Behaviour of phenol red pH-sensors in the presence of different surfactants using the sol-gel process

Phenol red was immobilised into a polysiloxane matrix using a sol-gel process to form pH optical sensors. The sol-gel was obtained by hydrolysis of tetraethoxysilane (TEOS) in the presence of phenol red (PR) and the appropriate surfactant. Different surfactants, namely cetyltrimethylammonium bromide (CTAB), dodecyldimetyl amino-oxide (GLA) and Triton X-100 (TX-100), were employed. Interestingly, the use of surfactants significantly improved the mesostructure of the silica and increased the porosity of the system. The two response pH ranges were shifted to pH 0.0–3.0 and pH 10.5–1.5M [OH^?] compared with those of the free PR (pH 0.0–3.0 and pH 6.5–9.5). It is found that the pH response and the pKa shift of the phenol red were dependent, not only on the silica matrix but also on the ionic properties of surfactants. In the case of ionic surfactants such as CTAB or GLA, there was further shift to more acidic and more basic pH, whereas in the case of non-ionic surfactants such as TX-100 no significant change of the pH curve was observed.     

Sol–gel encapsulation of cresol red in presence of surfactants

Cresol Red (CR) pH indicator was encapsulated into silica network using the sol–gel process. Transparent monolithic disks of entrapped CR were obtained in the presence of cetyl trimethyl ammonium bromide (CTAB) or dodecyl dimethyl amino oxide (Genaminox LA,GLA) alkyl hydroxyethyl dimethyl ammonium chloride (HY, R = 12–14) and TX-100 surfactants. UV/VIS spectra showed that the encapsulated CR retains its structure in terms of its response to pH. At the neutral conditions it is found that the HY surfactant is considered as proton donor as favor the cationic form of the indicator, while CTAB surfactant favor the neutral, however GLA surfactant, the anionic form of CR is more favored because GLA has a zwitterionic head. The surfactant GLA with TEOS has shifted the equilibrium to the ionized form of CR due to the electrostatic interaction between the surfactant and the CR anion. Therefore their pH range is dependent on the nature of a surfactant used. It is found that the HY surfactant is more efficient as far as loading of CR is concern and it widened the working pH range.     

Behavoir of Trapped Bromothymol Blue into Sol-Gel Matrix in Presence of CTAB

Encapsulation of bromothymol blue (BTB) into a polysiloxane network was prepared using sol-gel method without using a catalyst. The co-entrappment of the bromothymol blue (BTB) and surfactant cetyltrimethyl ammonium bromide (CTAB) was used to modify the properties of the sol-gel matrixes which may provide a highly porous materials and made the polysiloxane network an excellent host for sensing molecules. Monolithic disks of trapped BTB were obtained with no leaching. Polarized light microscopy shows that a almost unique particle sizes distributions were formed. The immobilized BTB shows a response for various pH solutions, the feature of absorption spectra of the immobilized BTB was almost the same as that of the solutions.     

Sol–gel encapsulation of bromothymol blue pH indicator in presence of Gemini 12-2-12 surfactant

A sol–gel approach was used to encapsulate bromothymol blue (BTB) C₂₇H₂₈Br₂O₅S pH indicator into mesoporous silica material, in presence of ethanediyl-1,2-bis(dimethyldodecylammonium chloride) (Gemini 12-2-12) surfactant. An ordered mesoporous inorganic matrix including Gemini 12-2-12 and BTB was obtained. It is found that encapsulated BTB/Gemini 12-2-12 exhibit same behavior for pH change as that of the free BTB, which indicate that only physical interaction between BTB molecules and host mesoporous silica network are obtained. The addition of Gemini 12-2-12 surfactant has increased the porosity of the host silica material and increased its sensing capability. The presence of Gemini 12-2-12 surfactant has shifted pKa values of the system to more acidic in comparison with that of free BTB, BTB entrapped silica and BTB/CTAB entrapped silica.     

Encapsulation of curcumin in cationic micelles suppresses alkaline hydrolysis

The alkaline hydrolysis of curcumin was studied in three types of micelles composed of the cationic surfactants cetyl trimethylammonium bromide (CTAB) and dodecyl trimethylammonium bromide (DTAB) and the anionic surfactant sodium dodecyl sulfate (SDS). At pH 13, curcumin undergoes rapid degradation by alkaline hydrolysis in the SDS micellar solution. In contrast, alkaline hydrolysis of curcumin is greatly suppressed in the presence of either CTAB or DTAB micelles, with a yield of suppression close to 90%. The results from fluorescence spectroscopic studies reveal that while curcumin remains encapsulated in CTAB and DTAB micelles at pH 13, curcumin is dissociated from the SDS micelles to the aqueous phase at this pH. The absence of encapsulation and stabilization in the SDS micellar solution results in rapid hydrolysis of curcumin.     

BPB dye confined growth of surfactant-assisted mesostructured silica matrix fiber optic sensing tracers

Thermally stable surfactant modified silica nano-matrix is synthesized by the sol–gel method at low temperature. The surfactant such as cetyltrimethylammonium bromide (CTAB) assisted silica matrix is encapsulated with bromophenol blue (BPB) for sensing activities. Prepared nano-matrix consists of numerous morphological structures such as a pseudo-spherical, hierarchal and islands. The morphology of mesoporous high surface area matrices is strongly affected by CTAB, BPB dye and the aging conditions that determine the transformation from disordered silica nano-matrix morphologies to ordered encapsulated structures. Furthermore, smooth surface matrices with low surface roughness 1.2 nm, low refractive index 1.36, large pores and small dimensions of heteroatoms contribute to the stable sensing activities. The response of coated fiber optic is determined at dynamic pH range 1–12. The prepared sensor has reversibility/repeatability, stability and fast response time of approximately 0.25 s in basic media. The accuracy of sensing device measurements in household ammonia solution and the borax solution suggested that prepared device has clear potential for daily life usage.     

Aggregation Properties of Metallic Tetrasulphophthalocyanines Encapsulated in Sol-Gel Materials

Metallic phthalocyanines exhibit, among many useful properties, the ability to protect sensors against short, intense optical pulses deleterious to efficient sensor operation. It is possible by means of low temperature sol-gel techniques to obtain porous monolithic materials encapsulating metallic ions, and all sorts of complex organic molecules. We report here the study of water-soluble metallic tetrasulphophthalocyanines (MTSPc) encapsulated in silica obtained by the sol-gel technique. These materials are transparent and stable and exhibit interesting optical properties. Absorption in the visible region of the spectrum reveals aggregation of the MTSPc species to form dimers which modify the optical absorption of excited states and the resulting optical properties. We investigate the relative importance of the various physicochemical parameters affecting dimer formation (dye concentration, pH, presence of species such as dimethylformamide, pyridine, etc.) in order to control and inhibit dimer formation. Two species are chosen as examples of the general behavior: CuTSPc, which shows a strong tendency to dimerize in water and in mixtures of solvents, and (OH)AlTSPc, which does not form dimers in aqueous solutions because of its hindering OH axial group. The experiments performed show that addition of dimethylformamide or pyridine does not inhibit aggregation in CuTSPc, simultaneously causing the blue color to disappear from the prepared gels. In the case of (OH)AlTSPc addition of relatively high concentrations of pyridine brings about the formation of non-monomeric species.     

Templated surfactant readsorption on polyelectrolyte-induced depleted surfactant surfaces

Changes in the structure of a surfactant adsorbed on oxidized silicon arising from interaction with a polyelectrolyte have been studied using polarized infrared attenuated total reflection spectroscopy. Specifically, the cationic surfactant cetyltrimethylammonium bromide (CTAB) was found to form a highly ordered layer on oxidized silicon at a concentration of 5.5 x 10(-5) M and a pH of 9.6. Addition of a solution of the anionic polyelectrolyte poly(styrenesulfonate) to the ordered CTAB layer resulted in a rapid and dramatic decrease in the surface excess of CTAB. Interestingly however, the interfacial order of the residual surfactant was retained for a time period greater than 1 h, before decreasing. Reintroduction of a surfactant solution prior to destabilization of the residual interfacial CTAB resulted in the readsorption of the surfactant, the recovery of the initial equilibrium coverage, and the maintenance of an ordered CTAB conformation. This desorption/readsorption process may be subsequently repeated without destroying the order of the CTAB on the surface. If however sufficient time is allowed for the residual interfacial surfactant to destabilize prior to readdition of CTAB, the degree of surfactant order remains low, despite the rapid reobtainment of a surface excess equal to or greater than that initially measured. These results are interpreted in terms of polymer/surfactant interfacial complexation and the removal of adsorbed surfactant into solution. The ordering behavior of the residual surfactant suggests that CTAB is left on the surface in isolated patches of highly ordered species that maintain their order until two-dimensional diffusion leads to a more homogeneous surfactant surface distribution and hence the loss of conformational order. The degree of orientation order assumed by surfactant readsorbing on a depleted surface appears to be templated by the order of the residual interfacial surfactant, suggestive of a two-dimensional epitaxial growth mechanism for CTAB readsorption.     

耐晒大红BBN与表面活性剂双组分光催化降解

以表面活性剂十六烷基三甲基溴化铵(CTAB)和难溶有机颜料耐晒大红BBN(简称BBN)为双组分降解底物, 以TiO2为光催化剂, 研究双组分底物的光催化降解的快慢及规律, 双组分降解的相互影响, 初步建立双组分和催化剂之间的作用模型. 结果表明, pH值及底物的浓度对双组分体系的降解都有显著影响, 碱性条件更适合体系的降解, 在中性(pH=6.8)环境中两种底物的降解效果明显高于单组分的降解. 在碱性条件下(pH=9.2), 加入BBN使CTAB的降解速率略有下降. CTAB的浓度对BBN褪色速率影响较大, 当CTAB 的浓度为1 cmc 时, BBN和CTAB的降解速率都达到最快. BBN在TiO2表面吸附性强, 且被优先降解.     

Phycobiliproteins encapsulated in sol-gel glass

Light transducing phycobiliproteins are encapsulated in optically transparent sol-gel matrices. Absorption and fluorescence spectroscopies are used to characterize the effect of the sol-gel encapsulation on the conformation and aggregation states of the three major phycobiliproteins present in phycobilisomes: phycoerythrin, phycocyanin, and allophycocyanin. It is found that the effects of sol-gel entrapment on the spectroscopic properties are significantly different for the three phycobiliproteins. The results indicate that phycoerythrin undergoes only minor change in its native structure when entrapped in sol-gel. However, significant changes in conformation and aggregation state occur when phycocyanin and allophycocyanin are entrapped in sol-gel matrices. A thin film of sol-gel encapsulated phycoerythrin is also coated on an optical fiber surface and strong fluorescence from the evanescent wave excitation is detected. The potential applications of sol-gel encapsulated phycobiliproteins in biosensors are discussed.     

Micro-DSC and rheological studies of interactions between methylcellulose and surfactants

The effects of a cationic surfactant, cetyltrimethylammonium bromide (CTAB), on the gelation of methylcellulose (MC) in aqueous solutions have been investigated by micro differential scanning calorimetry (micro DSC) and rheology. Methylcellulose had a weight average molecular weight of 310,000 and a degree of substitution of 1.8. The concentration of MC was kept at 0.5 wt % (0.016 mM) and 1 wt % (0.032 mM), and the concentration of CTAB in the MC solutions was varied from 0 to 0.6 wt % (16.5 mM). Upon heating, a single endothermic peak, which is due to the hydrophobic association and gelation of MC, shifts to lower temperatures with increasing CTAB for CTAB < or = CMC (0.93 mM or 0.034 wt %), and then it shifts to higher temperatures lineally with CTAB for CTAB > CMC. At the same time, the endothermic enthalpy decreases with increasing CTAB concentration. Even though CTAB shows a significant "salt-in" effect on the gelation of MC, it does not affect the pattern of the sol-gel transition as well as the gel strength of MC. At the highest concentration of CTAB, 0.60 wt %, MC is still able to form a gel. At a given ratio of CTAB/MC, the effect of CTAB on MC becomes stronger when the MC concentration is lower. The results for the MC-CTAB system are compared with an ionic surfactant, SDS and the significant differences in affecting the gelation of MC between two surfactants are recognized.     

Self-assembly of hydrophobin and hydrophobin/surfactant mixtures in aqueous solution

The self-assembly of the protein hydrophobin, HFBII, and its self-assembly with cationic, anionic, and nonionic surfactants hexadecylterimethyl ammonium bromide, CTAB, sodium dodecyl sulfate, SDS, and hexaethylene monododecyl ether, C(12)E(6), in aqueous solution have been studied by small-angle neutron scattering, SANS. HFBII self-assembles in solution as small globular aggregates, consistent with the formation of trimers or tetramers. Its self-assembly is not substantially affected by the pH or electrolytes. In the presence of CTAB, SDS, or C(12)E(6), HFBII/surfactant complexes are formed. The structure of the HFBII/surfactant complexes has been identified using contrast variation and is in the form of HFBII molecules bound to the outer surface of globular surfactant micelles. The binding of HFBII decreases the surfactant micelle aggregation number for increasing HFBII concentration in solution, and the number of hydrophobin molecules bound/micelle increases.     

A New Biochemical Way for Conversion of CO2 to Methanol via Dehydrogenases Encapsulated in SiO2 Matrix

CO2 is converted to nethanol through an enzymatic approach using formate dehydrogenase(FateDH),formaldehyde dehydrogenase(FaldDH）and alcohol dehydrogenase(ADH)coencapsulated in silica gel prepared by modified sol-gel process as catalysts,TEOS as precursor,NADH as an electron donor.The highest yield of methanol was up to 92.1% under 37℃,pH7.0 and 0.3Mpa.     

Encapsulation of Organic Pigment Particles with Silica via Sol-Gel Process

This paper presented a novel preparation method of silica coated organic pigment. In this approach, the surfaces of the organic pigment were first orderly modified by poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC), then coated by silica via sol-gel process of tetraethylorthosilicate (TEOS). The results showed that PVP, pH value, water and TEOS contents had significant influence on the morphology of the silica encapsulated organic pigment. Organic pigments coated silica by this approach could scatter UV ray with wavelength less than 270 nm, and this scattering property increased with more silica coated.     

Oxidation of dibenzothiophene catalyzed by heme-containing enzymes encapsulated in sol-gel glass

We have encapsulated several hemoproteins in the sol-gel glass to catalyze the oxidation reaction of dibenzothiophene (model for organic sulfur compounds in coal) with hydrogen peroxide. In addition to cytochrome c and myoglobin, which have previously been encapsulated in sol-gel glasses, two other hemoproteins, horseradish peroxidase and bovine blood hemoglobin, have now been successfully immobilized in sol-gel media with the retention of their spectroscopic properties. All four hemoproteins studied also demonstrate similar catalytic activities toward the oxidation of dibenzothiophene as compared with the results obtained with the proteins in solution. In the case of encapsulated cytochrome c, the more water-soluble S-oxide was obtained with much higher selectivity over the less water-soluble sulfone (S-oxide/sulfone = 7.1) as compared to what was obtained in the aqueous/organic medium (S-oxide/sulfone = 2.3). Because of the advantage of easy separation of the encapsulated proteins from the liquid reaction mixture, it is clear from these studies that the immobilization of active hemoproteins in the solid glass media could serve as more practical biocatalysts.     

Fluorescence Probing of Composite Organic/Inorganic Transparent Matrices

Transparent composite SiO2/organic matrices have been made by the sol-gel method using tetramethoxysilane and either cetyltrimethylammoniumbromide (CTAB) or a polyethylene glycol oligomer (PEG-200) or a cationic polyelectrolyte. We have investigated conditions under which transparent xerogel matrices are possible and we have characterized them mainly by time-resolved fluorescence probing using stretched exponentials. CTAB creates a hydrophobic and PEG-200 a hydrophilic subphase in the matrix. An important property of these composite matrices is that they allow molecular diffusion contrary to matrices made in the absence of surfactants or polymers.     

pH及有机小分子物质对SDS/CTAB/H2O系统双水相性质的影响

正离子表面活性剂与负离子表面活性剂混合物能产生比单一表面活性剂更高的表面活性[1 ] 。在适当条件下 ,正负离子表面活性剂的水溶液能产生两个互不相溶的水相 ,即表面活性剂双水相系统[2 ] (ＡｑｕｅｏｕｓＴｗｏ -ＰｈａｓｅＳｙｓｔｅｍ -ＡＴＰＳ)。作者曾指出双水相上相为液晶 (ＬｉｑｕｉｄＣｒｙｓｔａｌ -ＬＣ)结构 ,下相为各向同性溶液 ,盐离子通过改变双水相中表面活性剂有序组合体的反离子层的状态而对双水相的组成、结构等产生重要的影响[3,4] 。本文进一步研究ｐＨ及有机小分子物质在十二烷基硫酸钠 /十六烷基三甲基溴化铵 /…     

Effect of ortho-methoxycinnamic acid on the sol-gel transition of methylcellulose solutions in the presence of cetyltrimethylammonium bromide

The sol-gel transition of methylcellulose (MC) solutions in the presence of ortho-methoxycinnamic acid (OMCA) or cetyltrimethylammonium bromide (CTAB) and in the coexistence of OMCA and CTAB was determined by the rheological measurement. It has been found that the sol-gel transition temperature of MC solutions increases linearly with the concentration of either OMCA or CTAB in solution, respectively. However, in the coexistence of OMCA and CTAB, the sol-gel transition temperature of MC solutions remains invariable, independent of the concentration of CTAB in solution. The experimental results show that OMCA has priority to adsorb on the methyl group of MC chains to form polymer-bound aggregates. In particular, these aggregates inhibit the hydrophobic interaction between CTAB and the methyl group of MC chains completely. Taking into account the fact that OMCA is almost insoluble in MC-free solutions but dissolves very well in aqueous MC solutions, we propose the formation of the core-shell architecture prompted by OMCA and the methyl group of MC chains, with the methyl group of MC chains serving as the core and the self-assembly of OMCA molecules serving as the shell. Obviously, the formation of the core-shell structure increases the solubility of OMCA, improves the stability of methyl groups of MC chains at high temperatures and inhibits the hydrophobic interaction between CTAB and the methyl group of MC chains in solution. The abnormal behavior relating to the sol-gel transition of MC solutions in the presence of OMCA or in the coexistence of OMCA and CTAB is therefore explained. Upon UV irradiation, the sol-gel transition temperature of MC solutions in the presence of OMCA, or in the coexistence of OMCA and CTAB, decreases notably. However, the dependence of the sol-gel transition temperature of MC solutions as a function of OMCA concentration, or CTAB concentration in the presence of OMCA, does not change after UV irradiation.     

Adsorption behavior of hydrophobin and hydrophobin/surfactant mixtures at the air-water interface

The adsorption of the surface-active protein hydrophobin, HFBII, and the competitive adsorption of HFBII with the cationic, anionic, and nonionic surfactants hexadecyltrimethylammonium bromide, CTAB, sodium dodecyl sulfate, SDS, and hexaethylene monododecyl ether, C(12)E(6), has been studied using neutron reflectivity, NR. HFBII adsorbs strongly at the air-water interface to form a dense monolayer ～30 ? thick, with a mean area per molecule of ～400 ?(2) and a volume fraction of ～0.7, for concentrations greater than 0.01 g/L, and the adsorption is independent of the solution pH. In competition with the conventional surfactants CTAB, SDS, and C(12)E(6) at pH 7, the HFBII adsorption totally dominates the surface for surfactant concentrations less than the critical micellar concentration, cmc. Above the cmc of the conventional surfactants, HFBII is displaced by the surfactant (CTAB, SDS, or C(12)E(6)). For C(12)E(6) this displacement is only partial, and some HFBII remains at the surface for concentrations greater than the C(12)E(6) cmc. At low pH (pH 3) the patterns of adsorption for HFBII/SDS and HFBII/C(12)E(6) are different. At concentrations just below the surfactant cmc there is now mixed HFBII/surfactant adsorption for both SDS and C(12)E(6). For the HFBII/SDS mixture the structure of the adsorbed layer is more complex in the region immediately below the SDS cmc, resulting from the HFBII/SDS complex formation at the interface.     

Cationic double-chained surfactant as pseudostationary phase in micellar electrokinetic capillary chromatography for drug separations

The cationic double-chained surfactant didodecyldimethylammonium bromide (DDAB) was used as pseudostationary phase (PSP) in micellar electrokinetic capillary chromatography (MEKC). Its performance on the three kinds of drugs, i.e., basic, acidic, and neutral drugs, was systematically investigated. Nicotine, cotinine, caffeine, lidocaine, and procaine were selected as the model basic drugs. Good baseline separation and high efficiency were obtained under the optimal separation condition that consisted of 50mM phosphate (pH 4.0) and 0.08 mM DDAB. Three basic phenylenediamine isomers can also be well separated with DDAB in buffer. In addition, DDAB can form cationic bilayer on the capillary wall, thus the wall adsorption of basic analytes was greatly suppressed. Compared with commonly used CTAB, the separation of basic drugs was significantly improved with a much lower amount of DDAB present in the buffer. The DDAB-involved MEKC also showed superiority to CTAB upon the separation of acidic drugs, amoxicillin and ampicillin. In the case of neutral compounds, a good separation of resorcinol, 1-naphthol and 2-naphthol was achieved with 0.1mM DDAB and 30% (v/v) acetonitrile (ACN) present in buffer. Hence, it was concluded that the double-chained cationic surfactant DDAB can be a good substitute for traditional single-chained surfactant CTAB in MEKC.