Covalent microcontact printing of proteins for cell patterning

We describe a straightforward approach to the covalent immobilization of cytophilic proteins by microcontact printing, which can be used to pattern cells on substrates. Cytophilic proteins are printed in micropatterns on reactive self-assembled monolayers by using imine chemistry. An aldehyde-terminated monolayer on glass or on gold was obtained by the reaction between an amino-terminated monolayer and terephthaldialdehyde. The aldehyde monolayer was employed as a substrate for the direct microcontact printing of bioengineered, collagen-like proteins by using an oxidized poly(dimethylsiloxane) (PDMS) stamp. After immobilization of the proteins into adhesive "islands", the remaining areas were blocked with amino-poly(ethylene glycol), which forms a layer that is resistant to cell adhesion. Human malignant carcinoma (HeLa) cells were seeded and incubated onto the patterned substrate. It was found that these cells adhere to and spread selectively on the protein islands, and avoid the poly(ethylene glycol) (PEG) zones. These findings illustrate the importance of microcontact printing as a method for positioning proteins at surfaces and demonstrate the scope of controlled surface chemistry to direct cell adhesion.     

Advantages of Surface‐Initiated ATRP (SI‐ATRP) for the Functionalization of Electrospun Materials

Surface‐initiated atom transfer radical polymerization (SI‐ATRP) is successfully applied to electrospun constructs of poly(L ‐lactide). ATRP macroinitiators are adsorbed through polyelectrolyte complexation following the introduction of negative charges on the polyester surface through its blending with a six‐armed carboxy‐terminated oligolactide. SI‐ATRP of glycerol monomethacrylate (GMMA) or 2‐(N,N‐diethylamino)ethyl methacrylate (DEAEMA) allows then to grow surface films with controllable thickness, and in this way also to control the wetting and interactions of the construct.     

Thick Coating and Functionalization of Organic Surfaces via ATRP in Water

Atom‐transfer radical polymerization has been used for polymerizing water‐soluble monomers from solid polymeric particles, intended as a model for any polymeric functional surface. Depending on the polarity of substrate and solvent, homogeneous initiation throughout the particles or pure surface initiation could be obtained. In the last case, polymer layers were obtained with thicknesses up to several tens of microns, still active for block copolymerization.     

原子转移自由基聚合在智能型水凝胶制备中的应用

分别对原子转移自由基聚合和智能型水凝胶两者进行了综述,分析总结了利用原子转移自由基聚合制备智能型水凝胶方面的应用情况,并对其前景作了一定的展望.     

The synthesis of water‐soluble PHEMA via ARGET ATRP in protic media

2‐Hydroxyethyl methacrylate has been polymerized in methanol using activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP), to produce water‐soluble poly(2‐hydroxyethyl methacrylate) (PHEMA). The various parameters that determine control of the living polymerization have been explored. Using the Cu(II)/TPMA catalyst system (TPMA = tris(2‐pyridylmethyl)amine), controlled polymerization was achieved with Cu concentrations as low as 50 ppm relative to HEMA, with a [TPMA]/[Cu(II)] ratio of 5. Use of hydrazine as the reducing agent generally gave better control of polymerization than use of ascorbic acid. The polymerization conditions were tolerant of small amounts of air, and colorless polymers were easily isolated by simple precipitation and washing steps. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4084–4092, 2010     

One‐Reactant Photografting of ATRP Initiators for Surface‐Initiated Polymerization

Self‐initiated photografting polymerization is used to couple the polymerizable initiator monomer 2‐(2‐chloropropanoyloxy)ethyl acrylate to a range of polymeric substrates. The technique requires only UV light to couple the initiator to surfaces. The initiator surface density can be varied by inclusion of a diluent monomer or via selection of initiator and irradiation parameters. The functionality of the initiator surface is demonstrated by subsequent surface‐initiated atom transfer radical polymerization. Surfaces are characterized by x‐ray photoelectron spectroscopy (XPS), ellipsometry, and atomic force microscopy (AFM), and UV‐induced changes to the initiator are assessed by ¹H NMR and gel permeation chromatography (GPC). This is the first time this one‐reactant one‐step technique has been demonstrated for creating an initiator surface of variable density.

     

ATRP和点击化学结合法制备PDMAAm—PDMS—PDMAAm嵌段聚合物

采用原子转移自由基聚合（ATRP）法制得了端基分别为烯丙基和溴原子的聚二甲基丙烯酰胺（PDMAAm）,经叠氮基亲核取代后与端炔基聚二甲基硅氧烷进行点击反应,得到两亲三嵌段聚合物。利用^1HNMR、FTIR、GPC等测试方法对聚合物的结构进行了表征。结果表明：采用ATRP法合成的PDMAAm均聚物分子量分布较窄,通过点击化学法将热力学不相容的亲水性PDMAAm链段及疏水性聚二甲基硅氧烷（PDMS）链段制备PDMAAmPDMS—PDMAAm嵌段聚合物,是一种高效易行的方法。     

Regio‐selective peroxybromination of poly(vinyl methyl ketone) as versatile tool for generation active ATRP initiation sites on solid surfaces

Peroxybromination or so‐called radical bromination is an environmentally friendly process which involves the use of in situ generated bromine by action of hydrogen peroxide on sodium or ammonium bromide in acid medium. The reaction takes place at room temperature without eliminating hydrobromic acid and no needs the use of elemental bromine. The reaction with poly(vinyl methyl ketone) in biphasic system was demonstrated to result in quantitative bromination exclusively at the methyne carbon of the polymer. The brominated polymer was successfully used as multifunctional macroinitiator for atom transfer radical polymerization (ATRP) of styrene and MMA to give bottlebrush polymers, as evidenced by ¹H NMR and GPC. This strategy was demonstrated to provide a means of easy bromination of solid polystyrene microspheres (210–420 μm) constituting with vinyl methyl ketone copolymer segments. Bromoalkyl groups generated (1.3 mmol g^?1) in aqueous mixture were used for surface initiated ATRP of glycidyl methacrylate and styrene monomers to give dense graft chains tethered to the surfaces with hydrolysis‐proof linkages. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3892–3900     

Controlled Polymerization of Protic Ionic Liquid Monomer by ARGET‐ATRP and TERP

The direct synthesis of structurally well‐defined protic polymeric ionic liquid (PIL) with controlled molecular weight and molecular weight distribution is examined using N,N‐diethyl‐N‐(2‐methacryloylethyl) ammonium bis(tri‐fluoromethylsulfonyl)imide (DEMH‐TFSI) as a monomer. Three polymerization methods, namely, atom transfer radical polymerization (ATRP), activators regenerated by electron transfer (ARGET)‐ATRP, and organotellurium‐mediated living radical polymerization (TERP) are employed in this study. While the polymerization by ATRP is slow and does not reach high monomer conversion that under ARGET‐ATRP and TERP proceeds smoothly and affords structurally well‐defined poly(DEMH‐TFSI)s. TERP is especially efficient for the control and poly(DEMH‐TFSI)s with low to high molecular weights ( = 49 100–392 500) and narrow molecular weight distributions (/ = 1.17–1.46) are obtained. These results represent the first example of synthesis of a structurally well‐defined protic, ammonium PIL by direct polymerization of the protic ionic liquid monomer. The polymerization of N,N‐diethyl‐N‐(2‐methacryloylethyl)‐N‐methylammonium bis(trifluoromethylsulfonyl)imide (DEMM‐TFSI), which possesses a quaternary ammonium salt, also proceeds in a highly controlled manner under TERP conditions. A diblock copolymer, polystyrene‐block‐poly(DEMH‐TFSI), is also successfully synthesized by TERP.

     

Polymer Brushes via Controlled,Surface‐Initiated Atom Transfer Radical Polymerization (ATRP) from Graphene Oxide

A method for growing polymers directly from the surface of graphene oxide is demonstrated. The technique involves the covalent attachment of an initiator followed by the polymerization of styrene, methyl methacrylate, or butyl acrylate using atom transfer radical polymerization (ATRP). The resulting materials were characterized using a range of techniques and were found to significantly improve the solubility properties of graphene oxide. The surface‐grown polymers were saponified from the surface and also characterized. Based on these results, the ATRP reactions were determined to proceed in a controlled manner and were found to leave the structure of the graphene oxide largely intact.

     

ATRP与点击化学相结合制备环状聚甲基丙烯酸甲酯

利用原子转移自由基聚合(ATRP)与点击反应相结合制备环状聚合物. 根据ATRP原理, 用含端炔的有机卤化物作为引发剂时, 产物的一端为炔基, 另一端则为卤素原子, 而卤素原子本身可作为叠氮化物的原料, 从而可利用点击反应使聚合物成环.     

酶促聚合和原子转移自由基聚合“一锅法”合成嵌段聚合物及其性能表征

用酶促聚合和原子转移自由基聚合相结合的"一锅法"合成了聚甲基丙烯酸正丁酯嵌段聚10-羟基癸酸[PBMA-b-P(10-HD)],通过核磁共振(1H NMR)、傅里叶红外光谱(FTIR)和凝胶渗透色谱(GPC)对其结构以及分子量与其分子量分布进行了表征,并通过动态光散射仪(DLS)和原子力显微镜(AFM)对聚合物在水溶液中的性质进行了研究.所得嵌段聚合物纳米粒子呈球形结构,平均直径为135 nm左右.     

Kinetic studies of surface‐initiated atom transfer radical polymerization in the synthesis of magnetic fluids

We present results from kinetic studies on the surface‐initiated atom transfer radical polymerization in the preparation of polymer brush‐coated magnetic particles from a heterogeneous system. It is shown that a controlled reaction behavior and a reproducible surface functionalization with end‐tethered polymers are achieved, although the reaction advances gradually from a biphasic solid–liquid mixture to a stable colloidal dispersion of the nanoobjects. Although the initiator‐functional magnetite nanoparticles initially form a precipitate, the formation of a polymer layer on the particle surface in the course of the reaction contributes to a sterical stabilization in dispersion. We thoroughly investigated the development of the initial heterogeneous system with time and in various concentration regimes by simultaneously monitoring the monomer conversion, molar mass, the hydrodynamic diameter of the nanoobjects, and the magnetite content of the dispersions at different reaction times. The results indicate first‐order chain growth kinetics with respect to the monomer and narrow molar mass distributions, demonstrating good control on the particle architecture. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

ATRP法合成弹性蛋白接枝共聚物及其性能研究

弹性蛋白经α-溴异丁酰溴化制备了大分子ATRP引发剂溴化弹性蛋白(E-Br), 再以E-Br作为引发剂, 在CuCl/2,2-联吡啶催化体系下, 用原子转移自由基聚合方法合成了弹性蛋白-g-聚甲基丙烯酸-β-羟乙酯接枝聚合物. 用红外光谱(FTIR)、X射线光电子能谱(XPS)、热重分析(TGA)、扫描电镜(SEM)、离子色谱和动态接触角对接枝聚合物进行了表征. 结果表明, PHEMA键接到了弹性蛋白表面; SEM显示接枝改性后弹性蛋白的表面比未改性前光滑, 但改性后样品的热性能均比未改性样品的低, 起始热分解温度由改性前的307 ℃变为265 ℃; 动态接触角实验结果表明, 接枝改性后的样品具有良好的亲水性, 反应72 h后, 其前进角由接枝前的130.45°下降到29.80°.     

ATRP大分子引发剂的合成及应用

原子转移自由基聚合(ATRP)是一种新型的可控/活性聚合技术,现已广泛应用于聚合物分子结构设计、无机材料表面修饰、蛋白质检测以及生物大分子的分离和杀菌防污等.在此类反应过程中涉及的三大要素:单体、引发体系(引发剂、催化剂、配位剂)及反应介质,其中核心要素为ATRP引发剂,其结构与性质是ATRP反应成败的决定因素之一.本文在综述了小分子引发剂的种类与性质及ATRP的反应机理的基础上,着重综述了近年来官能团反应法、偶联反应法及自由基聚合法制备ATRP大分子引发剂的最新进展.同时还综述了大分子引发剂通过ATRP反应在聚合物结构设计中的应用,以及对无机材料和生物材料的表面修饰的最新进展,最后对ATRP引发体系的未来发展与应用进行了展望.     

ATRP synthesis and association properties of thermoresponsive anionic block copolymers

Thermosensitive anionic block copolymers of sodium 2‐acrylamido‐2‐methylpropanesulfonate (AMPS) and N‐isopropylacrylamide (NIPAAM) with different block lengths were prepared by atom transfer radical polymerization (ATRP). Controlled polymerization was achieved by using ethyl 2‐chloropropionate (ECP) as initiator and CuCl/CuCl₂/tris(2‐dimethylaminoethyl)amine (Me₆TREN) catalytic system in DMF:water 50:50 (v/v) mixtures at 20 °C. Blocks lengths ranging from 36 to 98 repeating units were obtained. The association properties in aqueous solutions at different NaCl ionic strengths were studied as a function of temperature and polymer concentration by dynamic light scattering, fluorescence spectroscopy, and energy‐filtered transmission electron microscopy. The block copolymers with a higher pNIPAAM/pAMPS ratio formed spherical core‐shell type micelles independently of the ionic strength. The block copolymers with lower pNIPAAM/pAMPS ratio formed core‐shell type micelles at high ionic strength. Larger particles were observed at low ionic strength, which could be due to the formation of vesicles or compound micelles/micellar clusters. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4830–4842, 2008     

Preparation of gradient copolymers via ATRP in miniemulsion. II. Forced gradient

A series of forced gradient copolymers with different controlled distribution of monomer units along the copolymer backbone were successfully prepared by atom transfer radical polymerization in miniemulsion. The newly developed initiation technique, known as activators generated by electron transfer, was beneficial for forced gradient copolymers preparation because all polymer chains were initiated within the miniemulsion droplets and the miniemulsion remained stable throughout the entire polymerization. Various monomer pairs with different reactivity ratios were examined in this study, including n‐butyl acrylate/t‐butyl acrylate, n‐butyl methacrylate/methyl methacrylate, and n‐butyl acrylate/styrene. In each case, the added monomer diffused across the aqueous suspending medium and gradient copolymers with different forced distributions of comonomer units along the polymer backbone were obtained. The shape of the gradient along the backbone of the copolymers was influenced by the molar ratio of the monomers, the reactivity ratio of the comonomers as well as the feeding rate. The shape of the gradient was also affected by the relative hydrophobicities of the comonomers. Copolymerizations exhibited good control for all feeding rates and comonomer feeding ratios, as evidenced by narrow molecular weight distribution (M_w/M_n = 1.20–1.40) and molecular weight increasing smoothly with polymer yield, indicating high initiation efficiency. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1413–1423, 2007     

A Facile Synthesis of Cleavable Block Copolymers via Tandem Polymerizations of NMRP and ATRP

A functionalized compound, 4‐(2‐bromoisobutyryl)‐2,2,6,6‐tetra‐methylpiperidine‐1‐oxyl (Br‐TEMPO), was synthesized and used to synthesize block copolymers through tandem nitroxide‐mediated radical polymerization (NMRP) and atom transfer radical polymerization (ATRP). First, Br‐TEMPO was used to mediate the polymerization of styrene. The kinetics of polymerization proved a typical “living” nature of the reaction and the effectiveness in the mediation of polymerization of Br‐TEMPO. Then the PS‐Br macroinitiator was used to initiate atom transfer radical polymerization (ATRP). A series of acrylates were initiated by PS‐Br macroinitiators in typical ATRP processes at various conditions. The controlled polymerization of ATRP was also confirmed by molecular weight and kinetic analysis. Several cleavable block copolymers of PS‐b‐P(t‐BA), PS‐b‐P(n‐BA), and PS‐b‐PMA, with different molecular weights, were synthesized via this strategy. Relatively low polydispersities (<1.5) were observed and the molecular weights were in agreement with the theoretical ones. Hydrolysis of PS‐b‐P(t‐BA) was carried out, giving amphiphilic block copolymer PS‐b‐PAA without the cleavage of C‐ON bond or ester bond. All the block copolymers have two T_gs as demonstrated by DSC. A typical cleavable block copolymer of PS‐b‐PMA was cleaved by adding phenylhydrazine at 120°C to produce homopolymers in situ.     

A novel route to the synthesis of PP-g-PMMA copolymer via ATRP reaction initiated by Si-Cl bond

The copolymerization of propylene with allyldimethylsilane (ADMS) was carried out with conventional Ziegler-Natta catalyst supported on MgCl₂. The effects of the concentration of ADMS in the feed on the polymerization reaction and copolymer properties were investigated. The resulting copolymer PP-co-ADMS was chlorinated to PP-Si-Cl by refluxing the copolymer with SOCl₂ in benzene. The chlorinated copolymer was used to initiate ATRP of MMA with CuCl/PMDETA as catalyst to produce graft copolymer PP-g-PMMA, which was characterized with ¹H NMR, ¹³C NMR, GPC and DSC. Polymer blend of iPP/PP-g-PMMA/PMMA was prepared and the results shown that PP-g-PMMA was an effective compatilizer.