on the inside of cancer cells, the result would be different. In this study, we demonstrate a method for in situ gelation inside cancer cells that can efficiently induce cell death. Glutathione-responsive proteinosomes with good biocompatibility were prepared as carriers for sodium alginate to be endocytosed by cancer cells, where the chelation between sodium alginate and free calcium ions in the culture medium occurs during the diffusion process. The uptake of the hydrogel-loaded proteinosomes into the cancer cells, and then the triggered release of hydrogel with concomitant aggregation, was well-confirmed by monitoring the change of the Young's modulus of the cells based on AFM force measurements. Accordingly, when a large amount of hydrogel formed in cells, the cell viability would be inhibited by ∼90% by MTT assay at a concentration of 5.0 μM of hydrogel-loaded proteinosomes after 48 h incubation, which clearly proves the feasibility of the demonstrated method for killing cancer cells. Although more details regarding the mechanism of cell death should be conducted in the near future, such a demonstrated method of in situ gelation inside cells provides another choice for killing cancer cells.

Method for preparing hydrous zirconium oxide gels and spherules

DOEpatents

Collins, Jack L.

2003-08-05

Methods for preparing hydrous zirconium oxide spherules, hydrous zirconium oxide gels such as gel slabs, films, capillary and electrophoresis gels, zirconium monohydrogen phosphate spherules, hydrous zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite sorbent, zirconium monohydrogen phosphate spherules having suspendable particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, zirconium oxide spherules having suspendable particles homogeneously embedded within to form a composite, hydrous zirconium oxide fiber materials, zirconium oxide fiber materials, hydrous zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, zirconium oxide fiber materials having suspendable particles homogeneously embedded within to form a composite and spherules of barium zirconate. The hydrous zirconium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process are useful as inorganic ion exchangers, catalysts, getters and ceramics.

The effect of ionotropic gelation residence time on alginate cross-linking and properties.

PubMed

Patel, Mitulkumar A; AbouGhaly, Mohamed H H; Schryer-Praga, Jacqueline V; Chadwick, Keith

2017-01-02

The ability to engineer biocompatible polymers with controllable properties is highly desirable. One such approach is to cross-link carbohydrate polymers using ionotropic gelation (IG). Previous studies have investigated the effect of curing time on alginate cross-linking. Herein, we discuss a novel study detailing the effect of IG residence time (IGRT) on the cross-linking of alginate with calcium ions (Ca 2+ ) along with water migration (syneresis) and their subsequent impact on the pharmaceutical properties of alginate particles. IGRT was shown to have a significant effect on particle size, porosity, density, mechanical strength and swelling of calcium alginate particles as well as drug release mechanism. Furthermore, we describe a novel application of electron dispersive spectroscopy (EDS), in conjunction with Fourier Transform- infra red (FT-IR) spectroscopy, to analyze and monitor the changes in Ca 2+ concentration during cross-linking. A simple procedure to determine the concentration and distribution of the surface and internal Ca 2+ involved in alginate cross-linking was successfully developed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Core-shell hydrogel beads with extracellular matrix for tumor spheroid formation.

PubMed

Yu, L; Grist, S M; Nasseri, S S; Cheng, E; Hwang, Y-C E; Ni, C; Cheung, K C

2015-03-01

Creating multicellular tumor spheroids is critical for characterizing anticancer treatments since they may provide a better model of the tumor than conventional monolayer culture. Moreover, tumor cell interaction with the extracellular matrix can determine cell organization and behavior. In this work, a microfluidic system was used to form cell-laden core-shell beads which incorporate elements of the extracellular matrix and support the formation of multicellular spheroids. The bead core (comprising a mixture of alginate, collagen, and reconstituted basement membrane, with gelation by temperature control) and shell (comprising alginate hydrogel, with gelation by ionic crosslinking) were simultaneously formed through flow focusing using a cooled flow path into the microfluidic chip. During droplet gelation, the alginate acts as a fast-gelling shell which aids in preventing droplet coalescence and in maintaining spherical droplet geometry during the slower gelation of the collagen and reconstituted basement membrane components as the beads warm up. After droplet gelation, the encapsulated MCF-7 cells proliferated to form uniform spheroids when the beads contained all three components: alginate, collagen, and reconstituted basement membrane. The dose-dependent response of the MCF-7 cell tumor spheroids to two anticancer drugs, docetaxel and tamoxifen, was compared to conventional monolayer culture.

Self-Assembly and Drug Release Capacities of Organogels via Some Amide Compounds with Aromatic Substituent Headgroups

PubMed Central

Zhang, Lexin; Jiao, Tifeng; Ma, Kai; Xing, Ruirui; Liu, Yamei; Xiao, Yong; Zhou, Jingxin; Zhang, Qingrui; Peng, Qiuming

2016-01-01

In this work, some amide compounds with different aromatic substituent headgroups were synthesized and their gelation self-assembly behaviors in 22 solvents were characterized as new gelators. The obtained results indicated that the size of aromatic substituent headgroups in molecular skeletons in gelators showed crucial effect in the gel formation and self-assembly behavior of all compounds in the solvents used. Larger aromatic headgroups in molecular structures in the synthesized gelator molecules are helpful to form various gel nanostructures. Morphological investigations showed that the gelator molecules can self-assembly and stack into various organized aggregates with solvent change, such as wrinkle, belt, rod, and lamella-like structures. Spectral characterizations suggested that there existed various weak interactions including π-π stacking, hydrogen bonding, and hydrophobic forces due to aromatic substituent headgroups and alkyl substituent chains in molecular structures. In addition, the drug release capacities experiments demonstrated that the drug release rate in present obtained gels can be tuned by adjusting the concentrations of dye. The present work would open up enormous insight to design and investigate new kind of soft materials with designed molecular structures and tunable drug release performance. PMID:28773663

Morphology of drying blood pools

NASA Astrophysics Data System (ADS)

Laan, Nick; Smith, Fiona; Nicloux, Celine; Brutin, David; D-Blood project Collaboration

2016-11-01

Often blood pools are found on crime scenes providing information concerning the events and sequence of events that took place on the scene. However, there is a lack of knowledge concerning the drying dynamics of blood pools. This study focuses on the drying process of blood pools to determine what relevant information can be obtained for the forensic application. We recorded the drying process of blood pools with a camera and measured the weight. We found that the drying process can be separated into five different: coagulation, gelation, rim desiccation, centre desiccation, and final desiccation. Moreover, we found that the weight of the blood pool diminishes similarly and in a reproducible way for blood pools created in various conditions. In addition, we verify that the size of the blood pools is directly related to its volume and the wettability of the surface. Our study clearly shows that blood pools dry in a reproducible fashion. This preliminary work highlights the difficult task that represents blood pool analysis in forensic investigations, and how internal and external parameters influence its dynamics. We conclude that understanding the drying process dynamics would be advancement in timeline reconstitution of events. ANR funded project: D-Blood Project.

Insights into the mechanical properties of a silicone oil gel with a 'latent' gelator, 1-octadecylamine, and CO(2) as an 'activator'.

PubMed

Carretti, Emiliano; George, Mathew; Weiss, Richard G

2010-10-15

A detailed study of the rheological properties of silicone oil gels, made from a low-molecular-mass organic gelator, a combination of 1-octadecylamine (a latent gelator) and carbon dioxide (an 'activating' molecule), is reported. Information gleaned from the mechanical measurements is used to characterize the gel networks and how they respond to temperature and strain. It is shown, for example, that very precise measurements of the gel-to-sol transitions can be obtained from plots of viscosity versus temperature.

Preparation and luminescence properties of organogel doped with Eu(TTA)3phen complex

NASA Astrophysics Data System (ADS)

Cocca, M.; Di Lorenzo, M. L.; Avella, M.; Gentile, G.; Aubouy, L.; Della Pirreira, M.; Gutiérrez-Tauste, D.; Kennedy, M.; Doran, J.; Norton, B.

2012-07-01

In this contribution we report the preparation and the luminescence property of Eu(TTA)3phen complex doped toluene gels. Gels were prepared by using either a low molecular weight gelator, 12-hydroxystearic acid (HSA), or a macromolecular gelator, syndiotactic polymethylmethacrylate (s-PMMA). The gelation properties and their reversible behavior from solid-like to liquid systems have been investigated. In addition, photophysical investigations, as well as morphology, thermal properties and ageing behavior of the gels were analyzed as a function of composition of the gels.

The physiological and pathological biophysics of phase separation and gelation of RNA binding proteins in amyotrophic lateral sclerosis and fronto-temporal lobar degeneration.

PubMed

St George-Hyslop, Peter; Lin, Julie Qiaojin; Miyashita, Akinori; Phillips, Emma C; Qamar, Seema; Randle, Suzanne J; Wang, GuoZhen

2018-04-30

Many RNA binding proteins, including FUS, contain moderately repetitive, low complexity, intrinsically disordered domains. These sequence motifs have recently been found to underpin reversible liquid: liquid phase separation and gelation of these proteins, permitting them to reversibly transition from a monodispersed state to liquid droplet- or hydrogel-like states. This function allows the proteins to serve as scaffolds for the formation of reversible membraneless intracellular organelles such as nucleoli, stress granules and neuronal transport granules. Using FUS as an example, this review examines the biophysics of this physiological process, and reports on how mutations and changes in post-translational state alter phase behaviour, and lead to neurodegenerative diseases such as amyotrophic lateral sclerosis and frontotemporal lobar degeneration. Copyright © 2018. Published by Elsevier B.V.

Surfaces wettability and morphology modulation in a fluorene derivative self-assembly system

NASA Astrophysics Data System (ADS)

Cao, Xinhua; Gao, Aiping; Zhao, Na; Yuan, Fangyuan; Liu, Chenxi; Li, Ruru

2016-04-01

A new organogelator based on fluorene derivative (gelator 1) was designed and synthesized. Organogels could be obtained via the self-assembly of the derivative in acetone, toluene, ethyl acetate, hexane, DMSO and petroleum ether. The self-assembly process was thoroughly characterized using field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), UV-vis, FT-IR and the contact angle. Surfaces with different morphologies and wetting properties were formed via the self-assembly of gelator 1 in the six different solvents. Interestingly, a superhydrophobic surface with a contact angle of 150° was obtained from organogel 1 in DMSO and exhibited the lotus-effect. The sliding angle necessary for a water droplet to move on the glass was only 15°. Hydrogen bonding and van der Waals forces were attributed as the main driving forces for gel formation.

Drop spreading and gelation of thermoresponsive polymers.

PubMed

de Ruiter, R; Royon, L; Snoeijer, J H; Brunet, P

2018-04-25

Spreading and solidification of liquid droplets are elementary processes of relevance for additive manufacturing. Here we investigate the effect of heat transfer on spreading of a thermoresponsive solution (Pluronic F127) that undergoes a sol-gel transition above a critical temperature Tm. By controlling the concentration of Pluronic F127 we systematically vary Tm, while also imposing a broad range of temperatures of the solid and the liquid. We subsequently monitor the spreading dynamics over several orders of magnitude in time and determine when solidification stops the spreading. It is found that the main parameter is the difference between the substrate temperature and Tm, pointing to a local mechanism for arrest near the contact line. Unexpectedly, the spreading is also found to stop below the gelation temperature, which we attribute to a local enhancement in polymer concentration due to evaporation near the contact line.

Oil core microcapsules by inverse gelation technique.

PubMed

Martins, Evandro; Renard, Denis; Davy, Joëlle; Marquis, Mélanie; Poncelet, Denis

2015-01-01

A promising technique for oil encapsulation in Ca-alginate capsules by inverse gelation was proposed by Abang et al. This method consists of emulsifying calcium chloride solution in oil and then adding it dropwise in an alginate solution to produce Ca-alginate capsules. Spherical capsules with diameters around 3 mm were produced by this technique, however the production of smaller capsules was not demonstrated. The objective of this study is to propose a new method of oil encapsulation in a Ca-alginate membrane by inverse gelation. The optimisation of the method leads to microcapsules with diameters around 500 μm. In a search of microcapsules with improved diffusion characteristics, the size reduction is an essential factor to broaden the applications in food, cosmetics and pharmaceuticals areas. This work contributes to a better understanding of the inverse gelation technique and allows the production of microcapsules with a well-defined shell-core structure.

The effect of polymer composition on the gelation behavior of PLGA-g-PEG biodegradable thermoreversible gels.

PubMed

Tarasevich, B J; Gutowska, A; Li, X S; Jeong, B-M

2009-04-01

Graft copolymers consisting of a poly(D,L-lactic acid-co-glycolic acid) backbone grafted with polyethylene glycol side chains were synthesized and formed thermoreversible gels in aqueous solutions that exhibited solution behavior at low temperature and sol-to-gel transitions at higher temperature. The composition of the polymer and relative amounts of polylactic acid, glycolic acid, and ethylene glycol were varied by controlling the precursor concentrations and reaction temperature. The gelation temperature could be systematically tailored from 15 to 34 degrees C by increasing the concentration of polyethylene glycol in the graft copolymer. The gelation temperature also depended on the polymer molecular weight and concentration. This work has importance for the development of water soluble gels with tailored compositions and gelation temperatures for use in tissue engineering and as injectable depots for drug delivery. Copyright 2008 Wiley Periodicals, Inc.

Rapid Room-Temperature Gelation of Crude Oils by a Wetted Powder Gelator.

PubMed

Ren, Changliang; Shen, Jie; Chen, Feng; Zeng, Huaqiang

2017-03-27

Phase-selective organogelators (PSOGs) not only exhibit ability to phase-selectively congeal oil from oily water but also allow easy separation of gelled oil from the body of water. However, all hitherto reported PSOGs either necessitate carrier solvents for their dissolution or suffer from an extremely slow action in gelling oil in the powder form. A previously unexplored generally applicable wetting strategy is now described to dramatically enhance, by up to two orders of magnitude, gelling speed of the resultant wet but non-sticky gelator in the powder form in crude oils of widely ranging viscosities. Such unprecedented rapid gelling speeds enable rapid gelation of six types of (un)weathered crude oils within minutes at room temperature, making PSOGs one step closer to their eventual practical uses as one of important oil spill control technologies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic control over supramolecular gel formation

NASA Astrophysics Data System (ADS)

Boekhoven, Job; Poolman, Jos M.; Maity, Chandan; Li, Feng; van der Mee, Lars; Minkenberg, Christophe B.; Mendes, Eduardo; van Esch, Jan H.; Eelkema, Rienk

2013-05-01

Low-molecular-weight gels show great potential for application in fields ranging from the petrochemical industry to healthcare and tissue engineering. These supramolecular gels are often metastable materials, which implies that their properties are, at least partially, kinetically controlled. Here we show how the mechanical properties and structure of these materials can be controlled directly by catalytic action. We show how in situ catalysis of the formation of gelator molecules can be used to accelerate the formation of supramolecular hydrogels, which drastically enhances their resulting mechanical properties. Using acid or nucleophilic aniline catalysis, it is possible to make supramolecular hydrogels with tunable gel-strength in a matter of minutes, under ambient conditions, starting from simple soluble building blocks. By changing the rate of formation of the gelator molecules using a catalyst, the overall rate of gelation and the resulting gel morphology are affected, which provides access to metastable gel states with improved mechanical strength and appearance despite an identical gelator composition.

Self-Assembly of Molecular Threads into Reversible Gels

NASA Astrophysics Data System (ADS)

Sayar, Mehmet; Stupp, Samuel I.

2001-03-01

Reversible gels formed by low concentrations of molecular gelators that self-assemble into fibers with molecular width and extremely long length have been studied via Monte Carlo simulations. The gelators of interest have two kinds of interactions, one governs self-assembly into fibers and the other provides inter-fiber connectivity to drive the formation of a network. The off-lattice Monte Carlo simulation presented here is based on a point particle representation of gelators. In this model each particle can form only two strong bonds, that enable linear fiber formation, but a variable number of weak bonds which provide inter-fiber connectivity. The gel formation has been studied as a function of concentration of monomers, the strength of interactions, number of bonding sites per particle for weak interactions, and the stiffness of the fibers. The simulation results are compared with two experimental systems synthesized in our group in order to understand gelation mechanisms.

Selective removals of heavy metals (Pb(2+), Cu(2+), and Cd(2+)) from wastewater by gelation with alginate for effective metal recovery.

PubMed

Wang, Fei; Lu, Xingwen; Li, Xiao-yan

2016-05-05

A novel method that uses the aqueous sodium alginate solution for direct gelation with metal ions is developed for effective removal and recovery of heavy metals from industrial wastewater. The experimental study was conducted on Pb(2+), Cu(2+), and Cd(2+) as the model heavy metals. The results show that gels can be formed rapidly between the metals and alginate in less than 10 min and the gelation rates fit well with the pseudo second-order kinetic model. The optimum dosing ratio of alginate to the metal ions was found to be between 2:1 and 3:1 for removing Pb(2+) and around 4:1 for removing Cu(2+) and Cd(2+) from wastewater, and the metal removal efficiency by gelation increased as the solution pH increased. Alginate exhibited a higher gelation affinity toward Pb(2+) than Cu(2+) and Cd(2+), which allowed a selective removal of Pb(2+) from the wastewater in the presence of Cu(2+) and Cd(2+) ions. Chemical analysis of the gels suggests that the gelation mainly occurred between the metal ions and the -COO(-) and -OH groups on alginate. By simple calcination of the metal-laden gels at 700 °C for 1 h, the heavy metals can be well recovered as valuable resources. The metals obtained after the thermal treatment are in the form of PbO, CuO, and CdO nanopowders with crystal sizes of around 150, 50, and 100 nm, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

Photodimerisation of a coumarin-dipeptide gelator.

PubMed

Draper, Emily R; McDonald, Tom O; Adams, Dave J

2015-08-18

Here we report a coumarin based hydrogelator that can form bulk gels, or homogeneous thin gels via an electrochemical pH drop. The gel can then be strengthened by post-gelation photodimerisation of the coumarin groups by irradiating with UV light.

The Effect of Various Acids to the Gelation Process to the Silica Gel Characteristic Using Organic Silica

NASA Astrophysics Data System (ADS)

Rahman, NA; Widiyastuti, W.; Sigit, D.; Ajiza, M.; Sujana, W.

2018-01-01

Bagasse ash is solid waste of cane sugar industry which contain of silica more than 51%. Some previous study of silica gel from bagasse ash have been conducted often and been applied. This study concerns about the effect of various acid used in the process of gelation to the characteristic of silica gel produced. Then, this silica gel will be used as adsorbent. As that, the silica gel must fulfill the requirements of adsorbent, as have good pores characteristics, fit in mesoporous size so that adsorbent diffusion process is not disturbed. A fitted pores size of silica gel can be prepared by managing acid concentration used. The effect of acid, organic acid (tartaric acid) and inorganic acid (hydrochloric acid), is investigated in detail. The acid is added into sodium silicate solution in that the gel is formed, the pores structures can be investigated with BET, the crystal form is analyzed with XRD and the pore structure is analyzed visually with SEM. By managing the acid concentration added, it gets the effect of acid to the pore structure of silica gel. The bigger concentration is, the bigger the pore’s size of silica gel produced.

Influence of adding Sea Spaghetti seaweed and replacing the animal fat with olive oil or a konjac gel on pork meat batter gelation. Potential protein/alginate association.

PubMed

Fernández-Martín, F; López-López, I; Cofrades, S; Colmenero, F Jiménez

2009-10-01

Standard and modulated differential scanning calorimetry (DSC, MDSC) and dynamic rheological thermal analysis (DRTA) were used to in situ simulate the batter gelation process. Texture profile analysis (TPA) and conventional quality evaluations were applied to processed products. Sea Spaghetti seaweed addition was highly effective at reinforcing water/oil retention capacity, hardness and elastic modulus in all formulations. Olive oil substituting half pork fat yielded a presumably healthier product with slightly better characteristics than control. A konjac-starch mixed gel replacing 70% of pork fat produced a similar product to control but with nearly 10% more water. DSC revealed the currently unknown phenomenon that Sea Spaghetti alginates apparently prevented thermal denaturation of a considerable protein fraction. MDSC confirmed that this mainly concerned non-reversing effects, and displayed glass transition temperatures in the range of 55-65°C. DRTA and TPA indicated however much stronger alginate-type gels. It is tentatively postulated that salt-soluble proteins associate athermally with seaweed alginates on heating to constitute a separate phase in a thermal composite-gelling process.

Gelator-doped liquid-crystal phase grating with multistable and dynamic modes

NASA Astrophysics Data System (ADS)

Lin, Hui-Chi; Yang, Meng-Ru; Tsai, Sheng-Feng; Yan, Shih-Chiang

2014-01-01

We demonstrate a gelator-doped nematic liquid-crystal (LC) phase grating, which can be operated in both the multistable mode and the dynamic mode. Thermoreversible association and dissociation of the gelator molecules can vary and fix the multistable diffraction efficiencies of the gratings. A voltage (V) can also be applied to modulate dynamically the diffraction efficiencies of the grating, which behaves as a conventional LC grating. Experimental results show that the variations of the diffraction efficiencies in the multistable and dynamic modes are similar. The maximum diffraction efficiency is approximately 30% at V = 2 V.

Gelator-doped liquid-crystal phase grating with multistable and dynamic modes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Hui-Chi, E-mail: huichilin@nfu.edu.tw; Yang, Meng-Ru; Tsai, Sheng-Feng

2014-01-06

We demonstrate a gelator-doped nematic liquid-crystal (LC) phase grating, which can be operated in both the multistable mode and the dynamic mode. Thermoreversible association and dissociation of the gelator molecules can vary and fix the multistable diffraction efficiencies of the gratings. A voltage (V) can also be applied to modulate dynamically the diffraction efficiencies of the grating, which behaves as a conventional LC grating. Experimental results show that the variations of the diffraction efficiencies in the multistable and dynamic modes are similar. The maximum diffraction efficiency is approximately 30% at V = 2 V.

Insights into the mechanical properties of a silicone oil gel with a ‘latent’ gelator, 1-octadecylamine, and CO2 as an ‘activator’

PubMed Central

George, Mathew

2010-01-01

Summary A detailed study of the rheological properties of silicone oil gels, made from a low-molecular-mass organic gelator, a combination of 1-octadecylamine (a latent gelator) and carbon dioxide (an ‘activating’ molecule), is reported. Information gleaned from the mechanical measurements is used to characterize the gel networks and how they respond to temperature and strain. It is shown, for example, that very precise measurements of the gel-to-sol transitions can be obtained from plots of viscosity versus temperature. PMID:21085496

Sericin Promotes Fibroin Silk I Stabilization Across a Phase-Separation.

PubMed

Kwak, Hyo Won; Ju, Ji Eun; Shin, Munju; Holland, Chris; Lee, Ki Hoon

2017-08-14

Natural silk spinning offers several advantages over the synthetic fiber spinning, although the underlying mechanisms of this process are yet to be fully elucidated. Silkworm silks, specifically B. mori, comprise two main proteins: fibroin, which forms the fiber, and sericin, a coextruded coating that acts as a matrix in the resulting nonwoven composite cocoon. To date, most studies have focused on fibroin's self-assembly and gelation, with the influence of sericin during spinning receiving little to no attention. This study investigates sericin's effects on the self-assembly of fibroin via their natural phase-separation. Through changes in sample opacity, FTIR, and XRD, we report that increasing sericin concentration retards the time to gelation and β-sheet formation of fibroin, causing it to adopt a Silk I conformation. Such findings have important implications for both the natural silk spinning process and any future industrial applications, suggesting that sericin may be able to induce long-range conformational and stability control in silk fibroin, while being in a separate phase, a factor that would facilitate long-term storage or silk feedstocks.

Preparation of lignin-based carbon aerogels as biomaterials for nano-supercapacitor

NASA Astrophysics Data System (ADS)

Yang, Bong Suk; Kang, Kyu-Young; Jeong, Myung-Joon

2017-10-01

Kraft and organosolv lignins, generally produced in chemical pulping and bio-refinery processes of lignocellulosic biomass, were used to prepare lignin-based carbon aerogels for supercapacitors as raw materials. The difference between lignins and lignin-based aerogels were compared by analyzing physical and chemical properties, including molecular weight, polydispersity, and reactivity with formaldehyde. Also, density, shrinkage, Brunauer-Emmett-Teller (BET) surface area and scanning electron microscope (SEM) images of the lignin-based aerogel were investigated. Kraft lignin consisting of coniferyl alcohol (G) and p-coumaryl alcohol (H) increased the reactivity of formaldehyde, formed a hydrogel well (porosity > 0.45), and specific surface area higher than organosolv lignin. In the case of kraft lignin, there were irregular changes such as oxidation and condensation in the pulping process. However, reaction sites with aromatic rings in lignin impacted the production of aerogel and required a long gelation period. The molecular weight of lignin influences the gelation time in producing lignin-based aerogel, and lignin composition affects the BET surface area and pore structures of the lignin-based carbon aerogels.

Bis(PheOH) maleic acid amide-fumaric acid amide photoizomerization induces microsphere-to-gel fiber morphological transition: the photoinduced gelation system.

PubMed

Frkanec, Leo; Jokić, Milan; Makarević, Janja; Wolsperger, Kristina; Zinić, Mladen

2002-08-21

The photoinduced gelation system based on 1 (non-gelling) to 2 (gelling) molecular photoisomerization in water results by microspheres (1) to gel fibers (2) transformation at the supramolecular level.

PCS: The First Fluid Physics Payload on ISS

NASA Technical Reports Server (NTRS)

Doherty, M.; Sankaran, S.

2002-01-01

The Physics of Colloids in Space (PCS) experiment was accommodated within International Space Station (ISS) EXpedite the PRocessing of Experiments to Space Station (EXPRESS) Rack 2 and was remotely operated from early June 2001 until February 2002 from NASA Glenn Research Center's Telescience Support Center in Cleveland, Ohio and from a remote site at Harvard University in Cambridge, Massachusetts. PCS is an experiment conceived by Professor David A. Weitz of Harvard University (the Principal Investigator), focusing on the behavior of three different classes of colloid mixtures. The sophisticated light scattering instrumentation comprising PCS is capable of color imaging, and dynamic and static light scattering from 11 to 169 degrees, Bragg scattering over the range from 10 to 60 degrees, and laser light scattering at low angles from 0.3 to 6.0 degrees. The PCS instrumentation performed remarkably well, demonstrating a flexibility that enabled experiments to be performed that had not been envisioned prior to launch. While on-orbit, PCS accomplished 2400 hours of science operations, and was declared a resounding success. Each of the eight sample cells worked well and produced interesting and important results. Crystal nucleation and growth and the resulting structures of two binary colloidal crystal alloys were studied, with the long duration microgravity environment of the ISS facilitating extended studies on the growth and coarsening characteristics of the crystals. In another experiment run, the de-mixing of the colloid-polymer critical-point sample was studied as it phase-separates into two phases, one that resembles a gas and one that resembles a liquid. This process was studied over four decades of length scale, from 1 micron to 1 centimeter, behavior that cannot be observed in this sample on Earth because sedimentation would cause the colloids to fall to the bottom of the cell faster than the de-mixing process could occur. Similarly, the study of gelation and aging of another colloid-polymer sample, the colloid-polymer gel, also provided valuable information on gelation mechanisms, as did investigations on the extremely the low concentration silica and polystyrene fractal gel samples.

Processing and Characterization of Sol-Gel Cerium Oxide Microspheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

McClure, Zachary D.; Padilla Cintron, Cristina

Of interest to space exploration and power generation, Radioisotope Thermoelectric Generators (RTGs) can provide long-term power to remote electronic systems without the need for refueling or replacement. Plutonium-238 (Pu-238) remains one of the more promising materials for thermoelectric power generation due to its high power density, long half-life, and low gamma emissions. Traditional methods for processing Pu-238 include ball milling irregular precipitated powders before pressing and sintering into a dense pellet. The resulting submicron particulates of Pu-238 quickly accumulate and contaminate glove boxes. An alternative and dust-free method for Pu-238 processing is internal gelation via sol-gel techniques. Sol-gel methodology createsmore » monodisperse and uniform microspheres that can be packed and pressed into a pellet. For this study cerium oxide microspheres were produced as a surrogate to Pu-238. The similar electronic orbitals between cerium and plutonium make cerium an ideal choice for non-radioactive work. Before the microspheres can be sintered and pressed they must be washed to remove the processing oil and any unreacted substituents. An investigation was performed on the washing step to find an appropriate wash solution that reduced waste and flammable risk. Cerium oxide microspheres were processed, washed, and characterized to determine the effectiveness of the new wash solution.« less

Pyrene-based fluorescent ambidextrous gelators: scaffolds for mechanically robust SWNT-gel nanocomposites.

PubMed

Mandal, Deep; Kar, Tanmoy; Das, Prasanta Kumar

2014-01-27

With the rapid progress in the development of supramolecular soft materials, examples of low-molecular-weight gelators (LMWGs) with the ability to immobilise both water and organic solvents by the same structural scaffold are very limited. In this paper, we report the development of pyrene-containing peptide-based ambidextrous gelators (AGs) with the ability to efficiently gelate both organic and aqueous solvents. The organo- and hydrogelation efficiencies of these gelators are in the range 0.7-1.1% w/v in various organic solvents and 0.5-5% w/v in water at certain acidic pH values (pH 2.0-4.0). Moreover, for the first time, AGs have been utilised to prepare single-walled carbon-nanotube (SWNT)-included soft nanocomposites in both hydro- and organogel matrices. The influence of different non-covalent interactions such as hydrogen bonding, hydrophobic, π-π and van der Waals interactions in self-assembled gelation has been studied in detail by circular dichroism, FTIR, variable-temperature NMR, 2D NOESY and luminescence spectroscopy. Interestingly, the presence of the pyrene moiety in the structure rendered these AGs intrinsically fluorescent, which was quenched upon successful integration of the SWNTs within the gel. The prepared hydro- and organogels along with their SWNT-integrated nanocomposites are thermoreversible in nature. The supramolecular morphologies of the dried gels and SWNT-gel nanocomposites have been studied by transmission electron microscopy, fluorescence microscopy and polarising optical microscopy, which confirmed the presence of three-dimensional self-assembled fibrillar networks (SAFINs) as well as the integrated SWNTs. Importantly, rheological studies revealed that the inclusion of SWNTs within the ambidextrous gels improved the mechanical rigidity of the resulting soft nanocomposites up to 3.8-fold relative to the native gels. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gelled oil particles: a new approach to encapsulate a hydrophobic metallophthalocyanine.

PubMed

Siqueira-Moura, Marigilson P; Franceschi-Messant, Sophie; Blanzat, Muriel; Ré, Maria Inês; Perez, Emile; Rico-Lattes, Isabelle; Lattes, Armand; Tedesco, Antonio C

2013-07-01

Chloroaluminum phthalocyanine (ClAlPc) is a promising sensitizer molecule for photodynamic therapy, but its hydrophobicity makes it difficult to formulate. In this study, we have efficiently encapsulated ClAlPc into gelled soybean oil particles dispersed in water. 12-Hydroxystearic acid (HSA) and polyethyleneimine (PEI) were the gelling and stabilizing agents, respectively. The preparation process involved hot emulsification above the gelation temperature (Tgel), followed by cooling to room temperature, which gave a colloidal dispersion of gelled particles of oil in aqueous medium. The gelled particles containing ClAlPc had a medium diameter of 280 nm, homogeneous size distribution (polydispersity index ≈0.3) and large positive zeta potential (about +50 mV) and showed a spherical morphology. The gelled oil particle formulations exhibited good physical stability over a 6-month period. ClAlPc interfered with the HSA self-assembly only slightly, and decreased the gelation temperature to a small extent; however it did not affect gelation process of the oil droplets. The amounts of PEI and HSA employed during the preparation allowed us to control particle size and the dispersion stability, a phenomenon that results from complex electrostatic interactions between the positively charged PEI and the negatively charged HSA fibers present on the gelled particles surface. In summary, by using the right ClAlPc, HSA, and PEI proportions, we prepared very stable dispersions of gelled soybean oil particles with excellent ClAlPc encapsulation efficiency. The obtained colloidal formulation of gelled oil particles loaded with ClAlPc shall be very useful for photodynamic therapy protocols. Crown Copyright © 2013. Published by Elsevier Inc. All rights reserved.

Detecting De-gelation through Tissue Using Magnetically Modulated Optical Nanoprobes (MagMOONs)

PubMed Central

Nguyen, KhanhVan T.; Anker, Jeffrey N.

2014-01-01

Alginate gels are widely used for drug delivery and implanted devices. The rate at which these gels break down is important for controlling drug release. Since the de-gelation may be different in vivo, monitoring this process in situ is essential. However, it is challenging to monitor the gel through tissue due to optical scattering and tissue autofluorescence. Herein we describe a method to detect through tissue the chemically-induced changes in viscosity and de-gelation process of alginate gels using magnetically modulated optical nanoprobes (MagMOONs). The MagMOONs are fluorescent magnetic microspheres coated with a thin layer of opaque metal on one hemisphere. The metal layer prevents excitation and emission light from passing through one side of the MagMOONs, which creates orientation-dependent fluorescence intensity. The magnetic particles also align in an external magnetic field and give blinking signals when they rotate to follow an external modulated magnetic field. The blinking signals from these MagMOONs are distinguished from background autofluorescence and can be tracked on a single particle level in the absence of tissue, or for an ensemble average of particles blinking through tissue. When these MagMOONs are dispersed in calcium alginate gel, they become sensors for detecting gel degradation upon addition of either ammonium ion or alginate lyase. Our results show MagMOONs start blinking approximately 10 minutes after 2 mg/mL alginate lyase addition and this blinking is clearly detected even through up to 4 mm chicken breast. This approach can potentially be employed to detect bacterial biofilm formation on medical implants by sensing specific proteases that either activate a related function or regulate biofilm formation. It can also be applied to other biosensors and drug delivery systems based on enzyme-catalyzed breakdown of gel components. PMID:26273129

Detecting De-gelation through Tissue Using Magnetically Modulated Optical Nanoprobes (MagMOONs).

PubMed

Nguyen, KhanhVan T; Anker, Jeffrey N

2014-12-15

Alginate gels are widely used for drug delivery and implanted devices. The rate at which these gels break down is important for controlling drug release. Since the de-gelation may be different in vivo , monitoring this process in situ is essential. However, it is challenging to monitor the gel through tissue due to optical scattering and tissue autofluorescence. Herein we describe a method to detect through tissue the chemically-induced changes in viscosity and de-gelation process of alginate gels using magnetically modulated optical nanoprobes (MagMOONs). The MagMOONs are fluorescent magnetic microspheres coated with a thin layer of opaque metal on one hemisphere. The metal layer prevents excitation and emission light from passing through one side of the MagMOONs, which creates orientation-dependent fluorescence intensity. The magnetic particles also align in an external magnetic field and give blinking signals when they rotate to follow an external modulated magnetic field. The blinking signals from these MagMOONs are distinguished from background autofluorescence and can be tracked on a single particle level in the absence of tissue, or for an ensemble average of particles blinking through tissue. When these MagMOONs are dispersed in calcium alginate gel, they become sensors for detecting gel degradation upon addition of either ammonium ion or alginate lyase. Our results show MagMOONs start blinking approximately 10 minutes after 2 mg/mL alginate lyase addition and this blinking is clearly detected even through up to 4 mm chicken breast. This approach can potentially be employed to detect bacterial biofilm formation on medical implants by sensing specific proteases that either activate a related function or regulate biofilm formation. It can also be applied to other biosensors and drug delivery systems based on enzyme-catalyzed breakdown of gel components.

An Injectable Hydrogel Prepared Using a PEG/Vitamin E Copolymer Facilitating Aqueous-Driven Gelation.

PubMed

Zhang, Jianfeng; Muirhead, Ben; Dodd, Megan; Liu, Lina; Xu, Fei; Mangiacotte, Nicole; Hoare, Todd; Sheardown, Heather

2016-11-14

Hydrogels have been widely explored for biomedical applications, with injectable hydrogels being of particular interest for their ability to precisely deliver drugs and cells to targets. Although these hydrogels have demonstrated satisfactory properties in many cases, challenges still remain for commercialization. In this paper, we describe a simple injectable hydrogel based on poly(ethylene glycol) (PEG) and a vitamin E (Ve) methacrylate copolymer prepared via simple free radical polymerization and delivered in a solution of low molecular weight PEG and Ve as the solvent instead of water. The hydrogel formed immediately in an aqueous environment with a controllable gelation time. The driving force for gelation is attributed to the self-assembly of hydrophobic Ve residues upon exposure to water to form a physically cross-linked polymer network via polymer chain rearrangement and subsequent phase separation, a spontaneous process with water uptake. The hydrogels can be customized to give the desired water content, mechanical strength, and drug release kinetics simply by formulating the PEGMA-co-Ve polymer with an appropriate solvent mixture or by varying the molecular weight of the polymer. The hydrogels exhibited no significant cytotoxicity in vitro using fibroblasts and good tissue compatibility in the eye and when injected subcutaneously. These polymers thus have the potential to be used in a variety of applications where injection of a drug or cell containing depot would be desirable.

Insights into gelation kinetics and gel front migration in cation-induced polysaccharide hydrogels by viscoelastic and turbidity measurements: Effect of the nature of divalent cations.

PubMed

Huynh, Uyen T D; Chambin, Odile; du Poset, Aline Maire; Assifaoui, Ali

2018-06-15

Polysaccharide-based hydrogels were prepared by the diffusion of various divalent cations (X 2+ ) into the polygalacturonate (polyGal) solution through a dialysis membrane. The diffusion of various divalent cations (Mg 2+ , Ca 2+ , Zn 2+ and Ba 2+ ) was investigated. The polyGal gel growth was studied as a function of the initial cation concentration by both viscoelastic and turbidity measurements. We have demonstrated for the first time that the determination of the spatiotemporal variation of turbidity during the gelation process allowed to study the gel front migration. For Ca-polyGal, Zn-polyGal and Ba-polyGal, the gel front migration was characterized by the presence of a peak at the sol/gel interface. This peak was not observed in the case of Mg-polyGal where the gel was not formed. The apparent diffusion coefficient of the gel front (D app ) which was calculated from the evolution of this peak increased when the initial cation concentration was increased. Moreover, we have suggested a gelation mechanism based on the presence of a threshold molar ratio R* (=[X 2+ ]/[Galacturonic unit]) in which some point-like crosslinks are precursors of the formation of dimers and multimers inducing the contraction of the gel and thus the formation of the gel front. Copyright © 2018 Elsevier Ltd. All rights reserved.

Coiled-Coil Hydrogels. Effect of Grafted Copolymer Composition and Cyclization on Gelation

PubMed Central

Dušek, Karel; Dušková-Smrčková, Miroslava; Yang, Jiyuan; Kopeček, Jindřich

2009-01-01

A mean-field theoretical approach was developed to model gelation of solutions of hydrophilic polymers with grafted peptide motifs capable of forming associates of coiled-coil type. The model addresses the competition between associates engaged in branching and cyclization. It results in relative concentrations of intra- and intermolecular associates in dependence on associate strength and motif concentration. The cyclization probability is derived from the model of equivalent Gaussian chain and takes into account all possible paths connecting the interacting motifs. Examination of the association-dissociation equilibria, controlled by the equilibrium constant for association taken as input information, determines the fractions of inter- and intramolecularly associated motifs. The gelation model is based on the statistical theory of branching processes and in combination with the cyclization model predicts the critical concentration delimiting the regions of gelled and liquid states of the system. A comparison between predictions of the model and experimental data available for aqueous solutions of poly[N-(2-hydroxypropyl)methacrylamide] grafted with oppositely charged pentaheptad peptides, CCE and CCK, indicates that the association constant of grafted motifs by four orders of magnitude lower than that of free motifs. It is predicted that at the critical concentration of each motif of about 6×10−7 mol/cm3, about half of motifs in associated state is engaged in intramolecular bonds. PMID:20160932

Silk Hydrogels of Tunable Structure and Viscoelastic Properties Using Different Chronological Orders of Genipin and Physical Cross-Linking.

PubMed

Elliott, Winston H; Bonani, Walter; Maniglio, Devid; Motta, Antonella; Tan, Wei; Migliaresi, Claudio

2015-06-10

Catering the hydrogel manufacturing process toward defined viscoelastic properties for intended biomedical use is important to hydrogel scaffolding function and cell differentiation. Silk fibroin hydrogels may undergo "physical" cross-linking through β-sheet crystallization during high pressure carbon dioxide treatment, or covalent "chemical" cross-linking by genipin. We demonstrate here that time-dependent mechanical properties are tunable in silk fibroin hydrogels by altering the chronological order of genipin cross-linking with β-sheet formation. Genipin cross-linking before β-sheet formation affects gelation mechanics through increased molecular weight, affecting gel morphology, and decreasing stiffness response. Alternately, genipin cross-linking after gelation anchored amorphous regions of the protein chain, and increasing stiffness. These differences are highlighted and validated through large amplitude oscillatory strain near physiologic levels, after incorporation of material characterization at molecular and micron length scales.

Reversible sol-to-gel transformation of uracil gelators: specific colorimetric and fluorimetric sensor for fluoride ions.

PubMed

Xing, Ling-Bao; Yang, Bing; Wang, Xiao-Jun; Wang, Jiu-Ju; Chen, Bin; Wu, Qianhong; Peng, Hui-Xing; Zhang, Li-Ping; Tung, Chen-Ho; Wu, Li-Zhu

2013-03-05

A new type of anthracene organogelator based on uracil was obtained using organic aromatic solvents, cyclohexane, DMSO, ethanol, and ethyl acetate. It was further characterized by field-emission scanning electron microscopy and transmission electron microscopy. Specifically, the resulting organogels were demonstrated to be promising colorimetric and fluorescent sensors toward fluoride ions with high sensitivity and selectivity, accompanying the disruption of the gelators. Spectroscopic study and (1)H NMR titration experiment revealed that the deprotonation of the hydrogen atom on the N position of uracil moiety by fluoride ions is responsible for the recognition events, evidenced by immediate transformation from the sol phase to the gel state upon adding a small amount of a proton solvent, methanol. The process is reversible, with zero loss in sensing activity and sol-to-gel transformation ability even after five runs.

Effect of Hyaluronic Acid on the Self Assembling Behaviour of PEO-PPO Copolymers in Aqueous Solution

NASA Astrophysics Data System (ADS)

Mayol, L.; Borzacchiello, A.; Quaglia, F.; La Rotonda, M. I.; Ambrosio, L.

2008-07-01

The influence of hyaluronic acid (HA) on the self assembling properties of pluronic (PEO-PPO-PEO block copolymers) blends has been studied with the aim of engineering thermosensitive and mucoadhesive polymeric platforms for drug delivery. The gelation temperature (Tgel), viscoelastic properties and mucoadhesive force of the systems were investigated and optimised by means of rheological analyses. Pluronic micellar radius was evaluated by Photon Correlation Spectroscopy (PCS). The addition of Low Molecular Weight HA did not hamper the self assembling process of pluronics just delaying the gelation temperature of few Celsius degrees. Furthermore, HA presence led to a strong increase of the pluronics gel rheological properties. PCS results show, in formulations containing HA, aggregates with hydrodynamic diameters values much higher than those of pluronic micelles. Mucoadhesive experiments indicate the possibility of interactions between the pluronic/HA gel and mucus glycoproteins.

The study of the structural properties of very low viscosity sodium alginate by small-angle neutron scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Badita, C. R., E-mail: ramona@tandem.nipne.ro; University of Bucharest, Faculty of Physics, Atomiştilor 405, CP MG - 11, RO – 077125, Bucharest-Magurele; Aranghel, D., E-mail: daranghe@nipne.ro

2016-03-25

Sodium alginate is a linear polymer extract from brown algae and it is used in the biomedical, food, cosmetics and pharmaceutical industries as solution property modifiers and gelling agents. But despite the extensive studies of the alginate gelation process, still some fundamental questions remain unresolved. The fractal behavior of very low viscosity sodium alginate solutions and their influence on the critical gelation of alginate induced by Ca{sup 2+} ions were investigated using Small-Angle Neutron Scattering (SANS) measurements. SANS data are interpreted using both standard linear plots and the Beaucage model. The scattering intensity is dependent by alginate concentration and Ca{supmore » 2+} concentration. From a critical concentration of 1.0 % w/w our polymer swelled forming spherical structures with rough surfaces. Also the addition of the salt induces the collapse and the appearance of the aggregation and clusters formation.« less

The study of the structural properties of very low viscosity sodium alginate by small-angle neutron scattering

NASA Astrophysics Data System (ADS)

Badita, C. R.; Aranghel, D.; Radulescu, A.; Anitas, E. M.

2016-03-01

Sodium alginate is a linear polymer extract from brown algae and it is used in the biomedical, food, cosmetics and pharmaceutical industries as solution property modifiers and gelling agents. But despite the extensive studies of the alginate gelation process, still some fundamental questions remain unresolved. The fractal behavior of very low viscosity sodium alginate solutions and their influence on the critical gelation of alginate induced by Ca2+ ions were investigated using Small-Angle Neutron Scattering (SANS) measurements. SANS data are interpreted using both standard linear plots and the Beaucage model. The scattering intensity is dependent by alginate concentration and Ca2+ concentration. From a critical concentration of 1.0 % w/w our polymer swelled forming spherical structures with rough surfaces. Also the addition of the salt induces the collapse and the appearance of the aggregation and clusters formation.

Glycerophosphate-based chitosan thermosensitive hydrogels and their biomedical applications.

PubMed

Zhou, Hui Yun; Jiang, Ling Juan; Cao, Pei Pei; Li, Jun Bo; Chen, Xi Guang

2015-03-06

Chitosan is non-toxic, biocompatible and biodegradable polysaccharide composed of glucosamine and derived by deacetylation of chitin. Chitosan thermosensitive hydrogel has been developed to form a gel in situ, precluding the need for surgical implantation. In this review, the recent advances in chitosan thermosensitive hydrogels based on different glycerophosphate are summarized. The hydrogel is prepared with chitosan and β-glycerophosphate or αβ-glycerophosphate which is liquid at room temperature and transits into gel as temperature increases. The gelation mechanism may involve multiple interactions between chitosan, glycerophosphate, and water. The solution behavior, rheological and physicochemical properties, and gelation process of the hydrogel are affected not only by the molecule weight, deacetylation degree, and concentration of chitosan, but also by the kind and concentration of glycerophosphate. The properties and the three-dimensional networks of the hydrogel offer them wide applications in biomedical field including local drug delivery and tissue engineering. Copyright © 2014 Elsevier Ltd. All rights reserved.

Chemically programmed self-sorting of gelator networks.

PubMed

Morris, Kyle L; Chen, Lin; Raeburn, Jaclyn; Sellick, Owen R; Cotanda, Pepa; Paul, Alison; Griffiths, Peter C; King, Stephen M; O'Reilly, Rachel K; Serpell, Louise C; Adams, Dave J

2013-01-01

Controlling the order and spatial distribution of self-assembly in multicomponent supramolecular systems could underpin exciting new functional materials, but it is extremely challenging. When a solution of different components self-assembles, the molecules can either coassemble, or self-sort, where a preference for like-like intermolecular interactions results in coexisting, homomolecular assemblies. A challenge is to produce generic and controlled 'one-pot' fabrication methods to form separate ordered assemblies from 'cocktails' of two or more self-assembling species, which might have relatively similar molecular structures and chemistry. Self-sorting in supramolecular gel phases is hence rare. Here we report the first example of the pH-controlled self-sorting of gelators to form self-assembled networks in water. Uniquely, the order of assembly can be predefined. The assembly of each component is preprogrammed by the pK(a) of the gelator. This pH-programming method will enable higher level, complex structures to be formed that cannot be accessed by simple thermal gelation.

From helical supramolecular arrays to gel-forming networks: lattice restructuring and aggregation control in peptide-based sulfamides to integrate new functional attributes.

PubMed

Raghava, Saripalli V; Srivastava, Bhartendu K; Ramshad, Kalluruttimmal; Antharjanam, Sudhadevi; Varghese, Babu; Muraleedharan, Kannoth M

2018-03-28

While supramolecular organisation is central to both crystallization and gelation, the latter is more complex considering its dynamic nature and multifactorial dependence. This makes the rational design of gelators an extremely difficult task. In this report, the assembly preference of a group of peptide-based sulfamides was modulated by making them part of an acid-amine two-component system to drive the tendency from crystallization to gelation. Here, the peptide core directed the assembly while the long-chain amines, introduced through salt-bridges, promoted layering and anisotropic development of primary aggregates. This proved to be very successful, leading to gelation of a number of solvents. Apart from this, it was possible to fine-tune their aggregation using an amphiphilic polymer like F-127 as an additive to get honey-comb-like 3D molecular architectures. These gels also proved to be excellent matrices for entrapping silver nanoparticles with superior emissive properties.

Gelator-polysaccharide hybrid hydrogel for selective and controllable dye release.

PubMed

Li, Ping; Dou, Xiao-Qiu; Tang, Yi-Tian; Zhu, Shenmin; Gu, Jiajun; Feng, Chuan-Liang; Zhang, Di

2012-12-01

In this paper, 1,4-bi(phenylalanine-diglycol)-benzene (PDB) based Low-Molecular-Weight-Gelator (LMWG) hydrogels are modified using hydrophilic polysaccharide (sodium alginate). A set of techniques including Fourier transform infrared (FT-IR) spectroscopy, (1)H Nuclear Magnetic Resonance ((1)H NMR), X-ray powder diffraction (XRD), Ultraviolet-Visible (UV-Vis), and circular dichroism (CD) had confirmed a β-turn arrangement of PDB gelators and a semi-interpenetrating network (semi-IPN), which was formed through hydrogen bonds between LMWG fibers and polysaccharide chains. The evaluation of physicochemical properties of hydrogels indicates that gelator-polysaccharide hybrid hydrogels possess better mechanical and water retention properties than LMWG hydrogels. The release study of dyes (model drug) from both LMWG and hybrid hydrogels was carried out. Compared with PDB based hydrogels, hybrid hydrogels show a selective and controllable release property for certain dyes. The results suggest LMWG-polysaccharide hybrid gels may find potential applications as promising drug delivery vehicles for drug molecules. Copyright © 2012 Elsevier Inc. All rights reserved.

Organogels resulting from competing self-assembly units in the gelator: Structure, dynamics, and photophysical behavior of gels formed from cholesterol-stilbene and cholesterol-squaraine gelators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geiger, C.; Stanescu, M.; Chen, L.

1999-03-30

Organogels formed from novel organic gelators containing a cholesterol tethered to squaraine dyes or trans-stilbene derivatives have been studied from several different perspectives. The two types of molecules are active toward several organic liquids, gelling in some cases at w/w percentages as low as 0.1. While relatively robust, macroscopically dry gels are formed in several cases, studies with a variety of probes indicate that much of the solvent may exist in domains that are essentially liquid-like in terms of their microenvironment. The gels have been imaged by atomic force microscopy and conventional and fluorescence microscopy, monitoring both the gelator fluorescencemore » in the case of the stilbene-cholesterol gels and, the fluorescence of solutes dissolved in the solvent. Remarkably, findings show that several of the gels are composed of similarly appearing fibrous structures visible at the nano-, micro-, and macroscale.« less

Acid gelation properties of heated skim milk as a result of enzymatically induced changes in the micelle/serum distribution of the whey protein/kappa-casein aggregates.

PubMed

Guyomarc'h, Fanny; Renan, Marie; Chatriot, Marc; Gamerre, Valérie; Famelart, Marie-Hélène

2007-12-26

Changes in the acid gelation properties of skim milk as a result of variations in the micelle/serum distribution of the heat-induced whey protein/kappa-casein aggregates, induced by the combination of heat treatment and limited renneting, were investigated. No dramatic change in the zeta potential or the isoelectric point of the casein micelles was suggested, whether the aggregates were all attached to the casein micelle or not. Fluorescence intensity measurement using 8-anilino-1-naphthalenesulfonic acid (ANS) showed that the heat-induced aggregates were highly hydrophobic. Dynamic oscillation viscosimetry showed that acid gelation using glucono-delta-lactone (GDL) started at a higher pH value in prerenneted milk. However, no change in the gelation profile of skim milk could be related to the proportion of aggregates bound to the surface of the casein micelles. The results support the idea of an early interaction between the serum aggregates and the casein micelles on acidification.

Temporal Control of Gelation and Polymerization Fronts Driven by an Autocatalytic Enzyme Reaction.

PubMed

Jee, Elizabeth; Bánsági, Tamás; Taylor, Annette F; Pojman, John A

2016-02-05

Chemical systems that remain kinetically dormant until activated have numerous applications in materials science. Herein we present a method for the control of gelation that exploits an inbuilt switch: the increase in pH after an induction period in the urease-catalyzed hydrolysis of urea was used to trigger the base-catalyzed Michael addition of a water-soluble trithiol to a polyethylene glycol diacrylate. The time to gelation (minutes to hours) was either preset through the initial concentrations or the reaction was initiated locally by a base, thus resulting in polymerization fronts that converted the mixture from a liquid into a gel (ca. 0.1 mm min -1 ). The rate of hydrolytic degradation of the hydrogel depended on the initial concentrations, thus resulting in a gel lifetime of hours to months. In this way, temporal programming of gelation was possible under mild conditions by using the output of an autocatalytic enzyme reaction to drive both the polymerization and subsequent degradation of a hydrogel.

Multistable Phase-Retardation Plate Based on Gelator-Doped Liquid Crystals

NASA Astrophysics Data System (ADS)

Ying-Guey Fuh, Andy; Chiang, Jou-Ting; Chien, Yu-Shein; Chang, Chih-Juang; Lin, Hui-Chi

2012-07-01

This work demonstrates a multistable, large phase-retardation plate using gelator-doped liquid crystals (LCs). Multistability is achieved by forming a rubbery LC gel at room temperature. Experimentally, the phase retardation (PR) of an LC-gel film can be varied and fixed by the thermoreversible association and dissociation of the gelator molecules. The PR of the LC plate ranging from 0.3-3.7π can be electrically controllable within 10 V. Half-wave and quarter-wave LC plates were also produced at applied voltages of 3.5 and 6.3 V, respectively. Their properties were examined and found to be stable.

Multistable Phase-Retardation Plate Based on Gelator-Doped Liquid Crystals

NASA Astrophysics Data System (ADS)

Fuh, Andy Ying-Guey; Chiang, Jou-Ting; Chien, Yu-Shein; Chang, Chih-Juang; Lin, Hui-Chi

2012-07-01

This work demonstrates a multistable, large phase-retardation plate using gelator-doped liquid crystals (LCs). Multistability is achieved by forming a rubbery LC gel at room temperature. Experimentally, the phase retardation (PR) of an LC-gel film can be varied and fixed by the thermoreversible association and dissociation of the gelator molecules. The PR of the LC plate ranging from 0.3--3.7π can be electrically controllable within 10 V. Half-wave and quarter-wave LC plates were also produced at applied voltages of 3.5 and 6.3 V, respectively. Their properties were examined and found to be stable.

Morphology of molecular soy protein fractions in binary composite gels.

PubMed

Kasapis, Stefan; Tay, Sok Li

2009-08-04

We investigate the structural properties of gels of binary mixtures of the three major soy protein fractions: 11S, 7S, and 2S. Gels are formed at 25 degrees C in the presence of glucono-delta-lactone and studied using a combination of dynamic rheology and scanning electron microscopy. The theological data was then modeled using a blending-law approach that yields insights into the solvent distribution between the gelled protein fractions and first-order reaction kinetics that follow the gelation process of the single fractions and their mixtures. Gelled mixtures of 11S and 7S yielded enhanced network strength with increasing solid content; in these gels, 50% more solvent partitioned into the 11S phase as compared to that in the 7S phase. In contrast, the addition of small-molecular-weight counterpart 2S to either 11S or 7S results in a catastrophic drop in the values of the overall strength of the mixture. The unexpected phase behavior has been rationalized on the basis of the high water-holding capacity of 2S; 450% more solvent partitions preferentially into the 2S phase as compared to that in the 11S phase. As the concentration of 2S is increased relative to that of 11S or 7S, it becomes the dominant phase and entraps the polymeric segments of 11S (or 7S), thus preventing them from becoming the structural knots of the gel. In addition to the solvent distribution in the gel, the rates of gelation differ markedly between 11S and 2S (with the 11S rate of gelation being up to 2 orders of magnitude greater); a fixed 11S concentration, the rate of gelation decreases with increasing amounts of 2S, further confirming that the latter essentially becomes the dominant phase in the composite gel.

Ultrastructure Processing and Environmental Stability of Advanced Structural and Electronic Materials

DTIC Science & Technology

1992-08-31

NC r") Form 1473, JUN 86 Previous editions are obsolete SECURITY CLASSIFICATION OF THIS PACE I 18. Subject Terms (Continued) I analysis, aging , band...detail the several steps involved in the processing of sol-gel derived optical silicas: I 1) mixing, 2) casting, 3) gelation, 4) aging , 5) drying, 6...ultrastructurcs, such as for doping applications and laser-enhanced densification. The possible disadvantages discussed in this Chapter are inherent

Properties of bioadhesive ketoprofen liquid suppositories: preparation, determination of gelation temperature, viscosity studies and evaluation of mechanical properties using texture analyzer by 4 × 4 factorial design.

PubMed

Ozgüney, Işık; Kardhiqi, Anita

2014-12-01

Development and evaluation of thermosensitive and bioadhesive liquid suppositories containing ketoprofen (KP). This study was conducted to develope thermosensitive and bioadhesive liquid suppositories containing KP using poloxamer and different bioadhesive polymers and to investigate their gelation temperature, viscosity and mechanical properties. Bioadhesive liquid suppositories were prepared by the cold method using poloxamer 407 (P 407), Poloxamer 188 (P 188) and various amounts of different bioadhesive polymers. Their gelation temperatures, viscosity values and mechanical properties were determined using texture analyzer by 4 × 4 factorial design. It was seen that in presence of KP, gelation temperature of formulation P 407/P 188 (4/20%) significantly decreased from 64 to 37.1 °C. It is to be noted that addition of increasing concentrations of bioadhesive polymers lowered gelation temperature and its decrease was highest with addition of Carbopol 934 P (C). Results of texture profile analysis (TPA) showed that formulations containing C have significantly higher hardness and adhesiveness values than other bioadhesive formulations. According to TPA, gel structure of liquid suppository formulation F5, containing P 407/P 188/KP/C (4/20/2.5/0.8%), exhibited the greatest hardness, compressibilty, adhesiveness and besides greatest viscosity. According to mechanical properties and viscosity values, it was concluded that F5 could be a promising formulation.

Innovative formulation of nystatin particulate systems in toothpaste for candidiasis treatment.

PubMed

Pinto Reis, Catarina; Vasques Roque, Luís; Baptista, Marina; Rijo, Patrícia

2016-01-01

Oral candidiasis is a mycosis on the mucous membranes of the mouth but not limited to the mouth. Nystatin is one of the most frequently employed antifungal agents to treat infections and may be safely given orally as well as applied topically but its absorption through mucocutaneous membranes such as the gut and the skin is minimal. The purpose of this study is to enhance the effectiveness of nystatin using particulate system such as beads, micro- and nanoparticles of alginate incorporated into toothpaste. Those particulate systems of nystatin were prepared by extrusion/external gelation for beads and emulsification/internal gelation for micro- and nanoparticles and characterized. Small, anionic charged and monodispersed particles were successfully produced. The type of particulate system influenced all previous parameters, being microparticles the most suitable particulate system of nystatin showing the slowest release, the highest inhibitory effect of Candida albicans over a period of one year. Those results allowed the conclusion that alginate exhibits properties that enable the in vitro functionality of encapsulated nystatin and thus may provide the basis for new successful approaches for the treatment of oral antifungal infections such as oral candidiasis.

High-level waste program progress report, January 1, 1980-March 31, 1980

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1980-05-01

FUETAP concretes cured at 100/sup 0/C and 0.1 or 0.6 MPa had essentially the same physical properties as those cured at higher temperatures and pressures. Standard specimens containing high concentrations of /sup 244/Cm showed little gasification after 1 month. The large (23-cm ID) spray calciner has been completed and is operating satisfactorily. Construction was completed on a sphere-forming system capable of producing 100-g batches of Synroc spheres by internal gelation, and several runs were made. Preparations for the compatibilty tests are underway. (DLC)

Synthesis, Photophysical Characterization, and Gelation Studies of a Stilbene-Cholesterol Derivative

ERIC Educational Resources Information Center

Geiger, H. Christina; Geiger, David K.; Baldwin, Christine

2006-01-01

Organogels are low molar mass organic compounds with the ability to immobilize an incredible quantity of solvent and fibrous aggregation of these compounds formed by noncovalent interaction usually involves hydrogen bonding. For stilbene-cholesterol based gelators, the driving force for molecular aggregation are weak van der Waal interactions…

Site-specific protein immobilization in a microfluidic chip channel via an IEF-gelation process.

PubMed

Shi, Mianhong; Peng, Youyuan; Yu, Shaoning; Liu, Baohong; Kong, Jilie

2007-05-01

A novel strategy for site-specific protein immobilization via combining chip IEF with low-temperature sol-gel technology, called IEF-GEL here, in the channel of a modified poly(methyl methacrylate) (PMMA) microfluidic chip is proposed in this work. The IEF-GEL process involves firstly IEF for homogeneously dissolved protein in PBS containing alumina sol and carrier ampholyte with prearranged pH gradient, and then gelation locally for protein encapsulation. The process and feasibility of proposed IEF-GEL were investigated by EOF measurements, fluorescence microscopic photography, Raman spectrum and further demonstrated by glucose oxidase (GOx) reactors integrated with end-column electrochemical detection. Site-controllable immobilization of protein was realized in a 30 mm long microfluidic chip channel by the strategy to create a approximately 1.7 mm concentrated FITC-BSA band, which leads to great improvement of the elute peak shape, accomplished with remarkably increased sensitivity, approximately 20 times higher than that without IEF-GEL treatment to GOx reactors. The kinetic response of GOx after IEF-GEL treatment was also investigated. The proposed system holds the advantages of IEF and low-temperature sol-gel technologies, i.e. concentrating the protein to be focused and retaining the biological activity for the gel-embedded protein, thus realizes site-specific immobilization of low-concentration protein at nL volume level.

Chiroptical studies on supramolecular chirality of molecular aggregates.

PubMed

Sato, Hisako; Yajima, Tomoko; Yamagishi, Akihiko

2015-10-01

The attempts of applying chiroptical spectroscopy to supramolecular chirality are reviewed with a focus on vibrational circular dichroism (VCD). Examples were taken from gels, solids, and monolayers formed by low-molecular mass weight chiral gelators. Particular attention was paid to a group of gelators with perfluoroalkyl chains. The effects of the helical conformation of the perfluoroalkyl chains on the formation of chiral architectures are reported. It is described how the conformation of a chiral gelator was determined by comparing the experimental and theoretical VCD spectra together with a model proposed for the molecular aggregation in fibrils. The results demonstrate the potential utility of the chiroptical method in analyzing organized chiral aggregates. © 2015 Wiley Periodicals, Inc.

Novel low-molecular-weight-gelator-based microcapsules with controllable morphology and temperature responsiveness.

PubMed

Patel, Ashok R; Remijn, Caroline; Heussen, Patricia C M; den Adel, Ruud; Velikov, Krassimir P

2013-02-04

A new type of microcapsules with controllable morphology is presented. They are based on a low-molecular-weight gelator and can be switched from temperature-stable to temperature-responsive by simply modifying the preparation method. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral signs of TPPS co-assemblies with chiral gelators: role of molecular and supramolecular chirality.

PubMed

Wang, Qiuling; Zhang, Li; Yang, Dong; Li, Tiesheng; Liu, Minghua

2016-10-13

A dianionic tetrakis(4-sulfonatophenyl)porphyrin (TPPS) self-assembled into J-aggregates when it co-assembled with a chiral cationic amphiphile via supramolecular gelation. The chiral signs of TPPS J aggregates followed the supramolecular chirality of amphiphilic assemblies rather than the molecular chirality of the amphiphile.

NOTE: Measuring oxidative gelation of aqueous flour suspensions using the Rapid Visco Analyzer

USDA-ARS?s Scientific Manuscript database

The Rapid Visco Analyzer (RVA) was investigated as a tool to measure oxidative gelation capacity (OGC) of aqueous wheat-flour suspensions. One, club-wheat patent flour was used to determine optimal hydration time and 33 straight-grade flours (representing 12 hard and 31 soft varieties) were used to ...

Method of dispensing droplets to penetration-resistive mediums. [Patent application

DOEpatents

Fowler, V.L.; Ryon, A.D.; Haas, P.A.

1982-06-10

Uniform, monosized microspheroids are produced in a gelation medium characterized by a high resistance to surface penetration by reducing the effect of impact on entry of the droplets into the medium by contacting the droplet with a stream of medium and by introducing the resulting stream into a gelation column.

Chirality of the 1,4-phenylene-silica nanoribbons at the nano and angstrom levels

NASA Astrophysics Data System (ADS)

Li, Yi; Wang, Sibing; Xiao, Min; Wang, Mingliang; Huang, Zhibin; Li, Baozong; Yang, Yonggang

2013-01-01

We reported the preparation of chiral 1,4-phenylene-silicas, using a sol-gel transcription approach, by self-assembly using low-molecular-weight gelators as templates. The silicas exhibited chirality at both the nano and angstrom levels. However, the relation between the chirality at the nano level and that at the angstrom levels has not been well studied. In this study, chiral 1,4-phenylene-silica nanoribbons were prepared by the self-assemblies of three chiral cationic gelators derived from amino acids as templates. These samples were characterized using field-emission scanning electron microscopy, transmission electron microscopy, x-ray diffraction, and circular dichroism. The results indicated that the handedness of the nanoribbons and the stacking of the aromatic rings were controllable. Although the nanoribbons exhibited left-handedness at the nano level, the stacking of the aromatic rings could exhibit left- or right-handedness. The handedness of the nanoribbons at the nano level was controlled by the organic self-assembly of the gelator. However, the stacking of the aromatic rings seemed to be controlled by the gelator itself.

Temporal Control of Gelation and Polymerization Fronts Driven by an Autocatalytic Enzyme Reaction.

PubMed

Jee, Elizabeth; Bánsági, Tamás; Taylor, Annette F; Pojman, John A

2016-02-05

Chemical systems that remain kinetically dormant until activated have numerous applications in materials science. Herein we present a method for the control of gelation that exploits an inbuilt switch: the increase in pH after an induction period in the urease-catalyzed hydrolysis of urea was used to trigger the base-catalyzed Michael addition of a water-soluble trithiol to a polyethylene glycol diacrylate. The time to gelation (minutes to hours) was either preset through the initial concentrations or the reaction was initiated locally by a base, thus resulting in polymerization fronts that converted the mixture from a liquid into a gel (ca. 0.1 mm min(-1)). The rate of hydrolytic degradation of the hydrogel depended on the initial concentrations, thus resulting in a gel lifetime of hours to months. In this way, temporal programming of gelation was possible under mild conditions by using the output of an autocatalytic enzyme reaction to drive both the polymerization and subsequent degradation of a hydrogel. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Amino Acid Chirality and Ferrocene Conformation Guided Self-Assembly and Gelation of Ferrocene-Peptide Conjugates.

PubMed

Adhikari, Bimalendu; Singh, Charanpreet; Shah, Afzal; Lough, Alan J; Kraatz, Heinz-Bernhard

2015-08-03

The self-assembly and gelation behavior of a series of mono- and disubstituted ferrocene (Fc)-peptide conjugates as a function of ferrocene conformation and amino acid chirality are described. The results reveal that ferrocene-peptide conjugates self-assemble into organogels by controlling the conformation of the central ferrocene core, through inter- versus intramolecular hydrogen bonding in the attached peptide chain(s). The chirality controlled assembling studies showed that two monosubstituted Fc conjugates FcCO-LFLFLA-OMe and FcCO-LFLFDA-OMe form gels with nanofibrillar network structures, whereas the other two diastereomers FcCO-DFLFLA-OMe and FcCO-LFDFLA-OMe exclusively produced straight nanorods and non-interconnected small fibers, respectively. This suggests the potential tuning of gelation behavior and nanoscale morphology by altering the chirality of constituted amino acids. The current study confirms the profound effect of diastereomerism and no influence of enantiomers on gelation. Correspondingly, the diastereomeric and enantiomeric Fc[CO-FFA-OMe]2 were constructed for the study of chirality-organized structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Role of Solvent-Solute Interactions on The Behavior of Low Molecular Mass Organo-Gelators

NASA Astrophysics Data System (ADS)

Cavicchi, Kevin; Feng, Li

2012-02-01

Low molecular mass organo-gelators (LMOGs) are a class of small molecules that can self-assemble in organic solvents to form three-dimensional fibrillar networks. This has a profound effect on the viscoelastic properties of the solution causing physical gelation. These gels have uses in a range of industries including cosmetics, foodstuffs, plastics, petroleum and pharmaceuticals. A fundamental question in this field is: What makes a good LMOG? This talk will discuss the relationships between the viscoelastic properties and thermodynamic phase behavior of LMOG/solvent solutions. The regular solution model was used to fit the liquidus line and sol/gel transition temperature vs. concentration in different solvents to determine LMOG-solvent interaction parameters (χ = A/T). This parameter A was found to scale with the solubility parameter of the solvent, especially for non-polar solvents. This demonstrates that gelation is strongly linked to LMOG solubility and indicates that the bulk thermodynamic parameters of the LMOG (solubility parameter and melting temperature) are useful to predict the solution behavior of LMOGs.

Single-handed helical carbonaceous nanotubes prepared using a pair of cationic low molecular weight gelators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Huayan; Wang, Qing; Guo, Yongmin

Highlights: • 3-aminophenol-formaldeyde resins were prepared through a templating method. • A pair of cationic gelators have been used as the templates. • Single-handed helical carbonaceous nanotubes were obtained after carbonization. • The carbonaceous nanotubes showed optical activity. - Abstract: We design a facile route to obtain enantiopure carbonaceous nanostructures, which have potential application as chiral sensors, electromagnetic wave absorbers, and asymmetric catalysts. A pair of cationic low molecular weight gelators was synthesized, which were able to self-assemble into twisted nanoribbons in ethanol at a concentration of 20 g L{sup −1} at 25 °C. Single-handed helical 3-aminophenol-formaldehyde resin nanotubes withmore » optical activity were prepared using the self-assembly of the low molecular weight gelators as templates. After carbonization, single-handed helical carbonaceous nanotubes were obtained and characterized using circular dichroism, wide-angle X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The results indicate that the walls of the nanotubes are amorphous carbon. Moreover, the left- and right-handed helical nanotubes exhibit opposite optical activity.« less

Method for preparing hydrous titanium oxide spherules and other gel forms thereof

DOEpatents

Collins, J.L.

1998-10-13

The present invention are methods for preparing hydrous titanium oxide spherules, hydrous titanium oxide gels such as gel slabs, films, capillary and electrophoresis gels, titanium monohydrogen phosphate spherules, hydrous titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite sorbent, titanium monohydrogen phosphate spherules having suspendible particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, titanium oxide spherules in the form of anatase, brookite or rutile, titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite, hydrous titanium oxide fiber materials, titanium oxide fiber materials, hydrous titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite, titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite and spherules of barium titanate. These variations of hydrous titanium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process offer more useful forms of inorganic ion exchangers, catalysts, getters and ceramics. 6 figs.

Method for preparing hydrous titanium oxide spherules and other gel forms thereof

DOEpatents

Collins, Jack L.

1998-01-01

The present invention are methods for preparing hydrous titanium oxide spherules, hydrous titanium oxide gels such as gel slabs, films, capillary and electrophoresis gels, titanium monohydrogen phosphate spherules, hydrous titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite sorbent, titanium monohydrogen phosphate spherules having suspendible particles of at least one different sorbent homogeneously embedded within to form a composite sorbent having a desired crystallinity, titanium oxide spherules in the form of anatase, brookite or rutile, titanium oxide spherules having suspendible particles homogeneously embedded within to form a composite, hydrous titanium oxide fiber materials, titanium oxide fiber materials, hydrous titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite, titanium oxide fiber materials having suspendible particles homogeneously embedded within to form a composite and spherules of barium titanate. These variations of hydrous titanium oxide spherules and gel forms prepared by the gel-sphere, internal gelation process offer more useful forms of inorganic ion exchangers, catalysts, getters and ceramics.

Recovery and recycling of uranium from rejected coated particles for compact high temperature reactors

NASA Astrophysics Data System (ADS)

Pai, Rajesh V.; Mollick, P. K.; Kumar, Ashok; Banerjee, J.; Radhakrishna, J.; Chakravartty, J. K.

2016-05-01

UO2 microspheres prepared by internal gelation technique were coated with pyrolytic carbon and silicon carbide using CVD technique. The particles which were not meeting the specifications were rejected. The rejected/failed UO2 based coated particles prepared by CVD technique was used for oxidation and recovery and recycling. The oxidation behaviour of sintered UO2 microspheres coated with different layers of carbon and SiC was studied by thermal techniques to develop a method for recycling and recovery of uranium from the failed/rejected coated particles. It was observed that the complete removal of outer carbon from the spheres is difficult. The crushing of microspheres enabled easier accessibility of oxygen and oxidation of carbon and uranium at 800-1000 °C. With the optimized process of multiple crushing using die & plunger and sieving the broken coated layers, we could recycle around fifty percent of the UO2 microspheres which could be directly recoated. The rest of the particles were recycled using a wet recycling method.

Study on the rheological properties and volatile release of cold-set emulsion-filled protein gels.

PubMed

Mao, Like; Roos, Yrjö H; Miao, Song

2014-11-26

Emulsion-filled protein gels (EFP gels) were prepared through a cold-set gelation process, and they were used to deliver volatile compounds. An increase in the whey protein isolate (WPI) content from 4 to 6% w/w did not show significant effect on the gelation time, whereas an increase in the oil content from 5 to 20% w/w resulted in an earlier onset of gelation. Gels with a higher WPI content had a higher storage modulus and water-holding capacity (WHC), and they presented a higher force and strain at breaking, indicating that a more compact gel network was formed. An increase in the oil content contributed to gels with a higher storage modulus and force at breaking; however, this increase did not affect the WHC of the gels, and gels with a higher oil content became more brittle, resulting in a decreased strain at breaking. GC headspace analysis showed that volatiles released at lower rates and had lower air-gel partition coefficients in EFP gels than those in ungelled counterparts. Gels with a higher WPI content had lower release rates and partition coefficients of the volatiles. A change in the oil content significantly modified the partition of volatiles at equilibrium, but it produced a minor effect on the release rate of the volatiles. The findings indicated that EFP gels could be potentially used to modulate volatile release by varying the rheological properties of the gel.

A novel smart supramolecular organic gelator exhibiting dual-channel responsive sensing behaviours towards fluoride ion via gel-gel states.

PubMed

Mehdi, Hassan; Pang, Hongchang; Gong, Weitao; Dhinakaran, Manivannan Kalavathi; Wajahat, Ali; Kuang, Xiaojun; Ning, Guiling

2016-07-07

A novel smart supramolecular organic gelator G-16 containing anion and metal-coordination ability has been designed and synthesized. It shows excellent and robust gelation capability as a strong blue fluorescent supramolecular organic gel OG in DMF. Addition of Zn(2+) produced Zn(2+)-coordinated supramolecular metallogel OG-Zn. Organic gel OG and organometallic gel OG-Zn exhibited efficient and different sensing behaviors towards fluoride ion due to the variation in self-assembling nature. Supramolecular metallogel OG-Zn displayed specific selectivity for fluoride ion and formed OG-Zn-F with dramatic color change from blue to blue green in solution and gel to gel states. Furthermore after directly addition of fluoride into OG produced fluoride containing organic gel OG-F with drastically modulation in color from blue to greenish yellow fluorescence via strong aggregation-induced emission (AIE) property. A number of experiments were conducted such as FTIR, (1)H NMR, and UV/Vis spectroscopies, XRD, SEM and rheology. These results revealed that the driving forces involved in self-assembly of OG, OG-Zn, OG-Zn-F and OG-F were hydrogen bonding, metal coordination, π-π interactions, and van der Waal forces. In contrast to the most anion responsive gels, particularly fluoride ion responsive gels showed gel-sol state transition on stimulation by anions, the gel state of OG and OG-Zn did not show any gel-to-sol transition during the whole F(-) response process.

Structural and thermo-rheological analysis of solutions and gels of a β-lactoglobulin fraction isolated from bovine whey.

PubMed

Estévez, Natalia; Fuciños, Pablo; Bargiela, Verónica; Pastrana, Lorenzo; Tovar, Clara Asunción; Luisa Rúa, M

2016-05-01

A β-Lactoglobulin fraction (r-βLg) was isolated from milk whey hydrolysates produced with cardosins from Cynara cardunculus. The impact of the technological process on the r-βLg structure and how in turn this determined its heat-induced gelation was investigated. Results were analysed taking pure β-Lg (p-βLg) as control sample. The process induced changes in the r-βLg native conformation causing exposure of hydrophobic groups, lower thermal stability and also, shorter thermal treatments needed to give rise to non-native and aggregated species. At pH 3.2, r-βLg and p-βLg solutions exhibited two gelation steps, with the advantage that r-βLg protein may form stable gels at lower temperature than p-βLg. At pH 7.2, a specific thermo-viscoelastic stability to 73 °C was found, which corresponded to the gel point in both protein solutions. The difference was that while for p-βLg solution in sol state δ<45° (solid-like), however for r-βLg solution δ>45° (fluid-like). Copyright © 2015 Elsevier Ltd. All rights reserved.

From kinetic-structure analysis to engineering crystalline fiber networks in soft materials.

PubMed

Wang, Rong-Yao; Wang, Peng; Li, Jing-Liang; Yuan, Bing; Liu, Yu; Li, Li; Liu, Xiang-Yang

2013-03-07

Understanding the role of kinetics in fiber network microstructure formation is of considerable importance in engineering gel materials to achieve their optimized performances/functionalities. In this work, we present a new approach for kinetic-structure analysis for fibrous gel materials. In this method, kinetic data is acquired using a rheology technique and is analyzed in terms of an extended Dickinson model in which the scaling behaviors of dynamic rheological properties in the gelation process are taken into account. It enables us to extract the structural parameter, i.e. the fractal dimension, of a fibrous gel from the dynamic rheological measurement of the gelation process, and to establish the kinetic-structure relationship suitable for both dilute and concentrated gelling systems. In comparison to the fractal analysis method reported in a previous study, our method is advantageous due to its general validity for a wide range of fractal structures of fibrous gels, from a highly compact network of the spherulitic domains to an open fibrous network structure. With such a kinetic-structure analysis, we can gain a quantitative understanding of the role of kinetic control in engineering the microstructure of the fiber network in gel materials.

A novel method for the production of core-shell microparticles by inverse gelation optimized with artificial intelligent tools.

PubMed

Rodríguez-Dorado, Rosalia; Landín, Mariana; Altai, Ayça; Russo, Paola; Aquino, Rita P; Del Gaudio, Pasquale

2018-03-01

Numerous studies have been focused on hydrophobic compounds encapsulation as oils. In fact, oils can provide numerous health benefits as synergic ingredient combined with other hydrophobic active ingredients. However, stable microparticles for pharmaceutical purposes are difficult to achieve when commonly techniques are used. In this work, sunflower oil was encapsulated in calcium-alginate capsules by prilling technique in co-axial configuration. Core-shell beads were produced by inverse gelation directly at the nozzle using a w/o emulsion containing aqueous calcium chloride solution in sunflower oil pumped through the inner nozzle while an aqueous alginate solution, coming out from the annular nozzle, produced the beads shell. To optimize process parameters artificial intelligence tools were proposed to optimize the numerous prilling process variables. Homogeneous and spherical microcapsules with narrow size distribution and a thin alginate shell were obtained when the parameters as w/o constituents, polymer concentrations, flow rates and frequency of vibration were optimized by two commercial software, FormRules® and INForm®, which implement neurofuzzy logic and Artificial Neural Networks together with genetic algorithms, respectively. This technique constitutes an innovative approach for hydrophobic compounds microencapsulation. Copyright © 2018 Elsevier B.V. All rights reserved.

Photophysical characterization of low-molecular weight organogels for energy transfer and light harvesting

NASA Astrophysics Data System (ADS)

Atsbeha, T.; Bussotti, L.; Cicchi, S.; Foggi, P.; Ghini, G.; Lascialfari, L.; Marcelli, A.

2011-05-01

The choice of a donor and an acceptor with suitable optical and self-assembly properties is essential in the design of organogel-based light harvesting systems. Organogels can provide supramolecular structures capable of enhancing energy transfer processes. In this work, we present the characterization of N-(naphthalene-1-carboxyamide)-(3 S,4 S)-pyrrolidin-(3,4)-bisdodecyl-carbamoyldiester ( 1) and N-(4-nitrobenzofurazan-7-amino)-(3 S,4 S)-pyrrolidin-(3,4)-bisdodecyl-carbamoyldiester ( 2) which are used as donor and acceptor moieties, respectively. The donor molecule is hardly capable to form a gelon its own but it can be assembled at reasonable concentrations with the acceptor gelator to form a two-component donor-acceptor organogels in cyclohexane. Stable organogels are formed from cyclohexane for gelator concentrations as low as ≈10 -3 M. UV-vis and steady-state fluorescence spectroscopies were used to provide a characterization of their molecular interactions. The optical changes observed during the cooling of two-component solutions of these systems are indicative of typical sol-gel transitions. The occurrence of excitation energy transfer processes in the gels is confirmed by comparison of their excitation and absorption spectra.

Crosslinking of Chitosan with Dialdehyde Derivatives of Nucleosides and Nucleotides. Mechanism and Comparison with Glutaraldehyde.

PubMed

Mikhailov, Sergey N; Zakharova, Alexandra N; Drenichev, Mikhail S; Ershov, Andrey V; Kasatkina, Mariya A; Vladimirov, Leonid V; Novikov, Valentin V; Kildeeva, Natalia R

2016-01-01

In medical and pharmaceutical applications, chitosan is used as a component of hydrogels-macromolecular networks swollen in water. Chemical hydrogels are formed by covalent links between the crosslinking reagents and amino functionalities of chitosan. To date, the most commonly used chitosan crosslinkers are dialdehydes, such as glutaraldehyde (GA). We have developed novel GA like crosslinkers with additional functional groups-dialdehyde derivatives of uridine (oUrd) and nucleotides (oUMP and oAMP)-leading to chitosan-based biomaterials with new properties. The process of chitosan crosslinking was investigated in details and compared to crosslinking with GA. The rates of crosslinking with oUMP, oAMP, and GA were essentially the same, though much higher than in the case of oUrd. The remarkable difference in the crosslinking properties of nucleoside and nucleotide dialdehydes can be clearly attributed to the presence of the phosphate group in nucleotides that participates in the gelation process through ionic interactions with the amino groups of chitosan. Using NMR spectroscopy, we have not observed the formation of aldimine bonds. It can be concluded that the real number of crosslinks needed to cause gelation of chitosan chains may be less than 1%.

Proton triggered circularly polarized luminescence in orthogonal- and co-assemblies of chiral gelators with achiral perylene bisimide.

PubMed

Han, Dongxue; Han, Jianlei; Huo, Shengwei; Qu, Zuoming; Jiao, Tifeng; Liu, Minghua; Duan, Pengfei

2018-05-29

The orthogonal- or co-assembly of achiral perylene bisimide (PBI) with chiral gelators can be regulated by solvents. While the coassembly leads to the formation of chiroptical nanofibers through chirality transfer, the orthogonal assemblies could not. Moreover, protonation on the coassembled nanofibers could light up the circularly polarized luminescence (CPL).

A saponification-triggered gelation of ester-based Zn(II) complex through conformational transformations.

PubMed

Kumar, Ashish; Dubey, Mrigendra; Kumar, Amit; Pandey, Daya Shankar

2014-09-11

Novel saponification-triggered gelation in an ester-based bis-salen Zn(II) complex (1) is described. Strategic structural modifications induced by NaOH in 1 tune the dipolar-/π-interactions leading to J-aggregation and the creation of an inorganic gel material (IGM), which has been established by photophysical, DFT and rheological studies.

Biscalix[4]arene derivative as a very efficient phase selective gelator for oil spill recovery.

PubMed

Tsai, Chia-Chen; Cheng, Ying-Tsai; Shen, Li-Ching; Chang, Kai-Chi; Ho, I-Ting; Chu, Jean-Ho; Chung, Wen-Sheng

2013-11-15

A biscalixarene framework, without long alkyl chains, has been readily synthesized in three steps starting from the parent calix[4]arene. The biscalix[4]arene 1 was able to form organogels in various alcoholic solvents; furthermore, it exhibited an excellent phase selective gelation property that is potentially useful in oil spill recovery.

Gelation of mucin: Protecting the stomach from autodigestion

NASA Astrophysics Data System (ADS)

Bansil, Rama

2011-03-01

In this talk I will describe the molecular mechanisms involved in the remarkable ability of the mucus lining of the stomach for protecting the stomach from being digested by the acidic gastric juices that it secretes. These physical properties can be attributed to the presence of a high molecular weight glycoprotein found in mucus, called mucin. Rheology and other measurements show that gastric mucin forms a gel under acidic pH. A model of gelation based on the interplay of hydrophobic and electrostatic interactions will be discussed. Molecular Dynamics simulation studies of folding and aggregation of mucin domains provide further support for this model. The relevance of gelation to the motion of the ulcer causing bacterium H. pylori will be discussed.

Development and characterization of a novel hydrogel adhesive for soft tissue applications

NASA Astrophysics Data System (ADS)

Sanders, Lindsey Kennedy

With laparoscopic and robotic surgical techniques advancing, the need for an injectable surgical adhesive is growing. To be effective, surgical adhesives for internal organs require bulk strength and compliance to avoid rips and tears, and adhesive strength to avoid leakage at the application site, while not hindering the natural healing process. Although a number of tissue adhesives and sealants approved by the FDA for surgical use are currently available, attaining a useful balance in all of these qualities has proven difficult, particularly when considering applications involving highly expandable tissue, such as bladder and lung. The long-term goal of this project is to develop a hydrogel-based tissue adhesive that provides proper mechanical properties to eliminate the need for sutures in various soft tissue applications. Tetronic (BASF), a 4-arm poly(propylene oxide)-poly(ethylene oxide) (PPO-PEO) block copolymer, has been selected as the base material for the adhesive hydrogel system. Solutions of Tetronic T1107 can support reverse thermal gelation at physiological temperatures, which can be combined with covalent crosslinking to achieve a "tandem gelation" process making it ideal for use as a tissue adhesive. The objective of this doctoral thesis research is to improve the performance of the hydrogel based tissue adhesive developed previously by Cho and co-workers by applying a multi-functionalization of Tetronic. Specifically, this research aimed to improve bonding strength of Tetronic tissue adhesive using bi-functional modification, incorporate hemostatic function to the bi-functional Tetronic hydrogel, and evaluate the safety of bi-functional Tetronic tissue adhesive both in vitro and in vivo. In summary, we have developed a fast-curing, mechanically strong hemostatic tissue adhesive that can control blood loss in wet conditions during wound treatment applications (bladder, liver and muscle). Specifically, the bi-functional Tetronic adhesive (TAS) with a proper blend ratio may be used to achieve an accurate balance in bulk and tissue bond strengths, as well as the compliance and durability for expandable organ application, such as the bladder. Incorporation of chitosan expanded the utility of the bi-functional modified T1107 (TAS) adhesive to tissue wounds on highly vascularized organs (e.g., liver, kidney). Further, we demonstrated that the modified Tetronic adhesive is biocompatible and safe for treatment of small soft tissue wounds on rat's muscle using FDA requirements. The current findings helped our understanding of the material and mechanical properties of the modified Tetronic adhesive and ultimately progress the field of surgical adhesives and sealants by providing a tunable adhesive system for various internal soft tissue wound applications.

Whey protein isolate modified by transglutaminase aggregation and emulsion gel properties

NASA Astrophysics Data System (ADS)

Qi, Weiwei; Chen, Chong; Liu, Mujun; Yu, Guoping; Cai, Xinghang; Guo, Peipei; Yao, Yuxiu; Mei, Sijie

2015-07-01

Whey protein isolate and commercial soybean salad oil were used to produce the WPI emulsion dispersions. The properties of TG-catalyzed emulsion gelation produced from WPI emulsion dispersions were investigated by the amount of TG, temperature, pH and reaction time. Specifically, the texture properties (hardness and springiness), water-holding capacity and rheological properties (G' and G") were assessed. The result of Orthogonal tests showed WPI emulsion can form better hardness and springiness gel when the ratio of TG and WPI was 20U/g, pH 7.5, treatment temperature and time were 50°C and 3 h, respectively. The microstructure of TG emulsion gels was more compact, gel pore is smaller, distribution more uniform, the oil droplets size smaller compared with untreated emulsion gels. Compared to the control of rheological properties, G' and G" were significantly increased and G' > G", results showed that the gel was solid state, and TG speeded up the process of gelation.

Encapsulation of ascorbyl palmitate in chitosan nanoparticles by oil-in-water emulsion and ionic gelation processes.

PubMed

Yoksan, Rangrong; Jirawutthiwongchai, Jatesuda; Arpo, Kridsada

2010-03-01

The encapsulation of ascorbyl palmitate (AP) in chitosan particles was carried out by droplet formation via an oil-in-water emulsion, followed by droplet solidification via ionic gelation using sodium triphosphate pentabasic (TPP) as a cross-linking agent. The success of AP encapsulation was confirmed by FT-IR, UV-vis spectrophotometry, TGA, and XRD techniques. The obtained AP-loaded chitosan particles were spherical in shape with an average diameter of 30-100nm as observed by SEM and TEM. Loading capacity (LC) and encapsulation efficiency (EE) of AP in the nanoparticles were about 8-20% and 39-77%, respectively, when the initial AP concentration was in the range of 25-150% (w/w) of chitosan. Augmentation of the initial AP concentration led to an increase of LC and a reduction of EE. The amount of AP released from the nanoparticles in ethanol and tris buffer (pH approximately 8.0) increased with increasing LC and decreasing TPP concentration.

Metal-oxide-based energetic materials and synthesis thereof

DOEpatents

Tillotson, Thomas M. , Simpson; Randall, L [Livermore, CA; Hrubesh, Lawrence W [Pleasanton, CA

2006-01-17

A method of preparing energetic metal-oxide-based energetic materials using sol-gel chemistry has been invented. The wet chemical sol-gel processing provides an improvement in both safety and performance. Essentially, a metal-oxide oxidizer skeletal structure is prepared from hydrolyzable metals (metal salts or metal alkoxides) with fuel added to the sol prior to gelation or synthesized within the porosity metal-oxide gel matrix. With metal salt precursors a proton scavenger is used to destabilize the sol and induce gelation. With metal alkoxide precursors standard well-known sol-gel hydrolysis and condensation reactions are used. Drying is done by standard sol-gel practices, either by a slow evaporation of the liquid residing within the pores to produce a high density solid nanocomposite, or by supercritical extraction to produce a lower density, high porous nanocomposite. Other ingredients may be added to this basic nanostructure to change physical and chemical properties, which include organic constituents for binders or gas generators during reactions, burn rate modifiers, or spectral emitters.

Unravelling the secret of seed-based gels in water: the nanoscale 3D network formation.

PubMed

Samateh, Malick; Pottackal, Neethu; Manafirasi, Setareh; Vidyasagar, Adiyala; Maldarelli, Charles; John, George

2018-05-09

Chia (Salvia hispanica) and basil (Ocimum basilicum) seeds have the intrinsic ability to form a hydrogel concomitant with moisture-retention, slow releasing capability and proposed health benefits such as curbing diabetes and obesity by delaying digestion process. However, the underlying mode of gelation at nanoscopic level is not clearly explained or explored. The present study elucidates and corroborates the hypothesis that the gelling behavior of such seeds is due to their nanoscale 3D-network formation. The preliminary study revealed the influence of several conditions like polarity, pH and hydrophilicity/hydrophobicity on fiber extrusion from the seeds which leads to gelation. Optical microscopic analysis clearly demonstrated bundles of fibers emanating from the seed coat while in contact with water, and live growth of fibers to form 3D network. Scanning electron microscope (SEM) and transmission electron microscope (TEM) studies confirmed 3D network formation with fiber diameters ranging from 20 to 50 nm.

The crucial effect of early-stage gelation on the mechanical properties of cement hydrates

NASA Astrophysics Data System (ADS)

Ioannidou, Katerina; Kanduč, Matej; Li, Lunna; Frenkel, Daan; Dobnikar, Jure; Del Gado, Emanuela

2016-07-01

Gelation and densification of calcium-silicate-hydrate take place during cement hydration. Both processes are crucial for the development of cement strength, and for the long-term evolution of concrete structures. However, the physicochemical environment evolves during cement formation, making it difficult to disentangle what factors are crucial for the mechanical properties. Here we use Monte Carlo and Molecular Dynamics simulations to study a coarse-grained model of cement formation, and investigate the equilibrium and arrested states. We can correlate the various structures with the time evolution of the interactions between the nano-hydrates during the preparation of cement. The novel emerging picture is that the changes of the physicochemical environment, which dictate the evolution of the effective interactions, specifically favour the early gel formation and its continuous densification. Our observations help us understand how cement attains its unique strength and may help in the rational design of the properties of cement and related materials.

The crucial effect of early-stage gelation on the mechanical properties of cement hydrates

PubMed Central

Ioannidou, Katerina; Kanduč, Matej; Li, Lunna; Frenkel, Daan; Dobnikar, Jure; Del Gado, Emanuela

2016-01-01

Gelation and densification of calcium–silicate–hydrate take place during cement hydration. Both processes are crucial for the development of cement strength, and for the long-term evolution of concrete structures. However, the physicochemical environment evolves during cement formation, making it difficult to disentangle what factors are crucial for the mechanical properties. Here we use Monte Carlo and Molecular Dynamics simulations to study a coarse-grained model of cement formation, and investigate the equilibrium and arrested states. We can correlate the various structures with the time evolution of the interactions between the nano-hydrates during the preparation of cement. The novel emerging picture is that the changes of the physicochemical environment, which dictate the evolution of the effective interactions, specifically favour the early gel formation and its continuous densification. Our observations help us understand how cement attains its unique strength and may help in the rational design of the properties of cement and related materials. PMID:27417911

Flow-induced gelation of living (micellar) polymers

NASA Technical Reports Server (NTRS)

Bruinsma, Robijn; Gelbart, William M.; Ben-Shaul, Avinoam

1992-01-01

The effect of shear velocity gradients on the size (L) of rodlike micelles in dilute and semidilute solution is considered. A kinetic equation is introduced for the time-dependent concentration of aggregates of length L, consisting of 'bimolecular' combination processes L + L-prime yield (L + L-prime) and unimolecular fragmentations L yield L + (L - L-prime). The former are described by a generalization (from spheres to rods) of the Smoluchowski mechanism for shear-induced coalesence of emulsions, and the latter by incorporating the tension-deformation effects due to flow. Steady-state solutions to the kinetic equation are obtained, with the corresponding mean micellar size evaluated as a function of the Peclet number P (i.e., the dimensionless ratio of the flow rate and the rotational diffusion coefficient). For sufficiently dilute solutions, only a weak dependence of the micellar size on P is found. In the semidilute regime, however, an apparent divergence in the micellar size at P of about 1 suggests a flow-induced first-order gelation phenomenon.

Multiple patterns of polymer gels in microspheres due to the interplay among phase separation, wetting, and gelation.

PubMed

Yanagisawa, Miho; Nigorikawa, Shinpei; Sakaue, Takahiro; Fujiwara, Kei; Tokita, Masayuki

2014-11-11

We report the spontaneous patterning of polymer microgels by confining a polymer blend within microspheres. A poly(ethylene glycol) (PEG) and gelatin solution was confined inside water-in-oil (W/O) microdroplets coated with a layer of zwitterionic lipids: dioleoylphosphatidylethanolamine (PE) and dioleoylphosphatidylcholine (PC). The droplet confinement affected the kinetics of the phase separation, wetting, and gelation after a temperature quench, which determined the final microgel pattern. The gelatin-rich phase completely wetted to the PE membrane and formed a hollow microcapsule as a stable state in the PE droplets. Gelation during phase separation varied the relation between the droplet size and thickness of the capsule wall. In the case of the PC droplets, phase separation was completed only for the smaller droplets, wherein the microgel partially wetted the PC membrane and had a hemisphere shape. In addition, the temperature decrease below the gelation point increased the interfacial tension between the PEG/gelatin phases and triggered a dewetting transition. Interestingly, the accompanying shape deformation to minimize the interfacial area was only observed for the smaller PC droplets. The critical size decreased as the gelatin concentration increased, indicating the role of the gel elasticity as an inhibitor of the deformation. Furthermore, variously patterned microgels with spherically asymmetric shapes, such as discs and stars, were produced as kinetically trapped states by regulating the incubation time, polymer composition, and droplet size. These findings demonstrate a way to regulate the complex shapes of microgels using the interplay among phase separation, wetting, and gelation of confined polymer blends in microdroplets.

The solvent-gelator interaction as the origin of different diffusivity behavior of diols in gels formed with sugar-based low-molecular-mass gelator.

PubMed

Kowalczuk, Joanna; Bielejewski, Michał; Lapiński, Andrzej; Luboradzki, Roman; Tritt-Goc, Jadwiga

2014-04-10

Organogels are soft materials consisting of low-molecular-mass gelators (LMOGs) self-assembled through noncovalent interactions into 3D structures, in which free spaces are filled by organic solvents. 4,6,4',6'-O-terephthylidene-bis(methyl-α-d-glucopyranoside) (1) is found to be a new LMOG. It gelatinizes only a limited number of solvents. Here, the gels of 1 with ethylene glycol (EG) and 1,3-propanediol (PG) are investigated with FT-IR, Raman, and UV-vis spectroscopies, the NMR relaxometry and diffusometry methods, and microscopic observation. The chemical structures of both solvents are closely related, but the variety of physical characteristics of the gels is large. The 1/PG gels are thermally more stable compared to 1/EG gels. The types of aggregates are most likely the H- and J-type in 1/EG gels and the J-type in 1/PG gels. Different microstructures are observed: bundles of crossing fibers for 1/EG and a honeycomb-like matrix for 1/PG gels. The diffusivity of the EG solvent in gels with 1 behaves as expected, decreasing with increasing gelator concentration, whereas the opposite behavior is observed for the PG solvent. This is a most fascinating result. To explain the diffusion enhancement, we suggest that a dynamic hydrogen bonding network of PG solvent in gel matrixes is disrupted due to solvent-gelator interaction. The direct proof of this interaction is given by the observed low frequency dispersion of the spin-lattice relaxation time of solvents in the gel matrixes.

Rheological signatures of gelation and effect of shear melting on aging colloidal suspension

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jatav, Shweta; Joshi, Yogesh M, E-mail: joshi@iitk.ac.in

2014-09-01

Colloidal suspensions that are out of thermodynamic equilibrium undergo physical aging wherein their structure evolves to lower the free energy. In aqueous suspension of Laponite, physical aging accompanies increases of elastic and viscous moduli as a function of time. In this work, we study temporal evolution of elastic and viscous moduli at different frequencies and observe that freshly prepared aqueous suspension of Laponite demonstrates identical rheological behavior reported for the crosslinking polymeric materials undergoing chemical gelation. Consequently at a certain time, tan δ is observed to be independent of frequency. However, for samples preserved under rest condition for longer duration beforemore » applying the shear melting, the liquid to solid transition subsequent to shear melting shows greater deviation from classical gelation. We also obtain continuous relaxation time spectra from the frequency dependence of viscous modulus. We observe that, with an increase in the rest time, continuous relaxation time spectrum shows gradual variation from negative slope, describing dominance of fast relaxation modes to positive slope representing dominance of slow relaxation modes. We propose that the deviation from gelation behavior for the shear melted suspensions originates from inability of shear melting to completely break the percolated structure thereby creating unbroken aggregates. The volume fraction of such unbroken aggregates increases with the rest time. For small rest times presence of fewer number of unbroken aggregates cause deviation from the classical gelation. On the other hand, at high rest times presence of greater fraction of unbroken aggregates subsequent to shear melting demonstrate dynamic arrest leading to inversion of relaxation time spectra.« less

Release of a wound-healing agent from PLGA microspheres in a thermosensitive gel.

PubMed

Machado, H A; Abercrombie, J J; You, T; Deluca, P P; Leung, K P

2013-01-01

The purpose of this research was to develop a topical microsphere delivery system in a thermosensitive 20% poloxamer 407 gel (Pluronic F127) to control release of KSL-W, a cationic antimicrobial decapeptide, for a period of 4-7 days for potential application in combat related injuries. KSL-W loaded microsphere formulations were prepared by a solvent extraction-evaporation method (water-oil-water), with poly (D,L-lactic-co-glycolic acid) (PLGA) (50 : 50, low-weight, and hydrophilic end) as the polymeric system. After optimization of the process, three formulations (A, B, and C) were prepared with different organic to water ratio of the primary emulsion while maintaining other components and manufacturing parameters constant. Formulations were characterized for surface morphology, porous nature, drug loading, in vitro drug release, and antimicrobial activity. Microspheres containing 20% peptide with porous surfaces and internal structure were prepared in satisfactory yields and in sizes varying from 25 to 50 μm. Gels of 20% Pluronic F127, which were liquid at or below 24.6°C and formed transparent films at body temperature, were used as carriers for the microspheres. Rheological studies showed a gelation temperature of 24.6°C for the 20% Pluronic F127 gel alone. Gelation temperature and viscosity of formulations A, B, and C as a function of temperature were very close to those of the carrier. A Franz diffusion cell system was used to study the release of peptide from the microspheres suspended in both, phosphate-buffered saline (PBS) and a 20% Pluronic F127 gel. In vitro release of greater than 50% peptide was found in all formulations in both PBS and the gel, and in one formulation there was a release of 75% in both PBS and the gel. Fractions collected from the release process were also tested for bactericidal activity against Staphylococcus epidermidis using the broth microdilution method and found to provide effective antimicrobial activity to warrant consideration and testing in animal wound models for treating combat-related injuries.

Loofah-like gel network formed by the self-assembly of a 3D radially symmetrical organic-inorganic hybrid gelator.

PubMed

Tang, Guodong; Chen, Si; Ye, Feng; Xu, Xiaopeng; Fang, Jing; Wang, Xu

2014-07-11

We report a unique loofah-like gel network that is supported by the sectional type hexagonal columnar assembly of flexuous furcate fibers, which are constructed by plane-to-plane stacking of a novel 3D radially symmetrical gelator with POSS as the core and L-lysine as the arm.

A novel multi-stimuli responsive gelator based on D-gluconic acetal and its potential applications.

PubMed

Guan, Xidong; Fan, Kaiqi; Gao, Tongyang; Ma, Anping; Zhang, Bao; Song, Jian

2016-01-18

We construct a simple-structured super gelator with multi-stimuli responsive properties, among which anion responsiveness follows the Hofmeister series in a non-aqueous system. Versatile applications such as being rheological and self-healing agents, waste water treatment, spilled oil recovery and flexible optical device manufacture are integrated into a single organogelator, which was rarely reported.

Self-Assembly and Nanostructures in Organogels Based on a Bolaform Cholesteryl Imide Compound with Conjugated Aromatic Spacer

PubMed Central

Jiao, Ti-Feng; Gao, Feng-Qing; Shen, Xi-Hai; Zhang, Qing-Rui; Zhang, Xian-Fu; Zhou, Jing-Xin; Gao, Fa-Ming

2013-01-01

The self-assembly of small functional molecules into supramolecular structures is a powerful approach toward the development of new nanoscale materials and devices. As a class of self-assembled materials, low weight molecular organic gelators, organized in special nanoarchitectures through specific non-covalent interactions, has become one of the hot topics in soft matter research due to their scientific values and many potential applications. Here, a bolaform cholesteryl imide compound with conjugated aromatic spacer was designed and synthesized. The gelation behaviors in 23 solvents were investigated as efficient low-molecular-mass organic gelator. The experimental results indicated that the morphologies and assembly modes of as-formed organogels can be regulated by changing the kinds of organic solvents. Scanning electron microscopy and atomic force microscopy observations revealed that the gelator molecule self-assemble into different aggregates, from wrinkle and belt to fiber with the change of solvents. Spectral studies indicated that there existed different H-bond formations between imide groups and assembly modes. Finally, some rational assembly modes in organogels were proposed and discussed. The present work may give some insight to the design and character of new organogelators and soft materials with special structures. PMID:28788428

A hydro/organo/hybrid gelator: a peptide lipid with turning aspartame head groups.

PubMed

Mukai, Masaru; Minamikawa, Hiroyuki; Aoyagi, Masaru; Asakawa, Masumi; Shimizu, Toshimi; Kogiso, Masaki

2013-04-01

This work presents a novel bola-type peptide lipid which can gelate water, organic solvents, and water/organic-solvent mixtures. In its molecular structure, an amphiphilic dipeptide aspartame (L-α-aspartyl-L-phenylalanine methyl ester) is connected at both ends of an alkylene linker. The different morphologies in the hydrogel (helical nanotapes) and the organogel (tape-like nanostructures) were visualized by energy-filtering transmission electron microscopy (EF-TEM) and energy-filtering scanning electron microscopy (FE-SEM), and the molecular arrangement was examined using X-ray diffraction (XRD), infrared (IR) spectroscopy, and circular dichroism (CD) spectroscopy. Possessing a hydrophilic aspartic acid group and a (relatively) hydrophobic phenylalanine methyl ester group, the dipeptide head group can turn about in response to solvent polarity. As a consequence, the solvent condition changed the molecular packing of the gelator and affected the overall supramolecular structure of the gel. It is noted that the peptide lipid gelated mixed solvents of water and organic solvents such as dichloromethane, liquid-paraffin, olive-oil, silicone-oils, and so on. The present hybrid gel can simultaneously hold hydrophilic and hydrophobic functional materials. Copyright © 2013 Elsevier Inc. All rights reserved.

Permanganate gel (PG) for groundwater remediation: compatibility, gelation, and release characteristics.

PubMed

Lee, Eung Seok; Olson, Pamela R; Gupta, Neha; Solpuker, Utku; Schwartz, Franklin W; Kim, Yongje

2014-02-01

Permanganate (MnO4(-)) is a strong oxidant that is widely used for treating chlorinated ethylenes in groundwater. This study aims to develop hyper-saline MnO4(-) solution (MnO4(-) gel; PG) that can be injected into aquifers via wells, slowly gelates over time, and slowly release MnO4(-) to flowing water. In this study, compatibility and miscibility of gels, such as chitosan, aluminosilicate, silicate, and colloidal silica gels, with MnO4(-) were tested. Of these gels, chitosan was reactive with MnO4(-). Aluminosilicates were compatible but not readily miscible with MnO4(-). Silicates and colloidal silica were both compatible and miscible with MnO4(-), and gelated with addition of KMnO4 granules. Colloidal silica has low initial viscosity (<15cP), exhibited delayed gelation characteristics with the lag times ranging from 0 to 200min. Release of MnO4(-) from the colloidal silica-based PG gel occurred in a delayed fashion, with maximum duration of 24h. These results suggested that colloidal silica can be used to create PG or delayed-gelling forms containing other oxidants which can be used for groundwater remediation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effects of heating and calcium and phosphate mineral supplementation on the physical properties of rennet-induced coagulation of camel and cow milk gels.

PubMed

Kamal, Mohammad; Foukani, Mohammed; Karoui, Romdhane

2017-05-01

The physical properties of rennet-induced coagulation of preheated camel and cow milk gels (50 and 70 °C for 10 min) enriched with calcium chloride (CaCl2) and hydrogen phosphate dihydrate (Na2HPO42H2O) were evaluated using the dynamic low amplitude oscillatory shear analysis. The storage modulus (G') and loss modulus (G") of camel milk gels showed significant (P < 0·05) lower values than those of cow milk gels. The preheating of camel milk at 50 °C affected negatively the gelation properties, while the preheating at 70 °C prevented the formation of rennet-induced milk gels. No effect was observed on the gelation properties of cow milk gels. The CaCl2 added at 10 and 20 mM to preheated camel and cow milk reduced significantly (P < 0·05) the gelation time and increased the gel firmness. In contrast, Na2HPO42H2O added at 10 and 20 mM induced the formation of weak gels for preheated camel and cow milk at 50 °C, and even no gelation for preheated camel milk at 70 °C.

Autonomic Composite Hydrogels by Reactive Printing: Materials and Oscillatory Response (Postprint)

DTIC Science & Technology

2013-11-01

properties such as polyacrylamide (PAAm)14,17 and gelatin ,2,15 and employing novel synthesis techniques and catalyst binding chemistries such as UV...compatible with additive processing (manufacturing) tech- niques. For example, the thermal gelation characteristics of gelatin enable printing of self...supporting structures by extruding hot gelatin (low viscosity) onto a cold substrate (high viscosity).2,15 Glutaraldehyde crosslinking of co-printed, or

Ionogel Electrolytes through Sol-Gel Processing

NASA Astrophysics Data System (ADS)

Horowitz, Ariel I.

Electrical energy needs have intensified due to the ubiquity of personal electronics, the decarbonization of energy services through electrification, and the use of intermittent renewable energy sources. Despite developments in mechanical and thermal methods, electrochemical technologies are the most convenient and effective means of storing electrical energy. These technologies include both electrochemical cells, commonly called batteries, and electrochemical double-layer capacitors, or "supercapacitors", which store energy electrostatically. Both device types require an ion-conducting electrolyte. Current devices use solutions of complex salts in organic solvents, leading to both toxicity and flammability concerns. These drawbacks can be avoided by replacing conventional electrolytes with room-temperature molten salts, known as ionic liquids (ILs). ILs are non-volatile, non-flammable, and offer high conductivity and good electrochemical stability. Device mass can be reduced by combining ILs with a solid scaffold material to form an "ionogel," further improving performance metrics. In this work, sol-gel chemistry is explored as a means of forming ionogel electrolytes. Sol-gel chemistry is a solution-based, industrially-relevant, well-studied technique by which solids such as silica can be formed in situ. Previous works used a simple acid-catalyzed sol-gel reaction to create brittle, glassy ionogels. Here, both the range of products that can be accomplished through sol-gel processing and the understanding of interactions between ILs and the sol-gel reaction network are greatly expanded. This work introduces novel ionogel materials, including soft and compliant silica-supported ionogels and PDMS-supported ionogels. The impacts of the reactive formulation, IL identity, and casting time are detailed. It is demonstrated that variations in formulation can lead to rapid gelation and open pore structures in the silica scaffold or slow gelation and more dense silica morphologies. The IL identity is shown to have an impact on the apparent strength of the acid catalyst, leading to significant shifts in gelation time. Delayed casting is proven to be an optimal technique for avoiding pore blockage when combining ionogels with high surface area electrodes for supercapacitor applications. Finally, a simple recycling process is proposed, establishing that ILs can be easily reclaimed from silica-supported ionogels and reused, thereby validating the reputation of ILs as "green" materials.

Chitosan-based biocatalytic nanoparticles for pollutant removal from wastewater.

PubMed

Alarcón-Payán, Dulce A; Koyani, Rina D; Vazquez-Duhalt, Rafael

2017-05-01

Chitosan, a renewable biopolymer has the prospective applications in different fields due to its gelation capacity. Nanoconfiguration of chitosan through ionotropic gelation to encapsulate enzymatic activity offers numerous potential applications. In the present study, the preparation and characterization of chitosan nanoparticles loaded with versatile peroxidase are reported. Their performance in bioremediation process and the resistance enhancement against natural microbial biodegradation were studied. The average diameter of enzymatic nanoparticles was 120nm and showed a high enzyme loading capacity. The kinetic parameters of nanoparticles exhibited a slightly lower catalytic activity (k cat ), similar affinity constant (Km) for hydrogen peroxide and higher Km value for the phenolic compound when compared with the free enzyme. The enzymatic nanoparticles showed higher thermostability and the same pH activity profile than those from free enzyme. Ten phenolic compounds, including pesticides, halogenated compounds, endocrine disruptors and antibacterials were transformed by the enzymatic nanoparticles. The transformation rate was lower than those obtained with free enzyme suggesting mass transfer limitations. But very importantly, the enzymatic nanoparticles showed a significant increase of the operational stability in real conditions of wastewater treatment process. Moreover, chemical modification of nanoparticles with different aldehydes still enhanced the operational stability of nanoparticulated enzymes. This enhancement of stability in real conditions and the potential use of biocatalytic nanoparticles in bioremediation processes are discussed. Copyright © 2017 Elsevier Inc. All rights reserved.

A novel poloxamers/hyaluronic acid in situ forming hydrogel for drug delivery: rheological, mucoadhesive and in vitro release properties.

PubMed

Mayol, Laura; Quaglia, Fabiana; Borzacchiello, Assunta; Ambrosio, Luigi; La Rotonda, Maria I

2008-09-01

The influence of hyaluronic acid (HA) on the gelation properties of poloxamers blends has been studied with the aim of engineering thermosensitive and mucoadhesive polymeric platforms for drug delivery. The gelation temperature (T(gel)), viscoelastic properties and mucoadhesive force of the systems were investigated and optimised by means of rheological analyses. Poloxamers micellar diameter was evaluated by photon correlation spectroscopy (PCS). Moreover in order to explore the feasibility of these platforms for drug delivery, the optimised systems were loaded with acyclovir and its release properties studied in vitro. By formulating poloxamers/HA platforms, at specific concentrations, it was possible to obtain a thermoreversible gel with a T(gel) close to body temperature. The addition of HA did not hamper the self assembling process of poloxamers just delaying the gelation temperature of few Celsius degrees. Furthermore, HA presence led to a strong increase of the poloxamer rheological properties thus indicating possible HA interactions with micelles through secondary bonds, such as hydrogen ones, which reinforce the gel structure. These interactions could also explain PCS results which show, in systems containing HA, aggregates with hydrodynamic diameters much higher than those of poloxamer micelles. Mucoadhesion experiments showed a rheological synergism between poloxamers/HA gels and mucin dispersion which led to a change of the flow behaviour from a quite Newtonian one of the separate solutions to a pseudoplastic one of their mixture. In vitro release experiments indicated that the optimised platform was able to prolong and control acyclovir release for more than 6h.

Gels with exceptional thermal stability formed by bis(amino acid) oxalamide gelators and solvents of low polarity.

PubMed

Makarević, Janja; Jokić, Milan; Frkanec, Leo; Katalenić, Darinka; Zinić, Mladen

2002-10-07

Some bis (amino acid) oxalamide gelators form common thermo-reversible gels with various organic solvents but also gels of exceptional thermal stability with some solvents of medium and low polarity; the latter gels can be heated up to 50 degrees C higher temperatures than the bp of the solvent without apparent gel-to-sol transition.

Universal sol state behavior and gelation kinetics in mixed clay dispersions.

PubMed

Pujala, Ravi Kumar; Pawar, Nisha; Bohidar, H B

2011-05-03

Sol and gel state behavior, in aqueous salt free dispersions, of clays Laponite (L) and Na montmorillonite (MMT) was studied at various mixing ratios (L:MMT = r = 1:0.5, 1:1, and 1:2). In the sol state, the zeta potential and gelation concentration of L-MMT obeyed the universal relation, X(L-MMT) = (rX(L) + X(MMT))/(1 + r), where X is zeta potential or gelation concentration (c(g)), implying that these properties are linear combinations of the same of their individual components. The low frequency storage modulus (G(0)'), relative viscosity (η(r)), and apparent cluster size (R) could be universally described by the power-law, G(0)' ∼ ((c/c(g)) - 1)(t) (c > c(g)), and η(r), R ∼ (1 - (c/c(g)))(-k,ν) (c < c(g)), with t = 1.5, k = 1.1, and υ = 0.8 close to the gelation concentration, for r = 1:1 cogel, consistent with the percolation model description of gelation. Interestingly, the hyperscaling relation δ = t/(k + t) yielded δ = 0.56 not too different from the predicted value ∼0.7, while the experimental value of δ obtained from G''(ω) ∼ ω(δ) close to c ≈ c(g) yielded δ = 1.5, which was at variance with the hyperscaling result. The experimental data, on hand, mostly supported percolation type gelation mechanism. As the cogels were slowly heated, at a characteristic temperature, T(g), a sharp increase in G' value was noticed, implying a transition to gel hardening (a new phase state). The temperature-dependent behavior followed the power-law description, G' ∼ (T(g) - T)(-γ) (T < T(g)), with γ = 0.40 ± 0.05 invariant of composition of the cogel, whereas for MMT and Laponite, γ = 0.25 and 0.55, respectively. It has been shown that the cogel has significantly enhanced mechanical (G(0) increased by 10 times for r = 1:1 cogel) and thermal properties (T(g) increased by 13 °C for 1:1 cogel) that can be exploited to design customized soft materials.

Characterization of a Bio-Based, Biodegradable Class of Copolymers, Poly[(R)-3-Hydroxybutyrate-Co-(R)-3- Hydroxyhexanoate], and Application Development

NASA Astrophysics Data System (ADS)

Sobieski, Brian

As modern society begins to focus on sustainability and renewable resources there is a growing need for the polymer industry to develop more environmentally friendly materials and practices. Part of this movement can be seen in the use of recycled materials in new products and in the development of bio-based, biodegradable polymers. Bio-based, biodegradable polymers are produced from renewable carbon sources, such as vegetable oils, typically polymerized using fermentation reactions via bacteria, and are able to be consumed by bacteria in landfills to completely convert the polymers to water and CO2. One class of such polymers are poly(hydroxyalkanoate)'s (PHAs), which are chiral, aliphatic polyesters. Within this class of polyesters are poly(hydroxybutyrate) (PHB) and the copolymer poly[(R)-3-hydroxybutyrate- co-(R)-3-hydroxyhexanoate] (PHBHx), which have received extensive study due to their material properties as thermoplastics. Although the properties of PHB have been widely explored, much still remains to be understood about these promising biodegradable polymers. Specifically, PHB and its copolymers exhibit physical gelation in most solvents, yet the origin and mechanism of gelation and the properties of the resulting gel state are unknown. This research effort was primarily focused on investigating the physical gel state of PHBHx. Five goals were laid out and completed: determining the origin of gelation, the mechanism of gelation, the structure of the gel state, the properties of the gel state, and the effects of gelation on electrospun fibers of PHBHx. These goals were achieved through material characterization of the gel state utilizing infrared spectroscopy/two-dimensional correlation spectroscopy, differential scanning calorimetry, X-ray diffraction, scanning electron microscopy, and many other analysis methods. Crystallization of the polymer in solution was found to cause gelation in PHBHx solutions, where the polymer crystals act as tie points forming an interconnected network. The process of crystallization in solution was determined to follow the same method as crystallization in the bulk, neat polymer as it is cooled from a molten state. Morphological studies revealed that the polymer forms sub-micron fibrils and ribbons in xxviii the gel system forming an interconnected polymer network. The utility of this morphology combined with the bio-compatibility of PHBHx were demonstrated through growth of stem cells on the gel samples. Surprisingly, the stem cells did not differentiate and thrived on the freeze-dried PHBHx gels. These results indicate that the gel state of PHBHx could be used as a tissue engineering scaffold whose material properties can be tuned to the desired application without the concern of the stem cells differentiating into an unwanted cell type. Combined with the ease of generation of the PHBHx gels, these results show promising potential for industrial production of excellent three-dimensional culturing scaffolds. It was also found that the gels do not show signs of aging after gelation is complete and that the polymer exists in the amorphous and primary alpha crystal phases when gelled. Electrospun fibers of the polymer in solution with a solvent that promotes gelation displayed a new morphology. Rather than the typical cylindrical fiber morphology, these fibers formed coiled fiber mats. It is proposed that the formation of crystals before the fibers are formed causes the fibers to collapse thus forming the coils. Additional research was conducted on the neat polymer itself to further explore its material properties. PHB and PHBHx tend to have multiple melting transitions when heated to the amorphous phase. This multiple melting behavior was caused by the same, primary crystal form recrystallizing and having a bimodal size distribution, rather than arising from two different crystal phases. Thermal degradation of the copolymers was also studied and the reaction pathway suggested, beginning with the formation of a six-member ring precursor leading to chain scission of the polymer. It was also found that the formation of this precursor may cause the higher 3HHx content copolymers to be slightly more stable at high temperatures due to steric hindrance. Strain-induced crystallization of the beta crystal of PHBHx was performed in the 13 mol % 3HHx PHBHx by stretching films of the copolymer. All the research conducted during this project were performed to generate additional applications and further the utility of this class of bio-based, biodegradable polyesters.

Production of BCG alginate-PLL microcapsules by emulsification/internal gelation.

PubMed

Esquisabel, A; Hernández, R M; Igartua, M; Gascón, A R; Calvo, B; Pedraz, J L

1997-01-01

A biocompatible emulsification method for microencapsulation of live cells and enzymes within a calcium alginate matrix applied to Bacillus Calmette-Guérin (BCG) has been developed. Small-diameter alginate beads (microcapsules) were formed via internal gelation of an alginate solution emulsified within vegetable oil. Five different oils (sesame, sweet almond, perhydrosqualene, camomile and jojoba) were used. The rheological analysis of the oils showed a Newtonian behaviour, with viscosities = 30.0, 37.7, 51.2, 59.3 and 67.1 mPa.s for perhydrosqualene, jojoba, camomile, sesame and sweet almond oil respectively. The particle size of the microcapsules obtained ranged from 30.3 microns for the microcapsules prepared with sweet almond oil to 57.0 microns for those made with perhydrosqualene. The mean particle diameter obtained was found to be dependent on the viscosity of the oil employed, according to the equation: phi (micron) = 76.6-0.628 eta (mPa.s) (r2 = 0.943). The encapsulated BCG was identified by the Difco TB stain set K, followed by observation under optical microscopy. Freeze-drying of the microcapsules was carried out to ensure their stability during storage. Two batches of microcapsules (those prepared with sesame and jojoba oil) and four types of cryoprotectors (glucose, trehalose, mannitol and sorbitol), at three concentration levels (5, 10 and 20% w/v) were studied. The parameters evaluated were particle size, physical appearance, reconstitution of lyophilizates and microscopical evaluation. For both batches of microcapsules the best results were obtained with trehalose 5%, showing particle sizes of 42.1 microns in the case of the microcapsules prepared with sesame oil, and of 45.3 microns for those prepared with jojoba.

Method for rapidly producing microporous and mesoporous materials

DOEpatents

Coronado, Paul R.; Poco, John F.; Hrubesh, Lawrence W.; Hopper, Robert W.

1997-01-01

An improved, rapid process is provided for making microporous and mesoporous materials, including aerogels and pre-ceramics. A gel or gel precursor is confined in a sealed vessel to prevent structural expansion of the gel during the heating process. This confinement allows the gelation and drying processes to be greatly accelerated, and significantly reduces the time required to produce a dried aerogel compared to conventional methods. Drying may be performed either by subcritical drying with a pressurized fluid to expel the liquid from the gel pores or by supercritical drying. The rates of heating and decompression are significantly higher than for conventional methods.

Synthesis and characterization of polymeric materials derived from 2,5-diketopiperazines and pyroglutamic acid

NASA Astrophysics Data System (ADS)

Parrish, Dennis Arch

The research presented in this dissertation describes the investigation of 2,5-diketopiperazines (DKPs) as property modifiers for addition polymers and the self association behavior of pyroglutamic acid derivatives. The first project involved the copolymerization of methyl methacrylate and styrene with DKP-based methacrylate monomers. Low incorporations of serine- and aspartame-based DKPs in the copolymer resulted in dramatic increases in the glass transition temperature (Ts). The research presented in Chapter II focuses on the ring-opening reactions of pyroglutamic diketopiperazine (pyDKP). The original intent was to synthesize polymers containing backbone DKPs through ring-opening polymerization of the five-membered rings. However, it was discovered that regioselective ring-opening occurs at the six-membered ring to give pyroglutamic acid derivatives. Since this reaction had not been reported previously, the focus of research was altered to investigate the scope and limitations of the new reaction. The ring-opening reactions of pyDKP with diamines to give bispyroglutamides is described in Chapter IV. While these materials are not polymeric, they display polymeric behavior. It was found that multi-functional pyroglutamides display Tgs during thermal analysis, exhibit high thermal stability, and form melt-drawn fibers. In contrast, the materials have low solution viscosities and are freely soluble in water, ethanol, and chloroform. This behavior is attributed to non-covalent supramolecular associations. The final part of this dissertation involved the investigation of thermoreversible organic solvent gelators. The ring-opening reaction of pyDKP with long alkyl amines unexpectedly gelled the reaction solvent. A series of analogous gelators were synthesized, and the minimum concentration required for gelation in various solvents was determined. It was found that the nature of the solvent, alkyl chain length, and optical activity of the gelator determined gelator efficiency and gel structure.

Role of S…O non-bonded interaction in controlling supramolecular assemblies in a new series of 2-aminobenzothiazole based organic salts/ co-crystals

NASA Astrophysics Data System (ADS)

Yadav, Priyanka; Patel, Vatsa; Ballabh, Amar

2018-07-01

A new series of 2-aminobenzothiazole based organic salts were synthesized with mono- / di-carboxylic acid and characterized with various physico-chemical methods. One of the synthesized salt 2-aminobenzothiazolium-hydrogen fumarate (BTzA4) was found to be capable of gelling water with minimum gelator concentration (MGC) around 1.25 wt% (w/v). The single crystal structures of gelator (BTzA4) and non-gelators were analyzed for the presence of various supramolecular synthons especially the rarely occurring non-bonded S…O interactions and their role in controlling the overall hydrogen bonded network in these series of salts/ cocrystals. Charge assisted hydrogen bonded network was found to be governing the weak non-bonded S…O supramolecular synthons in the present study.

Enhanced gelation of chitosan/β-sodium glycerophosphate thermosensitive hydrogel with sodium bicarbonate and biocompatibility evaluated.

PubMed

Deng, Aipeng; Kang, Xi; Zhang, Jing; Yang, Yang; Yang, Shulin

2017-09-01

The application of chitosan/β-sodium glycerophosphate (β-GP) thermosensitive hydrogel has been limited by the relatively slow gelation, weak mechanical resistance and poor cytocompatibility. In this study, sodium hydrogen carbonate (NaHCO 3 ) was applied with β-GP as gel agents to produce high-strength hydrogel. The hydrogels prepared with high NaHCO 3 concentration or more gel agents showed shorter gelation time, better thermostability, drastically enhanced resistance in compression. Meanwhile, the hydrogels presented obvious porous structures and excellent biocompatibility to HUVEC and NIH 3T3 cultured in vitro with higher NaHCO 3 concentration and moderate concentration of β-GP. Overall, appropriate concentration of β-GP combined with NaHCO 3 can be a good gel regent to improve properties of chitosan thermosensitive hydrogels. Copyright © 2017 Elsevier B.V. All rights reserved.

Structural Studies of Sol-Gel Glasses

DTIC Science & Technology

1992-07-14

were prepared from tetramethylorthosilicate (TMOS) and titanium isopropoxide in a six step process of mixing, casting, gelation, aging, drying and...glass matrix although the incorporation of low levels (3% by weight) of titanium into tetrahedral sites only, led to more disordered glasses than...between 615 and 1000"C. The addition of titanium also leads to a reduction in surface ’free’ silanol levels together with an increase in hydrogen bonded

Gelation-driven selection in dynamic covalent C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C/CN exchange.

PubMed

Liang, Chunshuang; Kulchat, Sirinan; Jiang, Shimei; Lehn, Jean-Marie

2017-10-01

Knoevenagel barbiturate derivatives bearing long alkyl chains were proven to form organogels in suitable solvents based on supramolecular interactions. Their reaction with imines allows for component exchange through CC/CN recombination. The effect of various parameters (solvents, chain length, and temperature) on the CC/CN exchange reaction has been studied. Mixing Knoevenagel compound K and imine I-16 in a 1 : 1 ratio generated a constitutional dynamic library containing the four constituents K , I-16 , K'-16 , and I' . The reversible exchange reaction was monitored by 1 H-NMR, showing marked changes in the fractions of the four constituents on sol-gel interconversion as a function of temperature. The library composition changed from statistical distribution of the four constituents in the sol state to selective amplification of the gel forming K'-16 constituent together with that of its agonist I' . The process amounts to self-organization driven component selection in a constitutional dynamic organogel system undergoing gelation. This process displays up-regulation of the gel-forming constituent by component redistribution through reversible covalent connections.

Colloidal Gelation-2 and Colloidal Disorder-Order Transition-2 Investigations Conducted on STS-95

NASA Technical Reports Server (NTRS)

Hoffmann, Monica T.

2000-01-01

The Colloidal Gelation-2 (CGEL 2) and Colloidal Disorder-Order Transition-2 (CDOT 2) investigations flew on Space Shuttle Discovery mission STS-95 (also known as the John Glenn Mission). These investigations were part of a series of colloid experiments designed to help scientists answer fundamental science questions and reduce the trial and error involved in developing new and better materials. Industries dealing with semiconductors, electro-optics, ceramics, and composites are just a few that may benefit from this knowledge. The goal of the CGEL 2 investigation was to study the fundamental properties of colloids to help scientists better understand their nature and make them more useful for technology. Colloids consist of very small (submicron) particles suspended in a fluid. They play a critical role in the technology of this country, finding uses in materials ranging from paints and coatings to drugs, cosmetics, food, and drink. Although these products are routinely produced and used, there are still many aspects of their behavior about which scientists know little. Understanding their structures may allow scientists to manipulate the physical properties of colloids (a process called "colloidal engineering") to produce new materials and products. Colloid research may even improve the processing of known products to enhance their desirable properties.

From Green Aerogels to Porous Graphite by Emulsion Gelation of Acrylonitrile

DTIC Science & Technology

2012-01-01

interesting uses of PAN aerogels is not dealing with monoliths at all but rather with films made by grafting PAN on carbon nanotubes that in turn are...REPORT From ‘Green’ Aerogels to Porous Graphite by Emulsion Gelation of Acrylonitrile 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: Porous carbons ...including carbon (C) aerogels, are technologically important materials, while polyacrylonitriile (PAN) is the main industrial source of graphite fiber

Changes in viscosity behavior from a normal organogelator to a heat-induced gelator for a long-chain amidoamine derivative.

PubMed

Morita, Clara; Sugimoto, Hiroki; Matsue, Keisuke; Kondo, Takeshi; Imura, Yoshiro; Kawai, Takeshi

2010-11-14

A long-chain amidoamine derivative (C18AA) acts as a normal organogelator in toluene, but changes to a heat-induced gelator, exhibiting a phase transition from sol to gel on heating upon addition of aqueous LiCl to the toluene gel. The thermal response of the heat-induced gel of C18AA was highly sensitive.

Development and characterisation of levosulpiride-loaded suppositories with improved bioavailability in vivo.

PubMed

Fakhar-Ud-Din; Khan, Gul Majid

2017-12-28

The purpose of this study was to develop and characterize levosulpiride loaded liquid suppository with improved bioavailability. The content of levosulpiride-loaded liquid suppositories were optimized in a series of experiments using various weight ratios of P188, P407, Tween 80, and drug. The suppositories were liquid at room temperature, however, when rectally administered, they became gel at body temperature. Their rheological properties and release characteristics were determined in vitro while pharmacokinetic study was performed after its rectal administration in rats and compared with drug suspension. Poloxamer 188 and Twee 80 decreased the gelation temperature and gelation time, but increased the gel strength and mucoadhesive force of liquid suppositories. Liquid suppository composed of [Levosulpiride/P 188/P 407/Tween 80 (1/15/17/3%)] with a gelation temperature of about 30.7 °C remained liquid at 25 °C, but converted to gel at 30-36.5 °C, resulting in easy administration and rapid gelation inside the body. This liquid suppository gave a considerably increased dissolution rate reflected in a meaningfully higher plasma concentration and 7.1-fold AUC values of levosulpiride in rats as compared to the drug suspension. Hence, liquid suppository system could be used for enhanced bioavailability of levosulpiride-loaded pharmaceutical products.

Sulfamide-Lattice Restructuring To Form Dimensionally Controlled Molecular Arrays and Gel-Forming Systems.

PubMed

Raghava, Saripalli V; Gopinath, Pushparathinam; Srivastava, Bhartendu K; Ramkumar, Venkatachalam; Muraleedharan, Kannoth M

2017-03-13

A design approach that incorporates structural requirements for the formation of a 1D assembly, fibril stability, and fibril-fibril interactions for gelation was attempted by using amino acid-based sulfamides with the general structure Aa-NH-SO 2 -NH-Aa (Aa=amino acid). A preference for 1D assembly alone was not a sufficient condition for gelation, which became evident from studies involving sulfamide esters 1-5. Reducing the crystallization tendency without hindering unidirectional growth was executed through diacids of the sulfamide precursors with various amines that form an envelope around the sulfamide core through salt bridges. This strategy was fruitful, and gels of a wide variety of solvents could be formed by varying the acid and amine components. The use of dodecylamine or benzylamine, which could stabilize the molecular layers through alkyl-chain segregation or π-π interactions improved the gelation tendency, whereas the nature of the amino acid side chain, especially the rotational freedom and hydrophobicity, had a direct role in dictating the solvent preference. Crystallographic studies of these two-component systems gave molecular-level insight into the assembly and showed the importance of anisotropy in the distribution of secondary interactions in gelation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of self-sorting and co-assembly on the mechanical properties of low molecular weight hydrogels

NASA Astrophysics Data System (ADS)

Colquhoun, Catherine; Draper, Emily R.; Eden, Edward G. B.; Cattoz, Beatrice N.; Morris, Kyle L.; Chen, Lin; McDonald, Tom O.; Terry, Ann E.; Griffiths, Peter C.; Serpell, Louise C.; Adams, Dave J.

2014-10-01

Self-sorting in low molecular weight hydrogels can be achieved using a pH triggered approach. We show here that this method can be used to prepare gels with different types of mechanical properties. Cooperative, disruptive or orthogonal assembled systems can be produced. Gels with interesting behaviour can be also prepared, for example self-sorted gels where delayed switch-on of gelation occurs. By careful choice of gelator, co-assembled structures can also be generated, which leads to synergistic strengthening of the mechanical properties.Self-sorting in low molecular weight hydrogels can be achieved using a pH triggered approach. We show here that this method can be used to prepare gels with different types of mechanical properties. Cooperative, disruptive or orthogonal assembled systems can be produced. Gels with interesting behaviour can be also prepared, for example self-sorted gels where delayed switch-on of gelation occurs. By careful choice of gelator, co-assembled structures can also be generated, which leads to synergistic strengthening of the mechanical properties. Electronic supplementary information (ESI) available: Full experimental and synthetic details for the dipeptides, full experimental descriptions, further NMR, single crystal diffraction data, fXRD data and SANS data. See DOI: 10.1039/c4nr04039b

Slow-release Permanganate Gel (SRP-G) for Groundwater Remediation: Spreading, Gelation, and Release in Porous and Low-Permeability Media

NASA Astrophysics Data System (ADS)

Lee, E. S.; Hastings, J.; Kim, Y.

2015-12-01

Dense nonaqueous phase liquids (DNAPLs) like trichloroethylene (TCE) serve as the most common form of groundwater pollution in the world. Pore-plugging by the solid oxidation product MnO2 and limited lateral dispersion of the oxidant are two common problems with existing in-situ chemical oxidation (ISCO) schemes that could be alleviated through the development of a delayed gelation method for oxidant delivery. The objective of the current study was to further develop and optimize slow-release permanganate gel (SRP-G), a solution comprising colloidal silica and KMnO4, as a novel low-cost treatment option for large and dilute TCE plumes in groundwater. Batch tests showed that gelation could be delayed through manipulation of KMnO4 concentration, pH, and silica particle size of the SRP-G solution. In flow-through columns and flow-tanks filled with saturated sands, silica concentration had little effect on the gelation lag stage and release rate, but increasing silica concentration was associated with increasing release duration. When compared to a pure KMnO4 solution, visual observations and [MnO4-] measurements from flow tank tests demonstrated that the SRP-G prolonged the release duration and enhanced lateral spreading of the oxidant.

Critical behavior of modulus of gel

NASA Astrophysics Data System (ADS)

Tokita, Masayuki; Niki, Ryoya; Hikichi, Kunio

1985-09-01

The critical behavior of the shear modulus of casein gel is studied. The shear modulus of casein gel scales with the conductivity exponent in the immediate vicinity of the sol-gel transition point. The asymptotic behavior of the modulus in the region far above the transition point is governed by a different exponent which is much larger than the conductivity exponent. These results are explainable by the crossover behavior of the percolation process. This study shows that the gelation of the casein micelle solution is a realization of the percolation process.

A catalyst-free, temperature controlled gelation system for in-mold fabrication of microgels.

PubMed

Krüger, Andreas J D; Köhler, Jens; Cichosz, Stefan; Rose, Jonas C; Gehlen, David B; Haraszti, Tamás; Möller, Martin; De Laporte, Laura

2018-06-19

Anisometric microgels are prepared via thermal crosslinking using an in-mold polymerization technique. Star-shaped poly(ethylene oxide-stat-propylene oxide) polymers, end-modified with amine and epoxy groups, form hydrogels, of which the mechanical properties and gelation rate can be adjusted by the temperature, duration of heating, and polymer concentration. Depending on the microgel stiffness, the rod-shaped microgels self-assemble into ordered or disordered structures.

Tunable emission in lanthanide coordination polymer gels based on a rationally designed blue emissive gelator.

PubMed

Sutar, Papri; Suresh, Venkata M; Maji, Tapas Kumar

2015-06-18

Rational design and synthesis of a new low molecular weight gelator (LMWG) having 9,10-diphenylanthracene core and terminal terpyridine is reported. Tb(III) and Eu(III) ion coordination to a LMWG results in green and pink emissive coordination polymer gels, respectively, with coiled nanofiber morphology. Further, control over stoichiometry of LMWG:Tb(III):Eu(III) leads to yellow and white light emitting bimetallic gels.

Easy Access to Supramolecular Gels of the Nonsteroidal Anti-inflammatory Drug Diflunisal: Synthesis, Characterization, and Plausible Biomedical Applications.

PubMed

Parveen, Rumana; Dastidar, Parthasarathi

2015-11-01

By exploiting salt formation, a new series of primary ammonium monocarboxylate salts of a nonsteroidal anti-inflammatory drug, namely, diflunisal, was synthesized. The majority of the salts thus synthesized turned out to be good gelators of various solvents, including the solvents (e.g., methyl salicylate and pure water) typically used for topical gel formulation. Single-crystal X-ray diffraction studies of a few gelator and nongelator salts in the series revealed details of the hydrogen-bonding networks present in the salts. Furthermore, one such gelator salt, namely, the diflunisal salt of serinol, was found to be biocompatible (MTT assay), and its anti-inflammatory (PGE2 assay) response turned out to be as good as that of the parent drug, which is indicative of its potential in biomedical applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methods for controlling pore morphology in aerogels using electric fields and products thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Worsley, Marcus A.; Baumann, Theodore F.; Satcher, Jr., Joe H.

In one embodiment, an aerogel or xerogel includes column structures of a material having minor pores therein and major pores devoid of the material positioned between the column structures, where longitudinal axes of the major pores are substantially parallel to one another. In another embodiment, a method includes heating a sol including aerogel or xerogel precursor materials to cause gelation thereof to form an aerogel or xerogel and exposing the heated sol to an electric field, wherein the electric field causes orientation of a microstructure of the sol during gelation, which is retained by the aerogel or xerogel. In onemore » approach, an aerogel has elongated pores extending between a material arranged in column structures having structural characteristics of being formed from a sol exposed to an electric field that causes orientation of a microstructure of the sol during gelation which is retained by the elongated pores of the aerogel.« less

Fluoride-responsive gelator and colorimetric sensor based on simple and easy-to-prepare cyano-substituted amide.

PubMed

Zhang, Yuping; Jiang, Shimei

2012-09-14

A new and easy-to-prepare gelator based on cyano-substituted amide (BPNIA) was designed and synthesized. BPNIA could form thermoreversible gel in DMSO-H(2)O (v/v, 9 : 1) and ultrasound-stimulated gel in DMSO. FT-IR, UV-vis and XRD spectra indicated that the gelator molecules self-assemble into a fibrous network resulting from the cooperation of intermolecular hydrogen bonding, π-π stacking and cyano interactions. BPNIA can act as a highly selective colorimetric sensor for fluoride in DMSO, overcoming the interference of H(2)PO(4)(-), AcO(-) and other halide anions. The deprotonation of the NH groups is responsible for the dramatic color change from colorless to yellow. Interestingly, the organogel of BPNIA could allow a two channel fluoride response by proton controlled reversible sol-gel transition and color changes.

Behaviour of a solvent trapped in a physical molecular gel

NASA Astrophysics Data System (ADS)

Morfin, I.; Spagnoli, S.; Rambaud, C.; Longeville, S.; Plazanet, M.

2016-03-01

Physical gels formed by amphiphilic molecules, namely in this study Methyl-4,6-O-benzylidene-? -D-mannopyranoside, can be form either in polar and protic liquid-like water or in organic apolar solvent such as toluene. The solvent, that influences the supramolecular organization of the gelators, plays an important role in the stability and formation of the gel phase. Gelator-solvent interactions govern not only the assembly but also the solvent diffusion in the material. We present here measurements of neutron scattering (Time of Flight and Neutron Spin Echo) characterizing this microscopic behaviour. In addition, we show that transient grating spectroscopy provides valuable information through the characterization of the longitudinal acoustic wave propagating in the system. Opposite effects on the speed of sound in the gels are observed for the two solvents investigated, being relevant of the interactions between the gelators and the surrounding liquid.

Rational construction of gel-based supramolecular logic gates by using a functional gelator with multiple-stimuli responsive properties.

PubMed

Fan, Kaiqi; Yang, Jun; Wang, Xiaobo; Song, Jian

2014-11-07

A gelator containing a sorbitol moiety and a naphthalene-based salicylideneaniline group exhibits macroscopic gel-sol behavior in response to four complementary input stimuli: temperature, UV light, OH(-), and Cu(2+). On the basis of its multiple-stimuli responsive properties, we constructed a rational gel-based supramolecular logic gate that performed OR and INH types of reversible stimulus responsive gel-sol transition in the presence of various combinations of the four stimuli when the gel state was defined as an output. Moreover, a combination two-output logic gate was obtained, owing to the existence of the naked eye as an additional output. Hence, gelator 1 could construct not only a basic logic gate, but also a two-input-two-output logic gate because of its response to multiple chemical stimuli and multiple output signals, in which one input could erase the effect of another input.

Pharmaceutical polymorph control in a drug-mimetic supramolecular gel† †Electronic supplementary information (ESI) available: Synthetic and crystallographic experimental details, rheology, full crystallization and calculation details. See DOI: 10.1039/c6sc04126d Click here for additional data file.

PubMed Central

Foster, Jonathan A.; Damodaran, Krishna K.; Maurin, Antoine; Thompson, Hugh P. G.; Cameron, Gary J.; Bernal, Jenifer Cuesta

2017-01-01

We report the synthesis of a bis(urea) gelator designed to specifically mimic the chemical structure of the highly polymorphic drug substance ROY. Crystallization of ROY from toluene gels of this gelator results in the formation of the metastable red form instead of the thermodynamic yellow polymorph. In contrast, all other gels and solution control experiments give the yellow form. Conformational and crystal structure prediction methods have been used to propose the structure of the gel and show that the templation of the red form by the targeted gel results from conformational matching of the gelator to the ROY substrate coupled with overgrowth of ROY onto the local periodic structure of the gel fibres. PMID:28451150

Effects of nano-scaled fish bone on the gelation properties of Alaska pollock surimi.

PubMed

Yin, Tao; Park, Jae W

2014-05-01

Gelation properties of Alaska pollock surimi as affected by addition of nano-scaled fish bone (NFB) at different levels (0%, 0.1%, 0.25%, 0.5%, 1% and 2%) were investigated. Breaking force and penetration distance of surimi gels after setting increased significantly as NFB concentration increased up to 1%. The first peak temperature and value of storage modulus (G'), which is known to relate to the unfolding and aggregation of light meromyosin, increased as NFB concentration increased. In addition, 1% NFB treatment demonstrated the highest G' after gelation was completed. The activity of endogenous transglutaminase (TGase) in Alaska pollock surimi increased as NFB calcium concentration increased. The intensity of myosin heavy chain cross-links also increased as NFB concentration increased indicating the formation of more ε-(γ-glutamyl) lysine covalent bond by endogenous TGase and calcium ions from NFB. Copyright © 2013 Elsevier Ltd. All rights reserved.

Hyper alginate gel microbead formation by molecular diffusion at the hydrogel/droplet interface.

PubMed

Hirama, Hirotada; Kambe, Taisuke; Aketagawa, Kyouhei; Ota, Taku; Moriguchi, Hiroyuki; Torii, Toru

2013-01-15

We report a simple method for forming monodispersed, uniformly shaped gel microbeads with precisely controlled sizes. The basis of our method is the placement of monodispersed sodium alginate droplets, formed by a microfluidic device, on an agarose slab gel containing a high-osmotic-pressure gelation agent (CaCl(2) aq.): (1) the droplets are cross-linked (gelated) due to the diffusion of the gelation agent from the agarose slab gel to the sodium alginate droplets and (2) the droplets simultaneously shrink to a fraction of their original size (<100 μm in diameter) due to the diffusion of water molecules from the sodium alginate droplets to the agarose slab gel. We verified the mass transfer mechanism between the droplet and the agarose slab gel. This method circumvents the limitations of gel microbead formation, such as the need to prepare microchannels of various sizes, microchannel clogging, and the deformation of the produced gel microbeads.

Heat-induced gelation of myosin in a low ionic strength solution containing L-histidine.

PubMed

Hayakawa, T; Yoshida, Y; Yasui, M; Ito, T; Iwasaki, T; Wakamatsu, J; Hattori, A; Nishimura, T

2012-01-01

Binding properties are important for meat products and are substantially derived from the heat-induced gelation of myosin. We have shown that myosin is solubilized in a low ionic strength solution containing L-histidine. To clarify its processing characteristics, we investigated properties and structures of heat-induced gels of myosin solubilized in a low ionic strength solution containing L-histidine. Myosin in a low ionic strength solution formed transparent gels at 40-50°C, while myosin in a high ionic strength solution formed opaque gels at 60-70°C. The gel of myosin in a low ionic strength solution with L-histidine showed a fine network consisting of thin strands and its viscosity was lower than that of myosin in a high ionic strength solution at 40-50°C. The rheological properties of heat-induced gels of myosin at low ionic strength are different from those at high ionic strength. This difference might be caused by structural changes in the rod region of myosin in a low ionic strength solution containing L-histidine. Copyright © 2011 Elsevier Ltd. All rights reserved.

Method for preparing hydrous iron oxide gels and spherules

DOEpatents

Collins, Jack L.; Lauf, Robert J.; Anderson, Kimberly K.

2003-07-29

The present invention is directed to methods for preparing hydrous iron oxide spherules, hydrous iron oxide gels such as gel slabs, films, capillary and electrophoresis gels, iron monohydrogen phosphate spherules, hydrous iron oxide spherules having suspendable particles homogeneously embedded within to form composite sorbents and catalysts, iron monohydrogen phosphate spherules having suspendable particles of at least one different sorbent homogeneously embedded within to form a composite sorbent, iron oxide spherules having suspendable particles homogeneously embedded within to form a composite of hydrous iron oxide fiber materials, iron oxide fiber materials, hydrous iron oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, iron oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, dielectric spherules of barium, strontium, and lead ferrites and mixtures thereof, and composite catalytic spherules of barium or strontium ferrite embedded with oxides of Mg, Zn, Pb, Ce and mixtures thereof. These variations of hydrous iron oxide spherules and gel forms prepared by the gel-sphere, internal gelation process offer more useful forms of inorganic ion exchangers, catalysts, getters, dielectrics, and ceramics.

Preparation of UC0.07-0.10N0.90-0.93 spheres for TRISO coated fuel particles

NASA Astrophysics Data System (ADS)

Hunt, R. D.; Silva, C. M.; Lindemer, T. B.; Johnson, J. A.; Collins, J. L.

2014-05-01

The US Department of Energy is considering a new nuclear fuel that would be less susceptible to ruptures during a loss-of-coolant accident. The fuel would consist of tristructural isotropic coated particles with dense uranium nitride (UN) kernels with diameters of 650 or 800 μm. The objectives of this effort are to make uranium oxide microspheres with adequately dispersed carbon nanoparticles and to convert these microspheres into UN spheres, which could be then sintered into kernels. Recent improvements to the internal gelation process were successfully applied to the production of uranium gel spheres with different concentrations of carbon black. After the spheres were washed and dried, a simple two-step heat profile was used to produce porous microspheres with a chemical composition of UC0.07-0.10N0.90-0.93. The first step involved heating the microspheres to 2023 K in a vacuum, and in the second step, the microspheres were held at 1873 K for 6 h in flowing nitrogen.

Fabrication of lead zirconate titanate actuator via suspension polymerization casting

NASA Astrophysics Data System (ADS)

Miao, Weiguo

2000-10-01

The research presented herein has focused on the fabrication of a lead zirconate titanate (PZT) telescopic actuator from Suspension Polymerization Casting (SPC). Two systems were studied: an acrylamide-based hydrogel, and an acrylate-based nonaqueous system. Analytical tools such as thermomechanical analysis (TMA), differential scanning calorimetry (DSC), chemorheology, thermogravimetric analysis (TGA), and differential thermal analysis (DTA) were used to investigate the polymerization and burnout processes. The acrylamide hydrogel polymerization casting process used hydroxymethyl acrylamide (HMAM) monofunctional monomer with methylenebisacrylamide (MBAM) difunctional monomer, or used methacrylamide (MAM) as monofunctional monomer. High solid loading PZT slurries with low viscosities were obtained by optimizing the amounts of dispersant and the PZT powders. The overall activation energy of gelation was calculated to be 60--76 kJ/mol for the monomer solution, this energy was increased to 91 kJ/mol with the addition of PZT powder. The results show that the PZT powder has a retardation effect on gelation. Although several PZT tubes were made using the acrylamide-based system, the demolding and drying difficulties made this process unsuitable for building internal structures, such as the telescopic actuator. The acrylate-based system was used successfully to build telescopic actuator. Efforts were made to study the influence of composition and experimental conditions on the polymerization process. Temperature was found to have the largest impact on polymerization. To adjust the polymerization temperature and time, initiator and/or catalyst were used. PZT powder has a catalytic effect on the polymerization process. Compared with acrylamide systems, acrylate provided a strong polymer network to support the ceramic green body. This high strength is beneficial for the demolding process, but it can easily cause cracks during the burnout process. To solve the burnout issue, non-reactive decalin was used as a solvent to lower the stress inside the green body. The addition of decalin has no large impact on the polymerization process. With 15 wt% decalin in the monomer solution, the burnout process was successfully solved. The burnout process was monitored by TGA/DTA and TMA. A 51 vol% PZT filled acrylate slurry was cast into a mold made by Stereolithography (SLA), and after curing, the telescopic actuator was removed from the mold. This indirect SLA method provides an efficient way to build ceramic parts. PZT samples were sintered at 1275°C for 4 hours, with density over 98%. SEM analysis showed the sample made by SPC has a uniform microstructure, which may be beneficial to the electric properties. The sample made by polymerization has a d33 value about 680 pm/V, which is better than the literature value (580 pm/V). The electric tests showed this telescopic actuator produced a maximum deflection of 24.7 mum at 250 kV/m, in line with theoretical calculations. Compared with actuators made by other methods, the actuator made by SPC provides a comparable structural factor (187.5). The distortion in actuators is caused by fabrication and sintering.

Dual Thermosensitive Hydrogels Assembled from the Conserved C-Terminal Domain of Spider Dragline Silk.

PubMed

Qian, Zhi-Gang; Zhou, Ming-Liang; Song, Wen-Wen; Xia, Xiao-Xia

2015-11-09

Stimuli-responsive hydrogels have great potentials in biomedical and biotechnological applications. Due to the advantages of precise control over molecular weight and being biodegradable, protein-based hydrogels and their applications have been extensively studied. However, protein hydrogels with dual thermosensitive properties are rarely reported. Here we present the first report of dual thermosensitive hydrogels assembled from the conserved C-terminal domain of spider dragline silk. First, we found that recombinant C-terminal domain of major ampullate spidroin 1 (MaSp1) of the spider Nephila clavipes formed hydrogels when cooled to approximately 2 °C or heated to 65 °C. The conformational changes and self-assembly of the recombinant protein were studied to understand the mechanism of the gelation processes using multiple methods. It was proposed that the gelation in the low-temperature regime was dominated by hydrogen bonding and hydrophobic interaction between folded protein molecules, whereas the gelation in the high-temperature regime was due to cross-linking of the exposed hydrophobic patches resulting from partial unfolding of the protein upon heating. More interestingly, genetic fusion of the C-terminal domain to a short repetitive region of N. clavipes MaSp1 resulted in a chimeric protein that formed a hydrogel with significantly improved mechanical properties at low temperatures between 2 and 10 °C. Furthermore, the formation of similar hydrogels was observed for the recombinant C-terminal domains of dragline silk of different spider species, thus demonstrating the conserved ability to form dual thermosensitive hydrogels. These findings may be useful in the design and construction of novel protein hydrogels with tunable multiple thermosensitivity for applications in the future.

Gelation of high-methoxy pectin by enzymic de-esterification in the presence of calcium ions: a preliminary evaluation.

PubMed

O'Brien, Aileen B; Philp, Kevin; Morris, Edwin R

2009-09-28

Cohesive gels have been obtained by de-esterification of 1.0wt% high-methoxy citrus pectin (degree of esterification approximately 68%) in the presence of Ca(2+) cations, using a commercial preparation (NovoShape) of fungal methyl esterase cloned from Aspergillus aculeatus. A convenient rate of network formation (gelation within approximately 30min) was achieved at an enzyme concentration of 0.2 PEU/g pectin. At a Ca(2+)-concentration of 40mM and incubation temperature of 20 degrees C, severe syneresis (>7% of sample mass) was observed, but release of fluid decreased with decreasing concentration of Ca(2+) and increasing temperature of incubation, becoming undetectable for 10mM Ca(2+) at 30 degrees C. Under these conditions, progressive development of solid-like character (storage modulus, G') was observed during 160min of enzymic de-esterification, and the mechanical spectrum recorded at the end of the incubation period had the form typical of a biopolymer gel. On subsequent heating to 70 degrees C, dissociation of the gel network (sigmoidal reduction in G' and G'') was observed. At or above the midpoint temperature of this melting process ( approximately 50 degrees C), there was no indication of gel formation on enzymic de-esterification (at 50 or 60 degrees C). At lower temperatures (20, 30 and 40 degrees C), the rate of gelation (assessed visually) showed no systematic increase as the incubation temperature was increased towards the temperature-optimum of the enzyme ( approximately 50 degrees C). This unexpected behaviour is attributed to competition between faster de-esterification and slower formation of Ca(2+)-induced 'egg-box' junctions.

Crystallinity enhancement of Nafion electrolyte membranes assisted by a molecular gelator.

PubMed

Zhang, Wenjing; Yue, Po-Lock; Gao, Ping

2011-08-02

Nanocrystallites, acting as physical cross-links in Nafion membranes, play a crucial role in building blocks for improving mechanical durability and stopping fuel crossover. However, Nafion membranes suffer from low crystallinity due to the irregular pendent side chains, which hinder self-aggregation of the poly(tetrafluoroethylene) (PTFE) backbones. For the first time, a molecular gelator was introduced in the membrane casting process to enhance the rate of self-assembly of PTFE backbones so as to increase the membrane's crystallinity as well as proton conductivity without sacrificing the purity of Nafion. The molecular gelator used was 3,4-dimethylbenzaldehyde (DMBA). Addition of 0.5 wt % DMBA led to a 42% increase in crystallinity, a 32% increase in yield strength, a 22% increase in tensile modulus and an 18% increase in proton conductivity at 60 °C and 90% relative humidity. Additionally, the membrane electrode assembly (MEA) prepared from the membranes cast from the solution containing 0.5 wt % DMBA also showed an increase of 17% in maximum power density in comparison to the MEA prepared from pure Nafion membrane in a single cell polarization test without any external humidification. Transmission electron microscopy (TEM) and molecular dynamics simulation were used to elucidate the structural changes in Nafion membrane due to the introduction of DMBA. It was observed that the presence of DMBA gives wider crystalline regions under TEM. The molecular dynamics simulation at 500 K shows that the PTFE backbones become elongated in the presence of DMBA due to the enhanced mobility. This is consistent with the observed increase in crystallinity in the membrane as it means reduced entropic change upon crystallization.

The effect of temperature and chitosan concentration during storage on the growth of chitosan nanoparticle produced by ionic gelation method

NASA Astrophysics Data System (ADS)

Handani, Wenny Rinda; Sediawan, Wahyudi Budi; Tawfiequrrahman, Ahmad; Wiratni, Kusumastuti, Yuni

2017-05-01

The objective of this research was to get the mechanism of nano size chitosan particle growth during storage by observing the effect of temperature and initial concentration of chitosan. The products were analyzed using PSA to have the average of particle radius. Nanochitosan solution was prepared by ionic gelation method. This method is described as an electrostatic interaction between positively charged amine with negatively charged polyanion, such as tripolyphosphate (TPP). Chitosan was dissolved in 1% acetic acid and was stirred for 30 minutes. Tween 80 was added to avoid agglomeration. TPP was prepared by dissolving 0.336 g into distilled water. The nano size chitosan was obtained by mixing TPP and chitosan solution dropwise while stirring for 30 minutes. This step was done at 15°C and ambient temperature (about 30°C) and chitosan concentration 0.2%, 0.4% and 0.6%. The results show that temperature during ionic gelation process (15°C and 30°C) does not affect the initial size of the nanoparticles produced as well as the growth of the nanoparticles during storage. On the other hand, initial chitosan concentration strongly affects initial size of the nanoparticles produced and the growth of the nanoparticles during storage. The concentration of chitosan at 0.2%, 0.4%, 0.6% gave initial size of nanoparticle chitosan of 175.3 nm, 337.9 nm, 643.3 nm respectively. On the other hand, the growth mechanism of chitosan nanoparticle depended on its radius(R). At R<500 nm, the growth rate of nanoparticles is controlled by adsorption at the surface of the particles, while at R>500 nm, it is controlled by diffusion in the liquid film around the particles.

Injectable collagen/RGD systems for bone tissue engineering applications.

PubMed

Kung, Fu-Chen

2018-01-01

Imbalance crosslink density and polymer concentration gradient is formed within the traditional alginate hydrogel using calcium chloride as a crosslinking agent in external gelation for instantaneously process. In this studying, type I collagen (Col I) blended calcium salt form of poly(γ-glutamic acid) (γCaPGA) was mixing with RGD-modified alginate with convenient gelation process and suitable for practical use. The hydrophilicity of the resulting hydrogels was evaluated through swelling tests, water retention capacity tests, and water vapor permeation tests. Mineralization was qualitatively evaluated by alizarin red dyeing at day 14, verifying the deposition of calcium. The in vitro osteogenic differentiation is monitored by determining the early and late osteocalcin (OCN) and osteopontin (OPN) markers with MG63 cells. Obtained results demonstrated that no extremely changes in mechanical properties. After 14 days of culture, hydrogels significantly stimulated OCN/OPN gene expressions and MG63 cell proliferation. Unusually, γCaPGA with RGD-modified alginate appeared better calcium deposition in 14 days than the other. However, addition of Col I can counterpoise RGD effect in blood coagulation and platelet adhesion made the hydrogel more flexibility and selectively in use. This studying provided that non-covalently crosslinked hydrogel by γCaPGA with alginate can be upgrading by RGD and Col I in water uptake capability, obviously effective for MG63 cells and are remarkably biocompatible and exhibited no cytotoxicity. Moreover, results also displayed the injectable process without complicated procedure, have high cost/performance ratio and have great potential for bone regeneration.

Method for rapidly producing microporous and mesoporous materials

DOEpatents

Coronado, P.R.; Poco, J.F.; Hrubesh, L.W.; Hopper, R.W.

1997-11-11

An improved, rapid process is provided for making microporous and mesoporous materials, including aerogels and pre-ceramics. A gel or gel precursor is confined in a sealed vessel to prevent structural expansion of the gel during the heating process. This confinement allows the gelation and drying processes to be greatly accelerated, and significantly reduces the time required to produce a dried aerogel compared to conventional methods. Drying may be performed either by subcritical drying with a pressurized fluid to expel the liquid from the gel pores or by supercritical drying. The rates of heating and decompression are significantly higher than for conventional methods. 3 figs.

Development of gastroretentive metronidazole floating raft system for targeting Helicobacter pylori.

PubMed

Abou Youssef, Nancy Abdel Hamid; Kassem, Abeer Ahmed; El-Massik, Magda Abd Elsamea; Boraie, Nabila Ahmed

2015-01-01

The study demonstrates the feasibility of prolonging gastric residence time and release rate of metronidazole (Mz) by preparing floating raft system (FRS) using ion-sensitive in situ gel forming polymers. FRSs contained 3, 4, 5 and 0.5, 0.75, 1% w/v sodium alginate (Alg) and gellan gum (G), respectively, 0.25% w/v sodium citrate and calcium carbonate (C). Lipids: glyceryl mono stearate (GMS), Precirol(®) and Compritol(®) were incorporated into G-based formulations (G1%C1%). Mz:lipid ratio was 1:1, except for Mz:GMS, ratios of 1:1.5 and 1:2 were also investigated. Buoyancy, gelation capacity and viscosity parameters were evaluated. Drug release and kinetics for selected formulae were examined. The selected lipid containing formula was subjected to an accelerated stability testing. Alg4%C2% FRS exhibited short gelation lag time (3s), long duration (>24h), floating lag time 1m in and duration >24h, and a reliable sustained drug release (MDT 6h). Gellan gum FRSs achieved successful floating gastroretention, but failed to achieve the required gelation capacity. Incorporation of GMS (Mz:GMS 1:1) enhanced the gelation lag time and duration (6s and >24h, respectively), keeping sustained drug release and formulation stability. The improved characteristics of the selected FRS make them excellent candidates for gastric targeting to eradicate Helicobacter pylori. Copyright © 2015 Elsevier B.V. All rights reserved.

Quasi-solid state electrolytes for low-grade thermal energy harvesting using a cobalt redox couple.

PubMed

Taheri, Abuzar; MacFarlane, Douglas; Pozo-Gonzalo, Cristina; Pringle, Jennifer M

2018-06-06

Thermoelectrochemical cells, also known as thermocells, are electrochemical devices for the conversion of thermal energy directly to electricity. They are a promising method for harvesting low-grade waste heat from a variety of different natural and man-made sources. The development of solid or quasi-solid state electrolytes for thermocells could address the possible leakage problems of liquid electrolytes and make this technology more applicable for wearable devices. Here we report the gelation of an organic solvent-based electrolyte system containing a redox couple, for application in thermocell technologies. The effect of gelation of the liquid electrolyte, comprising a cobalt bipyridyl redox couple dissolved in 3-methoxypropionitrile (MPN), on the performance of thermocells was investigated. Polyvinylidene difluoride (PVDF) and poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP) were used for gelation of the electrolyte, and the influence of the different polymers on the mechanical properties was studied. The Seebeck coefficient and diffusivity of the cobalt redox couple were measured in both liquid and gelled electrolytes and the effect of gelation on the thermocell performance is reported. Finally, the cell performance was further improved by optimising the redox couple concentration and the separation between the hot and cold electrode, and the stability of the device over 25 hours of operation is demonstrated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The properties of gelatin-poly (gamma-glutamic acid) hydrogels as biological glues.

PubMed

Hsu, Shan-Hui; Lin, Chen-Huan

2007-01-01

The influence of the molecular weight and the type of gelatin (A or B), as well as the molecular weight of poly (gamma-glutamic acid) (gamma-PGA), on the properties of gelatin/gamma-PGA mixed bioadhesives were studied. The gelation of the system was enhanced by a crosslinker, 1-(3-dimethylaminopropyl)-3-(ethylcarbodiimide) hydrochloride (EDC). The gelation time of the bioadhesives was analyzed using rheological measurements. The results indicated that the type of gelatin was a critical factor in determining the gelation time of the biological glues. The mixed glues had greater bonding strength and smaller gelation times as the molecular weight of gamma-PGA or gelatin increased. The swelling ratio decreased and the denaturation temperature increased upon raising the EDC concentration, indicating a greater degree of crosslinking at higher EDC concentrations. The mixed glues crosslinked with various concentrations of EDC (1.7-2.5%) showed no cytotoxicity to fibroblasts. In addition, no significant inflammatory response was observed in the rat subcutaneous implantation. The bioadhesives based on gelatin/gamma-PGA remained at the site for 7 days while the fibrin glue had almost completely degraded. By choosing the appropriate gelatin type and higher molecular weight gamma-PGA in the mixtures, the gelatin/gamma-PGA biological glues could serve as soft tissue adhesives. Rheological characterization was essential in the evaluation of biological glues.

Influence of several metal ions on the gelation activation energy of silicon tetraethoxide

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.

1988-01-01

The effects of nine metal cations (Li(+), Na(+), Mg(2+), Ca(2+), Sr(2+), Cu(2+), Al(3+), La(3+), and Y(3+) on silica gel formation has been investigated by studying the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) in the presence of metal nitrates. The influence of water: TEOS mole ratio, metal ion concentration, and the reaction temperature has been investigated. The overall activation energy for gel formation has been determined from the temperature dependence of the time of gelation for each system. The activation energy for -Si-O-Si- network formation is found to be 54.5 kJ/mol. The gel formation time as well as the activation energy sharply increase in the presence of Cu(2+), Al(3+), La(3+) and Y(3+). In contrast, the presence of Li(+), Na(+), Mg(2+), Ca(2+), or, Sr(2+) lowers the gelation time, but has no appreciable effect on the activation energy. This difference may be attributed to the participation or nonparticipation of the metal ions in the formation of the three-dimensional polymeric network during the polycondensation step. The concentration of metal ion (Mg(2+), Ca(2+), Y(3+) or the water: TEOS mole ratio had no appreciable effect on the gelation activation energy. A simple test has been proposed to determine whether a metal ion would act as a network intermediate or modifier in silica and other glassy networks.

Localized internal radiotherapy with 90Y particles embedded in a new thermosetting alginate gel: a feasibility study in pigs.

PubMed

Holte, Oyvind; Skretting, Arne; Bach-Gansmo, Tore; Hol, Per Kristian; Johnsrud, Kjersti; Tønnesen, Hanne Hjorth; Karlsen, Jan

2006-02-01

Internal radiotherapy requires the localization of the radionuclide to the site of action. A new injectable alginate gel formulation intended to undergo immediate gelation in tissues and capable of encapsulating radioactive particles containing 90Y was investigated. The formulation was injected intramuscularly, into the bone marrow compartment of the femur and intravenously, respectively, in pigs. The distribution of radioactivity in various tissues was determined. Following intramuscular injection, more than 90% of the radioactivity was found at the site of injection. Following injection into bone marrow, 30-40% of the radioactivity was retained at the site of injection, but a considerable amount of radioactivity was also detected in the lungs (35-45%) and the liver (5-18%). Following intravenous injection, 80-90% of the radioactivity was found in the lungs. The present formulation appears suitable for localized radiotherapy in organs and tissues having low perfusion.

Vitrification and gelation in sticky spheres

NASA Astrophysics Data System (ADS)

Royall, C. Patrick; Williams, Stephen R.; Tanaka, Hajime

2018-01-01

Glasses and gels are the two dynamically arrested, disordered states of matter. Despite their importance, their similarities and differences remain elusive, especially at high density, where until now it has been impossible to distinguish them. We identify dynamical and structural signatures which distinguish the gel and glass transitions in a colloidal model system of hard and "sticky" spheres. It has been suggested that "spinodal" gelation is initiated by gas-liquid viscoelastic phase separation to a bicontinuous network and the resulting densification leads to vitrification of the colloid-rich phase, but whether this phase has sufficient density for arrest is unclear [M. A. Miller and D. Frenkel, Phys. Rev. Lett. 90, 135702 (2003) and P. J. Lu et al., Nature 435, 499-504 (2008)]. Moreover alternative mechanisms for arrest involving percolation have been proposed [A. P. R. Eberle et al., Phys. Rev. Lett. 106, 105704 (2011)]. Here we resolve these outstanding questions, beginning by determining the phase diagram. This, along with demonstrating that percolation plays no role in controlling the dynamics of our system, enables us to confirm spinodal decomposition as the mechanism for gelation. We are then able to show that gels can be formed even at much higher densities than previously supposed, at least to a volume fraction of ϕ = 0.59. Far from being networks, these gels apparently resemble glasses but are still clearly distinguished by the "discontinuous" nature of the transition and the resulting rapid solidification, which leads to the formation of inhomogeneous (with small voids) and far-from-equilibrium local structures. This is markedly different from the glass transition, whose continuous nature leads to the formation of homogeneous and locally equilibrated structures. We further reveal that the onset of the attractive glass transition in the form of a supercooled liquid is in fact interrupted by gelation. Our findings provide a general thermodynamic, dynamic, and structural basis upon which we can distinguish gelation from vitrification.

Efficient Synthesis of MCu (M = Pd, Pt, and Au) Aerogels with Accelerated Gelation Kinetics and their High Electrocatalytic Activity.

PubMed

Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang; Song, Junhua; Xia, Haibing; Du, Dan; Lin, Yuehe

2016-10-01

To accelerate hydrogel formation and further simplify the synthetic procedure, a series of MCu (M = Pd, Pt, and Au) bimetallic aerogels is synthesized from the in situ reduction of metal precursors through enhancement of the gelation kinetics at elevated temperature. Moreover, the resultant PdCu aerogel with ultrathin nanowire networks exhibits excellent electrocatalytic performance toward ethanol oxidation, holding promise in fuel-cell applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new experimental design method to optimize formulations focusing on a lubricant for hydrophilic matrix tablets.

PubMed

Choi, Du Hyung; Shin, Sangmun; Khoa Viet Truong, Nguyen; Jeong, Seong Hoon

2012-09-01

A robust experimental design method was developed with the well-established response surface methodology and time series modeling to facilitate the formulation development process with magnesium stearate incorporated into hydrophilic matrix tablets. Two directional analyses and a time-oriented model were utilized to optimize the experimental responses. Evaluations of tablet gelation and drug release were conducted with two factors x₁ and x₂: one was a formulation factor (the amount of magnesium stearate) and the other was a processing factor (mixing time), respectively. Moreover, different batch sizes (100 and 500 tablet batches) were also evaluated to investigate an effect of batch size. The selected input control factors were arranged in a mixture simplex lattice design with 13 experimental runs. The obtained optimal settings of magnesium stearate for gelation were 0.46 g, 2.76 min (mixing time) for a 100 tablet batch and 1.54 g, 6.51 min for a 500 tablet batch. The optimal settings for drug release were 0.33 g, 7.99 min for a 100 tablet batch and 1.54 g, 6.51 min for a 500 tablet batch. The exact ratio and mixing time of magnesium stearate could be formulated according to the resulting hydrophilic matrix tablet properties. The newly designed experimental method provided very useful information for characterizing significant factors and hence to obtain optimum formulations allowing for a systematic and reliable experimental design method.

Solubilization of rehydrated frozen highly concentrated micellar casein for use in liquid food applications.

PubMed

Lu, Y; McMahon, D J; Metzger, L E; Kommineni, A; Vollmer, A H

2015-09-01

Highly concentrated micellar casein concentrate (HC-MCC), a potential ingredient of protein-fortified food, is a gel at cold temperature. It contains ~17 to 21% casein, with most serum proteins and lactose removed by microfiltration and diafiltration, and it is then further concentrated using vacuum evaporation. The HC-MCC can be stored frozen, and our objective was to determine the conditions needed to obtain complete solubility of thawed HC-MCC in water and to understand its gelation upon cooling. Dispersibility (ability to pass through a 250-µm mesh sieve), suspendability (percentage of protein not sedimented at 80 × g within 5min), and solubility (percentage of protein not sedimented at 20,000 × g within 5min) were measured at 4, 12, or 20°C after various mixing conditions. Gelation upon cooling from 50 to 5°C was monitored based on storage (G') and loss (G'') moduli. The gelled HC-MCC was also examined by transmission electron microscopy. Thawed HC-MCC was added to water to reach a protein concentration of 3% and mixed using high shear (7,500rpm) for 1min or low shear (800rpm) for 30min at 4, 12, 20, or 50°C and at pH 6.4 to 7.2. The HC-MCC completely dispersed at 50°C, or at ≤20°C followed by overnight storage at 4°C. Suspendability at 50°C was ~90% whereas mixing at ≤20°C followed by overnight storage resulted in only ~57% suspendability. Solubility followed a similar trend with ~83% at 50°C and only ~29% at ≤20°C. Mixing HC-MCC with 60mM trisodium citrate increased dispersibility to 99% and suspendability and solubility to 81% at 20°C. Cold-gelling temperature, defined as the temperature at which G'=G'' when cooling from 50 to 5°C, was positively correlated with protein level in HC-MCC. Gelation occurred at 38, 28, and 7°C with 23, 20, and 17% of protein, respectively. Gelation was reversible upon heating, although after a second cooling cycle the HC-MCC gel had lower G'. In micrographs of gelled HC-MCC, the casein micelles were observed to be within the normal size range but packed very closely together, with only ~20 to 50 nm of space between them. We proposed that cold-gelation of HC-MCC occurs when the kinetic energy of the casein micelles is sufficiently reduced to inhibit their mobility in relation to adjacent casein micelles. Understanding solubilization of rehydrated frozen HC-MCC and its rheological properties can help in designing process systems for using HC-MCC as a potential ingredient in liquid food. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Helicobacter pylori Couples Motility and Diffusion to Actively Create a Heterogeneous Complex Medium in Gastric Mucus

NASA Astrophysics Data System (ADS)

Mirbagheri, Seyed Amir; Fu, Henry Chien

2016-05-01

Helicobacter pylori swims through mucus gel by generating ammonia that locally neutralizes the acidic gastric environment, turning nearby gel into a fluid pocket. The size of the fluid zone is important for determining the physics of the motility: in a large zone swimming occurs as in a fluid through hydrodynamic principles, while in a very small zone the motility could be strongly influenced by nonhydrodynamic cell-mucus interactions including chemistry and adhesion. Here, we calculate the size of the fluid pocket. We model how swimming depends on the de-gelation range using a Taylor sheet swimming through a layer of Newtonian fluid bounded by a Brinkman fluid. Then, we model how the de-gelation range depends on the swimming speed by considering the advection-diffusion of ammonia exuded from a translating sphere. Self-consistency between both models determines the values of the swimming speed and the de-gelation range. We find that H. pylori swims through mucus as if unconfined, in a large pocket of Newtonian fluid.

Microwave dielectric study of an oligomeric electrolyte gelator by time domain reflectometry.

PubMed

Kundu, Shyamal Kumar; Yagihara, Shin; Yoshida, Masaru; Shibayama, Mitsuhiro

2009-07-30

The dynamics of water molecules in aqueous solutions of an oligomeric electrolyte gelator, poly[pyridinium-1,4-diyliminocarbonyl-1,4-phenylene-methylene chloride] (1-Cl) was characterized by microwave dielectric measurements using the time domain reflectometry method. The dielectric dispersion and absorption curves related to the orientational motion of water molecules were described by the Cole-Cole equation. Discontinuities were observed in the concentration dependence of the dielectric relaxation strength, Deltaepsilonh, as well as in the Cole-Cole parameter, betah. These discontinuities were observed between the samples with concentrations of 6 and 7 g/L 1-Cl/water, which correspond to a change in the transparency. Such a discontinuity corresponds to the observation of the critical concentration of gelation. The interaction between water and 1-Cl molecules was discussed from the tauh-betah diagram. As 1-Cl carries an amide group, it could be expected that 1-Cl may interact hydrophilically with water, but the present result suggests that 1-Cl interact hydrophobically with water.

Evaluation of in vitro and in vivo biocompatibility of a myo-inositol hexakisphosphate gelated polyaniline hydrogel in a rat model

NASA Astrophysics Data System (ADS)

Sun, Kwang-Hsiao; Liu, Zhao; Liu, Changjian; Yu, Tong; Shang, Tao; Huang, Chen; Zhou, Min; Liu, Cheng; Ran, Feng; Li, Yun; Shi, Yi; Pan, Lijia

2016-04-01

Recent advances in understanding the interaction between electricity and cells/biomolecules have generated great interest in developing biocompatible electrically conductive materials. In this study, we investigated the biocompatibility of a myo-inositol hexakisphosphate gelated polyaniline hydrogel using in vitro and in vivo experiments in a rat model. The polyaniline hydrogel was used to coat a polycaprolactone scaffold and was cultured with rat endothelial progenitor cells differentiated from rat adipose-derived stem cells. Compared with the control sample on a pristine polycaprolactone scaffold, the treated polyaniline hydrogel had the same non-poisonous/cytotoxicity grade, enhanced cell adhesion, and a higher cell proliferation/growth rate. In implant studies, the polyaniline hydrogel sample induced milder inflammatory responses than did the control at the same time points. Combining the advantages of a biocompatible hydrogel and an organic conductor, the inositol phosphate-gelated polyaniline hydrogel could be used in bioelectronics applications such as biosensors, neural probes, cell stimulators, medical electrodes, tissue engineering, and electro-controlled drug delivery.

Supramolecular ionogel lubricants with imidazolium-based ionic liquids bearing the urea group as gelator.

PubMed

Yu, Qiangliang; Wu, Yang; Li, DongMei; Cai, Meirong; Zhou, Feng; Liu, Weimin

2017-02-01

A new class of ionic liquid gels (ionogels) is prepared through the supramolecular self-assembly of imidazolium-based ionic liquids (ILs) bearing the urea group as gelators in normal ILs. The ILs gelator can self-assemble through hydrogen bonding and hydrophobic interaction to form analogous lamellar structures and solidify base ILs. The obtained ionogels exhibit superior anticorrosion and conductivity characteristics. Moreover, ionogels show fully thermoreversible and favorable thixotropic characteristics, such that they can be used as high-performance semisolid conductive lubricants. The tribological tests reveal that these ionogels lubricants can effectively reduce the friction of sliding pairs effectively and have better tribological performance than the pure ILs under harsh conditions. Ionogel lubricants not only maintain the excellent tribological properties and conductivity of ILs, but also prevent base liquids from creeping and leakage. Therefore, ionogel lubricants can be potentially used in the conductive parts of electrical equipments. Copyright © 2016 Elsevier Inc. All rights reserved.

A physical organogel electrolyte: characterized by in situ thermo-irreversible gelation and single-ion-predominent conduction

PubMed Central

Kim, Young-Soo; Cho, Yoon-Gyo; Odkhuu, Dorj; Park, Noejung; Song, Hyun-Kon

2013-01-01

Electrolytes are characterized by their ionic conductivity (σi). It is desirable that overall σi results from the dominant contribution of the ions of interest (e.g. Li+ in lithium ion batteries or LIB). However, high values of cationic transference number (t+) achieved by solid or gel electrolytes have resulted in low σi leading to inferior cell performances. Here we present an organogel polymer electrolyte characterized by a high liquid-electrolyte-level σi (~101 mS cm−1) with high t+ of Li+ (>0.8) for LIB. A conventional liquid electrolyte in presence of a cyano resin was physically and irreversibly gelated at 60°C without any initiators and crosslinkers, showing the behavior of lower critical solution temperature. During gelation, σi of the electrolyte followed a typical Arrhenius-type temperature dependency, even if its viscosity increased dramatically with temperature. Based on the Li+-driven ion conduction, LIB using the organogel electrolyte delivered significantly enhanced cyclability and thermal stability. PMID:23715177

Hybrid gels assembled from Fmoc-amino acid and graphene oxide with controllable properties.

PubMed

Xing, Pengyao; Chu, Xiaoxiao; Li, Shangyang; Ma, Mingfang; Hao, Aiyou

2014-08-04

A supramolecular gel is obtained from the self-assembly of an ultralow-molecular-weight gelator (N-fluorenyl-9-methoxycarbonyl glutamic acid) in good and poor solvents. The gelators can self-assemble into a lamellar structure, which can further form twisted fibers and nanotubes in the gel phase. Rheological studies show that the gels are robust and rigid, and are able to rapidly self-recover to a gel after being destroyed by shear force. Fluorescence experiments reveal the aggregation-induced emission effects of the gel system; the fluorescence intensity is significantly enhanced by gel formation. Graphene oxide (GO) is introduced into the system efficiently to give a hybrid material, and the interaction between gelators-GO sheets is studied. Rheological and fluorescent studies imply that the mechanical properties and the fluorescent emission of the hybrid materials can be fine-tuned by controlling the addition of GO. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heat-induced gelation of casein micelles in aqueous suspensions at different pH.

PubMed

Thomar, Peggy; Nicolai, Taco

2016-10-01

Heat-induced gelation of casein micelles in aqueous solution was investigated between pH 5.2 and pH 6.7 over a wide range of protein concentrations (C=25-160gL(-1)). For C≥40gL(-1) the casein micelles rapidly formed a self-supporting gel above a critical temperature (Tc). At C=160gL(-1), Tc decreased from 90°C at pH 6.5 to 30°C at pH 5.4 and increased with decreasing protein concentration. Oscillatory shear measurements during heating showed that the elastic modulus (Gel) of the gels increased strongly with increasing protein concentration, but was insensitive to the pH and the heating temperature except close to Tc where Gel decreased sharply with decreasing temperature. The microstructure of the gels was observed by confocal scanning laser microscopy. Heat-induced gelation of casein micelles was compared with that of sodium caseinate solutions free of calcium phosphate. Copyright © 2016 Elsevier B.V. All rights reserved.

Rheological study of the effect of polyethylene oxide (PEO) homopolymer on the gelation of PEO-PPO-PEO triblock copolymer in aqueous solution

NASA Astrophysics Data System (ADS)

Li, Xiaolei; Hyun, Kyu

2018-05-01

The effects of polyethylene oxide (PEO) homopolymer on the gelation behavior of a PEO100-PPO65-PEO100 triblock copolymer (Pluronic F127) were explored in aqueous solution under non-isothermal and isothermal conditions. Under non-isothermal conditions (temperature sweep test), two transition points were observed on increasing temperature, that is, at lower and upper gelation temperatures (LTgel and UTgel, respectively). Between LTgel and UTgel, F127 aqueous solutions maintained a hard gel state. Both molecular weight (MW) and PEO concentration affected these two gelation temperatures. In particular, relative molecular weight (MWrel ≡ molecular weight of PEO homopolymer/PEO segment of F127) affected LTgel. LTgel decreased on increasing PEO concentration at MWrel values of <1, but increased on increasing PEO concentration at MWrel values of >1. On the other hand, UTgel decreased with increasing PEO concentration regardless of MWrel. Under isothermal conditions (fixed temperature between LTgel and UTgel), the effects of PEO homopolymer on the mechanical properties of F127 hard gel were systemically investigated using small and large amplitude oscillatory shear tests. In the linear viscoelastic regime, total intra-cycle stress and elastic intra-cycle stress were similar, and viscous response increased on increasing PEO concentration. However, at large strain amplitudes, hard gels showed intra-cycle stiffening but inter-cycle softening behavior. In addition, on increasing PEO concentrations, viscous nonlinearities underwent strain-rate thickening followed by strain-rate thinning.

3D freeform printing of silk fibroin.

PubMed

Rodriguez, Maria J; Dixon, Thomas A; Cohen, Eliad; Huang, Wenwen; Omenetto, Fiorenzo G; Kaplan, David L

2018-04-15

Freeform fabrication has emerged as a key direction in printing biologically-relevant materials and structures. With this emerging technology, complex structures with microscale resolution can be created in arbitrary geometries and without the limitations found in traditional bottom-up or top-down additive manufacturing methods. Recent advances in freeform printing have used the physical properties of microparticle-based granular gels as a medium for the submerged extrusion of bioinks. However, most of these techniques require post-processing or crosslinking for the removal of the printed structures (Miller et al., 2015; Jin et al., 2016) [1,2]. In this communication, we introduce a novel method for the one-step gelation of silk fibroin within a suspension of synthetic nanoclay (Laponite) and polyethylene glycol (PEG). Silk fibroin has been used as a biopolymer for bioprinting in several contexts, but chemical or enzymatic additives or bulking agents are needed to stabilize 3D structures. Our method requires no post-processing of printed structures and allows for in situ physical crosslinking of pure aqueous silk fibroin into arbitrary geometries produced through freeform 3D printing. 3D bioprinting has emerged as a technology that can produce biologically relevant structures in defined geometries with microscale resolution. Techniques for fabrication of free-standing structures by printing into granular gel media has been demonstrated previously, however, these methods require crosslinking agents and post-processing steps on printed structures. Our method utilizes one-step gelation of silk fibroin within a suspension of synthetic nanoclay (Laponite), with no need for additional crosslinking compounds or post processing of the material. This new method allows for in situ physical crosslinking of pure aqueous silk fibroin into defined geometries produced through freeform 3D printing. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Chemistry and Processing of Nanostructured Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fox, G A; Baumann, T F; Hope-Weeks, L J

2002-01-18

Nanostructured materials can be formed through the sol-gel polymerization of inorganic or organic monomer systems. For example, a two step polymerization of tetramethoxysilane (TMOS) was developed such that silica aerogels with densities as low as 3 kg/m{sup 3} ({approx} two times the density of air) could be achieved. Organic aerogels based upon resorcinol-formaldehyde and melamine-formaldehyde can also be prepared using the sol-gel process. Materials of this type have received significant attention at LLNL due to their ultrafine cell sizes, continuous porosity, high surface area and low mass density. For both types of aerogels, sol-gel polymerization depends upon the transformation ofmore » these monomers into nanometer-sized clusters followed by cross-linking into a 3-dimensional gel network. While sol-gel chemistry provides the opportunity to synthesize new material compositions, it suffers from the inability to separate the process of cluster formation from gelation. This limitation results in structural deficiencies in the gel that impact the physical properties of the aerogel, xerogel or nanocomposite. In order to control the properties of the resultant gel, one should be able to regulate the formation of the clusters and their subsequent cross-linking. Towards this goal, we are utilizing dendrimer chemistry to separate the cluster formation from the gelation so that new nanostructured materials can be produced. Dendrimers are three-dimensional, highly branched macromolecules that are prepared in such a way that their size, shape and surface functionality are readily controlled. The dendrimers will be used as pre-formed clusters of known size that can be cross-linked to form an ordered gel network.« less

Method for producing nanostructured metal-oxides

DOEpatents

Tillotson, Thomas M.; Simpson, Randall L.; Hrubesh, Lawrence W.; Gash, Alexander

2006-01-17

A synthetic route for producing nanostructure metal-oxide-based materials using sol-gel processing. This procedure employs the use of stable and inexpensive hydrated-metal inorganic salts and environmentally friendly solvents such as water and ethanol. The synthesis involves the dissolution of the metal salt in a solvent followed by the addition of a proton scavenger, which induces gel formation in a timely manner. Both critical point (supercritical extraction) and atmospheric (low temperature evaporation) drying may be employed to produce monolithic aerogels and xerogels, respectively. Using this method synthesis of metal-oxide nanostructured materials have been carried out using inorganic salts, such as of Fe.sup.3+, Cr.sup.3+, Al.sup.3+, Ga.sup.3+, In.sup.3+, Hf.sup.4+, Sn.sup.4+, Zr.sup.4+, Nb.sup.5+, W.sup.6+, Pr.sup.3+, Er.sup.3+, Nd.sup.3+, Ce.sup.3+, U.sup.3+ and Y.sup.3+. The process is general and nanostructured metal-oxides from the following elements of the periodic table can be made: Groups 2 through 13, part of Group 14 (germanium, tin, lead), part of Group 15 (antimony, bismuth), part of Group 16 (polonium), and the lanthanides and actinides. The sol-gel processing allows for the addition of insoluble materials (e.g., metals or polymers) to the viscous sol, just before gelation, to produce a uniformly distributed nanocomposites upon gelation. As an example, energetic nanocomposites of Fe.sub.xO.sub.y gel with distributed Al metal are readily made. The compositions are stable, safe, and can be readily ignited to thermitic reaction.

Process Defects in Composites.

DTIC Science & Technology

1995-01-30

mean velocity, U, a high kinematic viscosity, v , and a small diameter of the fibers, D , lead to a very small Reynolds number Re = UD << 1 (1) where p is...partial credit to ARO). 9. D . Krajcinovic and S . Mastilovic, "Damage Evolution and Failure Modes", in: Proc. of the Int. Conf. on Computational...34Computer Simulation of a Model for Irreversible Gelation", Journal of Physics A, Vol. 16., pp. 1221-1239. Kuksenko, V . S . and Tamuzs, V . P., 1981

Horizontal insulating barriers as a way to protect groundwater

NASA Astrophysics Data System (ADS)

Cicha-Szot, Renata; Labus, Krzysztof; Falkowicz, Sławomir; Madetko, Norbert

2018-06-01

Trenchless Technology of Forming Horizontal Insulating Barriers (TFHB) can be considered a method of groundwater protection against inflow of pollutants. In TFHB technology, the working fluid (sodium silicate solution) and the gelling agent (CO2) are injected separately, using one tool, to different zones of the aquifer profile. Carbon dioxide injected into the saturation zone rises due to buoyancy forces and reaches the silicate which was injected at the water table level. This initiates the process of silicate gelation, resulting in the formation of an insulating barrier. For technological purposes, the gelation time must be controlled, and the resulting gel must have certain mechanical properties. In order to apply THFB in real conditions it was necessary to identify important technological and technical parameters, as well as to define interactions between the injected fluid and the aquifer rocks. Geochemical modelling (equilibrium, reaction path and reactive transport) was used to identify potential geochemical effects of the application of TFHB in sandy aquifers. Certain petrophysical parameters and mineralogical assemblages of aquifers were addressed, taking into account both low and strongly mineralized groundwater. The simulations revealed that TFHB does not have a negative impact on the chemistry of rock-water systems described in this work.

The spatial-temporal characteristics of type I collagen-based extracellular matrix.

PubMed

Jones, Christopher Allen Rucksack; Liang, Long; Lin, Daniel; Jiao, Yang; Sun, Bo

2014-11-28

Type I collagen abounds in mammalian extracellular matrix (ECM) and is crucial to many biophysical processes. While previous studies have mostly focused on bulk averaged properties, here we provide a comprehensive and quantitative spatial-temporal characterization of the microstructure of type I collagen-based ECM as the gelation temperature varies. The structural characteristics including the density and nematic correlation functions are obtained by analyzing confocal images of collagen gels prepared at a wide range of gelation temperatures (from 16 °C to 36 °C). As temperature increases, the gel microstructure varies from a "bundled" network with strong orientational correlation between the fibers to an isotropic homogeneous network with no significant orientational correlation, as manifested by the decaying of length scales in the correlation functions. We develop a kinetic Monte-Carlo collagen growth model to better understand how ECM microstructure depends on various environmental or kinetic factors. We show that the nucleation rate, growth rate, and an effective hydrodynamic alignment of collagen fibers fully determines the spatiotemporal fluctuations of the density and orientational order of collagen gel microstructure. Also the temperature dependence of the growth rate and nucleation rate follow the prediction of classical nucleation theory.

Effects of a Protic Ionic Liquid on the Reaction Pathway during Non-Aqueous Sol–Gel Synthesis of Silica: A Raman Spectroscopic Investigation

PubMed Central

Martinelli, Anna

2014-01-01

The reaction pathway during the formation of silica via a two-component “non-aqueou” sol-gel synthesis is studied by in situ time-resolved Raman spectroscopy. This synthetic route is followed with and without the addition of the protic ionic liquid 1-ethylimidazolium bis(trifluoromethanesulfonyl)imide (C2HImTFSI) in order to investigate its effect on the reaction pathway. We demonstrate that Raman spectroscopy is suitable to discriminate between different silica intermediates, which are produced and consumed at different rates with respect to the point of gelation. We find that half-way to gelation monomers and shorter chains are the most abundant silica species, while the formation of silica rings strongly correlates to the sol-to-gel transition. Thus, curling up of linear chains is here proposed as a plausible mechanism for the formation of small rings. These in turn act as nucleation sites for the condensation of larger rings and thus the formation of the open and polymeric silica network. We find that the protic ionic liquid does not change the reaction pathway per se, but accelerates the cyclization process, intermediated by the faster inclusion of monomeric species. PMID:24743891

Hydrogel films and coatings by swelling-induced gelation

PubMed Central

Moreau, David; Chauvet, Caroline; Etienne, François; Rannou, François P.

2016-01-01

Hydrogel films used as membranes or coatings are essential components of devices interfaced with biological systems. Their design is greatly challenged by the need to find mild synthesis and processing conditions that preserve their biocompatibility and the integrity of encapsulated compounds. Here, we report an approach to produce hydrogel films spontaneously in aqueous polymer solutions. This method uses the solvent depletion created at the surface of swelling polymer substrates to induce the gelation of a thin layer of polymer solution. Using a biocompatible polymer that self-assembles at high concentration [poly(vinyl alcohol)], hydrogel films were produced within minutes to hours with thicknesses ranging from tens to hundreds of micrometers. A simple model and numerical simulations of mass transport during swelling capture the experiments and predict how film growth depends on the solution composition, substrate geometry, and swelling properties. The versatility of the approach was verified with a variety of swelling substrates and hydrogel-forming solutions. We also demonstrate the potential of this technique by incorporating other solutes such as inorganic particles to fabricate ceramic-hydrogel coatings for bone anchoring and cells to fabricate cell-laden membranes for cell culture or tissue engineering. PMID:27821765

Effect of carrageenan addition on the rennet-induced gelation of skim milk.

PubMed

Wang, Fang; Zhang, Wei; Ren, Fazheng

2016-09-01

Carrageenan (CG) (κ-CG, ι-CG and λ-CG) was added to skim milk and the rennet-induced aggregation was studied. Caseinomacropeptide (CMP) release, diffusing wave spectroscopy (DWS) and rheology were used to follow the structural dynamics of casein micelles during gelation. The influence of carrageenan on the nature of protein interactions in the gels was investigated using a combination of ultracentrifugation and specific dissociating agents. For the recombined samples containing κ-CG and low concentrations of ι-CG and λ-CG, the CMP release was slowed down; however, the development of DWS and rheological parameters was similar to that of the control sample, and the increase in the incorporation of proteins through calcium bridges and hydrophobic interactions may be the most likely contributors. For the recombined samples containing high concentrations of ι-CG and λ-CG, other factors may impede the gel formation process. High concentrations of ι-CG and λ-CG strongly interfered with the rennet-induced aggregation, interrupted the interaction of caseins and therefore may contribute to good quality of low-fat cheese. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Insight on the formation of chitosan nanoparticles through ionotropic gelation with tripolyphosphate.

PubMed

Koukaras, Emmanuel N; Papadimitriou, Sofia A; Bikiaris, Dimitrios N; Froudakis, George E

2012-10-01

This work reports details pertaining to the formation of chitosan nanoparticles that we prepare by the ionic gelation method. The molecular interactions of the ionic cross-linking of chitosan with tripolyphosphate have been investigated and elucidated by means of all-electron density functional theory. Solvent effects have been taken into account using implicit models. We have identified primary-interaction ionic cross-linking configurations that we define as H-link, T-link, and M-link, and we have quantified the corresponding interaction energies. H-links, which display high interaction energies and are also spatially broadly accessible, are the most probable cross-linking configurations. At close range, proton transfer has been identified, with maximum interaction energies ranging from 12.3 up to 68.3 kcal/mol depending on the protonation of the tripolyphosphate polyanion and the relative coordination of chitosan with tripolyphosphate. On the basis of our results for the linking types (interaction energies and torsion bias), we propose a simple mechanism for their impact on the chitosan/TPP nanoparticle formation process. We introduce the β ratio, which is derived from the commonly used α ratio but is more fundamental since it additionally takes into account structural details of the oligomers.

Evaluation of thermal gelation behavior of different cellulose ether polymers by rheology

NASA Astrophysics Data System (ADS)

Balaghi, S.; Edelby, Y.; Senge, B.

2014-05-01

Hydroxypropylmethylcellulose (HPMC) and Methylcellulose (MC) are cellulose ethers which can be dispersed in water and used as thickeners, emulsifiers, binders, film formers, and water-retention agents due to their hydrophilic and hydrophobic characteristics. In this study, various types of HPMCs, in comparison with two types of MCs were examined. The formed gels of the different cellulose ethers showed specific and various structural formation and network properties. The degree of methylation (Meth.) and hydroxypropylation (HyPr.) affected drastically the heat-induced gelation of the examined cellulose ethers.

A composite hydrogels-based photonic crystal multi-sensor

NASA Astrophysics Data System (ADS)

Chen, Cheng; Zhu, Zhigang; Zhu, Xiangrong; Yu, Wei; Liu, Mingju; Ge, Qiaoqiao; Shih, Wei-Heng

2015-04-01

A facile route to prepare stimuli-sensitive poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) gelated crystalline colloidal array photonic crystal material was developed. PVA was physically gelated by utilizing an ethanol-assisted method, the resulting hydrogel/crystal composite film was then functionalized with PAA to form an interpenetrating hydrogel film. This sensor film is able to efficiently diffract the visible light and rapidly respond to various environmental stimuli such as solvent, pH and strain, and the accompanying structural color shift can be repeatedly changed and easily distinguished by naked eye.

Spin-echo small-angle neutron scattering (SESANS) measurements of needle-like crystallites of gelator compounds

NASA Astrophysics Data System (ADS)

Coumou, Pieter-Jan C. J. J.; Brizard, Aurelie M. A.; van Esch, Jan H.; de Schepper, Ignatz M.; Bouwman, Wim G.

2010-11-01

From dibenzoyl cystine, a low molecular weight gelator, we have prepared needle shaped crystals at relatively high concentrations. For the first time SESANS measurements are performed on objects with this geometry. From the measurements the average diameter can be seen directly. From a more careful analysis the width distribution is determined. The gel phase itself prepared at lower concentrations did not show any signal, in contrast to what one observes with conventional SANS. This shows the complementarity of SESANS and SANS.

Stress-enhanced gelation: a dynamic nonlinearity of elasticity.

PubMed

Yao, Norman Y; Broedersz, Chase P; Depken, Martin; Becker, Daniel J; Pollak, Martin R; Mackintosh, Frederick C; Weitz, David A

2013-01-04

A hallmark of biopolymer networks is their sensitivity to stress, reflected by pronounced nonlinear elastic stiffening. Here, we demonstrate a distinct dynamical nonlinearity in biopolymer networks consisting of filamentous actin cross-linked by α-actinin-4. Applied stress delays the onset of relaxation and flow, markedly enhancing gelation and extending the regime of solidlike behavior to much lower frequencies. We show that this macroscopic network response can be accounted for at the single molecule level by the increased binding affinity of the cross-linker under load, characteristic of catch-bond-like behavior.

1H, 15N and 13C assignments of domain 5 of Dictyostelium discoideum gelation factor (ABP-120) in its native and 8M urea-denatured states.

PubMed

Hsu, Shang-Te Danny; Cabrita, Lisa D; Christodoulou, John; Dobson, Christopher M

2009-06-01

The gelation factor from Dictyostelium discoideum (ABP-120) is an actin binding protein consisting of six immunoglobulin (Ig) domains in the C-terminal rod domain. We have recently used the pair of domains 5 and 6 of ABP-120 as a model system for studying multi-domain nascent chain folding on the ribosome. Here we present the NMR assignments of domain 5 in its native and 8M urea-denatured states.

Application of microbial transglutaminase in meat foods: A review.

PubMed

Santhi, D; Kalaikannan, A; Malairaj, P; Arun Prabhu, S

2017-07-03

Microbial transglutaminase (MTG) is an enzyme isolated from a variant of Streptomyces mobaraensis that forms covalent cross-links between protein molecules. Studies are being conducted since last two decades on utilization of MTG in meat foods to improve their characteristics, such as gelation, water-binding, emulsion stability, purge loss, cooking loss, etc. MTG is one of the important topics of interest in meat processing industry due to its advantages in practical utilization and commercial exploitation. This review will discuss about the overall applications of MTG in manipulating the functional properties of meat and meat products by means of various processes such as restructuring, value addition, etc.

Engineering controllable architecture in matrigel for 3D cell alignment.

PubMed

Jang, Jae Myung; Tran, Si-Hoai-Trung; Na, Sang Cheol; Jeon, Noo Li

2015-02-04

We report a microfluidic approach to impart alignment in ECM components in 3D hydrogels by continuously applying fluid flow across the bulk gel during the gelation process. The microfluidic device where each channel can be independently filled was tilted at 90° to generate continuous flow across the Matrigel as it gelled. The presence of flow helped that more than 70% of ECM components were oriented along the direction of flow, compared with randomly cross-linked Matrigel. Following the oriented ECM components, primary rat cortical neurons and mouse neural stem cells showed oriented outgrowth of neuronal processes within the 3D Matrigel matrix.

Self-assembly mechanism of 1,3:2,4-di(3,4-dichlorobenzylidene)-D-sorbitol and control of the supramolecular chirality.

PubMed

Li, Jingjing; Fan, Kaiqi; Guan, Xidong; Yu, Yingzhe; Song, Jian

2014-11-11

Dibenzylidene-D-sorbitol (DBS) and its derivatives are known to form gels in organic solvents; however, the mechanism of the gel formation has been a subject of much debate. The present work is undertaken to elucidate the organization mechanism of a DBS derivative, 1,3:2,4-di(3,4-dichlorobenzylidene)-D-sorbitol (DCDBS), by taking into account the solvent effects and comparing the experiment data with theoretical calculation. These molecules form smooth nonhelical fibers with a rest circular dichroism (CD) signal in polar solvents, in contrast to rope-liked left-helical fibers with a strong negative CD signal observed in nonpolar solvents. The molecular complexes thus formed were characterized by means of Fourier transform infrared spectra, ultraviolet-visible spectra, X-ray diffraction patterns, static contact angles, and theoretical calculations. It was proposed that the interactions between the gelator and the solvents could subtly change the stacking of the molecules and hence their self-assembled nanostructures. In nonpolar solvents, the gelator molecules appear as a distorted T-shaped structure with the 6-OH forming intermolecular hydrogen bonds with the acetal oxygens of adjacent gelator molecule. In addition, because of differential stacking interactions on both sides of the 10-member ring skeleton of the gelator, the oligomers may assemble in a helix fashion to minimize the energy, leading to helical fibers. In polar solvents, however, the gelator molecules show a rigid planelike structure and thus stack on top of each other because of strong parallel-displaced π interactions. The balanced driving force on both sides of the 10-member ring skeleton made it difficult for the dimers to bend, thus resulting in nonhelical nanostructure. As expected from the mechanisms proposed here, twisted ribbon fibers with a medium strength CD signal were obtained when solvents of different polarities were mixed. Thus, solvent effects revealed in this work represent an effective means of realizing in situ tuning of nanostructures and control of the expression of chirality at supramolecular levels.

Synthesis and characterization of sugar based low molecular weight gelators and the preparation of chiral sulfinamides

NASA Astrophysics Data System (ADS)

Mangunuru, Hari Prasad Reddy

Low molecular weight gelators (LMWGs) have received considerable attention in the field of chemistry from last few decades. These compounds form self-assembled fibrous networks like micelles, cylindrical, sheets, fibers, layers and so on. The fibrous network entraps the solvent and forms gel, because of the self-assembly phenomenon and their demonstrated potential uses in a variety of areas, ranging from environmental to medicinal applications. Sugars are good starting materials to synthesize the new class of LMWG's, because these are different from some expensive materials, these are natural products. We have synthesized and characterized the LMGS's based on D-glucose and D-glucosamine. D-glucosamine is the versatile starting material to make different peptoids and triazoles. Several series of compounds were synthesized using compounds 1-3 as starting material and studied the gelation behavior all the compounds. We have studied the self-assembling properties of a new class of tripeptoids, synthesized by one-pot Ugi reaction from simple starting materials. Among the focused library of tripeptoids synthesized, we found that several efficient low molecular weight organogelators were obtained for aqueous DMSO and ethanol mixtures. We have also synthesized and characterized a series of monosaccharide triazole derivatives. These compounds were synthesized from N-acetyl glucosamine and D-glucose via a Cu(I) catalyzed azide/alkyne cycloaddition reaction (CuAAc). The compounds have been screened for their gelation properties and several efficient low molecular weight organo/hydro gelators were obtained, among these compounds, five per-acetyl glucosamine derivatives and one peracetyl glucose derivative were able to form gels in water. These new molecules are expected to be useful in drug delivery and tissue engineering.*. Asymmetric synthesis of chiral amines is a challenging in synthetic organic chemistry. The development of new catalysts for asymmetric organic transformations is a very important research goal in modern synthetic organic chemistry. We have synthesized a new class of chiral oxathiozinone from chiral amino phenol. From this synthesized chiral sulfinamides, ketimines followed by reducing the ketimines synthesized the highly hindered chiral amines. *Please refer to dissertation for diagrams.

Modifying the Cold Gelation Properties of Quinoa Protein Isolate: Influence of Heat-Denaturation pH in the Alkaline Range.

PubMed

Mäkinen, Outi E; Zannini, Emanuele; Arendt, Elke K

2015-09-01

Heat-denaturation of quinoa protein isolate (QPI) at alkali pH and its influence on the physicochemical and cold gelation properties was investigated. Heating QPI at pH 8.5 led to increased surface hydrophobicity and decreases in free and bound sulfhydryl group contents. Heating at pH 10.5 caused a lesser degree of changes in sulfhydryl groups and surface hydrophobicity, and the resulting solutions showed drastically increased solubility. SDS PAGE revealed the presence of large aggregates only in the sample heated at pH 8.5, suggesting that any aggregates present in the sample heated at pH 10.5 were non-covalently bound and disintegrated in the presence of SDS. Reducing conditions partially dissolved the aggregates in the pH 8.5 heated sample indicating the occurrence of disulphide bonding, but caused no major alterations in the separation pattern of the pH 10.5 heated sample. Denaturation pH influenced the cold gelation properties greatly. Solutions heated at pH 8.5 formed a coarse coagulum with maximum G' of 5 Pa. Heat-denaturation at 10.5 enabled the proteins to form a finer and regularly structured gel with a maximum G' of 1140 Pa. Particle size analysis showed that the pH 10.5 heated sample contained a higher level of very small particles (0.1-2 μm), and these readily aggregated into large particles (30-200 μm) when pH was lowered to 5.5. Differences in the nature of aggregates formed during heating may explain the large variation in gelation properties.

Extemporaneously preparative biodegradable injectable polymer systems exhibiting temperature-responsive irreversible gelation.

PubMed

Yoshida, Yasuyuki; Takata, Kazuyuki; Takai, Hiroki; Kawahara, Keisuke; Kuzuya, Akinori; Ohya, Yuichi

2017-10-01

On clinical application of biodegradable injectable polymer (IP) systems, quick extemporaneous preparation of IP formulations and longer duration time gel state after injection into the body are the important targets to be developed. Previously, we had reported temperature-responsive covalent gelation systems via bio-orthogonal thiol-ene reaction by 'mixing strategy' of amphiphilic biodegradable tri-block copolymer (tri-PCG) attaching acryloyl groups on both termini (tri-PCG-Acryl) with reactive polythiol. In other previous works, we found 'freeze-dry with PEG/dispersion' method as quick extemporaneous preparation method of biodegradable IP formulations. In this study, we applied this quick preparative method to the temperature-triggered covalent gelation system. The instant formulation (D-sample) could be prepared by 'freeze-dry with PEG/dispersion' just mixing of tri-PCG-Acryl micelle dispersion and tri-PCG/DPMP micelle dispersion with PEG, that can be prepared in 30 s from the dried samples. The obtained D-sample showed irreversible gelation and long duration time of gel state, which was basically the same as the formulations prepared by the usual heating dissolution method (S-sample). Interestingly, the D-sample could maintain its sol state for a longer time (24 h) after preparing the formulation at r.t. compared with the S-sample, which became a gel in 3 h after preparing. The IP system showed good biocompatibility and long duration time of the gel state after subcutaneous implantation. These characteristics of D-samples, quick extemporaneous preparation and high stability in the sol state before injection, would be very convenient in a clinical setting.

Preparation of curcumin nanoparticle by using reinforcement ionic gelation technique

NASA Astrophysics Data System (ADS)

Suryani, Halid, Nur Hatidjah Awaliyah; Akib, Nur Illiyyin; Rahmanpiu, Mutmainnah, Nina

2017-05-01

Curcumin, a polyphenolic compound present in curcuma longa has a wide range of activities including anti-inflammatory properties. The potency of curcumin is limited by its poor oral bioavailability because of its poor solubility in aqueous. Various methods have been tried to solve the problem including its encapsulation into nanoparticle. The aim of this study is to develop curcumin nanoparticle by using reinforcement ionic gelation technique and to evaluate the stability of curcumin nanoparticles in gastrointestinal fluid. Curcumin nanoparticles were prepared by using reinforcement ionic gelation technique with different concentrations of chitosan, trypolyphosphate, natrium alginate and calcium chloride. Curcumin nanoparticles were then characterized including particle size and zeta potential by using particle size analyzer and morphology using a transmission electron microscope, entrapment efficiency using UV-Vis Spectrophotometer and chemical structure analysis by Infra Red Spectrophotometer (FTIR). Furthermore, the stability of curcumin nanoparticles were evaluated on artificial gastric fluid and artificial intestinal fluids by measuring the amount of curcumin released in the medium at a time interval. The result revealed that curcumin nanoparticles can be prepared by reinforcement ionic gelation technique, the entrapment efficiency of curcumin nanoparticles were from 86.08 to 91.41%. The average of particle size was 272.9 nm and zeta potential was 12.05 mV. The morphology examination showed that the curcumin nanoparticles have spherical shape. The stability evaluation of curcumin nanoparticles showed that the nanoparticles were stable on artificial gastric fluid and artificial intestinal fluid. This result indicates that curcumin nanoparticles have the potential to be developed for oral delivery.

Physical gelation of chitosan in the presence of beta-glycerophosphate: the effect of temperature.

PubMed

Cho, Jaepyoung; Heuzey, Marie-Claude; Bégin, André; Carreau, Pierre J

2005-01-01

When adding beta-glycerophosphate (beta-GP), a weak base, to chitosan aqueous solutions, the polymer remains in solution at neutral pH and room temperature, while homogeneous gelation of this system can be triggered upon heating. It is therefore one of the rare true physical chitosan hydrogels. In this study, physicochemical and rheological properties of chitosan solutions in the presence of acetic acid and beta-GP were investigated as a function of temperature in order to gain a better understanding of the gelation mechanisms. The gel structure formed at high temperature was only partially thermoreversible upon cooling to 5 degrees C because of the existence of remaining associations, confirmed by the spontaneous recovery of the gel after breakup at low temperature. Increasing temperature had no effect on the pH values of this system, while conductivity (and calculated ionic strength) increased. Values from the pH measurements were used to estimate the degree of protonation of each species as a function of temperature. The decreasing ratio of -NH3+ in chitosan and -OPO(O-)2 in beta-GP suggested reduced chitosan solubility along with a diminution of ionic interactions such as ionic bridging with increasing temperature. On the other hand, the increased ionic strength as a function of temperature, in the presence of beta-GP, enhanced screening of electrostatic repulsion and increased hydrophobic effect, resulting in favorable conditions for gel formation. Therefore, our study suggests that hydrophobic interactions and reduced solubility are the main driving force for chitosan gelation at high temperature in the presence of beta-GP.

Electrochemical and spectroscopic characterization of surface sol-gel processes.

PubMed

Chen, Xiaohong; Wilson, George S

2004-09-28

(3-Mercaptopropyl)trimethoxysilane (MTS) forms a unique film on a platinum substrate by self-assembly and sol-gel cross-linking. The gelating and drying states of the self-assembled MTS sol-gel films were probed by use of electrochemical and spectroscopic methods. The thiol moiety was the only active group within the sol-gel network. Gold nanoparticles were employed to detect the availability of the thiol group and their interaction further indicated the physicochemical states of the sol-gel inner structure. It was found that the thiol groups in the open porous MTS aerogel matrix were accessible to the gold nanoparticles while thiol groups in the compact MTS xerogel network were not accessible to the gold nanoparticles. The characteristics of the sol-gel matrix change with time because of its own irreversible gelating and drying process. The present work provides direct evidence of gold nanoparticle binding with thiol groups within the sol-gel structures and explains the different permeability of "aerogel" and "xerogel" films of MTS on the basis of electrochemical and spectroscopic results. Two endogenous species, hydrogen peroxide and ascorbic acid, were used to test the permeability of the self-assembled sol-gel film in different states. The MTS xerogel film on the platinum electrode was extremely selective against ascorbic acid while maintaining high sensitivity to hydrogen peroxide in contrast to the relatively high permeability of ascorbic acid in the MTS aerogel film. This study showed the potential of the MTS sol-gel film as a nanoporous material in biosensor development.

A supramolecular gel electrolyte formed from amide based co-gelator for quasi-solid-state dye-sensitized solar cell with boosted electron kinetic processes

NASA Astrophysics Data System (ADS)

Huo, Zhipeng; Wang, Lu; Tao, Li; Ding, Yong; Yi, Jinxin; Alsaedi, Ahmed; Hayat, Tasawar; Dai, Songyuan

2017-08-01

A supramolecular gel electrolyte (Tgel > 100 °C) is formed from N,N‧-1,8-octanediylbis-dodecanamide and iodoacetamide as two-component co-gelator, and introduced into the quasi-solid-state dye-sensitized solar cells (QS-DSSCs). The different morphologies of microscopic network between two-component and single-component gel electrolytes have influence on the diffusion of redox couple in gel electrolytes and further affect the electron kinetic processes in QS-DSSCs. Compared with the single-component gel electrolyte, the two-component gel electrolyte has less compact gel network and weaker steric hindrance effect, which provides more effective charge transport channel for the diffusion of I3/I- redox couple. Meanwhile, the sbnd NH2 groups of iodoacetamide molecules interact with Li+ and I3-, which also accelerate the transport of I3-/I- and decrease in the I3- concentration in the TiO2/electrolyte interface. As a result, nearly a 12% improvement in short-circuit photocurrent density (Jsc) and much higher open circuit potential (Voc) are found in the two-component gel electrolyte based QS-DSSC. Consequently, the QS-DSSC based on the supramolecular gel electrolyte obtains a 17% enhancement in the photoelectric conversion efficiency (7.32%) in comparison with the QS-DSSC based on the single-component gel electrolyte (6.24%). Furthermore, the degradations of these QS-DSSCs are negligible after one sun light soaking with UV cutoff filter at 50 °C for 1000 h.

Characterization of methyltrimethoxysilane sol-gel polymerization and the resulting aerogels

NASA Astrophysics Data System (ADS)

Dong, Hanjiang

Methyl-functionalized porous silica is of considerable interest as a low dielectric constant film for semiconductor devices. The structural development of these materials appears to affect their gelation behaviors and impact their mechanical properties and shrinkage during processing. 29Si solution NMR was used to follow the structural evolution of MTMS (methyltrimethoxysilane) polymerization to gelation or precipitation, and thus to better understand the species that affect these properties and gelation behaviors. The effects of pH, water concentration, type of solvents, and synthesis procedures (single step acid catalysis and two-step acid/base catalysis) on MTMS polymerization were discussed. The reactivity of silicon species with different connectivity and the extent of cyclization were found to depend appreciably on the pH value of the sol. A kinetic model is presented to treat the reactivity of both silicon species involved in condensations separately based on the inductive and steric effects of these silicon species. Extensive cyclization in the presence of acid, which was attributed to the steric effects among numerous reaction pathways for the first time, prevents MTMS gelation, whereas gels were obtained from the two-step method with nearly random condensations. The experimental degree of condensation (DC) at the gel point using the two-step procedure was determined to be 0.86, which is considerably higher than that predicted by the current accepted theories. Both chemical and physical origins of this high value were suggested. Aerogels dried by supercritical CO2 extraction were characterized by FTIR, 13C and 29Si solid-state NMR and nitrogen sorption. The existence of three residual groups (Si-OH, Si-OCH3, and Si-OC2H5) was confirmed, but their concentrations are very low compared to silica aerogels. The low concentrations of the residual groups, along with the presence of Si-CH3, make MTMS aerogels permanently hydrophobic. To enhance applicability, MTMS aerogels were successfully prepared that demonstrated shrinkage less than 10% after supercritical drying; proving that the rigidity of the gel network is not the sole factor, suggesting in the literature, to cause the huge shrinkage in many hybrid aerogels reported. An important finding of this work is that MTMS aerogels can be prepared without tedious solvent exchange and surface modification if the molar ratio of water/MTMS increases to 8, substantially reducing the cost of aerogel production. This result was attributed to MTMS's fully condensation and low concentrations of ring species.

Helicobacter pylori Couples Motility and Diffusion to Actively Create a Heterogeneous Complex Medium in Gastric Mucus

NASA Astrophysics Data System (ADS)

Fu, Henry; Mirbagheri, Seyed Amir

2016-11-01

Helicobacter pylori swims through mucus gel by generating ammonia that locally neutralizes the acidic gastric environment, turning nearby gel into a fluid pocket. The size of the fluid zone is important for determining the physics of the motility: in a large zone swimming occurs as in a fluid through hydrodynamic principles, while in a very small zone the motility could be strongly influenced by nonhydrodynamic cell-mucus interactions including chemistry and adhesion. We calculate the size of the fluid pocket. We model how swimming depends on the de-gelation range using a Taylor sheet swimming through a layer of Newtonian fluid bounded by a Brinkman fluid. Then, we model how the de-gelation range depends on the swimming speed by considering the advection-diffusion of ammonia exuded from a translating sphere. Self-consistency between both models determines the values of the swimming speed and the de-gelation range. We find that H. pylori swims through mucus as if unconfined, in a large pocket of Newtonian fluid. Funded by National Science Foundation award CBET-1252182.

Oil encapsulation in core-shell alginate capsules by inverse gelation II: comparison between dripping techniques using W/O or O/W emulsions.

PubMed

Martins, Evandro; Poncelet, Denis; Rodrigues, Ramila Cristiane; Renard, Denis

2017-09-01

In the first part of this article, it was described an innovative method of oil encapsulation from dripping-inverse gelation using water-in-oil (W/O) emulsions. It was noticed that the method of oil encapsulation was quite different depending on the emulsion type (W/O or oil-in-water (O/W)) used and that the emulsion structure (W/O or O/W) had a high impact on the dripping technique and the capsules characteristics. The objective of this article was to elucidate the differences between the dripping techniques using both emulsions and compare the capsule properties (mechanical resistance and release of actives). The oil encapsulation using O/W emulsions was easier to perform and did not require the use of emulsion destabilisers. However, capsules produced from W/O emulsions were more resistant to compression and showed the slower release of actives over time. The findings detailed here widened the knowledge of the inverse gelation and gave opportunities to develop new techniques of oil encapsulation.

A protocol for rheological characterization of hydrogels for tissue engineering strategies.

PubMed

Zuidema, Jonathan M; Rivet, Christopher J; Gilbert, Ryan J; Morrison, Faith A

2014-07-01

Hydrogels are studied extensively for many tissue engineering applications, and their mechanical properties influence both cellular and tissue compatibility. However, it is difficult to compare the mechanical properties of hydrogels between studies due to a lack of continuity between rheological protocols. This study outlines a straightforward protocol to accurately determine hydrogel equilibrium modulus and gelation time using a series of rheological tests. These protocols are applied to several hydrogel systems used within tissue engineering applications: agarose, collagen, fibrin, Matrigel™, and methylcellulose. The protocol is outlined in four steps: (1) Time sweep to determine the gelation time of the hydrogel. (2) Strain sweep to determine the linear-viscoelastic region of the hydrogel with respect to strain. (3) Frequency sweep to determine the linear equilibrium modulus plateau of the hydrogel. (4) Time sweep with values obtained from strain and frequency sweeps to accurately report the equilibrium moduli and gelation time. Finally, the rheological characterization protocol was evaluated using a composite Matrigel™-methylcellulose hydrogel blend whose mechanical properties were previously unknown. The protocol described herein provides a standardized approach for proper analysis of hydrogel rheological properties. © 2013 Wiley Periodicals, Inc.

Stronger Intermolecular Forces or Closer Molecular Spacing? Key Impact Factor Research of Gelator Self-Assembly Mechanism.

PubMed

Chen, Si; An, Zhihang; Tong, Xiaoqian; Chen, Yining; Ma, Meng; Shi, Yanqin; Wang, Xu

2017-12-19

The benzene ring of low-molecular-weight gelators provides strong intermolecular forces but increases molecular spacing during self-assembly. To explore both of the above influences on the gel properties, we synthesize two gelators (Glu-CBZ and Glu-DPA) consisting of the same terminal long side chain but different aliphatic functional groups. The aliphatic functional groups are carbobenzoxy group and diphenyl phosphate group. The self-assembly driving forces, self-organization patterns, network morphologies, rheological properties, and the influences of solvents are researched through 1 H NMR spectra, Fourier transform infrared spectra, field-emission scanning electron microscopy images, rheological characterizations curves, tube-inversion experiment, and calculation of van't Hoff plots. The results show that the carbobenzoxy group of Glu-CBZ makes molecules pack more tightly such that it improves the gel properties during static equilibrium. Whereas the diphenyl phosphate group of Glu-DPA provides stronger intermolecular forces, performing outstandingly during dynamic equilibrium. It is advantageous to further investigate the competitive relationship in gel system between the increased number of functional groups and the consequent steric effect.

A Glycyrrhetinic Acid-Modified Curcumin Supramolecular Hydrogel for liver tumor targeting therapy

PubMed Central

Chen, Guoqin; Li, Jinliang; Cai, Yanbin; Zhan, Jie; Gao, Jie; Song, Mingcai; Shi, Yang; Yang, Zhimou

2017-01-01

Curcumin (Cur), a phenolic anti-oxidant compound obtained from Curcuma longa plant, possesses a variety of therapeutic properties. However, it is suffered from its low water solubility and low bioavailability property, which seriously restricts its clinical application. In this study, we developed a glycyrrhetinic acid (GA) modified curcumin supramolecular pro-gelator (GA-Cur) and a control compound Nap-Cur by replacing GA with the naphthylacetic acid (Nap). Both compounds showed good water solubility and could form supramolecular gels by disulfide bond reduction triggered by glutathione (GSH) in vitro. Both formed gels could sustainedly release Cur in buffer solutions. We also investigated the cytotoxicity of pro-gelators to HepG2 cells by a MTT assay and determined the cellular uptake behaviours of them by fluorescence microscopy and LC-MS. Due to the over expression of GA receptor in liver cancer cells, our pro-gelator of GA-Cur showed an enhanced cellular uptake and better inhibition capacity to liver tumor cells than Nap-Cur. Therefore, the GA-Cur could significantly inhibit HepG2 cell growth. Our study provides a novel nanomaterial for liver tumor chemotherapy. PMID:28281678

Time-dependent gel to gel transformation of a peptide based supramolecular gelator.

PubMed

Baral, Abhishek; Basak, Shibaji; Basu, Kingshuk; Dehsorkhi, Ashkan; Hamley, Ian W; Banerjee, Arindam

2015-06-28

A dipeptide with a long fatty acid chain at its N-terminus gives hydrogels in phosphate buffer in the pH range 7.0-8.5. The hydrogel with a gelator concentration of 0.45% (w/v) at pH 7.46 (physiological pH) provides a very good platform to study dynamic changes within a supramolecular framework as it exhibits remarkable change in its appearance with time. Interestingly, the first formed transparent hydrogel gradually transforms into a turbid gel within 2 days. These two forms of the hydrogel have been thoroughly investigated by using small angle X-ray scattering (SAXS), powder X-ray diffraction (PXRD), field emission scanning electron microscopic (FE-SEM) and high-resolution transmission electron microscopic (HR-TEM) imaging, FT-IR and rheometric analyses. The SAXS and low angle PXRD studies substantiate different packing arrangements for the gelator molecules for these two different gel states (the freshly prepared and the aged hydrogel). Moreover, rheological studies of these two gels reveal that the aged gel is stiffer than the freshly prepared gel.

Solubility and dissolution improvement of ketoprofen by emulsification ionic gelation

NASA Astrophysics Data System (ADS)

Rachmaniar, Revika; Tristiyanti, Deby; Hamdani, Syarif; Afifah

2018-02-01

Ketoprofen or [2-(3-benzoylphenyl) propionic acid] is non-steroidal anti-inflammatory (NSAID) and an analgesic which has high permeability and low solubility. The purpose of this work was to improve the solubility and dissolution of poorly water-soluble ketoprofen prepared by emulsification ionic gelation method and utilizing polymer (chitosan) and cross linker (tripolyphosphate, TPP) for particles formulation. The results show that increasing pH value of TPP, higher solubility and dissolution of as-prepared ketoprofen-chitosan was obtained. The solubility in water of ketoprofen-chitosan with pH 6 for TPP increased 2.71-fold compared to untreated ketoprofen. While the dissolution of ketoprofen-chitosan with pH 6 of TPP in simulated gastric fluid without enzyme (0.1 N HCl), pH 4.5 buffer and simulated intestinal fluid without enzyme (phosphate buffer pH 6.8) was increased 1.9-fold, 1.6-fold and 1.2-fold compared to untreated ketoprofen for dissolution time of 30 minutes, respectively. It could be concluded that chitosan and TPP in the emulsification ionic gelation method for ketoprofen preparation effectively increases solubility and dissolution of poorly water-soluble ketoprofen.

A Glycyrrhetinic Acid-Modified Curcumin Supramolecular Hydrogel for liver tumor targeting therapy

NASA Astrophysics Data System (ADS)

Chen, Guoqin; Li, Jinliang; Cai, Yanbin; Zhan, Jie; Gao, Jie; Song, Mingcai; Shi, Yang; Yang, Zhimou

2017-03-01

Curcumin (Cur), a phenolic anti-oxidant compound obtained from Curcuma longa plant, possesses a variety of therapeutic properties. However, it is suffered from its low water solubility and low bioavailability property, which seriously restricts its clinical application. In this study, we developed a glycyrrhetinic acid (GA) modified curcumin supramolecular pro-gelator (GA-Cur) and a control compound Nap-Cur by replacing GA with the naphthylacetic acid (Nap). Both compounds showed good water solubility and could form supramolecular gels by disulfide bond reduction triggered by glutathione (GSH) in vitro. Both formed gels could sustainedly release Cur in buffer solutions. We also investigated the cytotoxicity of pro-gelators to HepG2 cells by a MTT assay and determined the cellular uptake behaviours of them by fluorescence microscopy and LC-MS. Due to the over expression of GA receptor in liver cancer cells, our pro-gelator of GA-Cur showed an enhanced cellular uptake and better inhibition capacity to liver tumor cells than Nap-Cur. Therefore, the GA-Cur could significantly inhibit HepG2 cell growth. Our study provides a novel nanomaterial for liver tumor chemotherapy.

Endotoxin Detection in Pharmaceuticals and Medical Devices with Kinetic-QCL, a Kinetic-Quantitative Chromogenic Limulus Amebocyte Lysate Assay.

PubMed

Berzofsky, Ronald N.

1995-01-01

The observation that endotoxin caused gelation in extracts of Limulus amebocytes has been expanded to the development of an in vitro kinetic, quantitative chromogenic LAL assay (Kinetic-QCL) for the detection of endotoxin in aqueous fluids. Within the last 15 years, the use of Limulus amebocyte lysate to detect and control the presence of pyrogenic substances in pharmaceuticals and medical devices has gained wide international acceptance. Both the United States and European Pharmacopoeias contain descriptions of and requirements for the LAL Bacterial Endotoxin Test. Both pharmacopoeias have begun to remove the rabbit pyrogen test requirement in a majority of drug monographs and have substituted endotoxin limits to be determined by LAL. The use of LAL has proved invaluable in controlling the level of endotoxin in finished product. The endotoxin contribution of raw materials and packaging material can be monitored as well. In-process testing at critical production steps can identify additional sources of endotoxin contamination, and depyrogenation processes can be validated by quantitating the degradation of endotoxin challenges. The speed, reproducibility, sensitivity, and economics of the Kinetic-QCL assay, in conjunction with the ppropriate equipment and software, over both the in vivo rabbit pyrogen test and the more traditional LAL gel-clot assay allow a more in-depth approach to the control of endotoxin in pharmaceuticals and medical devices.

Enzymatically-stable oxetane-based dipeptide hydrogels.

PubMed

McDougall, Laura; Draper, Emily R; Beadle, Jonathan D; Shipman, Michael; Raubo, Piotr; Jamieson, Andrew G; Adams, Dave J

2018-02-13

Low molecular weight gelators that are not easily degraded by enzymes have a range of potential applications. Here, we report new Fmoc-protected dipeptides in which the amide carbonyl group has been replaced by an oxetane ring. Remarkably one of these peptidomimetics, but not the corresponding dipeptide, is an effective gelator, forming hydrogels at a concentration of 3 mg mL -1 . On assembly, there is a lack of beta-sheet structure, implying that there is no requirement for this motif in such a gel. Furthermore, the modified dipeptide is also stable to proteolysis compared to the parent dipeptide.

Surface-enhanced Raman scattering on molecular self-assembly in nanoparticle-hydrogel composite.

PubMed

Miljanić, Snezana; Frkanec, Leo; Biljan, Tomislav; Meić, Zlatko; Zinić, Mladen

2006-10-24

Surface-enhanced Raman scattering has been applied to study weak intermolecular interactions between small organic gelling molecules involved in the silver nanoparticle-hydrogel composite formation. Assembly and disassembly of the gelator molecules in close vicinity to embedded silver nanoparticles were followed by changes in Raman intensity of the amide II and carboxyl vibrational bands, whereas the strength of the bands related to benzene modes remained constant. This implied that the gelator molecules were strongly attached to the silver particles through the benzene units, while participating in gel structure organization by intermolecular hydrogen bonding between oxalyl amide and carboxyl groups.

Gelation of Regenerated Fibroin Solution

NASA Astrophysics Data System (ADS)

Nagarkar, Shailesh; Lele, Ashish; Chassenieux, Christophe; Nicolai, Taco; Durand, Dominique

2008-07-01

Silk fibroin is a high molecular weight multiblock ampiphillic protein known for its ability to form high strength fibers. It is also biocompatible; silk sutures have been traditionally used for many centuries. Recently, there has been much interest in making silk hydrogels for applications ranging from tissue engineering to controlled delivery. Fibroin gels can be formed from aqueous solutions by changing one or more state variables such as pH, temperature and ionic strength. In this work we present our investigations on the gelation of aqueous fibroin solutions derived from Bombyx Mori silk using light scattering, confocal microscopy and rheological techniques.

Polyelectrolyte Complex Inclusive Biohybrid Microgels for Tailoring Delivery of Copigmented Anthocyanins.

PubMed

Tan, Chen; B Celli, Giovana; Lee, Michelle; Licker, Jonathan; Abbaspourrad, Alireza

2018-05-14

This study fabricated a novel biohybrid microgel containing polysaccharide-based polyelectrolyte complexes (PECs) for anthocyanins. Herein, anthocyanins were encapsulated into PECs composed of chondroitin sulfate and chitosan, followed by incorporation into alginate microgels using emulsification/internal gelation method. We demonstrated that PECs incorporation strongly affected the properties of microgels, dependent on the polysaccharide concentration and pH in which they were fabricated. The dense internal network surrounded by an alginate shell was clearly visualized in cross-sectioned PECs-microgels. Stability studies carried out under varying ionic strength and pH conditions demonstrated the stimuli-responsiveness of the PECs-microgels. Additionally, the presence of PECs conferred microgels with high rigidity during freeze-drying and excellent reconstitution capacity upon rehydration. These observations were attributed to the modulation of electrostatic and hydrogen-bonding cross-linking between PECs and the alginate gel matrix and suggest the PECs inclusive microgels hold promise as delivery vehicles for the controlled release of hydrophilic bioactive compounds.

A three-prong strategy to develop functional food using protein isolates recovered from chicken processing by-products with isoelectric solubilization/precipitation.

PubMed

Tahergorabi, Reza; Sivanandan, Litha; Beamer, Sarah K; Matak, Kristen E; Jaczynski, Jacek

2012-09-01

Skin-on bone-in chicken drumsticks were processed with isoelectric solubilization/precipitation to recover muscle proteins. The drumsticks were used as a model for dark chicken meat processing by-products. The main objective of this study was conversion of dark chicken meat processing by-products to restructured functional food product. An attempt was made to develop functional food product that would resemble respective product made from boneless skinless chicken breast meat. A three-prong strategy to address diet-driven cardiovascular disease (CVD)with a functional food was used in this study. The strategy included addition of three ingredients with well-documented cardiovascular benefits: (i) ω-3 polyunsaturated fatty acid-rich oil (flaxseed-algae, 9:1); (ii) soluble fiber; and (iii) salt substitute. Titanium dioxide, potato starch, polyphosphate, and transglutaminase were also added. The batters were formulated and cooked resulting in heat-set gels. Color (L*a*b*), texture (torsion test, Kramer shear test, and texture profile analysis), thermal denaturation (differential scanning calorimetry), and gelation (dynamic rheology) of chicken drumstick gels and chicken breast gels were determined and compared. Chicken drumstick gels generally had comparable color and texture properties to the gels made from chicken breast meat. The endothermic transition (thermal denaturation) of myosin was more pronounced and gelation properties were better for the drumstick gels. This study demonstrated a feasibility to develop functional food made of muscle proteins recovered with isoelectric solubilization/precipitation from low-value dark chicken meat processing by-products. The functional food developed in this study was enriched with CVD-beneficial nutrients and had comparable instrumental quality attributes to respective products made of chicken breast meat. Although the results of this study point towards the potential for a novel, marketable functional food product, sensory tests and storage stability study are recommended. Copyright © 2012 Society of Chemical Industry.

Compositional effects on the chemorheological properties and forming behavior of aqueous alumina-poly(vinyl alcohol) gelcasting suspensions

NASA Astrophysics Data System (ADS)

Morissette, Sherry L.

A new gelcasting system based on aqueous, alumina-poly(vinyl alcohol) (PVA) suspensions cross-linked by an organotitanate coupling agent has been developed. Both the chemorheological properties and forming behavior of this system exhibited a strong compositional dependence. A sol- gel phase diagram was established, which yielded the critical titanium concentration [Ti] c required for gelation at a given PVA volume fraction, as well as the minimum PVA volume fraction ( fminPVA = 0.0245) and titanium PVA concentration ([Ti]min = 9.984 x 10--4 g Ti/ml) below which gelation was not observed irrespective of solution composition. The gelation time of suspensions of constant PVA volume fraction ( fsolnPVA ) decreased with increasing cross-linking agent concentration, PVA temperature, and solids volume fraction. The steady-state viscosity and elastic modulus of polymer solutions ( fsolnPVA = 0.05) of varying [Ti] were well described by the PVA percolation model, giving scaling exponents of 0.84 and 1.79, respectively. The steady-state elastic modulus of gel casting suspensions, which provides a measure of their handling strength in the as-gelled state, increased with increasing solids volume fraction. Gelcasting suspensions were used as feedstock for solid free-form fabrication (SFF) of ceramic components. The influence of processing conditions (e.g., tip diameter, mixing rate, table speed, etc.) and suspension rheology on deposition behavior was investigated. Continuous printablity was achieved for tip diameters ranging from dt = 0.254 -- 1.370 mm for all mixing rates (Rmix 5 -- 300 rpm) and suspension compositions (i.e., fAl2O3 = 0.45, φPVA = 0.275, [Ti] 0 -- 6.30 x 10--3 g Ti/ml) probed, where the minimum tip diameter for continuous printing was 0.203 mm. Printed lines were uniform with good edge definition. Line dimensions were independent of mixing rate for the given process conditions. The as-cast alumina volume fraction ( fAl2O3 ) depended on casting conditions and cross-linking agent concentration, where fAl2O3 decreased with increasing tip diameter and increased with increasing cross-linking agent concentration. Free-fomied Al2O3 components exhibited uniform particle packing and had minimal macro-defects (e.g., slumping or stair casing) and no detectable micro-defects (e.g., bubbles or cracking).

Aerogel/Particle Composites for Thermoelectric Devices

NASA Technical Reports Server (NTRS)

Paik, Jong-Ah; Sakamoto, Jeffrey; Jones, Steven

2006-01-01

Optimizing solution chemistry and the addition of titania and fumed silica powder reduces shrinkage. These materials would serve to increase thermal efficiency by providing thermal insulation to suppress lateral heat leaks. They would also serve to prolong operational lifetime by suppressing sublimation of certain constituents of thermoelectric materials (e.g., sublimation of Sb from CoSb3) at typical high operating temperatures. [The use of pure silica aerogels as cast-in-place thermal-insulation and sublimation-suppression materials was described in "Aerogels for Thermal Insulation of Thermoelectric Devices" (NPO-40630), NASA Tech Briefs, Vol. 30, No. 7 (July 2006), page 50.] A silica aerogel is synthesized in a solgel process that includes preparation of a silica sol, gelation of the sol, and drying of the gel in a solvent at a supercritical temperature and pressure. The utility of pure silica aerogel is diminished by a tendency to shrink (and, therefore, also to crack) during the gelation and supercritical-drying stages. Moreover, to increase suppression of sublimation, it is advantageous to make an aerogel having greater density, but shrinkage and cracking tend to increase with density. A composite material of the type under investigation consists mostly of titania oxide powder particles and a small addition of fumed silica powder, which are mixed into the sol along with other ingredients prior to the gelation stage of processing. The silica aerogel and fumed silica act as a binder, gluing the titania particles together. It is believed that the addition of fumed silica stiffens the aerogel network and reduces shrinkage during the supercritical-drying stage. Minimization of shrinkage enables establishment of intimate contact between thermoelectric legs and the composite material, thereby maximizing the effectiveness of the material for thermal insulation and suppression of sublimation. To some extent, the properties of the composite can be tailored via the proportions of titania and other ingredients. In particular (see figure), the addition of a suitably large proportion of titania (e.g., 0.6 g/cu cm) along with a 10-percent increase in the amount of tetraethylorthosilicate [TEOS (an ingredient of the sol)] to an aerogel component having a density 40 mg/cm3makes it possible to cast a high-average-density (>0.1 g/cm3) aerogel/particle composite having low shrinkage (2.3 percent).

Chitosan-phosphotungstic acid complex as membranes for low temperature H2-O2 fuel cell

NASA Astrophysics Data System (ADS)

Santamaria, M.; Pecoraro, C. M.; Di Quarto, F.; Bocchetta, P.

2015-02-01

Free-standing Chitosan/phosphotungstic acid polyelectrolyte membranes were prepared by an easy and fast in-situ ionotropic gelation process performed at room temperature. Scanning electron microscopy was employed to study their morphological features and their thickness as a function of the chitosan concentration. The membrane was tested as proton conductor in low temperature H2-O2 fuel cell allowing to get peak power densities up to 350 mW cm-2. Electrochemical impedance measurements allowed to estimate a polyelectrolyte conductivity of 18 mS cm-1.

Metallo‐Supramolecular Gels that are Photocleavable with Visible and Near‐Infrared Irradiation

PubMed Central

Theis, Sabrina; Iturmendi, Aitziber; Gorsche, Christian; Orthofer, Marco; Lunzer, Markus; Baudis, Stefan; Ovsianikov, Aleksandr; Liska, Robert

2017-01-01

Abstract A photolabile ruthenium‐based complex, [Ru(bpy)2(4AMP)2](PF6)2, (4AMP=4‐(aminomethyl)pyridine) is incorporated into polyurea organo‐ and hydrogels via the reactive amine moieties on the photocleavable 4AMP ligands. While showing long‐term stability in the dark, cleavage of the pyridine–ruthenium bond upon irradiation with visible or near‐infrared irradiation (in a two‐photon process) leads to rapid de‐gelation of the supramolecular gels, thus enabling spatiotemporal micropatterning by photomasking or pulsed NIR‐laser irradiation PMID:28941025

Preparation of glass-forming materials from granulated blast furnace slag

NASA Astrophysics Data System (ADS)

Alonso, M.; Sáinz, E.; Lopez, F. A.

1996-10-01

Glass precursor materials, to be used for the vitrification of hazardous wastes, have been prepared from blast furnace slag powder through a sol-gel route. The slag is initially reacted with a mixture of alcohol (ethanol or methanol) and mineral acid (HNO3 or H2SO4) to give a sol principally consisting of Si, Ca, Al, and Mg alkoxides. Gelation is carried out with variable amounts of either ammonia or water. The gelation rate can be made as fast as desired by adding excess hydrolizing agent or else by distilling the excess alcohol out of the alkoxide solution. The resulting gel is first dried at low temperature and ground. The powder thus obtained is then heat treated at several temperatures. The intermediate and final materials are characterized by thermal analysis, infrared (IR) spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), and chemical analysis. From the results, the operating conditions yielding a variety of glass precursors differing in their composition are established. The method, in comparison with direct vitrification of slag, presents a number of advantages: (1) the glass precursor obtained devitrifies at higher temperatures; (2) it enables the adjustment, to a certain extent, of the chemical composition of the glass precursor; and (3) it permits recovering marketable materials at different stages of the process.

Functionality-Oriented Derivatization of Naphthalene Diimide: A Molecular Gel Strategy-Based Fluorescent Film for Aniline Vapor Detection.

PubMed

Fan, Jiayun; Chang, Xingmao; He, Meixia; Shang, Congdi; Wang, Gang; Yin, Shiwei; Peng, Haonan; Fang, Yu

2016-07-20

Modification of naphthalene diimide (NDI) resulted in a photochemically stable, fluorescent 3,4,5-tris(dodecyloxy)benzamide derivative of NDI (TDBNDI), and introduction of the long alkyl chains endowed the compound with good compatibility with commonly found organic solvents and in particular superior self-assembly in the solution state. Further studies revealed that TDBNDI forms gels with nine of the 18 solvents tested at a concentration of 2.0% (w/v), and the critical gelation concentrations of five of the eight gels are lower than 1.0% (w/v), indicating the high efficiency of the compound as a low-molecular mass gelator (LMMG). Transmission electron microscopy, scanning electron microscopy, and confocal laser scanning microscopy studies revealed the networked fibrillar structure of the TDBNDI/methylcyclohexane (MCH) gel. On the basis of these findings, a fluorescent film was developed via simple spin-coating of the TDBNDI/MCH gel on a glass substrate surface. Fluorescence behavior and sensing performance studies demonstrated that this film is photochemically stable, and sensitive and selective to the presence of aniline vapor. Notably, the response is instantaneous, and the sensing process is fully and quickly reversible. This case study demonstrates that derivatization of photochemically stable fluorophores into LMMGs is a good strategy for developing high-performance fluorescent sensing films.

Influence of pH, temperature, and concentration on stabilization of aqueous hornet silk solution and fabrication of salt-free materials.

PubMed

Kameda, Tsunenori

2015-01-01

We found that an aqueous solution of silk from cocoons produced by hornet larvae (hornet silk) can be obtained when the solution is adjusted to basic conditions of pH > 9.2. It is known that native hornet cocoons can be dissolved in concentrated aqueous solution of salts, such as lithium bromide (LiBr) and calcium chloride (CaCl2). Upon the removal of these salts from solution by dialysis, solidification, gelation, or sedimentation of hornet silk is known to occur. In the present study, under basic conditions, however, no such solidification occurred, even after salt removal. In this study, ammonia was used for alkalization of solution because it is volatilized during the casting process and pure hornet silk materials can be obtained after drying. The effects of the concentrations of hornet silk and ammonia, as well as dialysis temperature, on preventing gelation during dialysis were investigated. Dialysis conditions that limit the degradation of hornet silk by hydrolysis in alkali solution were identified. Moreover, casting conditions to prepare flexible and transparent hornet silk film from aqueous ammonia solution were optimized. Molecular structural analysis of hornet silk in aqueous ammonia solution and cast film indicated the formation of α-helix conformations. © 2014 Wiley Periodicals, Inc.

Incorporation of essential oil in alginate microparticles by multiple emulsion/ionic gelation process.

PubMed

Hosseini, Seyede Marzieh; Hosseini, Hedayat; Mohammadifar, Mohammad Amin; Mortazavian, Amir Mohammad; Mohammadi, Abdorreza; Khosravi-Darani, Kianoosh; Shojaee-Aliabadi, Saeedeh; Dehghan, Solmaz; Khaksar, Ramin

2013-11-01

In this study, an o/w/o multiple emulsion/ionic gelation method was developed for production of alginate microparticles loaded with Satureja hortensis essential oil (SEO). It was found that the essential oil concentration has significant influence on encapsulation efficiency (EE), loading capacity (LC) and size of microparticles. The values of EE, LC and particle mean diameter were about 52-66%, 20-26%, and 47-117 μm, respectively, when the initial SEO content was 1-3% (v/v) .The essential oil-loaded microparticles were porous, as displayed by scanning electron micrograph. The presence of SEO in alginate microparticles was confirmed by Fourier transform-infrared (FT-IR) spectroscopy and differential scanning calorimetry (DSC) analyses. SEO-loaded microparticles showed good antioxidant (with DPPH radical scavenging activity of 40.7-73.5%) and antibacterial properties; this effect was greatly improved when the concentration of SEO was 3% (v/v). S. aureus was found to be the most sensitive bacterium to SEO and showed a highest inhibition zone of 304.37 mm(2) in the microparticles incorporated with 3% (v/v) SEO. In vitro release studies showed an initial burst release and followed by a slow release. In addition, the release of SEO from the microparticles followed Fickian diffusion with acceptable release. Copyright © 2013 Elsevier B.V. All rights reserved.

Sol-gel method for encapsulating molecules

DOEpatents

Brinker, C. Jeffrey; Ashley, Carol S.; Bhatia, Rimple; Singh, Anup K.

2002-01-01

A method for encapsulating organic molecules, and in particular, biomolecules using sol-gel chemistry. A silica sol is prepared from an aqueous alkali metal silicate solution, such as a mixture of silicon dioxide and sodium or potassium oxide in water. The pH is adjusted to a suitably low value to stabilize the sol by minimizing the rate of siloxane condensation, thereby allowing storage stability of the sol prior to gelation. The organic molecules, generally in solution, is then added with the organic molecules being encapsulated in the sol matrix. After aging, either a thin film can be prepared or a gel can be formed with the encapsulated molecules. Depending upon the acid used, pH, and other processing conditions, the gelation time can be from one minute up to several days. In the method of the present invention, no alcohols are generated as by-products during the sol-gel and encapsulation steps. The organic molecules can be added at any desired pH value, where the pH value is generally chosen to achieve the desired reactivity of the organic molecules. The method of the present invention thereby presents a sufficiently mild encapsulation method to retain a significant portion of the activity of the biomolecules, compared with the activity of the biomolecules in free solution.

Assembly of phosphide nanocrystals into porous networks: formation of InP gels and aerogels.

PubMed

Hitihami-Mudiyanselage, Asha; Senevirathne, Keerthi; Brock, Stephanie L

2013-02-26

The applicability of sol-gel nanoparticle assembly routes, previously employed for metal chalcogenides, to phosphides is reported for the case of InP. Two different sizes (3.5 and 6.0 nm) of InP nanoparticles were synthesized by solution-phase arrested precipitation, capped with thiolate ligands, and oxidized with H₂O₂ or O₂/light to induce gel formation. The gels were aged, solvent-exchanged, and then supercritically dried to obtain aerogels with both meso- (2-50 nm) and macropores (>50 nm) and accessible surface areas of ∼200 m²/g. Aerogels showed higher band gap values relative to precursor nanoparticles, suggesting that during the process of assembling nanoparticles into 3D architectures, particle size reduction may have taken place. In contrast to metal chalcogenide gelation, InP gels did not form using tetranitromethane, a non-oxygen-transferring oxidant. The requirement of an oxygen-transferring oxidant, combined with X-ray photoelectron spectroscopy data showing oxidized phosphorus, suggests gelation is occurring due to condensation of phosphorus oxoanionic moieties generated at the interfaces. The ability to link discrete InP nanoparticles into a 3D porous network while maintaining quantum confinement is expected to facilitate exploitation of nanostructured InP in solid-state devices.

Surface Plasmon Resonance Evaluation of Colloidal Metal Aerogel Filters

NASA Technical Reports Server (NTRS)

Smith, David D.; Sibille, Laurent; Cronise, Raymond J.; Noever, David A.

1997-01-01

Surface plasmon resonance imaging has in the past been applied to the characterization of thin films. In this study we apply the surface plasmon technique not to determine macroscopic spatial variations but rather to determine average microscopic information. Specifically, we deduce the dielectric properties of the surrounding gel matrix and information concerning the dynamics of the gelation process from the visible absorption characteristics of colloidal metal nanoparticles contained in aerogel pores. We have fabricated aerogels containing gold and silver nanoparticles. Because the dielectric constant of the metal particles is linked to that of the host matrix at the surface plasmon resonance, any change 'in the dielectric constant of the material surrounding the metal nanoparticles results in a shift in the surface plasmon wavelength. During gelation the surface plasmon resonance shifts to the red as the average or effective dielectric constant of the matrix increases. Conversely, formation of an aerogel or xerogel through supercritical extraction or evaporation of the solvent produces a blue shift in the resonance indicating a decrease in the dielectric constant of the matrix. From the magnitude of this shift we deduce the average fraction of air and of silica in contact with the metal particles. The surface area of metal available for catalytic gas reaction may thus be determined.

Structure and gelation properties of casein micelles doped with curcumin under acidic conditions.

PubMed

Khanji, Aya N; Michaux, Florentin; Jasniewski, Jordane; Petit, Jeremy; Lahimer, Emna; Cherif, Mohamed; Salameh, Dominique; Rizk, Toufic; Banon, Sylvie

2015-12-01

In this study, the ability of micellar casein (MC) to interact with curcumin during acidification and to produce acid gel was investigated. Steady-state fluorescence spectroscopy of curcumin variation and fluorescence quenching of caseins upon binding with curcumin molecules were evidenced. Increasing the temperature from 20 to 35 °C enhanced MC-curcumin interactions as reflected by the increase in the binding constant from 0.6 ± 0.3 × 10(4) to 6.6 ± 0.6 × 10(4) M(-1). From changes in entropy, enthalpy and Gibbs free energy, hydrophobic interactions were proposed as major binding forces. Static fluorescence MC quenching was demonstrated for the MC-curcumin complex during acidification. From pH 7.4 to pH 5.0, the binding site numbers varied in the range from 1.25 ± 0.05 to 1.49 ± 0.05 and the binding constant kb varied from 3.9 ± 0.4 × 10(4) to 7.5 ± 0.7 × 10(4) M(-1). Small angle X-ray scattering profiles demonstrated that the MC internal structure was unchanged upon curcumin binding. The ζ-potential value of curcumin-doped MC indicated that curcumin did not modify the global charge of MC particles. Acid gelation studied by oscillation rheology and static multiple light scattering at 20 and 35 °C led to a similar behavior for native and curcumin-doped MC suspensions. For the first time, it was demonstrated that the colloidal and functional properties of MC were unchanged when doped with curcumin during acidification.

Morphology and kinetics of the formation of polyamide benzimidazole in N-methylpyrrolidone

NASA Astrophysics Data System (ADS)

Khanchich, O. A.; Larionov, V. B.; Biryukov, A. L.

2018-02-01

Polymerization-optical methods were used to study the supermolecular structure in the gelation of systems based on polyamidobenzimidazole (PABI) in N-methylpyrrolidone (N-MP) and the kinetics of phase transformations during polymer coagulation from a the solution. It was found that the use of N-MP leads to the appearance in the PABI-N-MP-H2O system of spherulites having a structure characteristic of LC structures. It is shown that the alternation of metastable structures upon gelation of the PABY - N-MP-H2O system is consistent with the appearance of the LC phase of the cholesteric type.

Microcapsules with Intrinsic Barium Radiopacity for Immunoprotection and X-ray/CT imaging of Pancreatic Islet Cells

PubMed Central

Arifin, D.R.; Manek, S.; Call, E.; Arepally, A.; Bulte, J.W.M.

2012-01-01

Microencapsulation is a commonly used technique for immunoprotection of engrafted therapeutic cells. We investigated a library of capsule formulations to determine the most optimal formulation for pancreatic beta islet cell transplantation, using barium as the gelating ion and clinical-grade protamine sulfate (PS) as a new cationic capsule cross-linker. Barium-gelated alginate/PS/alginate microcapsules (APSA, diameter = 444±21 μm) proved to be mechanically stronger and supported a higher cell viability as compared to conventional alginate/poly-L-lysine/alginate (APLLA) capsules. Human pancreatic islets encapsulated inside APSA capsules, gelated with 20 mM barium as optimal concentration, exhibited a sustained morphological integrity, viability, and functionality for at least 3–4 weeks in vitro, with secreted human C-peptide levels of 0.2–160 pg/ml/islet. Unlike APLLA capsules that are gelled with calcium, barium-APSA capsules are intrinsically radiopaque and, when engrafted into mice, could be readily imaged in vivo with micro-computed tomography (CT). Without the need of adding contrast agents, these capsules offer a clinically applicable alternative for simultaneous immunoprotection and real-time, non-invasive X-ray/CT monitoring of engrafted cells during and after in vivo administration. PMID:22444642

Rheology and microstructure of kefiran and whey protein mixed gels.

PubMed

Kazazi, Hosayn; Khodaiyan, Faramarz; Rezaei, Karamatollah; Pishvaei, Malihe; Mohammadifar, Mohammad Amin; Moieni, Sohrab

2017-04-01

The effect of kefiran on cold-set gelation of whey protein isolate (WPI) at 25 °C was studied using rheological measurements and environmental scanning electron microscopy (ESEM). The gelation of samples was induced by the addition of glucono-δ-lactone to the dispersions. WPI concentration was maintained at 8% (w/v) and the concentration of kefiran varied from 0 to 0.08% (w/v). According to rheological measurements, the addition of kefiran into WPI dispersions resulted in a significant increase in the gel strength, the yield stress, and the shear stress values at the flowing point. The gelling point and gelation pH of samples decreased significantly with an increase in kefiran concentration. ESEM micrographs showed that the presence of kefiran played an important role in the microstructure formation of gels. The microstructure of kefiran-WPI mixed gels was more compact and dense, compared to the WPI gel. Depletion interactions between kefiran and whey protein aggregates can be regarded as the chief factor which was responsible for these effects. The present work demonstrated that rheological and microstructural properties of acid-induced whey protein gels were improved by the addition of kefiran.

Effect of urea on heat-induced gelation of bovine serum albumin (BSA) studied by rheology and small angle neutron scattering (SANS)

NASA Astrophysics Data System (ADS)

Nnyigide, Osita Sunday; Oh, Yuna; Song, Hyeong Yong; Park, Eun-kyoung; Choi, Soo-Hyung; Hyun, Kyu

2017-05-01

This paper reports the effects of urea on the heat-induced gelation of bovine serum albumin (BSA), which was studied by the tube inversion method, rheological measurements, and small-angle neutron scattering (SANS). An increase in the urea concentration accelerated the rate of gelation because the protein molecules have already been unfolded to some extent during sample preparation in the urea solution. In addition, the BSA solution in the presence of urea underwent a sol-gel-sol transition during the time sweep test at a constant temperature of 80oC. On the other hand, the BSA solution without urea turned into a hard and brittle gel that did not return to the solution state during isothermal heating at a constant temperature of 80oC. Aggregation and re-bonding of the denatured and unfolded protein chains led to gel formation. Urea added to the protein denatures its tertiary and secondary structures by simultaneously disrupting the hydrogen bonds, hydrophobic interactions, and altering the solvent properties. Furthermore, urea induces thermoreversible chemical interactions in BSA solutions leading to the formation of a gel with dynamic properties under these experimental conditions.

Development and evaluation of floating alginate microspheres for oral delivery of anthocyanins - A preliminary investigation.

PubMed

Celli, Giovana B; Ghanem, Amyl; Brooks, Marianne S

2017-05-01

The goal of this study was to develop floating microspheres that could be used as gastroretentive systems for the delivery of anthocyanins (ACNs). These compounds are absorbed in the stomach and small intestine, and insufficient residence time in these organs could result in limited absorption and contribute to degradation. The microparticles containing freeze-dried haskap berry extract (321.96 ± 8.35 mg cyanidin 3-glucoside equivalents per g) were prepared by ionotropic gelation of alginate (9%, w/w) with calcium ions (CaCl 2 at 2%, w/v) in the gelation bath, with calcium carbonate as the gas-generating compound (added at different ratios in the alginate/extract mixture). The effect of acetic acid concentration (2 and 10%, v/v) in the gelation medium was investigated. Increasing the carbonate : alginate weigh ratio from 0 to 3:4 resulted in different degrees of floatability, larger particles, higher encapsulation efficiency, and lower amount of ACN released. The power law equation fitted the experimental data well, indicating that release occurred mainly by diffusion. This is the first time floating microspheres are proposed as gastroretentive platforms for the delivery of ACNs.

A chiroptical switch based on supramolecular chirality transfer through alkyl chain entanglement and dynamic covalent bonding.

PubMed

Lv, Kai; Qin, Long; Wang, Xiufeng; Zhang, Li; Liu, Minghua

2013-12-14

Chirality transfer is an interesting phenomenon in Nature, which represents an important step to understand the evolution of chiral bias and the amplification of the chirality. In this paper, we report the chirality transfer via the entanglement of the alkyl chains between chiral gelator molecules and achiral amphiphilic Schiff base. We have found that although an achiral Schiff base amphiphile could not form organogels in any kind of organic solvents, it formed co-organogels when mixed with a chiral gelator molecule. Interestingly, the chirality of the gelator molecules was transferred to the Schiff base chromophore in the mixed co-gels and there was a maximum mixing ratio for the chirality transfer. Furthermore, the supramolecular chirality was also produced based on a dynamic covalent chemistry of an imine formed by the reaction between an aldehyde and an amine. Such a covalent bond of imine was formed reversibly depending on the pH variation. When the covalent bond was formed the chirality transfer occurred, when it was destroyed, the transfer stopped. Thus, a supramolecular chiroptical switch is obtained based on supramolecular chirality transfer and dynamic covalent chemistry.

A smart gelator as a chemosensor: application to integrated logic gates in solution, gel, and film.

PubMed

Xue, Pengchong; Lu, Ran; Jia, Junhui; Takafuji, Makoto; Ihara, Hirotaka

2012-03-19

A gelator that consisted of one benzimidazole moiety and four amide units was used as a chemosensor. We found that its absorption and emission spectra in solution were sensitive to two complementary chemical stimuli: protons and anions. Thus, YES and INH logic gates were obtained when absorbance was defined as an output. A combination gate of XNOR and AND with an emission output was also obtained. Moreover, wet gels in two solvents were used to construct two more-complicated three-input-three-output gates, owing to the existence of the gel phase as an additional output. Finally, in xerogel films that were formed from two kinds of wet gels, reversible changes in their emission spectra were observed when they were sequentially exposed to volatile acid and NH(3). Another combination two-output logic gate was obtained for xerogel films. Finally, three states of the gelator were used to construct not only basic logic gate, but also some combination gates because of their response to multiple chemical stimuli and their multiple output signals, in which one chemical input could erase the effect of another chemical input. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A chiral BINOL-based Gemini amphiphilic gelator and its specific discrimination of native arginine by gelation in water.

PubMed

Jia, Lihua; Yin, Jianxin; Guo, Xiangfeng; Cao, Guangzhou; Tian, Xuhua; Zhu, Bo; Pu, Lin

2017-08-16

A novel axially chiral cationic Gemini amphiphile gelator (S1) derived from (S)-BINOL has been synthesized and characterized by 1 H NMR, 13 C NMR, ESI-MS and FT-IR analyses. The critical micelle concentration (CMC) of S1 was determined to be 0.21 mM in water at room temperature. A transparent hydrogel with S1 at 43 mM was obtained at room temperature and characterized using various methods including SEM, CD, fluorescence, 1 H NMR, FT-IR, and XRD. The results indicate that the hydrophobic effect of long alkyl chains, π-π stacking of naphthalene rings, and intermolecular hydrogen-bonding of the amide groups of S1 should be responsible for the hydrogel formation. Moreover, an 8.5 mM aqueous solution of S1 could gel by the addition of l-arginine, whereas it failed to gel in the presence of other 15 amino acids, respectively. It is suggested that S1 could discriminate native arginine by hydrogel formation, mainly due to the electrostatic interaction and hydrogen bonding effects between S1 and l-arginine molecules.

Two-component gelator isomers with different combination of amine and acid: Helical/non-helical morphology and selective adsorption of dyes.

PubMed

Han, Xiaoyu; Liu, Jiahui; Zhao, Chaoyue; Zhang, Bao; Xu, Xiufang; Song, Jian

2018-09-01

Hydrogels induced by two-component gelator isomers based on the different amine/acid interactions were investigated. Scanning electron microscopy and atomic force microscopy images of the xerogel obtained from the two hydrogels revealed different assembly morphologies. While left-handed helical fibers were observed for the amine-acid based xerogel, acid-amine underwent self-assembly to afford smooth fibers. Fourier transform infrared spectroscopy, fluorescence, and X-ray diffraction measurements combined with density functional theory calculations suggested that the different self-assembly patterns of gelators resulted in opposite electric charges on the xerogel surfaces, in line with Zeta potential measurements. Based on these opposite charges resulting from their different self-assemblies, both xerogels demonstrated efficient dye adsorption abilities with different selectivities. Interestingly, the adsorption performance was not influenced by the salt in the dye solution. Furthermore, the xerogels still showed high dye adsorption efficiency after four cycles. These results provide a two-component hydrogel method for the purification of dye-polluted water systems, while also paving the way for future design of functionalized supramolecular self-assembly systems. Copyright © 2018 Elsevier Inc. All rights reserved.

Influence of sodium chloride on the colloidal and rennet coagulation properties of concentrated casein micelle suspensions.

PubMed

Zhao, Z; Corredig, M

2016-08-01

The research investigated the influence of NaCl on the colloidal and rennet coagulation properties of concentrated milk. Milk was concentrated to 1×, 3×, and 5× using ultrafiltration. Rennet gelation was followed by rheology and diffusing wave spectroscopy. Soluble protein, total and diffusible calcium and phosphate, size, and zeta potential were also measured as a function of concentration history. In the presence of 300mM NaCl, colloidal calcium phosphate solubilized and pH and the negative charge on the surface of casein micelles decreased. Increasing the volume fraction caused the formation of stiffer gels for both samples with or without NaCl. The addition of NaCl caused a significant increase in the bulk viscosity of the milk concentrated 5× and a decrease in turbidity. The concentration had no effect on the gelation time of control samples, nor on the kinetics of caseinomacropeptide release. On the other hand, rennet gelation was retarded by the addition of NaCl, and the gels showed lower elastic moduli compared with those obtained with control milk. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Cement paste prior to setting: A rheological approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bellotto, Maurizio, E-mail: maurizio.bellotto@bozzetto.it

2013-10-15

The evolution of cement paste during the dormant period is analyzed via small amplitude oscillation rheological measurements. Cement paste, from the very first moments after mixing cement and water, shows the formation of an elastic gel whose strength is rapidly increasing over time. Up to the onset of Portlandite precipitation G′(t) increases by more than 2 orders of magnitude and in the acceleratory period G′(t) continues steadily to increase. A microstructural modification is likely to occur between the dormant and the acceleratory period. At low deformations in the linearity domain the storage modulus G′(ω) exhibits a negligible frequency dependence. Atmore » higher deformations cement paste shows a yield stress which increases on increasing paste concentration. The presence of superplasticizers decreases the yield stress and increases the gelation threshold of the paste. Above the gelation threshold the evolution of cement paste with superplasticizers follows similar trends to the neat paste. -- Highlights: •The gelation of cement paste during the dormant period is analyzed via rheometry. •The observed evolution is proposed to be related to the pore structure refinement. •Similarities are observed with colloidal gels and colloidal glasses.« less

Reversible gelation of rod-like viruses grafted with thermoresponsive polymers.

PubMed

Zhang, Zhenkun; Krishna, Naveen; Lettinga, M Paul; Vermant, Jan; Grelet, Eric

2009-02-17

The synthesis and selected macroscopic properties of a new model system consisting of poly(N-isopropylacrylamide) (PNIPAM)-coated rod-like fd virus particles are presented. The sticky rod-like colloids can be used to study effect of particle shape on gelation transition, the structure and viscoelasticity of isotropic and nematic gels, and to make both open isotropic as well as ordered nematic particle networks. This model system of rod-like colloids, for which the strength of attraction between the particles is tunable, is obtained by chemically grafting highly monodisperse rod-like fd virus particles with thermoresponsive polymers, e.g. PNIPAM. At room temperature, suspensions of the resulting hybrid PNIPAM-fd are fluid sols which are in isotropic or liquid crystalline phases, depending on the particle concentration and ionic strength. During heating/cooling, the suspensions change reversibly between sol and gel state near a critical temperature of approximately 32 degrees C, close to the lower critical solution temperature of free PNIPAM. The so-called nematic gel, which exhibits a cholesteric feature, can therefore be easily obtained. The gelation behavior of PNIPAM-fd system and the structure of the nematic gel have been characterized by rheology, optical microscopy and small-angle X-ray scattering.

The influence of polymer molecular weight in lamellar gels based on PEG-lipids.

PubMed Central

Warriner, H E; Keller, S L; Idziak, S H; Slack, N L; Davidson, P; Zasadzinski, J A; Safinya, C R

1998-01-01

We report x-ray scattering, rheological, and freeze-fracture and polarizing microscopy studies of a liquid crystalline hydrogel called Lalpha,g. The hydrogel, found in DMPC, pentanol, water, and PEG-DMPE mixtures, differs from traditional hydrogels, which require high MW polymer, are disordered, and gel only at polymer concentrations exceeding an "overlap" concentration. In contrast, the Lalpha,g uses very low-molecular-weight polymer-lipids (1212, 2689, and 5817 g/mole), shows lamellar order, and requires a lower PEG-DMPE concentration to gel as water concentration increases. Significantly, the Lalpha,g contains fluid membranes, unlike Lbeta' gels, which gel via chain ordering. A recent model of gelation in Lalpha phases predicts that polymer-lipids both promote and stabilize defects; these defects, resisting shear in all directions, then produce elasticity. We compare our observations to this model, with particular attention to the dependence of gelation on the PEG MW used. We also use x-ray lineshape analysis of scattering from samples spanning the fluid-gel transition to obtain the elasticity coefficients kappa and B; this analysis demonstrates that although B in particular depends strongly on PEG-DMPE concentration, gelation is uncorrelated to changes in membrane elasticity. PMID:9649387

Simultaneous acoustic and dielectric real time curing monitoring of epoxy systems

NASA Astrophysics Data System (ADS)

Gkikas, G.; Saganas, Ch.; Grammatikos, S. A.; Aggelis, D. G.; Paipetis, A. S.

2012-04-01

The attainment of structural integrity of the reinforcing matrix in composite materials is of primary importance for the final properties of the composite structure. The detailed monitoring of the curing process on the other hand is paramount (i) in defining the optimal conditions for the impregnation of the reinforcement by the matrix (ii) in limiting the effects of the exotherm produced by the polymerization reaction which create unwanted thermal stresses and (iii) in securing optimal behavior in matrix controlled properties, such as off axis or shear properties and in general the durability of the composite. Dielectric curing monitoring is a well known technique for distinguishing between the different stages of the polymerization of a typical epoxy system. The technique successfully predicts the gelation and the vitrification of the epoxy and has been extended for the monitoring of prepregs. Recent work has shown that distinct changes in the properties of the propagated sound in the epoxy which undergoes polymerization is as well directly related to the gelation and vitrification of the resin, as well as to the attainment of the final properties of the resin system. In this work, a typical epoxy is simultaneously monitored using acoustic and dielectric methods. The system is isothermally cured in an oven to avoid effects from the polymerization exotherm. Typical broadband sensors are employed for the acoustic monitoring, while flat interdigital sensors are employed for the dielectric scans. All stages of the polymerization process were successfully monitored and the validity of both methods was cross checked and verified.

t-Butyl-Oxycarbonylated Diamines as Building Blocks for Isocyanate-Free Polyurethane/Urea Dispersions and Coatings.

PubMed

Ma, Shuang; Zhang, Huiyi; Sablong, Rafaël J; Koning, Cor E; van Benthem, Rolf A T M

2018-05-01

t-Butyl-oxycarbonylated diamines ("di-Boc-carbamates") are investigated as dicarbamate monomers for diamine/dicarbamate polymerizations. Polyureas (PUs) and polyurethanes (PURs) with high molecular weights are prepared from stoichiometric polymerizations of diamines or diols with N-N'-di-t-butyl-oxycarbonyl isophorone diamine (DiBoc-IPDC) using KOt-Bu as a catalyst, while gelation is observed when an excess of DiBoc-IPDC is used with respect to the diamines or diols. Stable dispersions are obtained from PUs and PURs with 3,3'-diamino-N-methyldipropylamine (DMDPA) as internal dispersing agent. The corresponding PU-based coatings exhibit superior mechanical properties and solvent resistances compared to the polyurethane urea coatings synthesized from diols, DiBoc-IPDC, and DMDPA. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid engineering of endothelial cell-lined vascular-like structures in in situ crosslinkable hydrogels.

PubMed

Kageyama, Tatsuto; Kakegawa, Takahiro; Osaki, Tatsuya; Enomoto, Junko; Ito, Taichi; Nittami, Tadashi; Fukuda, Junji

2014-06-01

Fabrication of perfusable vascular networks in vitro is one of the most critical challenges in the advancement of tissue engineering. Because cells consume oxygen and nutrients during the fabrication process, a rapid fabrication approach is necessary to construct cell-dense vital tissues and organs, such as the liver. In this study, we propose a rapid molding process using an in situ crosslinkable hydrogel and electrochemical cell transfer for the fabrication of perfusable vascular structures. The in situ crosslinkable hydrogel was composed of hydrazide-modified gelatin (gelatin-ADH) and aldehyde-modified hyaluronic acid (HA-CHO). By simply mixing these two solutions, the gelation occurred in less than 20 s through the formation of a stable hydrazone bond. To rapidly transfer cells from a culture surface to the hydrogel, we utilized a zwitterionic oligopeptide, which forms a self-assembled molecular layer on a gold surface. Human umbilical vein endothelial cells adhering on a gold surface via the oligopeptide layer were transferred to the hydrogel within 5 min, along with electrochemical desorption of the oligopeptides. This approach was applicable to cylindrical needles 200-700 µm in diameter, resulting in the formation of perfusable microchannels where the internal surface was fully enveloped with the transferred endothelial cells. The entire fabrication process was completed within 10 min, including 20 s for the hydrogel crosslinking and 5 min for the electrochemical cell transfer. This rapid fabrication approach may provide a promising strategy to construct perfusable vasculatures in cell-dense tissue constructs and subsequently allow cells to organize complicated and fully vascularized tissues while preventing hypoxic cell injury.

STS-42 Space Shuttle mission report

NASA Technical Reports Server (NTRS)

Fricke, Robert W.

1992-01-01

The STS-42 Space Shuttle Program Mission Report contains a summary of the vehicle subsystem operations during the forty-fifth flight of the Space Shuttle Program and the fourteenth flight of the Orbiter vehicle Discovery (OV-103). In addition to the Discovery vehicle, the flight vehicle consisted of the following: an External Tank (ET) designated as ET-52 (LWT-45); three Space Shuttle main engines (SSME's), which were serial numbers 2026, 2022, and 2027 in positions 1, 2, and 3, respectively; and two Solid Rocket Boosters (SRB's) designated as BI-048. The lightweight redesigned Solid Rocket Motors (RSRM's) installed in each one of the SRB's were designated as 360L020A for the left SRM and 360Q020B for the right SRM. The primary objective of the STS-42 mission was to complete the objectives of the first International Microgravity Laboratory (IML-1). Secondary objectives were to perform all operations necessary to support the requirements of the following: Gelation of Sols: Applied Microgravity Research (GOSAMR); Student Experiment 81-09 (Convection in Zero Gravity); Student Experiment 83-02 (Capillary Rise of Liquid Through Granular Porous Media); the Investigation into Polymer Membrane Processing (IPMP); the Radiation Monitoring Equipment-3 (RME-3); and Get-Away Special (GAS) payloads carried on the GAS Beam Assembly.

A new approach to network heterogeneity: Polymerization Induced Phase Separation in photo-initiated, free-radical methacrylic systems

PubMed Central

Szczepanski, Caroline R.; Pfeifer, Carmem S.; Stansbury, Jeffrey W.

2012-01-01

Non-reactive, thermoplastic prepolymers (poly- methyl, ethyl and butyl methacrylate) were added to a model homopolymer matrix composed of triethylene glycol dimethacrylate (TEGDMA) to form heterogeneous networks via polymerization induced phase separation (PIPS). PIPS creates networks with distinct phase structure that can partially compensate for volumetric shrinkage during polymerization through localized internal volume expansion. This investigation utilizes purely photo-initiated, free-radical systems, broadening the scope of applications for PIPS since these processing conditions have not been studied previously. The introduction of prepolymer into TEGDMA monomer resulted in stable, homogeneous monomer formulations, most of which underwent PIPS upon photo-irradiation, creating heterogeneous networks. During polymerization the presence of prepolymer enhanced autoacceleration, allowing for a more extensive ambient cure of the material. Phase separation, as characterized by dynamic changes in sample turbidity, was monitored simultaneously with monomer conversion and either preceded or was coincident with network gelation. Dynamic mechanical analysis shows a broadening of the tan delta peak and secondary peak formation, characteristic of phase-separated materials, indicating one phase rich in prepolymer and another depleted form upon phase separation. In certain cases, PIPS leads to an enhanced physical reduction of volumetric shrinkage, which is attractive for many applications including dental composite materials. PMID:23109733

STS-42 Space Shuttle mission report

NASA Astrophysics Data System (ADS)

Fricke, Robert W.

1992-02-01

The STS-42 Space Shuttle Program Mission Report contains a summary of the vehicle subsystem operations during the forty-fifth flight of the Space Shuttle Program and the fourteenth flight of the Orbiter vehicle Discovery (OV-103). In addition to the Discovery vehicle, the flight vehicle consisted of the following: an External Tank (ET) designated as ET-52 (LWT-45); three Space Shuttle main engines (SSME's), which were serial numbers 2026, 2022, and 2027 in positions 1, 2, and 3, respectively; and two Solid Rocket Boosters (SRB's) designated as BI-048. The lightweight redesigned Solid Rocket Motors (RSRM's) installed in each one of the SRB's were designated as 360L020A for the left SRM and 360Q020B for the right SRM. The primary objective of the STS-42 mission was to complete the objectives of the first International Microgravity Laboratory (IML-1). Secondary objectives were to perform all operations necessary to support the requirements of the following: Gelation of Sols: Applied Microgravity Research (GOSAMR); Student Experiment 81-09 (Convection in Zero Gravity); Student Experiment 83-02 (Capillary Rise of Liquid Through Granular Porous Media); the Investigation into Polymer Membrane Processing (IPMP); the Radiation Monitoring Equipment-3 (RME-3); and Get-Away Special (GAS) payloads carried on the GAS Beam Assembly.

Influence of Commercial Saturated Monoglyceride, Mono-/Diglycerides Mixtures, Vegetable Oil, Stirring Speed, and Temperature on the Physical Properties of Organogels

PubMed Central

Rocha-Amador, Omar Gerardo; Huang, Qingrong; Rocha-Guzman, Nuria Elizabeth; Moreno-Jimenez, Martha Rocio; Gonzalez-Laredo, Ruben F.

2014-01-01

The objective of this study was to evaluate the influence of gelator, vegetable oil, stirring speed, and temperature on the physical properties of obtained organogels. They were prepared under varying independent conditions and applying a fractional experimental design. From there a rheological characterization was developed. The physical characterization also included polarized light microscopy and calorimetric analysis. Once these data were obtained, X-Ray diffraction was applied to selected samples and a microstructure lattice was confirmed. Commonly, the only conditions that affect crystallization have been analyzed (temperature, solvent, gelator, and cooling rate). We found that stirring speed is the most important parameter in the organogel preparation. PMID:26904637

Gel-based supramolecular ON-OFF switch from aryl-triazolyl peptides with excellent chiro-optical, thixotropic, and self-healing characteristics.

PubMed

Srivastava, Bhartendu K; Muraleedharan, Kannoth M

2018-02-28

Systematic structure-property optimization of an achiral gelator (aryl-triazolyl homo dipeptide, 1.0) through a fragment replacement approach led to the identification of a new chiral system (aryl-triazolyl dipeptide 1.4 having leucine as the C-terminal residue) which exhibits consistent and perfectly reversible chiro-optical responses on sol-gel transition that can work like an ON-OFF switch. The gelator 1.4 could also direct the assembly of 1.0 in a sergeant-soldier mode to give similar CD responses. In addition, its gels are mouldable, self-healing and highly thixotropic, making it important from an application standpoint.

The effects of intermolecular interactions on the physical properties of organogels in edible oils.

PubMed

Lupi, Francesca R; Greco, Valeria; Baldino, Noemi; de Cindio, Bruno; Fischer, Peter; Gabriele, Domenico

2016-12-01

The microstructure of organogels based on monoglycerides of fatty acids (MAGs) and policosanol and on different edible oils was investigated by using different techniques (calorimetry, nuclear magnetic resonance, infrared spectroscopy, rheology, polarized light microscopy) towards a better understanding and control of the oil gelation phenomena. Dynamic moduli were related via a fractal model to microstructural information such as solid content and fractal dimension. Infrared spectroscopy evidenced that network structure in MAGs gel is mainly due to hydrogen bonding, whereas in policosanol system is mainly given by van der Waals interactions. Because of the different relative contribution of molecular interactions, the investigated organogelators exhibit a distinguished macroscopic behavior. MAGs are sensitive to the utilized oil and structuration occurs quickly, even though at a temperature lower than policosanol. Policosanol organogels exhibit a behavior independent of the used oil and a slower gelation rate, as a result of the weaker van der Waals interactions. Nevertheless, at lower concentration a stronger final gel is obtained, probably due to of the large number of interactions arising among the long alkyl chains of the fatty alcohols. Obtained results evidenced that policosanol is very effective in gelation of different oils and seems promising for potential commercial uses. Copyright © 2016 Elsevier Inc. All rights reserved.

Spontaneous stacking of purple membranes during immobilization with physical cross-linked poly(vinyl alcohol) hydrogel with retaining native-like functionality of bacteriorhodopsin

NASA Astrophysics Data System (ADS)

Yokoyama, Yasunori; Tanaka, Hikaru; Yano, Shunsuke; Takahashi, Hiroshi; Kikukawa, Takashi; Sonoyama, Masashi; Takenaka, Koshi

2017-05-01

We previously discovered the correlation between light-induced chromophore color change of a photo-receptor membrane protein bacteriorhodopsin (bR) and its two-dimensional crystalline state in the membrane. To apply this phenomenon to a novel optical memory device, it is necessary that bR molecules are immobilized as maintaining their structure and functional properties. In this work, a poly(vinyl alcohol) (PVA) hydrogel with physical cross-linkages (hydrogen bonds between PVA chains) that resulted from repeated freezing-and-thawing (FT) cycles was used as an immobilization medium. To investigate the effects of physically cross-linked PVA gelation on the structure and function of bR in purple membranes (PMs), spectroscopic techniques were employed against PM/PVA immobilized samples prepared with different FT cycle numbers. Visible circular dichroism spectroscopy strongly suggested PM stacking during gelation. X-ray diffraction data also indicated the PM stacking as well as its native-like crystalline lattice even after gelation. Time-resolved absorption spectroscopy showed that bR photocycle behaviors in PM/PVA immobilized samples were almost identical to that in suspension. These results suggested that a physically cross-linked PVA hydrogel is appropriate for immobilizing membrane proteins in terms of maintaining their structure and functionality.

Microcapsules with intrinsic barium radiopacity for immunoprotection and X-ray/CT imaging of pancreatic islet cells.

PubMed

Arifin, Dian R; Manek, Sameer; Call, Emma; Arepally, Aravind; Bulte, Jeff W M

2012-06-01

Microencapsulation is a commonly used technique for immunoprotection of engrafted therapeutic cells. We investigated a library of capsule formulations to determine the most optimal formulation for pancreatic beta islet cell transplantation, using barium as the gelating ion and clinical-grade protamine sulfate (PS) as a new cationic capsule cross-linker. Barium-gelated alginate/PS/alginate microcapsules (APSA, diameter = 444 ± 21 μm) proved to be mechanically stronger and supported a higher cell viability as compared to conventional alginate/poly-l-lysine/alginate (APLLA) capsules. Human pancreatic islets encapsulated inside APSA capsules, gelated with 20 mm barium as optimal concentration, exhibited a sustained morphological integrity, viability, and functionality for at least 3-4 weeks in vitro, with secreted human C-peptide levels of 0.2-160 pg/ml/islet. Unlike APLLA capsules that are gelled with calcium, barium-APSA capsules are intrinsically radiopaque and, when engrafted into mice, could be readily imaged in vivo with micro-computed tomography (CT). Without the need of adding contrast agents, these capsules offer a clinically applicable alternative for simultaneous immunoprotection and real-time, non-invasive X-ray/CT monitoring of engrafted cells during and after in vivo administration. Copyright © 2012 Elsevier Ltd. All rights reserved.

Synergistic gelation of silica nanoparticles and a sorbitol-based molecular gelator to yield highly-conductive free-standing gel electrolytes.

PubMed

Basrur, Veidhes R; Guo, Juchen; Wang, Chunsheng; Raghavan, Srinivasa R

2013-01-23

Lithium-ion batteries have emerged as the preferred type of rechargeable batteries, but there is a need to improve the performance of the electrolytes therein. Specifically, the challenge is to obtain electrolytes with the mechanical rigidity of solids but with liquid-like conductivities. In this study, we report a class of nanostructured gels that are able to offer this unique combination of properties. The gels are prepared by utilizing the synergistic interactions between a molecular gelator, 1,3:2,4-di-O-methyl-benzylidene-d-sorbitol (MDBS), and a nanoscale particulate material, fumed silica (FS). When MDBS and FS are combined in a liquid consisting of propylene carbonate with dissolved lithium perchlorate salt, the liquid electrolyte is converted into a free-standing gel due to the formation of a strong MDBS-FS network. The gels exhibit elastic shear moduli around 1000 kPa and yield stresses around 11 kPa-both values considerably exceed those obtainable by MDBS or FS alone in the same liquid. At the same time, the gel also exhibits electrochemical properties comparable to the parent liquid, including a high ionic conductivity (~5 × 10(-3) S/cm at room temperature) and a wide electrochemical stability window (up to 4.5 V).

Influence of dialkyne structure on the properties of new click-gels based on hyaluronic acid.

PubMed

Testa, Gabriella; Di Meo, Chiara; Nardecchia, Stefania; Capitani, Donatella; Mannina, Luisa; Lamanna, Raffaele; Barbetta, Andrea; Dentini, Mariella

2009-08-13

Hydrogels have been widely used in tissue engineering as a support for tissue formation and/or to deliver drug locally. A novel procedure for the in situ rapid chemical gelation of aqueous solutions of hyaluronan (HA) was employed. HA was functionalised with an arm bearing a terminal azido group (HAAA). When HAAA was mixed with a series of dialkyne reagents of different length, a 1,3-dipolar cycloaddition ("click-chemistry") reaction took place in the presence of catalytic amount of Cu(I) resulting in fast gelation at room temperature. The resulting gels were characterised in terms of degree of cross-linking by (1)H HR-MAS NMR. The kinetic of gelation and the determination of elastic moduli as well as the degree of swelling and the controlled release of a model drug, were studied as a function of chemical nature of the dialkyne group, catalyst concentration, HAAA concentration and temperature. All these variables allowed the swelling ratio and the extent of release of a drug, doxorubicin, entrapped within the gel, to be modulated. In all cases the kinetic of release reached the stationary state within 150 h. The height of the plateau was dependent on the overall (chemical and topological) degree of cross-linking.

Dissolution and regeneration of non-mulberry Eriogyna Pyretorum silk fibroin

NASA Astrophysics Data System (ADS)

Guo, Yuhang; Li, Xiufang; Zhang, Qiang; Yan, Shuqin; You, Renchuan

2017-10-01

Protein-based materials have been actively pursued as biomaterials because of their nontoxicity, biocompatibility and biodegradability. In this work, we demonstrated the potential of Eriogyna pyretorum silk fibroin (ESF), a non-mulberry silk protein, as biomaterials. The degummed ESF fibers could be dissolved completely by Ca(NO3)2/H2O/C2H5OH solution to produce regenerated ESF. The solubility was strongly dependent on the addition of C2H5OH, heating temperature and dissolving time. α-helix and random coil are main molecular conformation in aqueous ESF solution. The sol-gel transition behavior of regenerated ESF was also studied, indicating that the conformational transition of regenerated ESF from random coil/α-helix to β-sheet during gelation. Especially, ESF showed more rapid gelation than mulberry silk fibroin (BSF). Consequently, the gelation rate of BSF could be controlled ranging from tens of minutes to days by changing the ESF ratio, providing useful options for the fabrication of silk hydrogels. Water-stable regenerated ESF film could be achieved by using aqueous ethanol to induce structural transition. Tensile tests showed that the ESF films have a dry strength of approximate 31.0 MPa and a wet strength of approximate 3.3 MPa. This study provides new opportunities as an alternative natural protein material for biomedical applications.

Exploration of the nature of a unique natural polymer-based thermosensitive hydrogel.

PubMed

Lu, Shanling; Yang, Yuhong; Yao, Jinrong; Shao, Zhengzhong; Chen, Xin

2016-01-14

The chitosan (CS)/β-glycerol phosphate (GP) system is a heat induced gelling system with a promising potential application, such as an injectable biomedical material. Unlike most thermosensitive gelling systems, the CS/GP system is only partially reversible. That is once the hydrogel is fully matured, it only softens but cannot go back to its initial liquid state when cooled down. Here, we perform both the small and large amplitude oscillatory shear (SAOS and LAOS) tests on the fully matured CS/GP hydrogel samples at a variety of temperatures within the cooling process. The purpose of such tests is to investigate the structural change of the hydrogel network and thus to understand the possible gelation mechanism of this unique thermosensitive hydrogel. From the LAOS results and the further analysis with the Chebyshev expansion method, it shows that the CS/GP hydrogel is composed of a colloidal network dominated by hydrophobic interactions at high temperature, and gradually turns into a flexible network dominated by hydrogen bonding when the temperature goes down. Therefore, we may conclude that LOAS is a powerful tool to study the nonlinear behaviour of a polymer system that is closely related to its structure, and as a practical example, we achieve a clearer vision on the gelation mechanism of the unique CS/GP thermosensitive hydrogel on the basis of considerable previous studies and assumptions in this laboratory and other research groups.

Supramolecular Gel-Templated In Situ Synthesis and Assembly of CdS Quantum Dots Gels

NASA Astrophysics Data System (ADS)

Zhu, Lili; He, Jie; Wang, Xiaoliang; Li, Dawei; He, Haibing; Ren, Lianbing; Jiang, Biwang; Wang, Yong; Teng, Chao; Xue, Gi; Tao, Huchun

2017-01-01

Although many studies have attempted to develop strategies for spontaneously organizing nanoparticles (NPs) into three-dimensional (3D) geometries, it remains a fascinating challenge. In this study, a method for in situ synthesis and self-assembly of a CdS quantum dots (QDs) gel using a Cd supramolecular gel as a scaffold was demonstrated. During the QDs formation process, the Cd ions that constituted the Cd gels served as the precursors of the CdS QDs, and the oleic acid (OA) that ligated with the Cd in the supramolecular gels was capped on the surface of the CdS QDs in the form of carboxylate. The OA-stabilized CdS QDs were in situ synthesized in the entangled self-assembled fibrillar networks (SAFIN) of the Cd gels through reactions between the gelator and H2S. As a result, the QDs exactly replicated the framework of the SAFIN in the CdS QD gels instead of simply assembling along the SAFIN of the supramolecular gels. Moreover, the CdS QDs showed extraordinary sensitivity in the fluorescence detection of IO4 - anions. The facile one-step method developed here is a new approach to assembling nanostructured materials into 3D architectures and has general implications for the design of low molecular mass gelators to bring desired functionality to the developed supramolecular gels.

Coordination Polymer Gels with Modular Nanomorphologies, Tunable Emissions, and Stimuli-Responsive Behavior Based on an Amphiphilic Tripodal Gelator.

PubMed

Sutar, Papri; Maji, Tapas Kumar

2017-08-21

The recent upsurge in research on coordination polymer gels (CPGs) stems from their synthetic modularity, nanoscale processability, and versatile functionalities. Here we report self-assembly of an amphiphilic, tripodal low-molecular weight gelator (L) that consists of 4,4',4-[1,3,5-phenyl-tri(methoxy)]-tris-benzene core and 2,2':6',2″-terpyridyl termini, with different metal ions toward the formation of CPGs that show controllable nanomorphologies, tunable emission, and stimuli-responsive behaviors. L can also act as a selective chemosensor for Zn II with very low limit of detection (0.18 ppm) in aqueous medium. Coordination-driven self-assembly of L with Zn II in H 2 O/MeOH solvent mixture results in a coordination polymer hydrogel (ZnL) that exhibits sheet like morphology and charge-transfer emission. On the other hand, coordination of L with Tb III and Eu III in CHCl 3 /tetrahydrofuran solvent mixture results in green- and red-emissive CPGs, respectively, with nanotubular morphology. Moreover, precise stoichiometric control of L/Eu III /Tb III ratio leads to the formation of bimetallic CPGs that show emissions over a broad spectral range, including white-light-emission. We also explore the multistimuli responsive properties of the white-light-emitting CPG by exploiting the dynamics of Ln III -tpy coordination.

Facile Synthesis of Radial-Like Macroporous Superparamagnetic Chitosan Spheres with In-Situ Co-Precipitation and Gelation of Ferro-Gels

PubMed Central

Yang, Chih-Hui; Wang, Chih-Yu; Huang, Keng-Shiang; Yeh, Chen-Sheng; Wang, Andrew H. -J.; Wang, Wei-Ting; Lin, Ming-Yu

2012-01-01

Macroporous chitosan spheres encapsulating superparamagnetic iron oxide nanoparticles were synthesized by a facile and effective one-step fabrication process. Ferro-gels containing ferrous cations, ferric cations and chitosan were dropped into a sodium hydroxide solution through a syringe pump. In addition, a sodium hydroxide solution was employed for both gelation (chitosan) and co-precipitation (ferrous cations and ferric cations) of the ferro-gels. The results showed that the in-situ co-precipitation of ferro-ions gave rise to a radial morphology with non-spheroid macro pores (large cavities) inside the chitosan spheres. The particle size of iron oxide can be adjusted from 2.5 nm to 5.4 nm by tuning the concentration of the sodium hydroxide solution. Using Fourier Transform Infrared Spectroscopy and X-ray diffraction spectra, the synthesized nanoparticles were illustrated as Fe3O4 nanoparticles. In addition, the prepared macroporous chitosan spheres presented a super-paramagnetic behaviour at room temperature with a saturation magnetization value as high as ca. 18 emu/g. The cytotoxicity was estimated using cell viability by incubating doses (0∼1000 µg/mL) of the macroporous chitosan spheres. The result showed good viability (above 80%) with alginate chitosan particles below 1000 µg/mL, indicating that macroporous chitosan spheres were potentially useful for biomedical applications in the future. PMID:23226207

Synergistic effect of divalent cations in improving technological properties of cross-linked alginate beads.

PubMed

Cerciello, Andrea; Del Gaudio, Pasquale; Granata, Veronica; Sala, Marina; Aquino, Rita P; Russo, Paola

2017-08-01

Gelling solution parameters are some of the most important variables in ionotropic gelation and consequently influence the technological characteristics of the product. To date, only a few studies have focused on the simultaneous use of multiple cations as gelling agents. With the aim to deeply explore this possibility, in this research we investigated the effect of two divalent cations (Ca 2+ and Zn 2+ ) on alginate beads formation and properties. Alginate beads containing prednisolone (P) as model drug were prepared by prilling technique. The main critical variables of the ionotropic gelation process i.e. composition of the aqueous feed solutions (sodium alginate and prednisolone concentration) and cross-linking conditions (Ca 2+ , Zn 2+ or Ca 2+ +Zn 2+ ), were studied. The obtained beads were characterized and their in vitro release performances were assessed in conditions simulating the gastrointestinal environment. Results evidenced a synergistic effect of the two cations, affecting positively both the encapsulation efficiency and the ability of the alginate polymeric matrix to control the drug release. A Ca 2+ /Zn 2+ ratio of 4:1, in fact, exploited the Ca 2+ ability of establish quicker electrostatic interactions with guluronic groups of alginate and the Zn 2+ ability to establish covalent-like bonds with carboxylate groups of both guluronic and mannuronic moieties of alginate. Copyright © 2017 Elsevier B.V. All rights reserved.

A shear-induced network of aligned wormlike micelles in a sugar-based molecular gel. From gelation to biocompatibility assays.

PubMed

Fitremann, Juliette; Lonetti, Barbara; Fratini, Emiliano; Fabing, Isabelle; Payré, Bruno; Boulé, Christelle; Loubinoux, Isabelle; Vaysse, Laurence; Oriol, Luis

2017-10-15

A new low molecular weight hydrogelator with a saccharide (lactobionic) polar head linked by azide-alkyne click chemistry was prepared in three steps. It was obtained in high purity without chromatography, by phase separation and ultrafiltration of the aqueous gel. Gelation was not obtained reproducibly by conventional heating-cooling cycles and instead was obtained by shearing the aqueous solutions, from 2 wt% to 0.25 wt%. This method of preparation favored the formation of a quite unusual network of interconnected large but thin 2D-sheets (7nm-thick) formed by the association side-by-side of long and aligned 7nm diameter wormlike micelles. It was responsible for the reproducible gelation at the macroscopic scale. A second network made of helical fibres with a 10-13nm diameter, more or less intertwined was also formed but was scarcely able to sustain a macroscopic gel on its own. The gels were analysed by TEM (Transmission Electronic Microscopy), cryo-TEM and SAXS (Small Angle X-ray Scattering). Molecular modelling was also used to highlight the possible conformations the hydrogelator can take. The gels displayed a weak and reversible transition near 20°C, close to room temperature, ascribed to the wormlike micelles 2D-sheets network. Heating over 30°C led to the loss of the gel macroscopic integrity, but gel fragments were still observed in suspension. A second transition near 50°C, ascribed to the network of helical fibres, finally dissolved completely these fragments. The gels showed thixotropic behaviour, recovering slowly their initial elastic modulus, in few hours, after injection through a needle. Stable gels were tested as scaffold for neural cell line culture, showing a reduced biocompatibility. This new gelator is a clear illustration of how controlling the pathway was critical for gel formation and how a new kind of self-assembly was obtained by shearing. Copyright © 2017 Elsevier Inc. All rights reserved.

Ultralow protein adsorbing coatings from clickable PEG nanogel solutions: Benefits of attachment under salt-induced phase separation conditions and comparison with PEG/albumin nanogel coatings

PubMed Central

Donahoe, Casey D.; Cohen, Thomas L.; Li, Wenlu; Nguyen, Peter K.; Fortner, John D.; Mitra, Robi D.; Elbert, Donald L.

2013-01-01

Clickable nanogel solutions were synthesized by using the copper catalyzed azide/alkyne cycloaddition (CuAAC) to partially polymerize solutions of azide and alkyne functionalized poly(ethylene glycol) (PEG) monomers. Coatings were fabricated using a second click reaction: a UV thiol-yne attachment of the nanogel solutions to mercaptosilanated glass. Because the CuAAC reaction was effectively halted by the addition of a copper-chelator, we were able to prevent bulk gelation and limit the coating thickness to a single monolayer of nanogels in the absence of the solution reaction. This enabled the inclusion of kosmotropic salts, which caused the PEG to phase-separate and nearly double the nanogel packing density, as confirmed by Quartz Crystal Microbalance with Dissipation (QCM-D). Protein adsorption was analyzed by single molecule counting with total internal reflection fluorescence (TIRF) microscopy and cell adhesion assays. Coatings formed from the phase-separated clickable nanogel solutions attached with salt adsorbed significantly less fibrinogen than other 100% PEG coatings tested, as well as poly-L-lysine-g-PEG (PLL-g-PEG) coatings. However, PEG/albumin nanogel coatings still outperformed the best 100% PEG clickable nanogel coatings. Additional surface crosslinking of the clickable nanogel coating in the presence of copper further reduced levels of fibrinogen adsorption closer to those of PEG/albumin nanogel coatings. However, this step negatively impacted long-term resistance to cell adhesion and dramatically altered the morphology of the coating by atomic force microscopy (AFM). The main benefit of the click strategy is that the partially polymerized solutions are stable almost indefinitely, allowing attachment in the phase-separated state without danger of bulk gelation, and thus, producing the best performing 100% PEG coating that we have studied to date. PMID:23441808

Enhancing the in vitro Fe(2+) bio-accessibility using ascorbate and cold-set whey protein gel particles.

PubMed

Martin, A H; de Jong, G A H

2012-03-01

This paper investigates the possibility for iron fortification of food using a new preparation method for protein gel particles in which iron is entrapped in the presence of ascorbate using cold-set gelation. The effect of ascorbate on the iron-induced cold-set gelation process of whey protein was studied in order to optimize the ratio of iron/ascorbate. Subsequently, the effect of ascorbate on iron bio-accessibility was assessed in vitro. Rheology was used to study the protein gel formation, and the stability of the gel particles was determined by measuring the iron and protein content at different pH. In vitro studies were performed with the TNO Intestinal Model (TIM). Ascorbate appeared to affect the gel formation process and increased the gel strength of the iron-induced cold-set gels at specific iron/ascorbate ratio. With the Fe-protein gel particles being stable at a broad pH range, the release of iron from the particles was studied as a function of time. The low release of iron indicated a good encapsulation efficiency and the capability of whey protein to keep iron bound at different conditions (pH and presence of calcium). Results obtained with the TIM showed that ascorbate, when added to the protein gel particles, was very successful in enhancing the recovery and absorption of iron. The in vitro Fe(2+) bio-accessibility in the presence of ascorbate in iron-protein particles increased from 10% to almost 80%. This suggests that the concept of using protein particles with iron and ascorbate can effectively be used to fortify food products with iron for human consumption.

Mechanistic Kinetic Modeling of Thiol-Michael Addition Photopolymerizations via Photocaged "Superbase" Generators: An Analytical Approach.

PubMed

Claudino, Mauro; Zhang, Xinpeng; Alim, Marvin D; Podgórski, Maciej; Bowman, Christopher N

2016-11-08

A kinetic mechanism and the accompanying mathematical framework are presented for base-mediated thiol-Michael photopolymerization kinetics involving a photobase generator. Here, model kinetic predictions demonstrate excellent agreement with a representative experimental system composed of 2-(2-nitrophenyl)propyloxycarbonyl-1,1,3,3-tetramethylguanidine (NPPOC-TMG) as a photobase generator that is used to initiate thiol-vinyl sulfone Michael addition reactions and polymerizations. Modeling equations derived from a basic mechanistic scheme indicate overall polymerization rates that follow a pseudo-first-order kinetic process in the base and coreactant concentrations, controlled by the ratio of the propagation to chain-transfer kinetic parameters ( k p / k CT ) which is dictated by the rate-limiting step and controls the time necessary to reach gelation. Gelation occurs earlier as the k p / k CT ratio reaches a critical value, wherefrom gel times become nearly independent of k p / k CT . The theoretical approach allowed determining the effect of induction time on the reaction kinetics due to initial acid-base neutralization for the photogenerated base caused by the presence of protic contaminants. Such inhibition kinetics may be challenging for reaction systems that require high curing rates but are relevant for chemical systems that need to remain kinetically dormant until activated although at the ultimate cost of lower polymerization rates. The pure step-growth character of this living polymerization and the exhibited kinetics provide unique potential for extended dark-cure reactions and uniform material properties. The general kinetic model is applicable to photobase initiators where photolysis follows a unimolecular cleavage process releasing a strong base catalyst without cogeneration of intermediate radical species.

Hierarchical self-assembly of switchable nucleolipid supramolecular gels based on environmentally-sensitive fluorescent nucleoside analogs

NASA Astrophysics Data System (ADS)

Nuthanakanti, Ashok; Srivatsan, Seergazhi G.

2016-02-01

Exquisite recognition and folding properties have rendered nucleic acids as useful supramolecular synthons for the construction of programmable architectures. Despite their proven applications in nanotechnology, scalability and fabrication of nucleic acid nanostructures still remain a challenge. Here, we describe a novel design strategy to construct new supramolecular nucleolipid synthons by using environmentally-sensitive fluorescent nucleoside analogs, based on 5-(benzofuran-2-yl)uracil and 5-(benzo[b]thiophen-2-yl)uracil cores, as the head group and fatty acids, attached to the ribose sugar, as the lipophilic group. These modified nucleoside-lipid hybrids formed organogels driven by hierarchical structures such as fibers, twisted ribbons, helical ribbons and nanotubes, which depended on the nature of fatty acid chain and nucleobase modification. NMR, single crystal X-ray and powder X-ray diffraction studies revealed the coordinated interplay of various non-covalent interactions invoked by modified nucleobase, sugar and fatty acid chains in setting up the pathway for the gelation process. Importantly, these nucleolipid gels retained or displayed aggregation-induced enhanced emission and their gelation behavior and photophysical properties could be reversibly switched by external stimuli such as temperature, ultrasound and chemicals. Furthermore, the switchable nature of nucleolipid gels to chemical stimuli enabled the selective two channel recognition of fluoride and Hg2+ ions through visual phase transition and fluorescence change. Fluorescent organogels exhibiting such a combination of useful features is rare, and hence, we expect that this innovative design of fluorescent nucleolipid supramolecular synthons could lead to the emergence of a new family of smart optical materials and probes.Exquisite recognition and folding properties have rendered nucleic acids as useful supramolecular synthons for the construction of programmable architectures. Despite their proven applications in nanotechnology, scalability and fabrication of nucleic acid nanostructures still remain a challenge. Here, we describe a novel design strategy to construct new supramolecular nucleolipid synthons by using environmentally-sensitive fluorescent nucleoside analogs, based on 5-(benzofuran-2-yl)uracil and 5-(benzo[b]thiophen-2-yl)uracil cores, as the head group and fatty acids, attached to the ribose sugar, as the lipophilic group. These modified nucleoside-lipid hybrids formed organogels driven by hierarchical structures such as fibers, twisted ribbons, helical ribbons and nanotubes, which depended on the nature of fatty acid chain and nucleobase modification. NMR, single crystal X-ray and powder X-ray diffraction studies revealed the coordinated interplay of various non-covalent interactions invoked by modified nucleobase, sugar and fatty acid chains in setting up the pathway for the gelation process. Importantly, these nucleolipid gels retained or displayed aggregation-induced enhanced emission and their gelation behavior and photophysical properties could be reversibly switched by external stimuli such as temperature, ultrasound and chemicals. Furthermore, the switchable nature of nucleolipid gels to chemical stimuli enabled the selective two channel recognition of fluoride and Hg2+ ions through visual phase transition and fluorescence change. Fluorescent organogels exhibiting such a combination of useful features is rare, and hence, we expect that this innovative design of fluorescent nucleolipid supramolecular synthons could lead to the emergence of a new family of smart optical materials and probes. Electronic supplementary information (ESI) available: Supplementary figures, tables, experimental procedures, crystallography data and NMR spectra. See DOI: 10.1039/c5nr07490h

Exploring the difference in xerogels and organogels through in situ observation

PubMed Central

Li, Zhiming; Wang, Haitao; Li, Min; Ozaki, Yukihiro; Wei, Jue

2018-01-01

Solvent–gelator interactions play a key role in mediating organogel formation and ultimately determine the physico-chemical properties of the organogels and xerogels. The ethanol organogels of 1,4-bis[(3,4,5-trihexyloxy phenyl)hydrazide]phenylene (TC6) were investigated in situ by FT-IR, Raman and fluorescence spectra, and XRD, and it was confirmed that the intermolecular interaction and aggregation structure of TC6 ethanol organogels were quite different from those of xerogels. Simultaneously, unprecedented phase transition from organogel to suspension upon heating was observed in ethanol organogel, and the suspension phase exhibited lytropic liquid crystalline behaviour with a rectangular columnar structure. This study may open the possibility to design new gelators with a new dimension of versatility. PMID:29410792

Electro-opto-thermal addressing bistable and re-addressable display device based on gelator-doped liquid crystals in a poly(N-vinylcarbazole) film-coated liquid crystal cell.

PubMed

Cheng, Ko-Ting; Tang, Yi; Liu, Cheng-Kai

2016-10-03

This paper reports an electro-opto-thermal addressing bistable and re-addressable display device based on gelator-doped liquid crystals (LCs) in a poly(N-vinylcarbazole) film-coated LC cell. The bistability and re-addressability of the devices were achieved through the formation of a rubbery LC/gel mixture at room temperature. The desired patterns were addressed, erased, and re-addressed by controlling the temperature, applied voltage, and UV light illumination. Moreover, grayscales were obtained by adjusting UV light intensity. The initiation, relaxation, rise, and fall times of photoconductive poly(N-vinylcarbazole) via UV light illumination of various intensities were also examined.

Revised state diagram of Laponite dispersions.

PubMed

Mongondry, Philippe; Tassin, Jean François; Nicolai, Taco

2005-03-15

We propose a state diagram of charged disk-like mineral particle (Laponite) dispersions as a function of the Laponite concentration (C) and the concentration of added salt (C(s)), based on simple observation and light-scattering measurements. At low C or high C(s) the dispersions separate into two domains due to sedimentation of Laponite aggregates, while at high C and low C(s) they form homogeneous gels that do not flow upon tube reversal. The aggregation rate and the structure factor of the Laponite dispersions is determined with light scattering as a function of C and C(s). We discuss in detail the controversy on the origin of gelation of Laponite dispersions in the absence of added salt. We argue that aggregation rather than glass formation causes gelation.

High-average-power laser medium based on silica glass

NASA Astrophysics Data System (ADS)

Fujimoto, Yasushi; Nakatsuka, Masahiro

2000-01-01

Silica glass is one of the most attractive materials for a high-average-power laser. We have developed a new laser material base don silica glass with zeolite method which is effective for uniform dispersion of rare earth ions in silica glass. High quality medium, which is bubbleless and quite low refractive index distortion, must be required for realization of laser action. As the main reason of bubbling is due to hydroxy species remained in the gelation same, we carefully choose colloidal silica particles, pH value of hydrochloric acid for hydrolysis of tetraethylorthosilicate on sol-gel process, and temperature and atmosphere control during sintering process, and then we get a bubble less transparent rare earth doped silica glass. The refractive index distortion of the sample also discussed.

Gelation kinetics and characterization of enzymatically enhanced fish scale gelatin-pectin coacervate.

PubMed

Huang, Tao; Tu, Zong-Cai; Shangguan, Xinchen; Wang, Hui; Zhang, Nanhai; Zhang, Lu; Sha, Xiaomei

2018-02-01

Protein-polysaccharide complex coacervations have been considered extensively for the development of functional foods. The main problem of the complex coacervates is that they are highly unstable under different conditions and that cross-linking is necessary to stabilize them. In this study, the effects of pectin at different concentrations on the gel and structural properties of fish scale gelatin (FSG)-high methoxyl citrus pectin (HMP) coacervate enhanced by microbial transglutaminase (MTGase) were studied. The gelation rates and gel strength of the MTGase-enhanced FSG-HMP coacervate gels decreased with increasing HMP concentration. However, the enhanced coacervate gels exhibited better thermal behavior and mechanical properties compared with the original gels. Also, TG-P 8 exhibited the highest melting point (27.15 ± 0.12 °C), gelation point (15.65 ± 0.01 °C) and stress (15.36 ± 0.48 kPa) as HMP was 8 g kg -1 . Particle size distribution, fluorescence emission and UV absorbance spectra indicated that MTGase and HMP could make FSG form large aggregates. Moreover, confocal laser scanning microscopy of treated coacervate gels showed a continuous protein phase at low HMP concentrations. FSG and HMP could form soluble coacervate, and MTGase could improve the thermal and mechanical properties of coacervate gels. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Chirp-Z analysis for sol-gel transition monitoring.

PubMed

Martinez, Loïc; Caplain, Emmanuel; Serfaty, Stéphane; Griesmar, Pascal; Gouedard, Gérard; Gindre, Marcel

2004-04-01

Gelation is a complex reaction that transforms a liquid medium into a solid one: the gel. In gel state, some gel materials (DMAP) have the singular property to ring in an audible frequency range when a pulse is applied. Before the gelation point, there is no transmission of slow waves observed; after the gelation point, the speed of sound in the gel rapidly increases from 0.1 to 10 m/s. The time evolution of the speed of sound can be measured, in frequency domain, by following the frequency spacing of the resonance peaks from the Synchronous Detection (SD) measurement method. Unfortunately, due to a constant frequency sampling rate, the relative error for low speeds (0.1 m/s) is 100%. In order to maintain a low constant relative error, in the whole speed time evolution range, Chirp-Z Transform (CZT) is used. This operation transforms a time variant signal to a time invariant one using only a time dependant stretching factor (S). In the frequency domain, the CZT enables us to stretch each collected spectrum from time signals. The blind identification of the S factor gives us the complete time evolution law of the speed of sound. Moreover, this method proves that the frequency bandwidth follows the same time law. These results point out that the minimum wavelength stays constant and that it only depends on the gel.

Comparison of selected physico-chemical properties of calcium alginate films prepared by two different methods.

PubMed

Crossingham, Yazmin J; Kerr, Philip G; Kennedy, Ross A

2014-10-01

Sodium alginate (SA) is a naturally occurring, non-toxic, polysaccharide that is able to form gels after exposure to calcium. These gels have been used in food and biomedical industries. This is the first direct comparison of two different methods of calcium alginate film production, namely interfacial gelation (IFG) and dry cast gelation (DCG). IFG films were significantly thicker than DCG films, and were more extensively rehydrated in water and 0.1M HCl than the DCG films. During rehydration in 0.1M HCl almost all calcium ions were lost. Under scanning electron microscopy, IFG films appeared less dense than DCG films. IFG films were mechanically weaker than DCG films, and both types of film were weaker after rehydration in 0.1M HCl compared with deionized water. Permeation of theophylline (TPL) was evaluated in-vitro; the diffusion coefficient (D) of the TPL was almost 90 times lower in DCG films than IFG films when both were rehydrated in water. Although the 0.1M HCl rendered both gels more permeable to TPL, D of TPL was still about five times lower in DCG compared to IFG films. The evaluation of selected physico-chemical properties of films is important, since this information may inform the choice of gelation technique used to produce calcium alginate coatings on pharmaceutical products. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and characterization of Poloxamer 188-grafted heparin copolymer.

PubMed

Tian, Ji-Lai; Zhao, Ying-Zheng; Jin, Zhuo; Lu, Cui-Tao; Tang, Qin-Qin; Xiang, Qi; Sun, Chang-Zheng; Zhang, Lu; Xu, Yan-Yan; Gao, Hui-Sheng; Zhou, Zhi-Cai; Li, Xiao-Kun; Zhang, Ying

2010-07-01

Poloxamer 188 is a safe biocompatible polymer that can be used in protein drug delivery system. In this study, a new heparin-poloxamer 188 conjugate (HP) was synthesized and its physicochemical properties were investigated. HP structure was confirmed by Fourier transform infrared spectroscopy (FTIR) and Hydrogen-1 nuclear magnetic resonance spectroscopy ((1)H-NMR). Content of the conjugated heparin was analyzed using Toluidine Blue. The critical micelle concentration (CMC) of the copolymer was determined by a fluorescence probe technique. The effect of HP on the gelation of poloxamer 188 was characterized by the rheological properties of the HP-poloxamer hydrogels. Solubility and viscosity of HP were also evaluated compared with poloxamer 188. From the results, the solubility of the conjugated heparin was increased compared with free heparin. The content of heparin in HP copolymer was 62.9%. The CMC of HP and poloxamer 188 were 0.483 and 0.743 mg/mL, respectively. The gelation temperature of 0.4 g/mL HP was 43.5 degrees C, whereas that of the same concentration of poloxamer 188 was 37.3 degrees C. With HP content in poloxamer 188 solution increasing, a V-shape change of gelation temperature was observed. Considering the importance of poloxamer 188 in functional material, HP may prove to be a facile temperature-sensitive material for protein drug-targeted therapy.

Gelation And Mechanical Response of Patchy Rods

NASA Astrophysics Data System (ADS)

Kazem, Navid; Majidi, Carmel; Maloney, Craig

We perform Brownian Dynamics simulations to study the gelation of suspensions of attractive, rod-like particles. We show that details of the particle-particle interactions can dramatically affect the dynamics of gelation and the structure and mechanics of the networks that form. If the attraction between the rods is perfectly smooth along their length, they will collapse into compact bundles. If the attraction is sufficiently corrugated or patchy, over time, a rigid space spanning network forms. We study the structure and mechanical properties of the networks that form as a function of the fraction of the surface that is allowed to bind. Surprisingly, the structural and mechanical properties are non-monotonic in the surface coverage. At low coverage, there are not a sufficient number of cross-linking sites to form networks. At high coverage, rods bundle and form disconnected clusters. At intermediate coverage, robust networks form. The elastic modulus and yield stress are both non-monotonic in the surface coverage. The stiffest and strongest networks show an essentially homogeneous deformation under strain with rods re-orienting along the extensional axis. Weaker, clumpy networks at high surface coverage exhibit relatively little re-orienting with strong non-affine deformation. These results suggest design strategies for tailoring surface interactions between rods to yield rigid networks with optimal properties. National Science Foundation and the Air Force Office of Scientific Research.

Gels and lyotropic liquid crystals: using an imidazolium-based catanionic surfactant in binary solvents.

PubMed

Cheng, Ni; Hu, Qiongzheng; Bi, Yanhui; Xu, Wenwen; Gong, Yanjun; Yu, Li

2014-08-05

The self-assembly behavior of an imidazolium-based catanionic surfactant, 1-butyl-3-methylimidazolium dodecylsulfate ([C4mim][C12H25SO4]), was investigated in water-ethylammonium nitrate (EAN) mixed solvents with different volume ratios. It is particular interesting that this simple surfactant could not only form lyotropic liquid crystals (LLC) with multimesophases, i.e., normal hexagonal (H1), lamellar liquid crystal (Lα), and reverse bicontinuous cubic phase (V2), in the water-rich environment but also act as an efficient low-molecular-weight gelator (LMWG) which gelated EAN-abundant binary media in a broad concentration range. The peculiar nanodisk cluster morphology of gels composed of similar bilayer units was first observed. FT-IR spectra and density functional theory (DFT) calculations reveal that strong H bonding and electrostatic interactions between EAN and the headgroups of [C4mim][C12H25SO4] are primarily responsible for gelation. The self-assembled gels displayed excellent mechanical strength and a thermoreversible sol-gel transition. It is for the first time that a rich variety of controllable ordered aggregates could be observed only by simply modulating the concentration of a single imidazolium-based catanionic surfactant or the ratio of mixed solvents. This environmentally friendly system is expected to have broad applications in various fields, such as materials science, drug delivery systems, and supramolecular chemistry.

Preparation and in vitro characterization of thermosensitive and mucoadhesive hydrogels for nasal delivery of phenylephrine hydrochloride.

PubMed

Xu, Xiaofeng; Shen, Yan; Wang, Wei; Sun, Chunmeng; Li, Chang; Xiong, Yerong; Tu, Jiasheng

2014-11-01

The aim of the present work was to develop a nasal delivery system of phenylephrine hydrochloride (PE) in spray form to make prolonged remedy of nasal congestion. The formulations contain the thermosensitive hydrogel, i.e., Poloxamer 407 (P407) and Poloxamer 188 (P188) mixtures, and mucoadhesives, i.e., ε-polylysine (ε-PL) and low molecular weight sodium hyaluronate (MW 11,000Da). The in vitro characterizations of formulations including rheology studies, texture profiles and in vitro mucoadhesion potential were investigated after gelation temperatures measurements. The results showed that the concentration of P407 or P188 had significant influence on gelation temperature and texture profiles. The addition of mucoadhesives, though lowered the gel strength of formulations, increased interaction with mucin. After screening, two formulations (i.e., 1.0% PE/0.5% ε-PL/17% P407/0.5% P188 or Formulation A; and 1.0% PE/0.5% HA/17% P407/0.8% P188 or Formulation B) presenting suitable gelation temperatures (∼32°C) were used for further studies on in vitro release behaviors and mucosa ciliotoxicity. Both formulations showed sustained release of PE for up to 8h and similar toxicity to saline, the negative control. Thus, the thermosensitive and mucoadhesive PE-containing hydrogels are promising to achieve prolonged decongestion in nasal cavity. Copyright © 2014 Elsevier B.V. All rights reserved.

On the kinetics of acid sodium caseinate gelation using particle tracking to probe the microrheology.

PubMed

Moschakis, Thomas; Murray, Brent S; Dickinson, Eric

2010-05-15

The sol-gel transition of a model dairy system (sodium caseinate solution) which undergoes gelation by acidification has been studied by conventional bulk rheology and particle tracking microrheology, via confocal microscopy. The Brownian diffusion of fluorescent microspheres (0.21, 0.32, 0.5, and 0.89 μm in diameter) with different surface coatings (polyethylene glycol, carboxylate groups and polystyrene) was used to probe spatial mechanical properties of the gels at the scale of microns. The microrheological results are compared with the macroscopic viscoelastic properties (storage and loss shear modulus) measured in a concentric cylinder rheometer (double gap, at shear strain of 0.005 and frequency of 1 Hz). At pH values close to pI of the caseins, where formation of a protein network, i.e., gelation, became obvious from the confocal microscopy and bulk rheological measurements, all the particles had a tendency to adhere to the network. In spite of this, the microrheological values of the moduli were only slightly lower than the macroscopically determined values and the gel points calculated via both techniques tended to be in good agreement. However, the particle tracking method has higher sensitivity and can detect changes in the structuring of the system before these are registered by the bulk rheological measurement. Copyright © 2010 Elsevier Inc. All rights reserved.

Effect of CMC Molecular Weight on Acid-Induced Gelation of Heated WPI-CMC Soluble Complex.

PubMed

Huan, Yan; Zhang, Sha; Vardhanabhuti, Bongkosh

2016-02-01

Acid-induced gelation properties of heated whey protein isolate (WPI) and carboxymethylcellulose (CMC) soluble complex were investigated as a function of CMC molecular weight (270, 680, and 750 kDa) and concentrations (0% to 0.125%). Heated WPI-CMC soluble complex with 6% protein was made by heating biopolymers together at pH 7.0 and 85 °C for 30 min and diluted to 5% protein before acid-induced gelation. Acid-induced gel formed from heated WPI-CMC complexes exhibited increased hardness and decreased water holding capacity with increasing CMC concentrations but gel strength decreased at higher CMC content. The highest gel strength was observed with CMC 750 k at 0.05%. Gels with low CMC concentration showed homogenous microstructure which was independent of CMC molecular weight, while increasing CMC concentration led to microphase separation with higher CMC molecular weight showing more extensive phase separation. When heated WPI-CMC complexes were prepared at 9% protein the acid gels showed improved gel hardness and water holding capacity, which was supported by the more interconnected protein network with less porosity when compared to complexes heated at 6% protein. It is concluded that protein concentration and biopolymer ratio during complex formation are the major factors affecting gel properties while the effect of CMC molecular weight was less significant. © 2016 Institute of Food Technologists®

Triarylamine-Cored Dendritic Molecular Gel for Efficient Colorometric, Fluorometric, and Impedometeric Detection of Picric Acid.

PubMed

Mondal, Sanjoy; Bairi, Partha; Das, Sujoy; Nandi, Arun K

2018-04-11

Detection of nitroaromatics at ultralow concentration is a major security concern in defense, forensics, and environmental science. To this end, a new triarylamine-cored dendritic gelator (OGR) was synthesized, which produced thermoreversible, thixotropic, and fluorescent gels in n-octanol. On gelation, both π-π* transitions and the emission peak of the gelator show redshifts with a 4.5-fold increase of fluorescence intensity in the gel state indicating J-aggregation. The nitrogen lone-pair electrons of OGR make it a donor, and electron transfer occurs to acceptor nitroaromatics causing fluorescence quenching, which is further promoted due to its acidity. The Stern-Volmer rate constants measured for different nitroaromatics showed that it senses picric acid (PA) best. The contact-mode technique with OGR-treated paper strips can allow naked-eye detection of PA under UV light down to 10 -11  m concentration within 30 s. Reusability of the gel is achieved by treating OGR@PA x with NaOH solution. Impedance spectroscopic results indicated a decrease of both charge-transport resistance and Warburg impedance on successive addition of PA. The limits of detection of PA determined from fluorescence and impedance measurements match well. Thus, the OGR gel is a reusable, low-cost, specific sensor for PA by naked-eye colorimetric, fluorescence, and impedance techniques. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tamoxifen-loaded lecithin organogel (LO) for topical application: Development, optimization and characterization.

PubMed

Bhatia, Amit; Singh, Bhupinder; Raza, Kaisar; Wadhwa, Sheetu; Katare, Om Prakash

2013-02-28

Lecithin organogels (LOs) are semi-solid systems with immobilized organic liquid phase in 3-D network of self-assembled gelators. This paper attempts to study the various attributes of LOs, starting from selection of materials, optimization of influential components to LO specific characterization. After screening of various components (type of gelators, organic and aqueous phase) and construction of phase diagrams, a D-optimal mixture design was employed for the systematic optimization of the LO composition. The response surface plots were constructed for various response variables, viz. viscosity, gel strength, spreadability and consistency index. The optimized LO composition was searched employing overlay plots. Subsequent validation of the optimization study employing check-point formulations, located using grid search, indicated high degree of prognostic ability of the experimental design. The optimized formulation was characterized for morphology, drug content, rheology, spreadability, pH, phase transition temperatures, and physical and chemical stability. The outcomes of the study were interesting showing high dependence of LO attributes on the type and amount of phospholipid, Poloxamer™, auxillary gelators and organic solvent. The optimized LO was found to be quite stable, easily applicable and biocompatible. The findings of the study can be utilized for the development of LO systems of other drugs for the safer and effective topical delivery. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

Gel Fabrication of Molybdenum “Beads”

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lowden, Richard Andrew; Armstrong, Beth L.; Cooley, Kevin M.

2016-11-01

Spherical molybdenum particles or “beads” of various diameters are of interest as feedstock materials for the additive manufacture of targets and assemblies used in the production of 99Mo medical isotopes using accelerator technology. Small metallic beads or ball bearings are typically fabricated from wire; however, small molybdenum spheres cannot readily be produced in this manner. Sol-gel processes are often employed to produce small dense microspheres of metal oxides across a broad diameter range that in the case of molybdenum could be reduced and sintered to produce metallic spheres. These Sol-gel type processes were examined for forming molybdenum oxide beads; however,more » the molybdenum trioxide was chemically incompatible with commonly used gelation materials. As an alternative, an aqueous alginate process being assessed for the fabrication of oxide spheres for catalyst applications was employed to form molybdenum trioxide beads that were successfully reduced and sintered to produce small molybdenum spheres.« less

Optimising low molecular weight hydrogels for automated 3D printing.

PubMed

Nolan, Michael C; Fuentes Caparrós, Ana M; Dietrich, Bart; Barrow, Michael; Cross, Emily R; Bleuel, Markus; King, Stephen M; Adams, Dave J

2017-11-22

Hydrogels prepared from low molecular weight gelators (LMWGs) are formed as a result of hierarchical intermolecular interactions between gelators to form fibres, and then further interactions between the self-assembled fibres via physical entanglements, as well as potential branching points. These interactions can allow hydrogels to recover quickly after a high shear rate has been applied. There are currently limited design rules describing which types of morphology or rheological properties are required for a LMWG hydrogel to be used as an effective, printable gel. By preparing hydrogels with different types of fibrous network structures, we have been able to understand in more detail the morphological type which gives rise to a 3D-printable hydrogel using a range of techniques, including rheology, small angle scattering and microscopy.

Chirality and energy transfer amplified circularly polarized luminescence in composite nanohelix

PubMed Central

Yang, Dong; Duan, Pengfei; Zhang, Li; Liu, Minghua

2017-01-01

Transfer of both chirality and energy information plays an important role in biological systems. Here we show a chiral donor π-gelator and assembled it with an achiral π-acceptor to see how chirality and energy can be transferred in a composite donor–acceptor system. It is found that the individual chiral gelator can self-assemble into nanohelix. In the presence of the achiral acceptor, the self-assembly can also proceed and lead to the formation of the composite nanohelix. In the composite nanohelix, an energy transfer is realized. Interestingly, in the composite nanohelix, the achiral acceptor can both capture the supramolecular chirality and collect the circularly polarized energy from the chiral donor, showing both supramolecular chirality and energy transfer amplified circularly polarized luminescence (ETACPL). PMID:28585538

Switching of liquid crystal devices between reflective and transmissive modes

NASA Astrophysics Data System (ADS)

Lin, Hui-Chi; Wang, Chih-Hung

Transflective liquid crystal displays (LCD) are commonly known that each pixel is divided into reflective (R) and transmissive (T) subpixels. The R mode uses ambient light, while the T mode utilizes a backlight to display images. However, the division of the pixel decreases the light efficiency and the resolution. This study demonstrates a gelator-doped liquid crystal (LC) devices, that is switchable between R and T modes, without sub-pixel division. The R and T modes are designed to have bend configurations with phase retardation of π/2 and π, respectively. The phase retardation of a LC device can be varied and fixed by the thermoreversible association and dissociation of the gelator molecules. It is believed that the proposed device is a potential candidate for portable information systems.

Chirality and energy transfer amplified circularly polarized luminescence in composite nanohelix

NASA Astrophysics Data System (ADS)

Yang, Dong; Duan, Pengfei; Zhang, Li; Liu, Minghua

2017-06-01

Transfer of both chirality and energy information plays an important role in biological systems. Here we show a chiral donor π-gelator and assembled it with an achiral π-acceptor to see how chirality and energy can be transferred in a composite donor-acceptor system. It is found that the individual chiral gelator can self-assemble into nanohelix. In the presence of the achiral acceptor, the self-assembly can also proceed and lead to the formation of the composite nanohelix. In the composite nanohelix, an energy transfer is realized. Interestingly, in the composite nanohelix, the achiral acceptor can both capture the supramolecular chirality and collect the circularly polarized energy from the chiral donor, showing both supramolecular chirality and energy transfer amplified circularly polarized luminescence (ETACPL).

GTP regeneration influences interactions of microtubules, neurofilaments, and microtubule-associated proteins in vitro.

PubMed

Flynn, G; Purich, D L

1987-11-15

Interactions of microtubules, neurofilaments, and microtubule-associated proteins were investigated by turbidity and falling-ball viscometry measurements. We found evidence of endogenous GTPase activity in neurofilaments and microtubule-associated proteins (MAPs) in preparations that do not include urea or heat treatment, respectively. The absence or presence of either adenyl-5'-yl imidodiphosphonic acid or a GTP-regenerating system markedly influenced observed polymerization and gelation characteristics. Most significantly, the apparent viscosity of neurofilament and microtubule samples did not display a biphasic optimal MAP concentration profile when a GTP-regenerating system was operant. Likewise, GTP regeneration promoted the recovery of gelation following mechanical disruption of neurofilament/MAP/microtubule mixtures. These and other observations require some reassessment of proposed roles for microtubule-associated proteins in modulating neurofilament-microtubule interactions in vitro.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krasniak, S. R.; Smith, R. D.

Enzymatic hydrolysis of biomass to produce glucose may become feasible if an inexpensive method to reuse the enzyme can be found. This study investigated one such method whereby ..beta..-D-glucosidase (E.C. 3.2.1.21) was immobilized in calcium alginate gel spheres, which were shown to catalyze the hydrolysis of cellobiose to glucose. There was a loss of 49% of the enzyme from the alginate slurry during gelation. After gelation, in the stable gel spheres, there was a 37% retention of the enzyme activity that was actually immobilized. The reason for the loss in activity was investigated and may be caused by inhibition ofmore » the enzyme within the sphere by the calcium cations and the alginate anions also present. Mass transfer effects were minimal in this system and were not responsible for the activity loss.« less

First report of charge-transfer induced heat-set hydrogel. Structural insights and remarkable properties

NASA Astrophysics Data System (ADS)

Bhattacharjee, Subham; Maiti, Bappa; Bhattacharya, Santanu

2016-05-01

The remarkable ability of a charge-transfer (CT) complex prepared from a pyrene-based donor (Py-D) and a naphthalenediimide-based acceptor (NDI-A) led to the formation of a deep-violet in color, transparent hydrogel at room temperature (RT-gel). Simultaneously, the RT-gel was diluted beyond its critical gelator concentration (CGC) to obtain a transparent sol. Very interestingly, the resultant sol, on heating above 70 °C, transformed into a heat-set gel instantaneously with a hitherto unknown CGC value. Detailed studies revealed the smaller globular aggregates of the RT-gels fuse to form giant globules upon heating, which, in turn, resulted in heat-set gelation through further aggregation. The thermoresponsive property of Py-D alone and 1 : 1 Py-D : NDI-A CT complex was investigated in detail which revealed the hydrophobic collapse of the oxyethylene chains of the CT complex upon heating was mainly responsible for heat-set gelation. Thixotropy, injectability, as well as stimuli responsiveness of the RT-gels were also addressed. In contrast, heat-set gel did not show thixotropic behavior. The X-ray diffraction (XRD) patterns of the xerogel depicted lamellar packing of the CT stacks in the gel phase. Single crystal XRD studies further evidenced the 1 : 1 mixed CT stack formation in the lamellae and also ruled out orthogonal hydrogen bonding possibilities among the hydrazide unit in the CT gel although such interaction was observed in a single crystal of NDI-A alone. In addition, a Ag+-ion triggered metallogelation of NDI-A and nematic liquid-crystalline property of Py-D were also observed.The remarkable ability of a charge-transfer (CT) complex prepared from a pyrene-based donor (Py-D) and a naphthalenediimide-based acceptor (NDI-A) led to the formation of a deep-violet in color, transparent hydrogel at room temperature (RT-gel). Simultaneously, the RT-gel was diluted beyond its critical gelator concentration (CGC) to obtain a transparent sol. Very interestingly, the resultant sol, on heating above 70 °C, transformed into a heat-set gel instantaneously with a hitherto unknown CGC value. Detailed studies revealed the smaller globular aggregates of the RT-gels fuse to form giant globules upon heating, which, in turn, resulted in heat-set gelation through further aggregation. The thermoresponsive property of Py-D alone and 1 : 1 Py-D : NDI-A CT complex was investigated in detail which revealed the hydrophobic collapse of the oxyethylene chains of the CT complex upon heating was mainly responsible for heat-set gelation. Thixotropy, injectability, as well as stimuli responsiveness of the RT-gels were also addressed. In contrast, heat-set gel did not show thixotropic behavior. The X-ray diffraction (XRD) patterns of the xerogel depicted lamellar packing of the CT stacks in the gel phase. Single crystal XRD studies further evidenced the 1 : 1 mixed CT stack formation in the lamellae and also ruled out orthogonal hydrogen bonding possibilities among the hydrazide unit in the CT gel although such interaction was observed in a single crystal of NDI-A alone. In addition, a Ag+-ion triggered metallogelation of NDI-A and nematic liquid-crystalline property of Py-D were also observed. Electronic supplementary information (ESI) available: General experimental section, synthesis and characterization, single crystal X-ray data including CIF files and additional experimental results. See DOI: 10.1039/c6nr01128d

Development of structure in natural silk spinning and poly(vinyl alcohol) hydrogel formation

NASA Astrophysics Data System (ADS)

Willcox, Patricia Jeanene

This research involves the characterization of structure and structure formation in aqueous systems. Particularly, these studies investigate the effect of various processing variables on the structure formation that occurs upon conversion from aqueous solution to fiber or hydrogel. The two processes studied include natural silk fiber spinning and physical gelation of poly(vinyl alcohol), PVOH, in water. The techniques employed combine cryogenic technology for sample preparation and direct observation by transmission electron microscopy with electron diffraction, atomic force microscopy, optical rheometry, X-ray scattering and optical microscopy. In order to explore the full range of structure formation in natural silk spinning, studies are conducted in vivo and in vitro. In vivo structural investigations are accomplished through the cryogenic quenching and subsequent microtoming of live silk-spinning animals, Nephila clavipes (spider) and Bombyx mori (silkworm). Observations made using transmission electron microscopy, electron diffraction and atomic force microscopy indicate a cholesteric liquid crystalline mesophase of aqueous silk fibroin in both species. The mechanism of structure formation in solution is studied in vitro using optical rheometry on aqueous solutions made from regenerated Bombyx mori cocoon silk. Concentrated solutions exhibit birefringence under flow, with a wormlike conformation of the silk molecules in concentrated salt solution. Changes in salt concentration and pH of the aqueous silk solutions result in differing degrees of alignment and aggregation. These results suggest that structural control in the natural silk spinning process is accomplished by chemical manipulation of the electrostatic interactions and hydrogen bonding between chains. Application of cryogenic methods in transmission electron microscopy also provides a unique look at hydration-dependent structures in gels of poly(vinyl alcohol) produced by freeze-thaw processing. Morphologies ranging from circular pores to fibrillar networks are observed in gels formed from aqueous PVOH solutions subjected to cycles of freezing and thawing. These morphologies can be directly associated with the progressive nature of the mechanism of gelation as it proceeds from liquid-liquid phase separation to crystallization with increased cycling. A comparison of the structures produced by cycling and by aging suggests that there is a similarity in structural changes, but a superposition of the effects of cycling and aging is not possible.

Separation of Anisotropy and Exchange Broadening Using 15N CSA- 15N- 1H Dipole-Dipole Relaxation Cross-Correlation Experiments

NASA Astrophysics Data System (ADS)

Renner, Christian; Holak, Tad A.

2000-08-01

Based on the measurement of cross-correlation rates between 15N CSA and 15N-1H dipole-dipole relaxation we propose a procedure for separating exchange contributions to transverse relaxation rates (R2 = 1/T2) from effects caused by anisotropic rotational diffusion of the protein molecule. This approach determines the influence of anisotropy and chemical exchange processes independently and therefore circumvents difficulties associated with the currently standard use of T1/T2 ratios to determine the rotational diffusion tensor. We find from computer simulations that, in the presence of even small amounts of internal flexibility, fitting T1/T2 ratios tends to underestimate the anisotropy of overall tumbling. An additional problem exists when the N-H bond vector directions are not distributed homogeneously over the surface of a unit sphere, such as in helix bundles or β-sheets. Such a case was found in segment 4 of the gelation factor (ABP 120), an F-actin cross-linking protein, in which the diffusion tensor cannot be calculated from T1/T2 ratios. The 15N CSA tensor of the residues for this β-sheet protein was found to vary even within secondary structure elements. The use of a common value for the whole protein molecule therefore might be an oversimplification. Using our approach it is immediately apparent that no exchange broadening exists for segment 4 although strongly reduced T2 relaxation times for several residues could be mistaken as indications for exchange processes.

Reactive hydroxyapatite fillers for pectin biocomposites.

PubMed

Munarin, Fabiola; Petrini, Paola; Barcellona, Giulia; Roversi, Tommaso; Piazza, Laura; Visai, Livia; Tanzi, Maria Cristina

2014-12-01

In this work, a novel injectable biocomposite hydrogel is produced by internal gelation, using pectin as organic matrix and hydroxyapatite either as crosslinking agent and inorganic reinforcement. Tunable gelling kinetics and rheological properties are obtained varying the hydrogels' composition, with the final aim of developing systems for cell immobilization. The reversibility by dissolution of pectin-hydroxyapatite hydrogels is achieved with saline solutions, to possibly accelerate the release of the cells or active agents immobilized. Texture analysis confirms the possibility of extruding the biocomposites from needles with diameters from 20 G to 30 G, indicating that they can be implanted with minimally-invasive approaches, minimizing the pain during injection and the side effects of the open surgery. L929 fibroblasts entrapped in the hydrogels survive to the immobilization procedure and exhibit high cell viability. On the overall, these systems result to be suitable supports for the immobilization of cells for tissue regeneration applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Microencapsulation techniques to develop formulations of insulin for oral delivery: a review.

PubMed

Cárdenas-Bailón, Fernando; Osorio-Revilla, Guillermo; Gallardo-Velázquez, Tzayhrí

2013-01-01

Oral insulin delivery represents one of the most challenging goals for pharmaceutical industry. In general, it is accepted that oral administration of insulin would be more accepted by patients and insulin would be delivered in a more physiological way than the parenteral route. From all strategies to deliverer insulin orally, microencapsulation or nanoencapsulation of insulin are the most promising approaches because these techniques protect insulin from enzymatic degradation in stomach, show a good release profile at intestine pH values, maintain biological activity during formulation and enhance intestinal permeation at certain extent. From different microencapsulation techniques, it seems that complex coacervation, multiple emulsion and internal gelation are the most appropriate techniques to encapsulate insulin due to their relative ease of preparation. Besides that, the use of organic solvents is not required and can be scaled up at low cost; however, relative oral bioavailability still needs to be improved.

Morphology Modulation of Direct Inkjet Printing by Incorporating Polymers and Surfactants into a Sol-Gel Ink System.

PubMed

Zhu, Zhennan; Ning, Honglong; Cai, Wei; Wei, Jinglin; Zhou, Shangxiong; Yao, Rihui; Lu, Xubing; Zhang, Jianhua; Zhou, ZhongWei; Peng, Junbiao

2018-06-05

Many methods have been reported to prevent the nonuniformity of inkjet printing structures. Most of them depend on the balance of the capillary flow in the printing pattern during the evaporation of the solvent. However, as the relation of evaporation and capillary flow can obviously vary among different ink systems, it is difficult for a method to fit most of the situations. Therefore, it would be a promising way to eliminate any capillary flow before solvent evaporation so that morphology of the printing structure will not be affected by the evaporation behavior of the ink system. In this paper, a novel method of direct inkjet printing of a uniform metal oxide structure is reported. We introduce a polymer polyacrylamide and a surfactant FSO into a sol-gel ink system, and the new ink system can gel from the printing pattern edge to center as temperature increases because of the cross-linking of the polymer chains. By that means, transport of solute molecules and solvent molecules is limited. Meanwhile, the surfactant can ensure that the solute in the central liquid phase deposits uniformly by enhancing the Marangoni flow during the gelation process. The ZrO 2 film with uniform morphology was fabricated by drying and annealing the gelating film and afforded a leakage current density of 7.48 × 10 -7 A cm -2 at 1 MV and a breakdown field of 1.9 MV cm -1 at an annealing temperature of 250 °C.

Fluorescent Hydrogel Generated Conveniently from a Perylene Tetracarboxylate Derivative of Titanium(IV) Alkoxide.

PubMed

Zou, Dan-Hong; Wang, Peng; Luo, Wen; Hou, Jin-Le; Zhu, Qin-Yu; Dai, Jie

2018-02-05

Organic gelators and metal-coordination frameworks based on perylene derivatives as functional materials have attracted great attention because of their intense fluorescence emission as well as unique electronic and photonic properties. We report here the structures and properties of a luminescent titanium(IV) coordination compound of a perylene tetracarboxylate (PTC) derivative, [Ti 2 (O i Pr) 6 (L 1 )(phen) 2 ] (1), along with its two naphthalene analogues, [Ti 2 (O i Pr) 6 (L 2 )(phen) 2 ] (2) and [Ti 2 (O i Pr) 6 (L 2 )(bpy) 2 ] (3), where L 1 = 3,9-dicarboxylate-(4,10-diisopropanolcarboxylate)perylene, phen = 1,10-phenanthroline, L 2 = 1,5-dicarboxylate-(2,6-diisopropanolcarboxylate)naphthalene, and bpy = 2,2'-bipyridine. Compound 1 is a rare early-transition-metal PTC coordination compound that can be simply prepared in one pot as crystals by a low-heat synthesis. Unlike those of paramagnetic late-transition-metal PTC compounds, compound 1 showed intense fluorescence emission. More remarkably, the crystals of 1 can be turned immediately to a fluorescent hydrogel just through a simple procedure, putting the crystals in water and then treating with ultrasound. No acid catalyst or pH adjustment is needed. Hydrolysis of the titanium isopropanol group in water and π-π interaction of the perylene and phen play important roles in the gelation process. The film prepared from the gel can be used as a visual fluorescence sensor for aromatic amines and phenols, which are hazards for the human and environment.

Isocyanate Cross-Linked Silica: Structurally Strong Aerogels

NASA Technical Reports Server (NTRS)

Leventis, Nicholas; Sotiriou-Leventis, Chariklia; Zhang, Guo-Hui; Rawashdeh, Abdel-Monem M.

2002-01-01

Molecular-level synergism between the silica nanoparticles of pre-formed monoliths and molecular cross-linkers inverts the relative host-guest roles in glass-polymer composites, leading to new strong low-density materials. Attempts to load gels with variable amounts of polyurethane precursors such as di-ISO and diol end-capped polybutylene adipate followed by heat treatment, washing, and supercritical drying led to opaque materials, somewhat stronger than silica but still quite brittle and much inferior to the materials described above. Direct mixing of a diisocyanate and an alcohol-free sol has been attempted recently by Yim et al. Reportedly, that procedure leads to week-long gelation times and requires an at least equally long aging period. In our attempt to add various amounts of di-ISO in a base-catalyzed sol in PC, we also noticed a week-long gelation time. The resulting aerogels were translucent but no less brittle than native silica. According to more recent studies, if propylene carbonate is replaced with acetone, it leads not only to shorter processing times, but also to much stronger gels that can tolerate loads in excess of 40 kg in the arrangement presented. We attribute that behavior to the lower viscosity of acetone, that allows faster diffusion of the di-ISO solution within the pores before di-ISO has time to react with the surface of silica. Further studies are underway to vary the chemical identity of the diisocyanate, as well as the composition and density of silica.

Results From the Physics of Colloids Experiment on ISS

NASA Technical Reports Server (NTRS)

Weitz, David; Bailey, Arthur; Manley, Suliana; Prasad, Vikram; Christianson, Rebecca; Sankaran, Subramanian; Doherty, Michael; Jankovsky, Amy; Lorik, Tibor; Shiley, William

2002-01-01

The Physics of Colloids in Space (PCS) experiment was accommodated within International Space Station (ISS) EXpedite the PRocessing of Experiments to Space Station (EXPRESS) Rack 2 and was remotely operated from early June 2001 until February 2002 from NASA Glenn Research Center's Telescience Support Center (TSC) in Cleveland, Ohio, and from the remote site at Harvard University in Cambridge, Massachusetts. PCS was launched on 4/19/2001 on Space Shuttle STS-100. The experiment was activated on 5/31/2001. The entire experimental setup performed remarkably well, and accomplished 2400 hours of science operations on-orbit. The sophisticated instrumentation in PCS is capable of dynamic and static light scattering from 11 to 169 degrees, Bragg scattering over the range from 10 to 60 degrees, dynamic and static light scattering at low angles from 0.3 to 6.0 degrees, and color imaging. The long duration microgravity environment on the ISS facilitated extended studies on the growth and coarsening characteristics of binary crystals. The de-mixing of the colloid-polymer critical-point sample was also studied as it phase-separated into two phases. Further, aging studies on a col-pol gel, gelation rate studies in extremely low concentration fractal gels over several days, and studies on a glass sample, all provided valuable information. Several exciting and unique aspects of these results are discussed here.

Short communication: the effect of dry period duration and dietary energy density in early lactation on the rennet gelation properties of milk.

PubMed

Butler, S T; de Feu, M A; O'Brien, B; Guinee, T P; Murphy, J J

2010-02-01

This study was carried out to examine the effects of decreasing the dry period (DP) duration and altering the energy density of the diet during early lactation on the rheological characteristics of milk. Forty mature Holstein-Friesian cows were used in a completely randomized design with a 2 x 2 factorial arrangement of treatments. Cows were randomly assigned to 1 of 2 dry period treatments and 1 of 2 nutritional treatments. The DP treatments were continuous milking (CM) or an 8-wk standard dry period (SDP), and the nutritional treatments were a standard energy diet (SE) or a high energy diet (HE). Actual DP lengths were 6.3+/-1.7 d and 62.1+/-1.9 d for cows on the CM and SDP treatments, respectively. Milk samples were collected at 2, 6, and 10 wk postpartum. The concentrations of fat, protein, and lactose were determined in each sample. The rennet gelation properties were measured at 31 degrees C using dynamic low-amplitude strain oscillatory rheometry. The following parameters were obtained from the resultant elastic shear modulus (G'): gelation time, maximum curd firming rate, and gel strength. Reducing the DP duration from 62 to 6 d resulted in increases in milk protein concentration (31.8 vs. 34.7 g/kg), maximum curd firming rate (2.58 vs. 3.60 Pa/min), and gel strength (69.4 vs. 90.5Pa). Increasing the dietary energy density decreased percentage milk fat (43.1 vs. 37.7 g/kg) but otherwise had no effect. Gel strength was correlated with maximum curd firming rate (r=0.99), and both variables were correlated with milk protein concentration (r=0.71 and r=0.73, respectively). The results indicate that decreasing the duration of the DP increased milk protein concentration and improved the rennet gelation properties of milk, but that dietary energy density had little effect. Copyright 2010 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

A time to search: finding the meaning of variable activation energy.

PubMed

Vyazovkin, Sergey

2016-07-28

This review deals with the phenomenon of variable activation energy frequently observed when studying the kinetics in the liquid or solid phase. This phenomenon commonly manifests itself through nonlinear Arrhenius plots or dependencies of the activation energy on conversion computed by isoconversional methods. Variable activation energy signifies a multi-step process and has a meaning of a collective parameter linked to the activation energies of individual steps. It is demonstrated that by using appropriate models of the processes, the link can be established in algebraic form. This allows one to analyze experimentally observed dependencies of the activation energy in a quantitative fashion and, as a result, to obtain activation energies of individual steps, to evaluate and predict other important parameters of the process, and generally to gain deeper kinetic and mechanistic insights. This review provides multiple examples of such analysis as applied to the processes of crosslinking polymerization, crystallization and melting of polymers, gelation, and solid-solid morphological and glass transitions. The use of appropriate computational techniques is discussed as well.

Composite carbon foam electrode

DOEpatents

Mayer, Steven T.; Pekala, Richard W.; Kaschmitter, James L.

1997-01-01

Carbon aerogels used as a binder for granularized materials, including other forms of carbon and metal additives, are cast onto carbon or metal fiber substrates to form composite carbon thin film sheets. The thin film sheets are utilized in electrochemical energy storage applications, such as electrochemical double layer capacitors (aerocapacitors), lithium based battery insertion electrodes, fuel cell electrodes, and electrocapacitive deionization electrodes. The composite carbon foam may be formed by prior known processes, but with the solid particles being added during the liquid phase of the process, i.e. prior to gelation. The other forms of carbon may include carbon microspheres, carbon powder, carbon aerogel powder or particles, graphite carbons. Metal and/or carbon fibers may be added for increased conductivity. The choice of materials and fibers will depend on the electrolyte used and the relative trade off of system resistivty and power to system energy.

Morphology Dependent Photocatalytic Activity of α-MoO3 Nanostructures Towards Mutagenic Acridine Orange Dye.

PubMed

2015-06-01

The morphological evolutions of orthorhombic molybdenum oxide nanostructures with high crystalline nature have been successfully synthesized by combining low-temperature sol-gel and annealing processes. Strong influence of gelation temperature is a factor facilitated to control the material morphology. Morphological transformations like nanospheres, nanoplatelets, mixtures of hexagonal platelets, and one-dimensional nanobars were obtained. The possible morphological formation mechanism has been proposed as a self-assemble process of nucleation and a mechanism for particle growth by Ostwald ripening. The as-prepared nanostructures were recognized as photocatalysts for the degradation of Acridine Orange under Ultra Violet light. The obtained mixed morphology (hexagonal nanoplatelets and nanobars) showed a high photocatalytic property to degrade mutagenic Acridine Orange dye. Moreover, they could be easily recycled without changing the photocatalytic activity due to their 1-Dimensional and 2-Dimensional nanostructure property.

Cell encapsulation in biodegradable hydrogels for tissue engineering applications.

PubMed

Nicodemus, Garret D; Bryant, Stephanie J

2008-06-01

Encapsulating cells in biodegradable hydrogels offers numerous attractive features for tissue engineering, including ease of handling, a highly hydrated tissue-like environment for cell and tissue growth, and the ability to form in vivo. Many properties important to the design of a hydrogel scaffold, such as swelling, mechanical properties, degradation, and diffusion, are closely linked to the crosslinked structure of the hydrogel, which is controlled through a variety of different processing conditions. Degradation may be tuned by incorporating hydrolytically or enzymatically labile segments into the hydrogel or by using natural biopolymers that are susceptible to enzymatic degradation. Because cells are present during the gelation process, the number of suitable chemistries and formulations are limited. In this review, we describe important considerations for designing biodegradable hydrogels for cell encapsulation and highlight recent advances in material design and their applications in tissue engineering.

Mechanically Tunable, Readily Processable Ion Gels by Self-Assembly of Block Copolymers in Ionic Liquids.

PubMed

Lodge, Timothy P; Ueki, Takeshi

2016-01-01

Room temperature ionic liquids are of great interest for many advanced applications, due to the combination of attractive physical properties with essentially unlimited tunability of chemical structure. High chemical and thermal stability, favorable ionic conductivity, and complete nonvolatility are just some of the most important physical characteristics that make ionic liquids promising candidates for emerging technologies. Examples include separation membranes, actuators, polymer gel electrolytes, supercapacitors, ion batteries, fuel cell membranes, sensors, printable plastic electronics, and flexible displays. However, in these and other applications, it is essential to solidify the ionic liquid, while retaining the liquid state properties of interest. A broadly applicable solidification strategy relies on gelation by addition of suitable triblock copolymers with the ABA architecture, producing ion gels or ionogels. In this paradigm, the A end blocks are immiscible with the ionic liquid, and consequently self-assemble into micellar cores, while some fraction of the well-solvated B midblocks bridge between micelles, forming a percolating network. The chemical structures of the A and B repeat units, the molar mass of the blocks, and the concentration of the copolymer in the ionic liquid are all independently tunable to attain desired property combinations. In particular, the modulus of the resulting ion gel can be readily varied between 100 Pa and 1 MPa, with little sacrifice of the transport properties of the ionic liquid, such as ionic conductivity or gas diffusivity. Suitable A blocks can impart thermoreversible gelation (with solidification either on heating or cooling) or even photoreversible gelation. By virtue of the nonvolatility of ionic liquids, a wide range of processing strategies can be employed directly to prepare ion gels in thin or thick film forms, including solvent casting, spin coating, aerosol jet printing, photopatterning, and transfer printing. For higher modulus ion gels it is even possible to employ a manual "cut and stick" strategy for easy device fabrication. Ion gels prepared from common triblock copolymers, for example, with A = polystyrene and B = poly(ethylene oxide) or poly(methyl methacrylate), in imidazolium based ionic liquids provide exceptional performance in membranes for separating CO 2 from N 2 or CH 4 . The same materials also are the best available gate dielectrics for printed plastic electronics, because their high capacitance endows organic transistors with milliamp output currents for sub-1 V applied bias, with switching speeds that can go well beyond 100 kHz, while being amenable to large area roll-to-roll printing. Incorporation of well-designed electroluminescent (e.g., Ru(bpy) 3 -based) or electrochromic (e.g., viologen-based) moieties into ion gels held between transparent electrodes yields flexible color displays operating with sub-1 V dc inputs.

Core–shell PdPb@Pd aerogels with multiply-twinned intermetallic nanostructures: facile synthesis with accelerated gelation kinetics and their enhanced electrocatalytic properties

DOE PAGES

Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang; ...

2018-04-04

Delicately engineering well-defined noble metal aerogels with favorable structural and compositional features is of vital importance for wide applications. Here, we reported a one-pot and facile method for synthesizing core–shell PdPb@Pd hydrogels/aerogels with multiply-twinned grains and an ordered intermetallic phase using sodium hypophosphite as a multifunctional reducing agent. Due to the accelerated gelation kinetics induced by increased reaction temperature and the specific function of sodium hypophosphite, the formation of hydrogels can be completed within 4 h. As a result, owing to their unique porous structure and favorable geometric and electronic effects, the optimized PdPb@Pd aerogels exhibit enhanced electrochemical performance towardsmore » ethylene glycol oxidation with a mass activity of 5.8 times higher than Pd black.« less

Synthesis and characterization of maltose-based amphiphiles as supramolecular hydrogelators.

PubMed

Clemente, María J; Fitremann, Juliette; Mauzac, Monique; Serrano, José L; Oriol, Luis

2011-12-20

Low molecular mass amphiphilic glycolipids have been prepared by linking a maltose polar head and a hydrophobic linear chain either by amidation or copper(I)-catalyzed azide-alkyne [3 + 2] cycloaddition. The liquid crystalline properties of these amphiphilic materials have been characterized. The influence of the chemical structure of these glycolipids on the gelation properties in water has also been studied. Glycolipids obtained by the click coupling of the two components give rise to stable hydrogels at room temperature. The fibrillar structure of supramolecular hydrogels obtained by the self-assembly of these gelators have been characterized by electron microscopy. Fibers showed some torsion, which could be related with a chiral supramolecular arrangement of amphiphiles, as confirmed by circular dichroism (CD). The sol-gel transition temperature was also determined by differential scanning calorimetry (DSC) and NMR. © 2011 American Chemical Society