Hydrophilization of gigaporous polystyrene microspheres with saccharide as high-speed protein chromatography base support

Gigaporous poly(styrene–divinylbenzene) (PS) microspheres were hydrophilically modified with natural saccharide to minimize their nonspecific adsorption to proteins. The microspheres were chloroacetylated through Friedel–Crafts acetylation with chloroacetyl chloride, and then coupled with diacetone-D-glucose (DAGlu) through the Williamson reaction, and the protecting groups were removed on DAGlu. Results showed that the PS microspheres were successfully coupled with DAGlu and that the gigaporous structure was well maintained. After hydrophilization (Glu-PS), nonspecific adsorption of proteins on PS microspheres was greatly reduced. The high surface density of hydroxyl groups on Glu-PS microspheres surface make it easy to derivatize the spheres by classical methods. Flow experiments showed that the Glu-PS column had low backpressure, good permeability, and mechanical stability. All results indicate that the Glu-PS microspheres have great potential applications in high-speed protein chromatography.     

Surface DEAE groups facilitate protein transport on polymer chains in DEAE‐modified‐and‐DEAE‐dextran‐grafted resins

Sepharose FF was modified with diethylaminoethyl‐dextran (DEAE‐dextran, DexD) and/or DEAE (D) to fabricate three types of ion exchangers FF‐DexD (grafting‐ligand resin), FF‐D (surface‐ligand resin), and FF‐D‐DexD (mixed‐ligand resin), for protein adsorption equilibria and kinetics study. It was found that both adsorption capacity and uptake rate (effective diffusivity, D_e) were significantly enhanced by grafting DEAE‐dextran. Notably, the D_e values on FF‐DexD and FF‐D‐DexD (D_e/D₀ > 1.4) were six times greater than those on FF‐D (D_e/D₀ < 0.3). More importantly, the increase of surface‐ligand density greatly enhanced uptake kinetics on FF‐D‐DexD. The results indicate that the surface ligands assisted the transport of bound proteins on polymer chains in the mixed‐ligand resins. That is, surface ligands worked as “transfer stations” between two neighboring chains, resulting in enhanced transport of bound proteins on chains. The research thus disclosed the unique role of surface ligands in facilitating protein uptake kinetics onto polymer‐grafted ion‐exchangers. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3812–3819, 2016     

Heterocoagulation behavior of carbon black with surface encapsulation through emulsion polymerization

Nanocomposite microspheres containing styrene–acrylate resin, wax, and carbon black (CB) with desired CB dispersion were prepared through heterocoagulation. The CB surface was modified using conventional anionic emulsifier and anionic dispersants with different lengths of nonionic chains and reactivities or through polymer encapsulation via emulsion polymerization to regulate the dispersion and concentration of CB in the microspheres. Experimental results showed that anionic dispersants with long nonionic chains effectively dispersed and stabilized CB particles. Polystyrene (PS) was then encapsulated on the CB surface by using a reactive dispersant and a water‐soluble initiator of polymerization. The CB particles exhibited comparable pH stability with other heterocoagulation components. Overall, encapsulation through emulsion polymerization can be used to obtain not only high CB content but also improved CB distribution in the resulting microspheres. High coagulation efficiency can also be achieved using polystyrene‐encapsulated dispersed CB because of its high affinity to emulsifiers and reactive dispersants during dispersion. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43516.     

Preparation and characterization of magnetic poly(styrene–glycidyl methacrylate) microspheres for highly efficient protein adsorption by two‐stage dispersion polymerization

Micrometer‐sized superparamagnetic poly(styrene–glycidyl methacrylate)/Fe₃O₄ spheres were synthesized by two‐stage dispersion polymerization with modified hydrophobic Fe₃O₄ nanoparticles, styrene (St), and glycidyl methacrylate (GMA). The morphology and properties of the magnetic Fe₃O₄–P (St‐GMA) microspheres were examined by scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometry, thermogravimetric analysis, and attenuated total reflectance. The average size of the obtained magnetic microspheres was 1.50 μm in diameter with a narrow size distribution, and the saturation magnetization of the magnetic microspheres was 8.23 emu/g. The magnetic Fe₃O₄–P (St‐GMA) microspheres with immobilized iminodiacetic acid–Cu²⁺ groups were used to investigate the adsorption capacity and selectivity of the model proteins, bovine hemoglobin (BHb) and bovine serum albumin (BSA). We found that the adsorption capacity of BHb was as high as 190.66 mg/g of microspheres, which was 3.20 times greater than that of BSA, which was only 59.64 mg/g of microspheres as determined by high‐performance liquid chromatography. With a rather low nonspecific adsorption, these microspheres have great potential for protein separation and purification applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43005.     

大豆7S球蛋白与葡聚糖共价键合纳米凝胶的制备与表征

基于蛋白质与多糖的Maillard反应与自组装制备一种新型的绿色的具备核壳结构的纳米凝胶。利用干热反应制备大豆7S球蛋白与葡聚糖的共价接枝物（soy β-conglycinin-dextran conjugates,SDC）,通过对SDC热处理使其自组装成大豆7S球蛋白-葡聚糖纳米凝胶（soy β-conglycinin-dextran nanogels,SDN）,对其形貌、结构及性质进行分析,并利用多糖的空间位阻效应抑制蛋白质宏观过度聚集的理论指导,探讨尺寸均一SDN的形成机制。形貌学与zeta电位分析表明SDN为具备核壳结构的球状粒子,其外壳由亲水性的葡聚糖构成,内核由凝胶化的蛋白构成;表面疏水性分析表明内核蛋白的三级结构发生转变,疏水基团暴露,从而形成多个疏水空腔;稳定性分析表明SDN具有高度的pH稳定性与储存稳定性,对疏水活性物质的输送载体构建具有重要的借鉴意义。     

Adsorption of trypsin onto poly(2-hydroxyethyl methacrylate)/polystyrene composite microspheres and its enzymatic activity

Poly(2-hydroxyethyl methacrylate)/polystyrene (PHEMA/PS) composite microspheres were produced by emulsifier-free seeded emulsion polymerization for styrene in the presence of PHEMA seed particles. Effects of the surface characteristics of the PHEMA/PS composite microspheres on the adsorption immobilization of trypsin and on its enzymatic activity were discussed. Above 5 mol% of HEMA content, trypsin molecules adsorbed had high activity, 65–100% of the activity of free trypsin. The excellence of the composite microspheres as a carrier for trypsin seems to be closely related with the surface heterogeneity consisting of both hydrophilic and hydrophobic parts.     

Synthesis of PS‐g‐POSS hybrid graft copolymer by click coupling via ”graft onto” strategy

Polystyrene (PS)‐incorporated polyhedral oligomeric silsesquioxanes (POSS) organic–inorganic hybrid graft copolymer could be achieved by click coupling reaction between alkyne groups in POSS and azido groups in PS via “graft onto” strategy. Alkyne‐functionalized POSS was synthesized via thiol‐ene facile click reaction and subsequent amidation reaction with very high yield. Azido‐multifunctionalized PS could be synthesized by chloromethylation and subsequent azido reaction. The chemical structures of PS‐(CH₂Cl)_m, PS‐(CH₂N₃)_m, and PS‐g‐POSS were determined by Fourier transform infrared and ¹H NMR characterization. PS‐g‐POSS presented a better hydrophobic property with contact angle of 113° than that of PS (85°). And PS‐g‐POSS with ≤5% of grafting degree had lower glass transition temperature (T_g) than that of PS and then it increased up to 112°C with grafting degree. An obvious aggregation of POSS phase with 10–80 nm in size was formed in PS‐g‐POSS matrix. In addition, 5 wt % of PS‐g‐POSS was added to general purpose polystyrene (GPPS) to remarkably improve its tensile strength from 45 to 57 MPa. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Macroporous crosslinked hydrophobic/hydrophilic polystyrene/polyamide interpenetrating polymer network: Synthesis,characterization, and adsorption behaviors for quercetin from aqueous solution

In the present study, a novel hydrophobic/hydrophilic polystyrene/polyamide interpenetrating polymer network (PS/PAM IPN) was synthesized and its molecular structure was characterized by Fourier transform infrared ray (FT‐IR) spectrum, chemical analysis, swelling test, and N₂ adsorption‐desorption experiment. The obtained PS/PAM IPN was employed as a polymeric adsorbent to adsorb quercetin from aqueous solution, and the adsorption thermodynamics were calculated according to thermodynamic equations. It was found that no chemical bond was formed between PS and PAM and PS/PAM IPN held characters of amphiphilic polymer network (APN). The adsorption isotherms could be well fitted by Freundlich isotherm, and the adsorption was shown to be an exothermic, spontaneous, and more ordered process. The total adsorption capacity from the column adsorption experiment was measured to be 8.6 mg/mL wet resin, and the adsorbed quercetin on PS/PAM IPN could be easily desorbed by 10% of hydrochloric acid‐ethanol. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Grafting of poly[styrene‐co‐N‐(4‐vinylbenzyl)‐N,N‐diethylamine] polymer film onto the surface of silica microspheres and their application as an effective sorbent for lead ions

Amino containing polymer of poly[styrene‐co‐N‐(4‐vinylbenzyl)‐N,N‐diethylamine] (PS‐co‐PVEA) was successfully grafted onto the surface of silica microspheres via the seed dispersion polymerization of styrene and N‐(4‐vinylbenzyl)‐N,N‐diethylamine in the presence of divinylbenzene employing the 3‐(methacryloxy)propyltrimethoxysilane activated silica microspheres as the seed. The polymerization led to thin chelating polymer films (30 nm) coated silica microspheres (silica@polymer) as determined by transmission electron microscopy. The synthesized silica@polymer composites were used as sorbents for lead ions (Pb²⁺). The adsorption properties, such as the pH effect, the adsorption kinetic, adsorption isotherm as well as the reuse of the silica@polymer sorbent were evaluated. The results demonstrated that the optimized adsorption condition was under neutral and the silica@polymer sorbent was efficient since it showed higher adsorption amounts (8.0 mg/g) and shorter adsorption equilibrium time (8 h) than that of the PS‐co‐PVEA microspheres and the pristine silica microspheres. Moreover, the silica@polymer sorbent was reusable even after four cycles of adsorption. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39973.     

Preparation and protein adsorption of hydrogel polysucrose microspheres

A series of novel hydrogel polysucrose microspheres with the mean size ranging from 200 to 500 μm were prepared via two‐step method. First, soluble polysucrose was synthesized by solution polymerization between sucrose and epichlorohydrin; second, a reversed phase suspension crosslinking reaction was performed to prepare polysucrose microspheres. The SEM images indicated that these spherical beads had smooth surface and hydrogel interior structure. FTIR was used to characterize the chemical structure of the beads. The hydrated and dry densities, equilibrium water content, and hydroxyl content of polysucrose microspheres were also investigated. The characteristic of high hydroxyl content (15.48–19.04 mmol/g) make these microspheres suitable for protein adsorption. Meanwhile, bovine serum albumin was used to examine the adsorption capacity of the microspheres. These microspheres had a capacity as high as 49.28 mg/g. The adsorption kinetics and recycling of the beads were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5934–5940, 2006     

多孔聚(甲基丙烯酸环氧丙酯-二乙烯基苯)微球的改性及作为蛋白质疏水层析介质的应用

用悬浮聚合方法合成了富含环氧基团的多孔聚(甲基丙烯酸环氧丙酯-二乙烯基苯) [Poly(Glycidyl Methacrylate-Divinylbenzene), P(GMA-DVB)]微球,为了消除其对蛋白质的不可逆吸附,探索用聚乙二醇(Polyethylene Glycol, PEG)对微球进行改性,制备了带有PEG配基的P(GMA-DVB)微球. 实验考察了反应条件对PEG固载量的影响规律,发现最适反应温度为80℃. 以牛血清白蛋白(Bovine Serum Albumin, BSA)和胰蛋白酶作为模型蛋白,考察了PEG改性前后P(GMA-DVB)微球对蛋白质的吸附性能. 改性前P(GMA-DVB)微球有30%~40%的不可逆吸附,蛋白质回收率仅为60%~70%. 改性后介质消除了不可逆吸附,对蛋白质的吸附作用表现为可逆的疏水相互作用,吸附BSA和胰蛋白酶的质量回收率和活性回收率都在97%以上. 结果表明,PEG-P(GMA-DVB)微球可以作为一种新型介质进一步应用于蛋白质的吸附与分离.     

Full factorial design‐of‐experiments for preparation of crosslinked dextran microspheres

This work describes full factorial design‐of‐experiment methodology for exploration of effective parameters on physical properties of dextran microspheres prepared via an inverse emulsion (W/O) technique. Microspheres were prepared by chemical crosslinking of dextran dissolved in internal phase of the emulsion using epichlorohydrin. The input parameters were dextran concentration in the aqueous phase, crosslinking ratio, and concentrations of sodium hydroxide and span 80 as the reaction catalyst and surfactant, respectively. Chemical structure of the resulting microspheres was analyzed spectroscopically using Fourier‐transform infrared technique. Final decomposition temperature, mean particle size and its distribution and equilibrium swelling ratio were selected as output responses. Microspheres with smooth surface were obtained according to scanning electron micrographs. It was found that an increase in dextran concentration in the aqueous internal phase increases mean particle diameter of the resulting microspheres, significantly. Moreover, water uptake capacity for the microspheres was dependent on both the dextran concentration and crosslinking ratio. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of polyaniline coated polystyrene‐poly(styrene‐co‐sodium 4‐styrenesulfonate) microparticles and the further fabrication of hollow polyaniline microspheres

In this article, the microparticles of polystyrene‐poly(styrene‐co‐sodium 4‐styrenesulfonate) (PS‐PSS) coated by polyaniline (PANI) were prepared and hollow PANI microspheres were further obtained by dissolving the core. First, surface‐sulfonated monodispersed PS was prepared by copolymerization of sodium 4‐styrenesulfonate (SSS) and styrene with dispersion polymerization method. Then aniline was polymerized on the surface of the surface‐sulfonated PS (PS‐PSS) by chemical oxidative polymerization. After purification, we prepared core‐shell (PS‐PSS)/PANI particles. Hollow PANI microspheres were prepared by dissolving the plastic PS core of the (PS‐PSS)/PANI particles in chloroform. The growth process of PANI on the surface of PS‐PSS particles was investigated and the hollow PANI microspheres were characterized. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Photopatterning and degradation study of dextran‐glycidyl methacrylate hydrogels

An approach to synthesizing photopatternable enzymatic degradable dextran hydrogel is presented. The glycidyl methacrylate derivatized dextran (Dex‐GMA) was first prepared by reacting dextran with glycidyl methacrylate at 45°C with grafting efficiency of 10%. The degree of substitution (DS) was confirmed by ¹H‐NMR. Next, Dex‐GMA hydrogels were prepared by crosslinking in the presence of a crosslinker: N,N′‐ methylene‐bisacrylamide (NMBA), and a photoinitiator: 2,2′‐dimethoxy‐2‐phenyl acetophenone (DMPA) in dimethyl sulfoxide (DMSO) solution. Further, the Dex‐GMA hydrogels were photopatterned using liquid‐phase photopolymerization (LP³) technique. The structure size ranged from 5 mm to 300 μm and three different shapes of structures‐ ‐ —round, square, and star‐ ‐ —were demonstrated. The patterned Dex‐GMA hydrogel structures not only exhibited mechanical robustness but also biodegradability. The dextranase‐catalyzed degradation of Dex‐GMA hydrogels with different DS was investigated at 37°C. The morphology of the degraded Dex‐GMA hydrogels determined by SEM revealed the degree of enzymatic degradation due to dextranase. The Dex‐GMA hydrogel was fully degraded by dextranase with concentration of 2 U/ml in 5 days. The Dex‐GMA hydrogel also showed the ability to be readily integrated with microfluidics. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Zwitterionic‐polymer‐functionalized poly(vinyl alcohol‐co‐ethylene) nanofiber membrane for resistance to the adsorption of bacteria and protein

A zwitterionic poly(vinyl alcohol‐co‐ethylene) (PVA‐co‐PE) nanofiber membrane for resistance to bacteria and protein adsorption was fabricated by the atom transfer radical polymerization of sulfobetaine methacrylate (SBMA). The PVA‐co‐PE nanofiber membrane was first surface‐activated by α‐bromoisobutyryl bromide, and then, zwitterionic SBMA was initiated to polymerize onto the surface of nanofiber membrane. The chemical structures of the functionalized PVA‐co‐PE nanofiber membranes were confirmed by attenuated total reflectance–Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. The morphologies of the PVA‐co‐PE nanofiber membranes were characterized by scanning electron microscopy. The results show that the poly(sulfobetaine methacrylate) (PSBMA) was successfully grafted onto the PVA‐co‐PE nanofiber membrane, and the surface of the nanofiber membrane was more hydrophilic than that of the pristine membrane. Furthermore, the antibacterial adsorption properties and resistance to protein adsorption of the surface were investigated. This indicated that the PSBMA‐functionalized surface possessed good antibacterial adsorption activity and resistance to nonspecific protein adsorption. Therefore, this study afforded a convenient and promising method for preparing a new kind of soft and nonwoven dressing material with antibacterial adsorption and antifouling properties that has potential use in the medical field. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44169.     

How to circumvent untoward drug crystallization during emulsion‐templated microencapsulation process

Unwanted drug crystals often form on the surface of PLGA microspheres or in an aqueous phase when a hydrophobic drug undergoes emulsion‐templated microencapsulation processes. In our study, over 70% of progesterone crystallizes in the aqueous phase when microencapsulation proceeds with a typical oil‐in‐water solvent evaporation process. During filtration employed for microsphere recovery, unentrapped drug crystals are collected alongside with progesterone‐containing microspheres. This phenomenon accompanies unfavorable consequences on the microsphere quality. In contrast, when microspheres are prepared with a new solvent extraction‐evaporation hybrid process, it is possible to completely avoid drug crystallization. Consequently, the new microencapsulation technique yields high drug encapsulation efficiencies of ≥ 90.8%, and the resultant microspheres show a homogeneous size distribution pattern. Also, the microsphere surface is free of drug crystals. For loading hydrophobic drugs into PLGA microspheres, the new microencapsulation process reported in this study has distinct advantages over commonly used emulsion‐templated solvent evaporation processes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43768.     

Protein‐imprinted polyurethane‐grafted calcium alginate hydrogel microspheres

Protein‐imprinted polyurethane‐grafted calcium alginate hydrogel microspheres were prepared and characterized. The samples were investigated with optical microscopy, scanning electron microscopy, ¹³C‐NMR, and Fourier transform infrared spectroscopy. We proved that polyurethane side chains were successfully grafted, and this led to a relatively rough and dense surface. The samples exhibited better swelling durability when applied in specific adsorption tests. The adsorption kinetic and recognition properties indicated that the imprinted modified microspheres had excellent rebinding affinity toward the target proteins. Moreover, the influence of the preassembly pH, rebinding pH, and grafting ratio on the adsorption capacity and imprinting efficiency (IE) were systematically investigated. The study results suggest that the modified samples possessed a higher IE toward the target protein under the optimum pH and grafting ratio. Upon polyurethane grafting modification, the alginate hydrogel microspheres showed improved mechanical stability and recognition specificity. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42140.     

Hydrogels from dextran and soybean oil by UV photo‐polymerization

In this work, hydrogels were synthesized by UV photo‐polymerization of hydrophilic dextran functionalized with acrylate groups (Dex‐A) and hydrophobic acrylate epoxidized soybean oil (AESO). The acrylation of dextran was accomplished by reacting dextran (M_w 70,000 g mol^?1) with acryloyl chloride and pyridine. The Dex‐A was characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). Five rigid hydrogels were prepared using the weight ratios of Dex‐A and AESO as 10/90, 20/80, 30/70, 40/60, and 50/50. The hydrogels were characterized by FTIR, thermal gravimetric analyses (TGA) and scanning electronic microscopy (SEM). The experimental results demonstrated that the swelling and release profiles of the Dex‐A/AESO hydrogels can be tailored by varying the ratio of Dex‐A and AESO thus varying the balance of hydrophilicity and hydrophobicity of the network structures and the crosslinking density. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41446.     

Advanced antistatic/anticorrosion coatings prepared from polystyrene composites incorporating dodecylbenzenesulfonic acid‐doped SiO2@polyaniline core–shell microspheres

We present the preparation of advanced antistatic and anticorrosion coatings of polystyrene (PS) incorporating a suitable amount of dodecylbenzenesulfonic acid (DBSA)‐doped SiO₂@polyaniline (SP) core–shell microspheres. First, aniline‐anchored SiO₂ (AS) microspheres that were about 850 nm in diameter were synthesized using the conventional base‐catalyzed sol–gel process with tetraethyl orthosilicate in the presence of N‐[3‐(trimethoxysilyl)propyl]aniline. SP core–shell microspheres were then synthesized by chemical oxidative polymerization of aniline monomers with ammonium persulfate as an oxidizing agent in the presence of the AS microspheres. The polyaniline shell thickness of the as‐prepared core–shell microspheres was estimated to be about 120 nm. The AS and SP microspheres were further characterized using Fourier transform infrared spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy. The as‐synthesized DBSA‐doped SP core–shell microspheres were then blended into PS using N‐methyl‐2‐pyrrolidone as solvent and then cast onto a cold–rolled steel (CRS) electrode to obtain antistatic and anticorrosion coatings with a thickness of about 10 µm. The corrosion protection efficiency of the as‐prepared coating materials on the CRS electrode was investigated using a series of systematic electrochemical measurements under saline conditions. The enhanced corrosion protection ability of the PS/SP composite coatings may be attributed to the formation of a dense passive metal oxide layer induced by the redox catalytic effect of the polyaniline shell of the as‐synthesized core–shell microspheres, as evidenced by electron spectroscopy for chemical analysis and SEM observations. Moreover, the PS composite coating containing 10 wt% of the SP core–shell microspheres showed an electrical resistance of about 3.65 × 10⁹Ω cm^?2, which meets the requirements for antistatic applications. Copyright © 2012 Society of Chemical Industry     

等离子体引发微孔板接枝SMCC及蛋白吸附性能

用丙烯酰胺等离子体引发活化聚苯乙烯（PS）微孔板，接枝4-(N-马来酰亚胺基甲基)环己 烷-1-羧酸琥珀酰亚胺酯（SMCC）联接剂，制备了易于固定蛋白的PS-g-SMCC微孔板。利用FTIR、EDS、XPS、SEM、接触角测试仪和酶标仪对其表面组成、结构、形貌及蛋白吸附性能进行了表征。结果表明，PS微孔板表面成功接枝了丙烯酰胺与SMCC，当等离子体处理参数为500 W，300 s时，接枝丙烯酰胺的效果最好，PS-g-SMCC微孔板表面达到超亲水；当SMCC质量浓度为5 g/L 时，PS-g-SMCC微孔板对牛血清蛋白的吸附量最大，为903.08 ng/cm2，与未处理的PS微孔板相比，吸附量提高了2.93倍，有效提高了PS微孔板的检测灵敏性。