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1.
Curcumin shows huge potential as an anticancer and anti-inflammatory agent. However, to achieve a satisfactory bioavailability and stability of this compound, its liposomal form is preferable. Our detailed studies on the curcumin interaction with lipid membranes are aimed to obtain better understanding of the mechanism and eventually to improve the efficiency of curcumin delivery to cells. Egg yolk phosphatidylcholine (EYPC) one-component monolayers and bilayers, as well as mixed systems containing additionally dihexadecyl phosphate (DHP) and cholesterol, were studied. Curcumin binding constant to EYPC liposomes was determined based on two different methods: UV/Vis absorption and fluorescence measurements to be 4.26 × 104 M−1 and 3.79 × 104 M−1, respectively. The fluorescence quenching experiment revealed that curcumin locates in the hydrophobic region of EYPC liposomal bilayer. It was shown that curcumin impacts the size and stability of the liposomal carriers significantly. Loaded into the EYPC/DPH/cholesterol liposomal bilayer curcumin stabilizes the system proportionally to its content, while the EYPC/DPH system is destabilized upon drug loading. The three-component lipid composition of the liposome seems to be the most promising system for curcumin delivery. An interaction of free and liposomal curcumin with EYPC and mixed monolayers was also studied using Langmuir balance measurements. Monolayer systems were treated as a simple model of cell membrane. Condensing effect of curcumin on EYPC and EYPC/DHP monolayers and loosening influence on EYPC/DHP/chol ones were observed. It was also demonstrated that curcumin-loaded EYPC liposomes are more stable upon interaction with the model lipid membrane than the unloaded ones.  相似文献   

2.
The surface of a titanium (Ti) alloy substrate was modified by a simple and quick process using a water-soluble polymer, and the effects of 3,4-dihydroxyphenyl (DHP) groups in the polymer side chain on the modification process were examined. The polymers (PMDP) composed of both 2-methacryloyloxyethyl phosphorylcholine (MPC) unit and 3,4-dihydroxyphenyl methacrylate unit were synthesized for surface anchoring. The Ti alloy substrate was coated with PMDP using an aqueous solution of the polymer. A PMDP layer with a thickness of 20 nm was formed on the Ti alloy substrate simply by dip coating for 10 s without drying. Even when the Ti alloy substrate with PMDP coating was immersed in the aqueous medium for 1 week, no change in the thickness was observed, i.e., the PMDP layer was bound to the surface very stably. Oxidation of the DHP groups reduced the stability of the polymer layer significantly. Thus, the DHP groups play a significant role in achieving stable binding. Protein was adsorbed on the Ti alloy substrate; however, this was not observed for the PMDP-coated Ti alloy substrate. In conclusion, we confirmed the effects of DHP groups in PMDP on the stability of the coating on the Ti alloy substrate. Moreover, we found that surface treatment using PMDP was simple, quick, and reliable, and thus, it has great potential for improving biofouling of Ti alloy substrates used in medical devices.  相似文献   

3.
Most lipid components of cell membranes are either neutral, like cholesterol, or zwitterionic, like phosphatidylcholine and sphingomyelin. Very few lipids, such as sphingosine, are cationic at physiological pH. These generally interact only transiently with the lipid bilayer, and their synthetic analogs are often designed to destabilize the membrane for drug or DNA delivery. However, anionic lipids are common in both eukaryotic and prokaryotic cell membranes. The net charge per anionic phospholipid ranges from − 1 for the most abundant anionic lipids such as phosphatidylserine, to near − 7 for phosphatidylinositol 3,4,5 trisphosphate, although the effective charge depends on many environmental factors. Anionic phospholipids and other negatively charged lipids such as lipopolysaccharides are not randomly distributed in the lipid bilayer, but are highly restricted to specific leaflets of the bilayer and to regions near transmembrane proteins or other organized structures within the plane of the membrane. This review highlights some recent evidence that counterions, in the form of monovalent or divalent metal ions, polyamines, or cationic protein domains, have a large influence on the lateral distribution of anionic lipids within the membrane, and that lateral demixing of anionic lipids has effects on membrane curvature and protein function that are important for biological control.  相似文献   

4.
Cyclic voltammetric investigation of the interaction of methylene blue (MB) with heparin (hep) at a gold electrode is presented. The combination of MB with heparin formed a nonelectroactive complex MB-hep, which resulted in the peak current decrease of MB. The anodic peak current difference of MB was found to be proportional to the concentration of heparin in the range of 0.666-64.5 μg mL−1 with a detection limit of 270 ng mL−1 and a satisfactory result was obtained for the determination of heparin in injection samples. The equilibrium constant for MB-hep complex was calculated to be 7.32 × 105. The dynamic process of competition of Ba2+ with methylene blue for binding heparin was monitored using quartz crystal microbalance (QCM) technique. The reaction rate constant between Ba2+ and MB-hep was estimated to be 0.0022 s−1.  相似文献   

5.
An experimental study was performed to investigate the effects of column parameters and gradient conditions on the separation of intact proteins using styrene-based monolithic columns. The effect of flow rate on peak width was investigated at constant gradient steepness by normalizing the gradient time for the column hold-up time. When operating the column at a temperature of 60 °C a small C-term effect was observed in a flow rate range of 1–4 μL/min. However, the C-term effect on peak width is not as strong as the decrease in peak width due to increasing flow rate. The peak capacity increased according to the square root of the column length. Decreasing the macropore size of the polymer monolith while maintaining the column length constant, resulted in an increase in peak capacity. A trade-off between peak capacity and total analysis time was made for 50, 100, and 250 mm long monolithic columns and a microparticulate column packed with 5 μm porous silica particles while operating at a flow rate of 2 μL/min. The peak capacity per unit time of the 50 mm long monolithic column with small pore size was superior when the total analysis time is below 120 min, yielding a maximum peak capacity of 380. For more demanding separations the 250 mm long monolith provided the highest peak capacity in the shortest possible time frame.  相似文献   

6.
The modification of poly(4-vinylpyridine) with ω-bromocarboxylic acids and alkyl bromides yields three types of polyampholytes: polyampholytes containing both cationic and anionic groups in each monomer unit (polybetaines), polyampholytes containing betaine and cationic units, and polyampholytes containing betaine units and side cetyl radicals. Their complex formation with liposomes formed from zwitterionic (electroneutral) phosphatidylcholine and anionic diphosphatidylglycerol (cardiolipin) is investigated. The method for fixation of polymers on the liposomal membrane and the stability of the formed complexes are determined by the chemical structure of macromolecules. For the most part, polyelectrolytes are electrostatically adsorbed on the membrane and are fully removed from it with an increase in the salt concentration in the surrounding solution. An exception is the polybetaine obtained through the modification of poly(4-vinylpyridine) with ω-bromobutyric acid, which irreversibly binds to liposomes probably owing to the incorporation of macromolecular fragments into the hydrophobic part of the lipid bilayer. The insertion of side cetyl radicals into polybetaine molecules stabilizes their complexes with liposomes in the presence of salts. The cytotoxicity of the synthesized polyampholytes is one to two orders of magnitude lower than that of a cationic polymer with the same degree of polymerization.  相似文献   

7.
This work reports the preparation of molecularly imprinted polymer (MIP) particles for selective extraction and determination of selenium ions from aqueous media. Polymerization was achieved in a glass tube containing SeO2, o-phenylenediamine, 2-vinylpyridine (VP), ethyleneglycoldimethacrylate (EDMA), 2,2′-azobisisobutyronitrile (AIBN). The polymer block obtained was ground and sieved (55-75 μm) and the Se-o-phenylenediamine complex was removed from polymer particles by leaching with 2 M of HCl, which leaves a cavity in the polymer particles. The polymer particles both prior to and after leaching have been characterized by IR and thermogravimetric (TG) studies. The effect of different parameters, such as pH, extraction time, type and least amount of eluent for elution of complex from polymer were evaluated. Extraction efficiencies >99% were obtained by elution of the polymers with 15 mL of methanol-acetonitrile mixture (1:2, v/v). The limit of detection of the proposed method followed by hydride generation atomic absorption spectroscopy (HG-AAS) was found to be 3.3 μg L−1 and a dynamic linear range (DLR) of 10-200 μg L−1 was obtained. The relative standard deviations (R.S.D.s) at 30.0 μg L−1 of Se were below than 8.1%. The influence of various cationic interferences on percent recovery of complex was studied. The method was applied to the recovery and determination of selenium in different real samples.  相似文献   

8.
The ultrasensitive detection of 2,4,6-trinitrotoluene (TNT) was accomplished on the basis of sandwich-type TNT immunoassay combined with electrogenerated chemiluminescence (ECL) technology. Biotinylated anti-TNT species were attached to the surface of 1-μm diameter streptavidin-coated magnetic beads (MB) and 10-μm diameter avidin-coated polystyrene microspheres/beads (PSB) pre-loaded with ECL labels (∼7 billion hydrophobic ruthenium(II) tris(2,2′-bipyridine) (RuII) molecules per bead) to form anti-TNT ↔ MB and anti-TNT ↔ PSB(RuII) conjugates, respectively. Sandwich-type PSB(RuII) ↔ anti-TNT < TNT > anti-TNT ↔ MB aggregates were formed when PSB(RuII) ↔ anti-TNT was mixed with anti-TNT ↔ MB conjugates in the presence of analyte TNT and 2.0% bovine serum albumin blocking agent. The newly formed aggregates were magnetically separated from the aqueous reaction media and dissolved in acetonitrile containing 0.10 M tri-n-propylamine ECL coreactant-0.055 M trifluoroacetic acid-0.10 M tetrabutylammonium tetrafluoroborate electrolyte. ECL as well as cyclic voltammetric measurements were carried out with a potential scan from 0 to 2.8 V vs Ag/Ag+, and the integrated ECL intensity was found to be linearly proportional to the analyte TNT concentration over the range of 0.10-1000 ppt (pg mL−1). The limit of detection (≤0.10 ± 0.01 ppb) is about 600× lower as compared with the most sensitive TNT detection method in the literature, and the absolute detection limit in mass (∼0.1 pg) is only ∼0.5% of that from mass spectroscopy. The approach coupled with the standard addition method was applied to measure the TNT contaminations in soil and creek water samples collected from a military training base.  相似文献   

9.
This work presented a novel method for specific detection of sulfate-reducing bacteria (SRB) based on the photocatalytic property of ZnS nanoparticles. ZnS semiconductor nanoparticles were synthesized by taking advantage of the characteristic bacterial metabolite, sulfide, and then ZnS nanomaterials were used as photocatalyst for methylene blue (MB) photodegradation. As the amount of ZnS photocatalyst synthesized from microbe metabolized sulfide was affected by initial bacterial concentration before cultivation, the photodegradation ratio of MB was highly related with initial SRB concentration. Under the optimized conditions, a linear relationship between the MB photodegradation ratio and the logarithm of SRB concentration was observed in the range of 1.0 × 103–1.0 × 108 cfu mL−1. Besides, this proposed method showed excellent specificity for SRB detection. To the best of our knowledge, this is the first example of using the photocatalytic property of microbial synthesized ZnS for bacterial detection.  相似文献   

10.
Kynurenic acid (KYNA), an endogenous antagonist of ionotropic glutamate and α7 nicotinic receptors, was fluorometrically determined by column-switching high-performance liquid chromatography (HPLC) with fluorescence detection. The HPLC system consists of two octadecyl silica (ODS) columns, both of which are connected with an anion-exchange column (trapping column). Following sample injection onto the HPLC column, KYNA was separated on the first ODS column with a mobile phase of H2O/acetonitrile (95/5) containing 0.1% acetic acid. The peak fraction of KYNA was trapped on the anion-exchange column by changing the position of a six-port valve and then introduced into the second ODS column. Subsequently, KYNA was detected fluorometrically as a fluorescence complex formed with zinc ion which was pumped constantly. Instrumental limit of detection was approximately 0.16 nM, which corresponded to 8.0 fmol (per 50 μl injection, signal to noise ratio 3), and the limit of quantification was 0.53 nM (signal to noise ratio 10). Intra- and inter-day relative standard deviations were 1.1-3.9% (n = 3) and 3.0-5.3% (n = 3), respectively. The peak of KYNA in rat plasma was clearly detected by the proposed column-switching HPLC system after a facile pretreatment procedure. Intra- and inter-day relative mean errors were −1.6-1.4% (n = 3) and −2.4 to −0.4% (n = 3), respectively, with a satisfactory precision (within 5.0%). A calibration curve for the determination of KYNA showed a good linearity (r2 > 0.999) in the range of 25-200 nM. The KYNA concentrations in the plasma of male Sprague-Dawley rats (8-week-old) were 44 ± 5.5 nM (mean ± S.E., n = 5). In ketamine-treated rats, which are animal models of schizophrenia, the plasma KYNA concentrations were significantly increased compared with those in the control rats (p < 0.05).  相似文献   

11.
The lower critical solution temperature (LCST) of hydroxypropylcellulose bearing lignin (HPC-L) prepared from unbleached pulp depends on the amount of residual lignin. An HPC-L gel having thermal properties reflective of original HPC-L was prepared using ethyleneglycol diglycidylether as a crosslinker, as previously reported [Uraki et al. (2004) Carbohydr. Polym. 58:123–130], and the volume transition temperature was detected as an endothermic peak by differential scanning calorimetry (DSC). The adsorption and release behavior of the guest molecules to/from this gel was then examined. When the adsorption of cationic and anionic guests was compared, cationic methylene blue (MB) was adsorbed in larger amounts than anionic methyl orange (MO). In addition, MB adsorption into the HPC-L gel was greater than MB adsorption into the HPC gel prepared from commercially available HPC. This suggests that residual lignin affects the adsorption of organic dyes. Significant differences were not observed with respect to the release of MB from HPC-L at 38 °C and lower temperatures. In the adsorption of surfactants, marked adsorption at around the critical micelle concentration of the ionic surfactants and gel swelling were observed. Such swelling did not occur in the aqueous nonionic surfactant solution, although the nonionic surfactant was adsorbed into the gel. Gel swelling may have been caused by the electrostatic repulsion of the ionic surfactants adsorbed onto the polymer chains within the gel structure.  相似文献   

12.
A novel complexing membrane was used for the removal of heavy metal ions such as Pb(II), Cd(II) and Cu(II) from aqueous solutions. The membrane consists in a semi-interpenetrating polymer network of crosslinked poly(vinyl alcohol) as the matrix and poly(ethyleneimine) as the complexing polymer. The absorption reactions followed pseudo-first-order kinetics with similar rate constants for the three cations. A model is proposed for the absorption–desorption process in order to rationalize the data obtained for the retention ratio and the retention efficiency ratio. The corresponding equilibrium constants were determined for the three metal ions, showing that the affinity order of the membrane is Pb > Cu > Cd. This sequence is consistent with the order of maximum uptake of the ions per gram of membrane: 0.59, 0.47 and 0.33 mmol g−1, respectively. On the other hand, the uptake order is different on a mass basis: 123, 30 and 37 mg g−1, respectively. Regeneration of the membrane and metal recovery were studied with HCl and HNO3 at different concentrations. Filtration of solutions of each metal ion showed large elimination ratios (96–99.5%) with a retention sequence Cd > Cu > Pb. The membrane remained efficient until complete saturation of its sites. Moreover, Cu retention is larger than expected, indicating possible additional chelation by the PVA matrix. Better retention ratios were observed when the concentration of the feed solution was kept constant. Filtration of a mixture of the three cations (all at 100 ppm concentration) resulted in the same retention sequence, but the elimination ratios were smaller and Pb was eventually displaced by Cu and Cd that were present in larger molar concentrations.  相似文献   

13.
Aqueous miconazole (MCZ) aggregates were solubilized and/or colloidally stabilized by bilayer-forming synthetic amphiphiles such as dioctadecyldimethylammonium bromide (DODAB) or sodium dihexadecylphosphate (DHP) dispersions. Particle sizing, light absorption and scattering from drug particles, zeta-potential determination, and drug aggregation kinetics from turbidity changes in the presence or absence of lipid dispersions were obtained over a range of drug and lipid concentrations. The very low solubility of MCZ in water made possible the determination of size distributions for drug particles in water and comparison to those in the presence of DODAB or DHP nanosized bilayer fragments or entire and closed bilayer vesicles. Large drug aggregates disappeared upon incubation with nanosized bilayer fragments produced by ultrasonic dispersion with tip. Light-absorption spectra for MCZ in a poor solvent (water), in a good organic solvent (methanol), and in different lipid dispersions showed that solubilization depended on the presence of bilayer fragments. MCZ was poorly soluble in dispersions formed of closed bilayers (vesicles) of DODAB or DHP in the gel state and in phosphatidylcholine (PC) vesicles in the liquid-crystalline state. Increased hydrophobicity at the borders of bilayer fragments explained MCZ solubilization. At [MCZ]>0.4 mM, kinetics of drug aggregation, zeta-potential measurements, and size minimization were obtained upon addition of minute amounts of oppositely charged bilayer fragments ([DHP]=0.05 mM), making possible determination of a remarkable stabilizing effect of drug particles by coverage with anionic bilayer fragments. High drug colloid stability in the presence of charged bilayer fragments was achieved by two different means: (1). at large drug concentrations and small concentrations of bilayer fragments, coverage of large drug particles with bilayer fragments; (2). at large amounts of bilayer fragments, drug solubilization in its monomeric form at the borders of bilayer fragments. Inexpensive, synthetic bilayer fragments offered a large area of hydrophobic nanosurfaces dispersed and electrostatically stabilized in water, opening new prospects for drug solubilization and colloid stabilization of insoluble drug particles.  相似文献   

14.
In this study, high-efficiency LC–MS/MS separations of complex proteolytic digests are demonstrated using 50 mm, 250 mm, and 1 m long poly(styrene-co-divinylbenzene) monolithic capillary columns. The chromatographic performance of the 50 and 250 mm monoliths was compared at the same gradient steepness for gradient durations between 5 and 150 min. The maximum peak capacity of 400 obtained with a 50 mm column, increased to 485 when using the 250 mm long column and scaling the gradient duration according column length. With a 5-fold increase in column length only a 20% increase in peak capacity was observed, which could be explained by the larger macropore size of the 250 mm long monolith. When taking into account the total analysis time, including the dwell time, gradient time and column equilibration time, the 50 mm long monolith yielded better peptide separations than the 250 mm long monolithic column for gradient times below 80 min (nc = 370). For more demanding separation the 250 mm long monolith provided the highest peak production rate and consequently higher sequence coverage. For the analysis of a proteolytic digest of Escherichia coli proteins a monolithic capillary column of 1 m in length was used, yielding a peak capacity of 1038 when applying a 600 min gradient.  相似文献   

15.
A new strategy has been developed for the controlled release of a hydrophobic anticancer drug, camptothecin (CPT), which suffers a limited therapeutical utility because of its poor water solubility. CPT was first solubilized in the solution of a cationic surfactant, dodecyltrimethylammonium bromide (DTAB). It has been demonstrated that the presence of DTAB has increased the solubility of CPT significantly. In a 50 mM DTAB solution, the drug’s solubility was enhanced to 85 μM, 22 times of its solubility in pure water. The micellar drug solution of CPT-DTAB was subsequently used to prepare agarose hydrogels, which act as the drug carriers in the release studies. To fully take advantage of the cationic property of DTAB, negatively charged κ-carrageenan was added as a guest polymer in some hydrogel samples. The release of CPT from these hydrogel-surfactant systems was performed at 37 °C and the effects of DTAB and κ-carrageenan on the release of CPT were studied respectively. By fitting to the well-known Fickian diffusion model, the diffusion coefficients of CPT were obtained.  相似文献   

16.
This work reports the synthesis and characterization of a hybrid molecularly imprinted polymer (MIP) membrane for removal of methylene blue (MB) in an aqueous environment. MB-MIP powders were hybridized into a polymer membrane (cellulose acetate (CA) and polysulfone (PSf)) after it was ground and sieved (using 90 μm sieve). MB-MIP membranes were prepared using a phase inversion process. The MB-MIP membranes were characterized using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscope (SEM). Parameters investigated for the removal of MB by using membrane MB-MIP include pH, effect of time, concentration of MB, and selectivity studies. Maximum sorption of MB by PSf-MB-MIP membranes and CA-MB-MIP membranes occurred at pH 10 and pH 12, respectively. The kinetic study showed that the sorption of MB by MB-MIP membranes (PSf-MB-MIP and CA-MB-MIP) followed a pseudo-second-order-model and the MB sorption isotherm can be described by a Freundlich isotherm model.  相似文献   

17.
In this paper, the electrochemical current rectification phenomenon exhibited at an electrochemical interface constituted by a glassy carbon electrode covered with a bilayer of polymer films is discussed. The authors have shown that Methylene Blue (MB) redox species can be confined to a very thin insulating polymer film formed from orthophenylene diamine. The poly(opd) film exhibited excellent blocking properties to redox molecules in solution. On the other hand, the insulating poly(opd) film trapped with MB could mediate electron transfer between the redox molecules in solution and the electrode. Further, a second polymeric layer (Nafion film) trapped with ferrocene redox species was formed as the outer layer over the inner poly (opd) film containing MB. This bilayer-modified electrode, due to the significant difference in the redox potentials of the MB and ferrocene species immobilized in the inner and outer layers, respectively, exhibits unidirectional current flow and the results of the voltammetric investigations on the modified electrodes are described in this communication.  相似文献   

18.
Vidigal SS  Tóth IV  Rangel AO 《Talanta》2011,84(5):1298-1303
A sequential injection lab-on-valve (SI-LOV) system was used to develop a new methodology for the determination of iron in wine samples exploiting the bead injection (BI) concept for solid phase extraction and spectrophotometric measurement. Nitrilotriacetic Acid (NTA) Superflow resin was used to build the bead column of the flow through sensor. The iron (III) ions were retained by the bead column and react with SCN producing an intense red colour. The change in absorbance was monitored spectrophotometrically on the optosensor at 480 nm. It was possible to achieve a linear range of 0.09-5.0 mg L−1 of iron, with low sample and reagent consumption; 500 μL of sample, 15 μmol of SCN, and 9 μmol of H2O2, per assay. The proposed method was successfully applied to the determination of iron in wine, with no previous treatment other than dilution, and to other food samples.  相似文献   

19.
In this study, cellulose acetate (CA) ultrafiltration (UF) membranes were prepared using the phase inversion method. Effects of CA and polyethylene glycol (PEG) concentrations in the casting solution and coagulation bath temperature (CBT) on morphology of the synthesized membranes were investigated. Based on L9 orthogonal array of Taguchi experimental design 18 membranes were synthesized (with two replications) and pure water permeation flux through them were measured. It was found out that increasing PEG concentration in the casting solution and CBT, accelerate diffusional exchange rate of solvent 1-methyl-2-pyrrolidone (NMP) and nonsolvent (water) and consequently facilitate formation of macrovoids in the membrane structure. Increasing CA concentration, however, slows down the demixing process. This prevents instantaneous growth of nucleuses in the membrane structure. Hence, a large number of small nucleuses are created and distributed throughout the polymer film and denser membranes are synthesized. Rate of water flux through the synthesized membranes is directly dependent on the size and number of macrovoids in the membrane structure. Thus, maximum value of flux is obtained at the highest levels of PEG concentration and CBT (10 wt.% and 23 °C, respectively) and the lowest level of CA concentration (13.5 wt.%). Analysis of variance (ANOVA) showed that all parameters have significant effects on the response. However, CBT is the less influential factor than CA and PEG concentrations on the response (flux).  相似文献   

20.
The objective of this work was to synthesize nanocomposites based on cationic polyelectrolytes and silver nanoparticles using poly(N-vinylbenzyl-N-triethylammonium chloride) as polymer phase. For that, a nanostructured crosslinker was synthesized from silver nanoparticles (AgNPs) and acrylic acid. Molybdate retention properties of nanocomposites were studied in function of pH and ionic strength. In addition, their antimicrobial properties were evaluated against E. coli and S. aureus. It was evidenced that AgNPs can be stabilized using acrylic acid and that this material can be incorporated to the polymer phase during polymerization by free radical of cationic monomers. The effect of pH on retention of molybdate, by the nanostructured polymer, was significant only to low ionic strength (the order seen was pH 5.0 > pH 7.0 > pH 9.0 for 0.0% NaCl). Results suggest that the main interaction influencing the molybdate retention is electrostatic in nature. Finally, antimicrobial activity was enhanced by incorporation of polymerizable nanostructured crosslinker based on AgNPs.  相似文献   

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