首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 46 毫秒
1.
Ultrathin nylon capsule membranes coated with synthetic bilayers, the hydrophilic head groups of which had cationic, anionic, zwitterionic and nonionic charges, were prepared. Permeation of NaCl trapped in the inner aqueous phase was reduced by a factor of 10-1000 relative to that of the uncoated, semipermeable capsules, and drastically changed at the phase transition temperature, Tc, of the coating bilayers, depending on the charge of their hydrophilic head group. In the case of capsules coated with positively or negatively charged bilayers, NaCl permeation was enhanced at temperatures above the Tc of the coating bilayers, as expected. On the other hand, NaCl release of capsules coated with neutral charged (nonionic and zwitterionic) bilayers was largely reduced at temperatures above the Tc. From activation energy data of Arrhenius plots, the permeation mechanism of NaCl, depending on the membrane surface charge, below and above the Tc was discussed.  相似文献   

2.
A novel positively charged polymer of quaternary ammonium substituted agarose (Q-agarose) has been synthesized and explored for use as a coating in capillary electrophoresis. The fast and simple coating procedure is based on a multi-site electrostatic interaction between the polycationic agarose polymer and the negatively charged fused-silica surface. By simply flushing fused-silica capillaries with hot polymer solution a positively charged, hydrophilic deactivation layer is achieved. The polymer surface provides an intermediate electroosmotic flow of reversed direction, over a range of pH 2-11, compared to unmodified fused-silica. The coating procedure was highly reproducible with an RSD of 4%, evaluated as the electroosmotic flow mobility for 30 capillaries prepared at 10 different occasions. The application of Q-agarose coated capillaries in separation science was investigated using a set of basic drugs and model proteins and peptides. Due to the intermediate electroosmotic flow generated, the resolution of basic drugs could be increased, compared to using bare fused-silica capillaries. Moreover, the coating enabled separation of proteins and peptides with efficiencies up to 300.000 plates m(-1).  相似文献   

3.
Antifouling polymer coating surfaces are used in widespread industries applications. Zwitterionic polymers have been identified as promising materials in developing polymer coating surfaces. Importantly, the density of the polymer chains is crucial for acquiring superior antifouling performance. This study introduces two different zwitterionic polymer density surfaces by applying molecular modeling tools. To assess the antifouling performance, we mimic static adsorption test, by placing the foulant model bovine serum albumin (BSA) on the surfaces. Our findings show that not only the density of the polymer chain affect antifouling performance, but also the initial orientation of the BSA on the surface. Moreover, at a high-density surface, the foulant either detaches from the surface or anchor on the surface. At low-density surface, the foulant does not detach from the surface, but either penetrates or anchors on the surface. The anchoring and the penetrating mechanisms are elucidated by the electrostatic interactions between the foulant and the surface. While the positively charged ammonium groups of the polymer play major role in the interactions with the negatively charged amino acids of the BSA, in the penetrating mechanism the ammonium groups play minor role in the interactions with the contact with the foulant. The sulfonate groups of the polymer pull the foulant in the penetrating mechanism. Our work supports the design of a high-density polymer chain surface coating to prevent fouling phenomenon. Our study provides for the first-time insights into the molecular mechanism by probing the interactions between BSA and the zwitterion surface, while testing high- and low-densities polymer chains.  相似文献   

4.
A novel phosphorylcholine type zwitterionic stationary phase was synthesized by graft polymerization of 2-methacryloyloxyethyl phosphorylcholine onto the surface of porous silica particles. The resulting material possesses both negatively charged phosphoric acid and positively charged quaternary ammonium groups, which renders it a low net charge over a wide pH range. The composition of the surface grafts were determined by elemental analysis and solid state NMR, and the surface charge (zeta-potential) in different buffer solutions were measured using photon correlation spectroscopy. Separation of several peptides was investigated on packed columns in the hydrophilic interaction liquid chromatography (HILIC) separation mode. It was shown that small peptides can be separated based on hydrophilic interaction and ionic interaction between the stationary phase and analyte. The organic solvent composition, the pH and the salt concentration of the eluent have strong effects on the retention time. Compared to native silica before grafting, the newly synthesized zwitterionic material gave more stable retention times for basic peptides over pH range 3-7 due to elimination of the dissociation of silanol groups.  相似文献   

5.
Surface‐bonded zwitterionic stationary phases have shown highlighted performances in separation of polar and hydrophilic compounds under hydrophilic interaction chromatography mode. So, it would be helpful to evaluate the characteristics of zwitterionic stationary phases with different arranged charged groups. The present work involved the preparation and comparison of three zwitterionic stationary phases. An imidazolium ionic liquid was designed and synthesized, and the cationic and anionic moieties respectively possessed positively charged imidazolium ring and negatively charged sulfonic groups. Then, the prepared ionic liquid, phosphorylcholine and an imidazolium‐based zwitterionic selector were bonded on the surface of silica to obtain three zwitterionic stationary phases. The selectivity properties were characterized and compared through the relative retention of selected solute pairs, and different kinds of hydrophilic solutes mixtures were used to evaluate the chromatographic performances. Moreover, the zwitterionic stationary phases were further characterized by the modified linear solvation energy relationship model to probe the multiple interactions. All the results indicated that the types and arrangement of charged groups in zwitterionic stationary phases mainly affect the retention and separation of ionic or ionizable compounds, and for interaction characteristics the contribution from n and π electrons and electrostatic interactions displayed certain differences.  相似文献   

6.
Marine organisms such as plants, algae or small animals can adhere to surfaces of materials that are submerged in ocean. The accumulation of these organisms on surfaces is a marine biofouling process that has considerable adverse effects. Marine biofouling on ship hulls can cause severe fuel consumption increase. Investigations on antifouling polymers are therefore becoming important research topics for marine vessel operations. Antifouling polymers can be applied as coating layers on the ship hull, protecting it against the settlement and growth of sea organisms. Polyethylene glycol (PEG) is a hydrophilic polymer that can effectively resist the accumulation of marine organisms. PEG-based antifouling coatings have therefore been extensively researched and developed. However, the inferior stability of PEG makes it subject to degradation, rendering it ineffective for long-term services. Zwitterionic polymers have also emerged as promising antifouling materials in recent years. These polymers consist of both positively charged and negatively charged functional groups. Various zwitterionic polymers have been demonstrated to exhibit exceptional antifouling properties. Previously, surface characterizations of zwitterionic polymers have revealed that strong surface hydration is critical for their antifouling properties. In addition to these hydrophilic polymers, amphiphilic materials have also been developed as potential antifouling coatings. Both hydrophobic and hydrophilic functional groups are incorporated into the backbones or sidechains of these polymers. It has been demonstrated that the antifouling performance can be enhanced by precisely controlling the sequence of the hydrophobic-hydrophilic functionalities. Since biofouling generally occurs at the outer surface of the coatings, the antifouling properties of these coatings are closely related to their surface characteristics in water. Therefore, understanding of the surface molecular structures of antifouling materials is imperative for their future developments. In this review, we will summarize our recent advancements of antifouling material surface analysis using sum frequency generation (SFG) vibrational spectroscopy. SFG is a surface-sensitive technique which can provide molecular information of water and polymer structures at interfaces in situ in real time. The antifouling polymers we will review include zwitterionic polymer brushes, mixed charged polymers, and amphiphilic polypeptoids. Interfacial hydration studies of these polymers by SFG will be presented. The salt effect on antifouling polymer surface hydration will also be discussed. In addition, the interactions between antifouling materials and protein molecules as well as algae will be reviewed. The above research clearly established strong correlations between strong surface hydration and good antifouling properties. It also demonstrated that SFG is a powerful technique to provide molecular level understanding of polymer antifouling mechanisms.  相似文献   

7.
Two hydrophilic polymer systems, multivalent N-(2-hydroxypropyl)methacrylamide-based copolymers bearing thiazolidine-2-thione (TT) reactive groups randomly distributed along the polymer chain and monovalent semitelechelic pHPMA with the TT end group, were designed for surface modification of gene delivery vectors, namely, DNA polyelectrolyte complexes (PECs) and adenoviruses. In this study, the amino group-modified polystyrene latex nanoparticles were selected as a suitable model of a nanoparticulate delivery system bearing NH2 groups on the surface. The coating process was monitored by changes in molecular weight and hydrodynamic parameters of the nanoparticles by light scattering methods. It was shown that for study of the coating process the model latex particles are more suitable than the original PEC vectors due to better chemical and physical stability of latexes. The results obtained in the model study (reaction conditions, methods of evaluation) suggest an optimal polymer structure and a method of efficient and complete coating of nanoparticle surface well applicable to the real gene delivery vectors.  相似文献   

8.
成晓东  李云萍  贺银菊 《色谱》2019,37(7):683-691
将不同比例的氨基和巯基的硅烷偶联剂键合到硅胶表面,再利用巯基与乙烯基膦酸之间的点击化学反应将膦酸基团引入到硅胶表面,制备了一种可调节正负离子比例的两性亲水色谱固定相。通过测定固定相中C、H、N、P元素的含量,证明了氨基与膦酸基团已成功键合到固定相的表面,同时通过N元素与P元素的质量分数确定固定相表面氨基与膦酸基团的比例。制备了3种不同电荷比例的氨基膦酸固定相,将其作为亲水模式下的固定相填料填装在150 mm×4.6 mm不锈钢色谱柱中。以一系列经典的极性小分子作为探针,研究了流动相中乙腈含量、缓冲盐pH值及缓冲盐浓度等因素对探针分子在3种色谱柱上的保留的影响,结果表明,分析物在固定相上是多重保留机理。最后通过比较核苷、水溶性维生素、碱性化合物、苯甲酸这几类标准物质在3种色谱柱上的保留行为来对比3种不同电荷比例的固定相的分离选择性与色谱性能。结果表明,对于不同的分析物,3种固定相表现出完全不同的分离选择性和色谱行为。可以根据分析物的特征选取不同电荷比例的固定相,表明此种固定相在极性化合物的分离上具有良好的应用前景。  相似文献   

9.
A cationic cyclodextrin was used as dynamic coating for the capillary electrophoresis of a model mixture of proteins (i.e., ubiquitin, α‐lactoglobulin, cytochrome‐c, and myoglobin) as positively charged species in a fused silica capillary. An interesting feature of the coating is that by simple adjustment of the concentration of cyclodextrin added into the background electrolyte, a neutral or positively charged surface, which was beneficial in preventing protein adsorption at the inner capillary wall surface, was obtained. This is the first demonstration of a dynamic coating that yielded a neutral surface for protein separations in capillary electrophoresis. Based on electro‐osmotic flow measurements, addition of 0.05 to 0.10 mg/mL quaternary β‐cyclodextrin in a low pH electrolyte resulted in a neutral or positive surface (undetectable to very slow anodic electro‐osmotic flow). The coating approach afforded the electrophoretic separation of the mixture of proteins at positive polarity with good repeatability and separation performance.  相似文献   

10.
Surfaces coated with poly(ethylene oxide) containing nonionic polymers are of interest in medical applications due to, among other things, the low adsorption of proteins on such surfaces. In this paper we have studied the interfacial properties of surfaces coated with PEO by measuring the forces acting between two such surfaces in water and across a protein solution as well as between one such surface and a surface carrying adsorbed proteins. One type of surface coating was a graft copolymer of poly(ethylene imine) and poly(ethylene oxide) where the cationic poly(ethylene imine) group anchored the polymer to negatively charged mica surfaces. Three different ways to prepare this coating was used and compared. It was found that this coating was not stable in the presence of lysozyme, a small positively charged protein, when the PEO graft density was low. The other type of coating was obtained by adsorbing ethyl(hydroxyethyl)-cellulose onto hydrophobised mica surfaces. The driving force for adsorption is in this case the hydrophobic interaction between nonpolar segments of the polymer and the surface. The EHEC coating was stable in the presence of lysozyme and the interactions between adsorbed layers of lysozyme and EHEC coated surfaces are purely repulsive due to long-range steric forces.  相似文献   

11.
Immunoassay detection of O-pinacolyl methylphosphonic acid (PMPA) employing direct coating of N-2-aminoethyl-O-pinacolyl methylphosphonate (hapten B) on microtiter plates is reported. Coating was achieved by covalently linking hapten B to a glutaraldehyde (GA) polymer network directly bound to the polystyrene (PS) surface of a standard 96-well microtiter plate. 4-(2-(O-Pinacolylmethylphosphoryl amino)ethyl amino)-4-oxobutanoic acid (hapten A)-ovalbumin (OVA) conjugate served as the coating antigen for comparison with direct hapten B-coated plates in the CIELISA format. The developed assay employing direct hapten B coated plates demonstrated enhanced sensitivity with the IC(50) value for PMPA being 0.027 μg mL(-1). The assay could detect PMPA even at the concentration of 0.006 μg mL(-1). The mean recovery of standard PMPA (spiked in water) was found to be 83.7%.  相似文献   

12.
Giant cell-like polymer vesicles, polymersomes, made from the diblock copolymer poly(ethylene oxide)-polybutadiene (PEO-PBD), have bilayer structures similar to the cell membrane but have superior and tunable properties for storage and stability. We have modified the terminal hydroxyl of the hydrophilic block with biotin-lysine (biocytin), a biologically derived group that imparts specific adhesiveness to a polymer colloid coated with avidin. The functionalized polymer will form vesicles, either on its own or when mixed with unmodified block copolymers that also form vesicles. The incorporation and mixing of the functionalized polymer into vesicle bilayers is measured using a fluorescent version ofbiocytin with confocal microscopy. The fluorescence signal associated with the vesicle is in proportion with the concentration of functional polymer added during vesicle construction. The adhesiveness of polymer vesicles containing functionalized biotinylated polymer to avidin coated microspheres is measured with micropipet aspiration. Two types of polymer vesicles were constructed: one where the functionalized polymer (molecular weight (MW), 10400 Da) was longer than the surrounding unfunctionalized polymer (MW, 3600 Da) and one where the functionalized polymer (MW, 10400 Da) was the same length as the unfunctionalized polymer. In all cases, the avidin-biotin bonds form kinetically trapped crossbridges that impart little tension as they form but require significantly more tension to break. The relative length of the functionalized polymer on the surface of the vesicle is an important determinant for the adhesion of a polymer vesicle but not for the adsorption of soluble avidin. Greater adhesion strengths are seen where the functionalized polymer is longer than the surrounding polymer. The concentration of functionalized polymer at which adhesion is maximal depends on the relative lengths of the polymers. When the functionalized polymer is the same length as the surface brush of the polymersome membrane, the critical tension is maximal at 10 mol % functionalized polymer concentration. However, when the biocytin groups are attached to a polymer which is larger than the surface brush, the critical tension is maximal at 55 mol % functionalized polymer. These results indicate that polymer mixing and length can control the interfacial adhesion of polymer brushes and must be understood to tune polymersome adhesiveness.  相似文献   

13.
The salt effects on the water solubility of thermoresponsive hyperbranched polyethylenimine and polyamidoamine possessing large amounts of isobutyramide terminal groups (HPEI-IBAm and HPAMAM-IBAm) were studied systematically. Eight anions with sodium as the counterion and ten cations with chloride as the counterion were used to measure the anion and cation effects on the cloud point temperature (T(cp)) of these dendritic polymers in water. It was found that the T(cp) of these dendritic polymers was much more sensitive to the addition of salts than that of the traditional thermoresponsive linear polymers. At low anion concentration, the electrostatic interaction between anions and the positively charged groups of these polymers was dominant, resulting in the unusual anion effect on the T(cp) of these polymers in water, including (1) T(cp) of these dendritic polymers decreasing nonlinearly with the increase of kosmotropic anion concentration; (2) the chaotropic anions showing abnormal salting-out property at low salt concentration and the stronger chaotropes having much pronounced salting-out ability; (3) anti-Hofmeister ordering at low salt concentration. At moderate to high salt concentration, the specific ranking of these anions in reducing the T(cp) of HPEI-IBAm and HPAMAM-IBAm polymers was PO(4)(3-) > CO(3)(2-) > SO(4)(2-) > S(2)O(3)(2-) > F(-) > Cl(-) > Br(-) > I(-), in accordance with the well-known Hofmeister series. At moderate to high salt concentration, the specific ranking order of inorganic cations in reducing the T(cp) of HPEI-IBAm polymer was Sr(2+) ≈ Ba(2+) > Na(+) ≈ K(+) ≈ Rb(+) > Cs(+) > NH(4)(+) ≈ Ca(2+) > Li(+) ≈ Mg(2+). This sequence was only partially similar to the typical Hofmeister cation series, whereas at low salt concentration the cation effect on T(cp) of the dendritic polymer was insignificant and no obvious specific ranking order could be found.  相似文献   

14.
In order to accomplish the analysis of peptides and proteins by capillary electrophoresis, Lupamin, a high-molecular-weight linear polyvinylamine (PVAm) polymer, was introduced to modify the inner wall of fused-silica capillaries by physical absorption. Thanks to the high density of positively charged amino groups in Lupamin under acidic conditions, not only is a strong reversed electroosmotic flow generated in the coated capillary but the adsorption of analytes on the inner wall of the capillary is also efficiently eliminated. It has been demonstrated that the Lupamin-coated capillary can be used to advantage for the rapid analysis of amino acids, peptides, and proteins with good resolution and peak shape by capillary electrophoresis. In order to evaluate the basic feature of a Lupamin-coated capillary, electroosmotic flows generated by a Lupamin coating layer under different conditions including pH, coating time, concentration, and the composition of electrolytes on Lupamin-coated and uncoated capillaries were investigated. Furthermore, electrospray ionization-mass spectrometry (ESI-MS) detection was carried out for the analysis of amino acids and peptides.  相似文献   

15.
Herein, we report on the functionalization of silica nanoparticles with a small molecule, the amino acid cysteine, in order to create a low-fouling zwitterionic surface for nanomedicine applications. The cysteine functionalization was shown to impart the particles with excellent stability in both salt and single-protein solutions of lysozyme (positively charged) and bovine serum albumin (negatively charged). Bare silica particles precipitated immediately in a lysozyme solution, while cysteine-functionalized particles were stable for 20 h. Furthermore, the particles displayed excellent long-term stability in solutions of human serum showing no aggregation over a period of 14 days. The functionalized particles also possess multiple reactive surface groups for further coupling reactions. We believe that the surface functionalization schemes described in this report represent a versatile and effective method of stabilizing nanoparticle systems in biological media for their use in a variety of therapeutic and diagnostic applications.  相似文献   

16.
ζ-potential measurements on LUVs allow to evidence the influence of pH, ionic salt concentration, and polyelectrolyte charge on the interaction between polyelectrolyte (chitosan and hyaluronan) and zwitterionic lipid membrane. First, chitosan adsorption is studied: adsorption is independent on the chitosan molecular weight and corresponds to a maximum degree of decoration of 40% in surface coverage. From the dependence with pH and independence with MW, it is concluded that electrostatic interactions are responsible of chitosan adsorption which occurs flat on the external surface of the liposomes. The vesicles become positively charged in the presence of around two repeat units of chitosan added per lipid accessible polar head in acid medium down to pH = 7.2. Direct optical microscopy observations of GUVs shows a stabilization of the composite liposomes under different external stresses (pH and salt shocks) which confirms the strong electrostatic interaction between the chitosan and the lipid membrane. It is also demonstrated that the liposomes are stabilized by chitosan adsorption in a very wide range of pH (2.0 < pH < 12.0). Then, hyaluronan (HA), a negatively charged polyelectrolyte, is added to vesicles; the vesicles turn rapidly negatively charged in presence of adsorbed HA Finally, we demonstrated that hyaluronan adsorbs on positively charged chitosan-decorated liposomes at pH < 7.0 leading to charge inversion in the liposome decorated by the chitosan-hyaluronan bilayer. Our results demonstrate the adsorption of positive and/or negative polyelectrolyte at the surface of lipidic vesicles as well as their role on vesicle stabilization and charge control.  相似文献   

17.
A hydrophobic 96‐well multiplate was incubated with aqueous poly(uridine 5′‐p‐styrenesulfonate) (PUSS). Analysis of the PUSS‐coated surface indicated that the surface incubated at higher polymer concentration (50 mg·mL–1) was hydrophilic while the surface incubated at lower polymer concentration (1 mg·mL–1) was hydrophobic. Adhesion of 3T3‐L1, which has GalTase on the cell membrane, on the hydrophobic PUSS‐coated surface was greater than on the non‐coated surface. 3T3‐L1 adhesion on the hydrophilic PUSS‐coated surface was even greater. On the other hand, the adhesion of HeLa cells, which did not show GalTase on the cell membrane, on the hydrophilic surface was quite weak. It may well be said that the 3T3‐L1 adhesion on the hydrophilic PUSS‐coated surface was GalTase‐mediated.  相似文献   

18.
ABSTRACT

It is our concept to use a polymer as a hydrophilic cushion to stabilize a lipid bilayer on a solid support. This can be accomplished by using polyacrylamides with disulfides and DMPE anchors as a hydrophilic cushion. These polymers have the additional functionalities to chemisorb on gold surfaces through the disulfides and to bind a lipid bilayer on it through the insertion of the lipid anchors into the lipid bilayer. This paper shows that a polymer with the additional functionality of charged groups increases the attraction of vesicles to form a tethered supported lipid bilayer. By varying the amount of charged groups in the polymer, we are able to control the hydrophilic behavior of the polymer and therefore are able to change the wetting on a surface. This was examined by measuring the contact angles. Using the technique of the surface plasmon spectroscopy, we are able to monitor the process of vesicle fusion on the polymer support.  相似文献   

19.
For the first time the four block copolymers derived from 1-alkyl[2-(acryloyloxy)ethyl]dimethylammonium bromides with hexyl (ADA) or cetyl (ADHA) groups and 2-hydroxyethylacrylate (HEA) or N-isopropylacrylamide (NIPAM) were synthesized and employed for functionalization of monodisperse iron oxide nanoparticles (NPs). The polyADA (pADA) or polyADHA (pADHA) block consists of long hydrophobic tails (C(6) or C(16)) connected to a positively charged quaternary ammonium group, making this block amphiphilic. The second block was either fully hydrophilic (pHEA) or thermoresponsive (pNIPAM). The dependence of the NP coating on the length of the hydrophobic tail in the amphiphilic block, the composition of the hydrophilic block, and the NP sizes have been studied. Unusual self-assembling of iron oxide NPs into well-defined composite submicrometer particles was observed for pADHA-b-pNIPAM in the wide range of concentrations (at the pADHA repeating unit concentrations of 0.065 × 10(-2)-2.91 × 10(-2) mmol/mL per 1 mg/mL NPs) but only two concentrations, 1.62 × 10(-2) and 1.94 × 10(-2) mmol/mL, led to regular spherical particles. The thermoresponsive behavior of these composite particles was tested using ζ-potential and dynamic light scattering measurements, while the morphology of particles was characterized by transmission electron microscopy. Coating of NPs with pADHA-b-pHEA results in the formation of individually coated NPs. The different composite particle morphologies are explained by different properties of pHEA and pNIPAM. It is demonstrated that the composite particles based on pADHA-b-pNIPAM are responsive to a magnetic field and can be recommended as magnetic stoppers in biorelated membrane separations. The incorporation of Pd species in submicrometer particles makes them promising candidates for catalytic applications as magnetically recoverable catalysts with a high magnetic response.  相似文献   

20.
A model study was investigated to develop colloidal supramolecular assemblies consisting of particles coated with lipid layers. The interactions between monodisperse sulfate-charged poly(styrene) submicrometer particles and zwitterionic/cationic lipid vesicles composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine and 1,2-dipalmitoyl-3-trimethylammonium propane were considered. The influence of relevant experimental parameters on the final associations was examined by quasi-elastic light scattering to point out some new phenomena occurring in these colloidal systems. The major role of electrostatic interactions as driving forces to control the organization between cationic lipids and oppositely charged poly(styrene) particles was clearly evident, whereas this influence was less pronounced when considering the zwitterionic lipids. The characterization of these original complex assemblies was completed by a thorough study of the surface modification. The combination of zeta potential measurements, X-ray photoelectron spectroscopy analyses, and microscopy observations proved that the envisioned model can really correspond to polymer particles surrounded by lipids.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号