A mechanistic approach on the self-organization of the two-component thermoreversible hydrogel of riboflavin and melamine

The riboflavin (R) and melamine (M) supramolecular complex in the mole ratio of 3:1 (RM31) produces a thermoreversible gel in aqueous medium. The gelation mechanism has been elucidated from morphological investigations using optical, electron, and atomic force microscopy together with time-dependent circular dichroism (CD) and photoluminescence (PL) spectroscopy. Optical microscopy indicates spherulitic morphology at lower gelation temperature (相似文献   

A synthetic hydrogel with thermoreversible gelation,III: an NMR study of the sol–gel transition

The sol–gel transition mechanism of a thermoreversible hydrogel composed of a copolymer comprising poly(N-isopropylacrylamide) and poly(ethylene glycol) (PNIPAAm–PEG) was studied by NMR. The ¹H– and ¹³C–NMR spectra measured on a PNIPAAm–PEG solution in 99.9% D₂O showed a remarkable line width broadening of the PNIPAAm block of more than that of the PEG block, during thermally induced hydrogel formation. This result suggested that the mobility of the PNIPAAm block is more restricted than that of the PEG block during gelation. A crosslinked polymer network formation was ascertained by a sudden reduction in the spin-lattice relaxation time (T₁) of the residual HDO proton during gelation. The temperature dependency of the T₁ values for the PNIPAAm and PEG blocks revealed that the microscopic condition of the PNIPAAm block in water was drastically changed during gelation, while that of the PEG block was unchanged. The experimental results from NMR supported the following gelation mechanism; that an aggregation of PNIPAAm blocks in the separate copolymers caused by hydrophobic interaction forms crosslinking points to give an infinite three-dimensional network structure. The hydrated PEG chains in the copolymers provide the network with a swelling property in water, and prevent the aggregation from causing a macroscopic phase separation.     

A thermoreversible ion gel by triblock copolymer self-assembly in an ionic liquid

A new thermoreversible ion gel with high ionic conductivity was developed through the self-assembly of a triblock copolymer, by choosing appropriate associating end-blocks for the ionic liquid.     

A low-molecular-weight supramolecular hydrogel of riboflavin bolaamphiphile for VEGF-siRNA delivery

A low-molecular-weight hydrogel derived from riboflavin (vitamin B(2)) that self-assembles to provide supramolecular nanofibers, biocompatible material, can be used to deliver VEGF-siRNA efficiently into human cells by the endocytosis pathway, where the siRNA is functionalized.     

Monitoring of melamine contamination in fat watery milk by the photoluminescence analysis

A photoluminescence method to detect the toxic melamine contamination in fat watery milk has been proposed. Despite the quite different luminescence origins of milk and melamine patterns, their wide emission spectra under UV excitation are similar and in the range of 2.2-3.5 eV. The complex milk photoluminescence spectrum composed of riboflavin, furosine, lactulose, Vitamin E and tryptophan emitting species can be modified if milk pattern is undergone by acid treatment (for example, in vinegar). At the same time the melamine emission is not subjected to any modification in vinegar. It allows quantitatively discriminating the melamine contamination in milk in linear range, at least, 0.05-7 g/l from different photoluminescence spectra of milk (water) with and without melamine. Limit of melamine detection achieves 0.01 g/l.     

三聚氰胺分子印迹光子晶体水凝胶膜传感器的制备及应用

该文将光子晶体与分子印迹技术结合，制备了分子印迹光子晶体水凝胶膜（MIPHs）作为光学传感器，用于样品中三聚氰胺的快速识别检测。以三聚氰胺为模板分子，通过垂直沉降自组装、填充聚合、去除模板3个步骤，制备得到了反蛋白石结构的三聚氰胺MIPHs。扫描电子显微镜的形貌表征表明，MIPHs具有高度有序的三维大孔结构。该MIPHs作为光学传感器可以将三聚氰胺的分子特异识别过程转换成光学信号，在对目标分析物分析时具有选择性高、响应快、灵敏度高的优点。此外，可以根据MIPHs的颜色变化利用图像软件分析或裸眼识别的方式实现目标分析物快速识别。实验结果表明，在最优条件下，三聚氰胺浓度为10^-11~10^-6mol/L时，MIPHs的布拉格衍射峰位移从563 nm红移到608 nm，而对三聚氰胺的结构类似物没有明显响应。     

Formulation and evaluation of thermoreversible,mucoadhesive in situ intranasal gel of rizatriptan benzoate

The present study was aimed to formulate and evaluate in situ thermoreversible intranasal gel of an antimigraine drug rizatriptan benzoate. The poloxamer 407 and carbopol 934 were used as thermoreversible and mucoadhesive polymers respectively. The gels were prepared with cold method. The phase transition temperature was determined with visual method. The gels were evaluated for their pH, mucoadhesive strength, in vitro release and ex vivo drug permeation through goat nasal mucosa. The histopathological study of the nasal mucosa was carried out to check for its damage during drug permeation. The 18 % w/v poloxamer solution was found to be showing phase transition at physiologic conditions (34–35 °C). As the percentage of carbopol 934 was increased from 0.1 to 0.5 % w/v the gelling temperature was found to be decreased. All formulations were showing mucoadhesive strength above 4,000 dynes/cm². Drug permeation studies have indicated that the drug permeation rate can be increased by using carbopol 934 above 0.3 % w/v concentration. The histopathological evaluation of nasal mucosa after drug permeation study has not shown any evidence of damage. Thus in situ thermoreversible mucoadhesive gel of rizatriptan benzoate can be a promising approach to treat migraine.     

A thermoreversible double gel: characterization of a methylcellulose and kappa-carrageenan mixed system in water by SAXS, DSC and rheology

Sol-gel and gel-sol thermal transition of methylcellulose/water, kappa-carrageenan/water and methylcellulose/kappa-carrageenan/water mixtures was investigated utilizing small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC) and oscillatory rheological experiments in temperature regime from 20 to 80 degrees C. Methylcellulose (E461) and kappa-carrageenan (E407) are well-known additives used for gelation in various nutrition and other products. The formulation and characterization of a mixed thermoreversible methylcellulose/kappa-carrageenan/water gel with very interesting double thermal transition gel-sol-gel upon heating was possible. This specific thermal behavior provides a liquid state of the system between the low-temperature and high-temperature gel-state and at the same time allows for the easy temperature tuning of the system's state. As such this system is suggested to be further tested as potential carrier for various functional colloidal systems.     

Effect of complementary small molecules on the properties of bicomponent hydrogel of riboflavin

Three new bicomponent hydrogels of riboflavin (R) with salicylic acid (S), dihydroxybenzoic acid (B) and acetoguanamine (D) in 1:1 molar ratio have been reported. FTIR and UV-vis spectra suggest formation of H-bonded complexes in 1:1 molar ratio of the components. The network consists of tape, bar and helical tubes for RB11, RS11 and RD11 systems, respectively. Reversible first order phase transition and invariant storage modulus (G') with angular frequency (ω) characterise the systems as forming thermoreversible hydrogels. The RD11 gel has the highest gel melting temperature and highest critical strain compared to other gels. WAXS study indicates different crystal structures for different gels. NMR spectra reveals higher shielding of protons in RD11 gel suggesting better π-stacking compared to RS11 and RB11 gels. RD11 gel shows two-fold enhancement of photoluminescence (PL) intensity with a substantial red shift of emission peak but RB11 and RS11 gels show PL-quenching. The gels exhibit a small decrease in lifetime and the PL property is very much temperature and pH dependent. So the complementary molecules have a pronounced effect on morphology, structure, stability and optical property of riboflavin gels.     

Novel linear-globular thermoreversible hydrogel ABA type copolymers from dendritic citric acid as the A blocks and poly(ethyleneglycol) as the B block

The syntheses of novel linear-dendritic thermoreversible hydrogel copolymers were achieved via two procedures. In the first procedure synthesis of linear-dendritic copolymers carried out through an esterification step using thionylchloride and pyridine. In the second procedure linear-dendritic copolymers were prepared using dicyclohexylcarbodiimide and pyridine. The citric acid as the monomer unit was used for the preparation of ester-linked fragments. Diacid poly(ethyleneglycol) was chlorinated and diacyl halide poly(ethyleneglycol) prepared and used as the core. The formation of water soluble inclusion complexes with a variety of small size guest molecules is also described. Moreover, the thermoreversible behavior of the prepared hydrogels of both citric acid-poly(ethyleneglycol)-citric acid (CA-PEG-CA) triblock copolymers and the complexes derived from CA-PEG-CA triblock copolymers with various drugs have been investigated. The structure definition and analysis of the new resulted triblock copolymers and their complexes were carried out using NMR, optical microscopy, viscosimetry, FT-IR and UV-VIS spectrometry methods.     

A thermoreversible conformational change in two poly(zwitterions) evidenced by thermally stimulated depolarization currents

A thermally induced conformational change of zwitterionic groups of two polymers has been observed by thermally stimulated depolarization currents. Different dipole moments of the two conformations is a prerequisite. The appearance of peaks of opposite sign confirms the process. Giant dielectric constants can be obtained at room temperature using high-temperature poling and rapid cooling.     

Enhancement of the photoluminescence of a thioamide-based pincer palladium complex in the crystalline state

A thioamide-based pincer Pd complex, [2,6-bis(benzylaminothiocarbonyl-κS)phenyl-κC¹]chloropalladium(II), was crystallized from different solvents. The structure of the complex in the solid state depends on hydrogen bonding interactions of cocrystallized solvent molecules with the metal complex in the crystal. The arrangement affects the intensity of the photoluminescence from the crystals. Strong emission was observed from the crystal having a densely packed arrangement of the complex, whereas the solutions and powders of the complex did not exhibit emission.     

Comparative characterization of polymethylsiloxane hydrogel and silylated fumed silica and silica gel

Polymethylsiloxane (PMS) hydrogel (C(PMS)=10 wt%, soft paste-like hydrogel), diluted aqueous suspensions, and dried/wetted xerogel (powder) were studied in comparison with suspensions and dry powders of unmodified and silylated nanosilicas and silica gels using (1)H NMR, thermally stimulated depolarization current (TSDC), quasielastic light scattering (QELS), rheometry, and adsorption methods. Nanosized primary PMS particles, which are softer and less dense than silica ones because of the presence of CH(3) groups attached to each Si atom and residual silanols, form soft secondary particles (soft paste-like hydrogel) that can be completely decomposed to nanoparticles with sizes smaller than 10 nm on sonication of the aqueous suspensions. Despite the soft character of the secondary particles, the aqueous suspensions of PMS are characterized by a higher viscosity (at concentration C(PMS)=3-5 wt%) than the suspension of fumed silica at a higher concentration. Three types of structured water are observed in dry PMS xerogel (adsorbed water of 3 wt%). These structures, characterized by the chemical shift of the proton resonance at delta(H) approximately 1.7,3.7, and 5 ppm, correspond to weakly associated but strongly bound water and to strongly associated but weakly or strongly bound waters, respectively. NMR cryoporometry and QELS results suggest that PMS is a mesoporous-macroporous material with the textural porosity caused by voids between primary particles forming aggregates and agglomerates of aggregates. PMS is characterized by a much smaller adsorption capacity with respect to proteins (gelatin, ovalbumin) than unmodified fumed silica A-300.     

Stimulus response and molecular structural modification of polyacrylamide gel in nitric acid: A study by Raman,FTIR, and photoluminescence techniques

Stimulus response of photopolymerized 1% and 0.5% N,N′‐methylene bisacrylamide (MBA) crosslinked 10% polyacrylamide (PAAm) hydrogels was studied in nitric acid. The hydrogels swelled exponentially to saturation in 13 h due to the osmotic pressure arising from diffusion of ions in to the gel. MBA (0.5%) gels swell more with larger time constant than 1% MBA gels due to lower bulk modulus. Diffusion coefficient of nitric acid in the hydrogel and polymer‐solvent interaction parameter were estimated from the swelling behavior and discussed. At longer times, the hydrogels deswelled linearly in nitric acid due to molecular modification of amide group by acidic hydrolysis. Degree of swelling and deswelling increase with nitric acid concentration. Raman and FTIR investigations revealed the formation of carboxylic acid due to acidic hydrolysis. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 710–720, 2008     

Heat-set gels and egg-like vesicles using two component gel system based on chiral calix[4]arenes

Chiral calix[4]arenes bearing long tertiary alkyl groups at the upper rim and S-1-phenylethylamine groups at the lower rim can form heat-set gels and egg-like vesicles enantioselectively with d-2,3-dibenzoyltartaric acid in cyclohexane, which is the first example of heat-set gels resulting from difference in interactions between two component gelators: in addition, the diameter of vesicles decreased with the increase in length of alkyl groups, which could be used to control the size of the vesicles.     

Fourier transform infrared study of the gel form of isotactic polystyrene

Infrared spectra of isotactic polystyrene gel films are observed to be significantly different from those of amorphous and crystalline polymer, indicating that the gel form is in a different conformation than the usual 3₁ helical crystal structure. Computer-assisted subtraction indicates that approximately 35% of the chains participate in the gel component, effectively ruling out structural defects as the origin of the ordered gel component.     

室温光致发光含钒硅胶的制备和研究

钒掺杂的硅胶显示出有广阔应用前景的催化和光催化特性,引起了人们在其催化机理和应用方面的研究热潮[1-6]。硅胶中氧化钒的微观分子结构和电子状态与它的催化特性密切相关,而荧光谱和磷光谱是研究分子结构,电子状态和光反应的重要工具,目前关于发光机制的研究已经取得巨大进展     

Enhancement and stabilization of the photoluminescence from porous silicon prepared by Ag‐assisted electrochemical etching

In this paper, we present the results of studies on the photoluminescence (PL) of porous silicon (PSi) samples obtained by etching with the assistance of silver metal in different ways. If the Si sample, after being coated with a layer of silver nanoparticles, is electrochemically etched, its PL intensity becomes hundreds of times stronger than the PL intensity when it is chemically etched in the similar conditions. The difference in the PL intensities is explained partly by the anodic oxidation of silicon which occurs during the electrochemical etching process. The most obvious evidence that silicon had been oxidized anodically in the electrochemical etching process is the disappearance of the PSi layer and the appearance of the silicon oxide layer with mosaic structure when the anodization current density is large enough. The anodic oxidation has the effect of PSi surface passivation. Because of that, the PL of obtained PSi becomes stronger and more stable with time. Copyright © 2012 John Wiley & Sons, Ltd.     

Enhancement of the chemiluminescence of permanganate-formaldehyde system by gold/silver nanoalloys and its application to trace determination of melamine

We have examined the specificity of electrosynthesized poly-o-phenylenediamine as a kind of material molecularly imprinted with metal chelates. Molecularly imprinted polymers (MIPs) were prepared in situ by an electrochemical method. The EDTA chelate complexes of Cu(II), Zn(II), Fe(III) and Cd(II) ions were used as templates of the MIPs deposited on a gold electrode of a quartz crystal microbalance (QCM). The binding ability and specificity of the MIPs were investigated via the frequency response of the QCM to the adsorption of the template chelates and their analogs. Linear relationships are observed between the frequency shift and the concentration of the template chelates over a typical range of ~10^?6 to ~10^?4?mol·L^?1. The results reveal good binding specificity of such MIPs for their templates over structurally related analogs, but the selectivity coefficients are less significant than that for enantiomers. The results also suggest no significant correlation between binding specificity and the ionic (or atomic) radius of the investigated metal ions. The observed specificity is qualitatively attributed to the overall conformational difference of the metal-EDTA complexes resulting from their difference in both ionic radius and electronic structures.