Functionalized SBA-15 materials as carriers for controlled drug delivery: influence of surface properties on matrix-drug interactions

Mesoporous SBA-15 materials were functionalized with amine groups through postsynthesis and one-pot synthesis, and the resulting functionalized materials were investigated as matrixes for controlled drug delivery. The materials were characterized by FTIR, N(2) adsorption/desorption analysis, zeta potential measurement, XRD, XPS, and TEM. Ibuprofen (IBU) and bovine serum albumin (BSA) were selected as model drugs and loaded onto the unmodified and functionalized SBA-15. It was revealed that the adsorption capacities and release behaviors of these model drugs were highly dependent on the different surface properties of SBA-15 materials. The release rate of IBU from SBA-15 functionalized by postsynthesis is found to be effectively controlled as compared to that from pure SBA-15 and SBA-15 functionalized by one-pot synthesis due to the ionic interaction between carboxyl groups in IBU and amine groups on the surface of SBA-15. However, SBA-15 functionalized by one-pot synthesis is found to be more favorable for the adsorption and release of BSA due to the balance of electrostatic interaction and hydrophilic interaction between BSA and the functionalized SBA-15 matrix.     

人工细胞外基质对血管内皮细胞生存的影响

通过物理吸附方法, 利用胶原、 聚赖氨酸和融合蛋白VEGF-Fc对聚苯乙烯培养板表面进行改性, 以研究细胞外基质材料对血管内皮细胞的影响. 结果表明, 3种蛋白显著提高了聚苯乙烯表面的亲水性. 内皮细胞的黏附、 增殖、 细胞骨架蛋白染色和血管性血友病因子(vWF)免疫染色实验结果表明, 胶原、 聚赖氨酸和VEGF-Fc基质均能有效提高血管内皮细胞的黏附, 其中胶原可与VEGF协同作用促进内皮细胞分化表型的表达; VEGF-Fc基质兼具了VEGF的生物学活性, 可促进内皮细胞的黏附和增殖以及vWF功能性蛋白的表达. 本研究为诱导材料表面内皮化和血管新生的生物活性材料的设计开发提供了新思路.     

In-vitro protein interactions with a bioactive gel-glass

Recent theories suggest that the local adsorption of biologically active peptide growth factors onto the surface of an implant may contribute to the unique osteogenic nature of silica-containing bioactive ceramics. A sol-gel derived glass is used as a model of the in-vivo reaction product of 45S5 bioactive glass at relatively short times (<48 hrs.) to investigate protein adsorption/desorption behavior. The adsorption kinetics of three heme-class proteins (cytochrome c, myoglobin, and hemoglobin) are measured spectroscopically. The rate of adsorption is shown to increase with average pore size, which is determined by the silica content of the gel. Adsorption rate decreases as protein size is increased and as solution pH is decreased. Biological function of an adsorbed peroxidase enzyme on pre-reacted Bioglass^® is shown to be retained. Desorption during physiologic conditions is shown to be linear with time and pH dependant, while independent of gel bioactivity.     

Laser desorption/ionization mass spectrometry on porous silica and alumina for peptide mass fingerprinting

We investigated a variant of desorption/ionization on porous silicon (DIOS) mass spectrometry utilizing an aqueous suspension of either porous silica gel or porous alumina (pore size of 60 and 90 A, respectively). Laser desorption/ionization (LDI) from samples directly deposited on a stainless steel surface without any inorganic substrates was also achieved. Synthetic peptides designed to cover large sequence diversity constituted our model compounds. Sample preparation, including material conditioning, peptide solubilization, and deposition protocol onto standard matrix-assisted laser desorption/ionization (MALDI) probe, as well as ionization source tuning were optimized to perform sensitive reproducible LDI analyses. The addition of either a cationizing agent or an alkali metal scavenger to the sample suspension allowed modification of the ionization output. Comparing hydrophilic silica gel to hydrophobic reversed-phase silica gel as well as increasing material pore size provided further insights into desorption/ionization processes. Furthermore, mixtures of peptides were analyzed to probe the spectral suppression phenomenon when no interfering organic matrix was present. The results gathered from synthetic peptide cocktails indicated that LDI mass spectrometry on silica gel or alumina constitutes a promising complementary method to MALDI in proteomics for peptide mass fingerprinting.     

Novel column-based protein refolding strategy using dye-ligand affinity chromatography based on macroporous biomaterial

A novel column-based chromatographic protein refolding strategy was developed using dye-ligand affinity chromatography (DLAC) based on macroporous biomaterial. Chitosan–silica (CS–silica) biomaterial with macroporous surface was used as the supporting matrix for the preparation of the DLAC material. The dye-ligand Cibacron Blue F3GA (CBF) was selected as affinity handle and could be covalently immobilized to form dye-ligand affinity adsorbent (CBF–CS–silica) using the reactivity of NH₂ on CS–silica biomaterial. After the model protein catalase was denatured with 6 mol/L urea, the denaturant could be rapidly removed and catalase could be successfully refolded as facilitated by the adsorption of CBF–CS–silica. The urea denaturation process and the elute condition for the chromatographic refolding were optimized by measuring tryptophan fluorescence and activity of catalase. The refolding performance of the proposed DLAC was compared with dilution refolding. The protein concentration during the proposed chromatographic refolding increased by a factor of 20 without reducing the yield achieved as compared to dilution refolding. The column-based protein refolding strategy based on dye-ligand affinity chromatography with porous biomaterial being matrix possessed potential in chromatographic refolding of protein.     

Molecularly imprinted polymeric shell coated monodisperse‐porous silica microspheres as a stationary phase for microfluidic boronate affinity chromatography

Molecular imprinting of cis‐diol functionalized agents via boronate affinity interaction has been usually performed using nanoparticles as a support which cannot be utilized as a stationary phase in continuous microcolumn applications. In this study, monodisperse‐porous, spherical silica particles in the micron‐size range, with bimodal pore diameter distribution were selected as a new support for the synthesis of a molecularly imprinted boronate affinity sorbent, using a cis‐diol functionalized agent as the template. A specific surface area of 158 m²/g was achieved with the imprinted sorbent by using monodisperse‐porous silica microspheres containing both mesoporous and macroporous compartments as the support. High porosity originating from the macroporous compartment and sufficiently high particle size provided good column permeability to the imprinted sorbent in microcolumn applications. The mesoporous compartment provided a large surface area for the parking of imprinted molecules while the macroporous compartment facilitated the intraparticular diffusion of imprinted target within the microsphere interior. A microfluidic boronate affinity system was first constructed by using molecularly imprinted polymeric shell coated monodisperse‐porous silica microspheres as a stationary phase. The synthetic route for the imprinting process, the reversible adsorption/ desorption behavior of selected target and the selectivity of imprinted sorbent in both batch and microfluidic boronate affinity chromatography systems are reported.     

Dynamic Adsorption and Desorption Behaviors of Cu(II), Ag(I), and Au(III) on Silica Gel Microspheres Encapsulated by Salicylic Acid–Functionalized Polystyrene

Composite material silica gel microspheres encapsulated by salicylic acid functionalized polystyrene(SG–PS–azo–SA) have been synthesized, and the dynamic adsorption and desorption properties of this silica gel matrix inorganic–organic composite material for Cu(II), Ag(I), and Au(III) have been investigated. The results displayed that SG–PS–azo–SA had excellent adsorption for Cu(II), and the film diffusion dominated the adsorption process of SG–PS–azo–SA for Cu(II), Ag(I), and Au(III). These metal ions could be desorbed with the eluent solution of 2.5 mol/L HCl, 3% thiourea in 0.5 mol/L HCl, and 0.5% thiourea in 1 mol/L HCl, respectively. When the elution was carried out for 30 min, 30 min, and 132 min, the desorption ratio ω could reach 91.1%, 99.4%, and 60.84%, respectively. Thus, silica gel encapsulated by polystyrene coupled with salicylic acid (SG–PS–azo–SA) is favorable and useful for the removal of metal ions Cu(II), Ag(I), and Au(III), and the high adsorption capacity make it a promising candidate material for the metal ions removal.     

Surface precipitation of highly porous hydrotalcite-like film on Al from a zinc aqueous solution

A hydrotalcite-like film has been successfully deposited on an Al-bearing glass substrate based on an interface reaction between an Al layer and a zinc aqueous solution. The film selectively grew on the Al surface but not on the glass surface. The film on Al was composed of layered nanosheets of a hydrotalcite-like compound containing Al and Zn. Comparably, deposits on the plastic surface and precipitates in solution were wurzite-type ZnO with various morphologies depending upon the preparation conditions. At low supersaturation degrees, single crystals and superstructures of Zn-Al hydrotalcite were also obtained. This porous hydrotalcite film has a potential application as catalyst supports, environmental materials, or matrixes for hydrotalcite-based nanocomposite films. Using Al as a reaction interface makes it easy to coat porous hydrotalcites on a series of matrix materials varying in shapes and properties, which is important for achieving practical applications. In addition, the method developed should be widely applicable to other systems for the preparation of porous or oriented hydrotalcite-like thin films by an appropriate combination of divalent/trivalent solution-substrate systems.     

负载氯的分级多孔炭制备及其脱汞性能的研究

以纳米碳酸钙为模板,水稻秸秆为碳前驱体,采用共热解法制备了负载氯的分级多孔生物质炭。在模拟烟气条件下,利用固定床实验台架研究了生物质碳材料对烟气中的单质汞（Hg⁰）的脱除性能。采用扫描电镜（SEM）、透射电镜（TEM）、N₂吸附-脱附（BET）、程序升温脱附（Hg-TPD）以及X射线光电子能谱（XPS）等方法对材料进行表征。结果表明,盐酸浸渍不仅可去除模板产物生成多孔结构,并且有效地将氯负载到材料表面。负载氯的分级多孔炭B1C1-Cl2的比表面积和总孔容分别达到398.1 m²/g和0.4923 cm³/g。在120℃,空速（GHSV）为225000 h^-1时,脱汞效率可达95%。多孔结构有利于气体扩散,高比表面积为材料提供了更多的反应位点,微孔-介孔内表面上的C-Cl共价键为脱汞的主要化学吸附活性位点。     

A comprehensive study of concepts and phenomena of the nonspecific adsorption of beta-lactoglobulin.

We investigate nonspecific protein adsorption processes by comparing experimentally measured adsorption kinetics of beta-lactoglobulin with mathematical models. The adsorption and desorption behavior of this protein on a hydrophilic glass surface in citrate buffer (pH 3.0), monitored for a large set of different bulk concentrations (0.5x10(-8) M-1.5x10(-6) M) using a supercritical angle fluorescence (SAF) biosensor, is reported. Increasing adsorption rates and overshootings in the beginning of the adsorption are observed as well as a transition to an almost irreversibly bound state of the protein in the long term. Furthermore, rinsing experiments prove that adsorbed proteins abruptly change their desorption behavior from irreversible to reversible when a critical surface coverage theta(crit) is reached. Based on all experimental observations, a mathematical model composed of three adsorbed states differing in their surface affinity is proposed. Terms to account for lateral interactions between surface-bound proteins are included, which yield an excellent fit of the measured kinetics. For the first time, several phenomena that have been discussed in theoretical studies are confirmed by comparing experimental data with a single model.     

Research of protein adsorption on the different surface topography of the zinc oxide

The effect of the surface topography on the protein adsorption process is of great significance for designing biomaterial surfaces and the biocompatibility for specific biomedical applications. In this work, we have systematically investigated the mono‐protein adsorption kinetics of bovine serum albumin (BSA) and fibrinogen (Fg) adsorbed on the four different surface topographies (nanoparticles (NPs), nanorods (NRs), nanosheets (NSs) and nanobeams (NBs) of Zinc oxide (ZnO), respectively. The competition of multi‐protein adsorbed on them has been studied as well. Results showed that each protein had a singular process of adsorption that fitted well by Spreading Particle Model (SPM). It confirmed that ZnO NRs compared with other samples had more adsorption sites, which could provide more opportunities for the interaction between material and protein molecules. In addition, the Fg compared to the BSA could be more tightly adsorbed to the surface, both of which existed slight conformational changes by Fourier transform infrared (FTIR) and circular dichroism spectra (CD). Taken together, all these consequences well demonstrated that NRs may have wider applications in designing biomaterial surfaces and the biocompatibility for implanted biomaterials. Copyright © 2014 John Wiley & Sons, Ltd.     

A highly selective and sensitive dopamine and uric acid biosensor fabricated with functionalized ordered mesoporous carbon and hydrophobic ionic liquid

An ordered mesoporous carbon material functionalized with carboxylic acid groups was synthesized. It was characterized by powder X-ray diffraction, transmission electron microscopy, Fourier transform IR spectroscopy and N₂ adsorption/desorption. Furthermore, this material was used to modify an electrode surface combined with a hydrophobic ionic liquid. The functionalized ordered mesoporous carbon/ionic liquid gel modified electrode shows excellent electrocatalytic performances for the oxidation of dopamine, uric acid and ascorbic acid. The presence of the ionic liquid promotes the electron transfer. Linear responses for dopamine and uric acid were obtained in the ranges of 0.1 to 500 μM and from 0.1 to 100 μM with detection limits of 4.1 and 2.5 nM (signal-to-noise ratio of 3), respectively, under optimum conditions. A quick and sensitive biosensor based on functionalized ordered mesoporous carbon and an ionic liquid has been developed for the first time for the detection of dopamine and uric acid in the presence of a large amount of ascorbic acid.     

Surface modification of glass beads with poly(acrylic acid)

Non‐porous P₂ glass beads were etched with sodium hydroxide to increase the number of silanol groups that could be used to modify the surface. The etched glass beads were then functionalized with 3‐aminopropyltriethoxysilane (APS) and/or glycidoxypropyltrimethoxysilane (GPS). The surface of the glass beads were further modified with poly(acrylic acid) (PAA) by reacting the carboxyl groups on PAA with the amino groups of the pregrafted APS. The chemical modifications were characterized by FT‐IR spectroscopy, particle size analyzer and tensiometry for contact angle and porosity measurements. Five different molecular weight PAA polymers ranging from 2000 to 3,000,000 were grafted with less than expected increase of grafted PAA with molecular weight. The amount of APS and PAA on the surface was determined from thermogravimetric analysis and elemental analysis data. The surface properties of the surface modified glass beads were determined by measuring water and hexane penetration rate and contact angle. The surface morphology was examined by scanning electron microscopy. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis and Characterization of Microporous Silica Prepared with Sodium Silicate and Organosilane Compounds

Microporous silica gels were prepared in the pH range of 3–4 using sodium silicate as a silica source. Surface polarity of these gels was modified by grafting hydrophobic groups into the silica gel matrix with the help of hydrophilic solvents (acetone, acetonitrile, ethanol and methanol) and alkoxysilane compounds containing nonhydrolyzable alkyl groups. The porous framework and hydrophobicity of the silica gels were evaluated using nitrogen adsorption/desorption and water adsorption measurement techniques. All the measured isotherms were found to be type I which is indicative of microporosity. The surface area and microporosity of these samples were estimated by analyzing the measured nitrogen adsorption/desorption data using BET, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The micropore size distribution was determined from their nitrogen adsorption isotherms using the slit-pore model of the Horvath-Kawazoe equation. Silica gels with high surface area (over 500 m²/g) as well as high microporosity (over 0.2 cc/g) were obtained at gelation pH of 3.50 from the water-solvent system.     

Surface Modification of Porous Silica with Bi-thiophene Tripodal Ligand and Aplication to Adsorption of Toxic Metal Cations

The immobilization of a thiophene-based tripodal ligand, with a donor sulfur, on the surface of an epoxide group containing a silica gel phase for the synthesis of a newly functionalized material based on porous silica-bound bi-thiophene tripodal ligand (SGBT) is described. The modified silica surface was characterized by ¹³C NMR of a solid sample, elemental analysis, and infrared spectra. This new material was also studied and evaluated by determination of the surface area using the BET equation, the adsorption and desorption capability using the isotherm of nitrogen and BJH pore sizes, respectively. The target material exhibits good thermal stability as determined by thermogravimetry curves. The synthesized material was utilized in column and batch methods for adsorption of Hg²⁺, Cd²⁺, Pb²⁺, Cu²⁺, Zn²⁺, K⁺, Na⁺, and Li⁺, and the material exhibits an affinity only towards toxic heavy metals.     

微纳米多孔不锈钢表面高效吸附活性生物大分子

不锈钢(AISI 316L)是目前在医药器械中应用最为广泛的商业化材料. 下一代的不锈钢智能材料将特殊功能的生物活性分子(或纳米粒子)修饰在金属表面以模拟组织功能、提高生物/细胞相容性, 这是目前材料科学研究的热点领域之一. 本文研究了具有微纳米多孔表面结构的316L 不锈钢对抗体和生物酶分子的吸附作用,并与这些生物分子在光滑表面以及镀金表面的吸附进行了比较. 研究发现不锈钢可通过简单的电化学腐蚀方法在表面产生微纳米多孔结构. 微纳米孔不锈钢表面可稳定地吸附抗体或辣根过氧化物酶分子, 其吸附量与喷镀金表面相当或更好. 用表面活性剂(10%牛血清白蛋白(BSA)或0.2% Tween-20)洗涤不能除去吸附的蛋白.用5% Tween-20 预处理金属表面, 则可减少一半的抗体吸附量; 但表面活性剂预处理对辣根过氧化物酶的吸附没有影响. 吸附蛋白质后的金属表面湿润度大大增加; 蛋白质修饰的微纳米孔不锈钢表面表现出了很好的亲水性(水接触角小于50°), 指示了很好的生物相容性. 而金属表面的湿润度则主要取决于蛋白质物种, 并与蛋白质的吸附量正相关. 吸附于不锈钢微纳米孔表面的抗体仍保持了良好的生物活性; 用此种方式制备的抗CD34抗体修饰的不锈钢血管支架可以高密度并高选择性地吸附其目标细胞(如KG-1细胞). 本文工作为未来制备新型的无高聚物涂层的不锈钢智能医学生物材料提供了基础.     

Porous phosphate heterostructures containing CdS quantum dots: assembly, characterization and photoluminescence

The synthesis and characterization of cadmium sulphide (CdS) quantum dots, conjugated in a porous phosphate heterostructure functionalized with aminopropyl groups is described. The resulting material has fluorescence properties with maximum emission intensity at 575 nm. The fluorescent materials are not soluble in water and exhibit high stability in aqueous solution in the pH ranges from 2 to 9. Energy dispersive X-ray spectroscopy confirmed the qualitative elemental composition of the synthesized materials and X-ray photoelectron spectra showed a surface S/Cd atomic ratio of 1.09. SEM images show that the materials are amorphous, possessing porous with sizes of several tens nanometres, homogeneous and exhibit a layered morphology. The adsorption–desorption analysis by N₂ at 77 K showed the accessibility of the CdS quantum dots onto the pores of the structure. The CdS quantum dots were stabilized by mercaptopropionic acid and bounded to the host materials by amine groups.     

Enhanced Nucleation and Crystallization in PLA/CNT Composites via Disperse Orange 3 with Corresponding Improvement in Nanomechanical Properties

The potential for the material property improvement through the addition of carbon nanotubes (CNTs) in composite materials is often limited due to CNT agglomeration. In this work, Disperse Orange 3 (DO3) was investigated to determine its effectiveness in dispersing CNTs in a poly (lactic acid) (PLA) matrix. First, adsorption studies of DO3 onto CNTs were performed to determine the appropriate amount of DO3 to add so that the CNT surface will be nearly saturated with DO3 while limiting the excess DO3 dissolved in the polymer. The resultant improvements in the mechanical properties were determined via nanoindentation. Highly stable dispersion of CNTs in tetrahydrofuran with DO3 was observed 72 hours after sonication. Scanning electron microscopy confirmed that DO3‐functionalized CNTs were able to separate and disperse well inside of the PLA matrix. Addition of DO3 to the nanocomposite resulted in an increase in the glass transition temperature and crystallinity of the composite due to the more effective dispersion of the nanofiller which serves as a nucleation agent. The CNTs treated with DO3 also increased the elastic modulus and hardness of the composite compared to neat PLA and untreated PLA‐CNT composites. From this study, DO3 was demonstrated to be an effective dispersing agent in the solvent and the PLA matrix which allowed for enhanced crystallization and improved nanomechanical properties in the resultant composite.     

螺吡喃功能化UiO-66光响应吸附剂的制备及其性能

将光响应分子甲基螺吡喃SP-CH₃引入UiO-66的非极性孔笼中,构筑吸附活性位可光控调节的光响应吸附剂。SP-CH₃功能化的吸附剂完好保留了载体UiO-66的骨架和孔道结构。以阴离子染料甲基橙为探针,研究了吸附剂在不同光照条件下的吸附和解吸性能。结果表明,经紫外光照后,吸附剂对甲基橙的吸附量为41.99 mg·g^-1,相较于可见光照后样品的吸附量提升57.56%,吸附作用增强;经可见光照后,甲基橙的脱附量为81.6%。本策略通过光照刺激改变UiO-66孔笼中SP-CH₃的构型及表面电荷性质,即对吸附活性位进行光控调节,在不同光照条件下实现对吸附质的高效吸附和有效脱附。     

螺吡喃功能化UiO-66光响应吸附剂的制备及其性能

将光响应分子甲基螺吡喃SP-CH₃引入UiO-66的非极性孔笼中,构筑吸附活性位可光控调节的光响应吸附剂。SP-CH₃功能化的吸附剂完好保留了载体UiO-66的骨架和孔道结构。以阴离子染料甲基橙为探针,研究了吸附剂在不同光照条件下的吸附和解吸性能。结果表明,经紫外光照后,吸附剂对甲基橙的吸附量为41.99 mg·g^-1,相较于可见光照后样品的吸附量提升57.56%,吸附作用增强;经可见光照后,甲基橙的脱附量为81.6%。本策略通过光照刺激改变UiO-66孔笼中SP-CH₃的构型及表面电荷性质,即对吸附活性位进行光控调节,在不同光照条件下实现对吸附质的高效吸附和有效脱附。