Flocculation‐resistant multimolecular micelles with thermoresponsive corona from dendritic heteroarm star copolymers

In this article, we report the self‐assembly of flocculation‐resistant multimolecular micelles with thermoresponsive corona from novel dendritic heteroarm star copolymers. The micelles have a core‐shell‐corona structure at room temperature according to pyrene probe fluorescence spectrometry, proton nuclear magnetic resonance (¹H NMR), transmission electron microscopy, and dynamic light scattering measurements. Increasing the temperature above the lower critical solution temperature (LCST), the micelles show high flocculation‐resistant ability resulting from a structure transition from core‐shell‐corona to core‐shell confirmed by a quantitative variable temperature ¹H NMR analysis method using potassium hydrogen phthalate as an external standard. A big volume change of the micelles is observed during the LCST transition. The drug loading and temperature‐dependent release properties of the micelles are also investigated by using coumarin 102 as a model drug, which displays a rapid drug release at a temperature above the LCST. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis of biocompatible and thermally sensitive poly(N‐vinylcaprolactam) nanogels via inverse miniemulsion polymerization: Effect of the surfactant concentration

The goal of this study was to develop a new route to prepare thermally responsive polymer nanogels. Poly(N‐vinylcaprolactam) nanogels were prepared via inverse miniemulsion polymerization (W/O) at 70 °C using n‐hexadecane as a nonpolar continuous phase, potassium persulfate as an initiator, and N,N′‐methylenebisacrylamide as a crosslinker. Sorbitan monooleate (Span 80) was used as surfactant and its influence on the polymerization kinetics and on the colloidal characteristics of the nanogels were principally investigated. It was observed that the addition of a strong “lipophobe” is required to stabilize the resulting miniemulsion. The nanogels were characterized in terms of morphology, size, zeta potential, and thermoproperties using transmission electron microscopy and dynamic light scattering. It was observed that all the nanogels obtained collapsed when the lower critical solution temperature (LCST) was raised. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3932–3941, 2010     

Control of thermoresponsive property of urea end‐functionalized poly(N‐isopropylacrylamide) based on the hydrogen bond‐assisted self‐assembly in water

The precise synthesis and variation in the thermoresponsive property based on the supramolecular assembly of a novel urea end‐functionalized poly(N‐isopropylacrylamide) (PNIPAM) were studied. A series of PNIPAMs with different diphenylurea groups at the chain end (X? Ph? NH? CO? NH? Ph? trz? PNIPAM: X = H, OCH₃, CH₃, NO₂, Cl, and CF₃) were synthesized by using a combination of the atom transfer radical polymerization and the copper(I)‐catalyzed azide‐alkyne cycloaddition. The cloud point of the obtained polymers depended on the hydrogen‐bonding ability of the introduced urea group. The ¹H NMR measurement suggested that the obtained PNIPAM assembled in water via the intermolecular hydrogen bonding by the terminal urea group. From the dynamic light scattering and transmission electron microscopy measurements, the aggregated nanoparticles of the resulting polymer were directly observed in water at a temperature below its cloud point. The hydrogen‐bonding property of the chain end urea group was concluded to be involved in the aggregation of the PNIPAM in water, leading to the variation in its cloud point. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6259–6268, 2009     

Novel thermoresponsive fluorinated double‐hydrophilic poly{[N‐(2,2‐difluoroethyl)acrylamide]‐b‐[N‐(2‐fluoroethyl)acrylamide]} block copolymers

Novel thermoresponsive double‐hydrophilic fluorinated block copolymers were successfully synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization. Poly[N‐(2,2‐difluoroethyl)acrylamide] (P2F) was synthesized via RAFT polymerization of N‐(2,2‐difluoroethyl)acrylamide (M2F) using 2‐dodecylsulfanylthiocarbonylsulfanyl‐2‐methylpropionic acid (DMP) as the chain transfer agent (CTA) and 2,2′‐azobisisobutyronitrile (AIBN) as the initiator. The resulting P2F macroCTA was further chain extended with N‐(2‐fluoroethyl)acrylamide (M1F) to yield poly{[N‐(2,2‐difluoroethyl)acrylamide]‐b‐[N‐(2‐fluoroethyl)acrylamide]} (P2F‐b‐P1F) block copolymers with different lengths of the P1F block. Molecular weight and molecular weight distribution were determined by gel permeation chromatography. The average molecular weight (M_n) of the resulting polymers ranged from 2.9 × 10⁴ to 5.8 × 10⁴ depending on the length of the P1F block. The molecular weight distribution was low (M_w/M_n = 1.11–1.19). Turbidimetry by UV‐Visble (UV‐Vis) spectroscopy, dynamic light scattering, and in situ temperature‐dependent ¹H NMR measurements demonstrated that the P2F block underwent a thermal transition from hydrophilic to hydrophobic, which in turn induced self‐assembly from unimers to aggregates. Transmission electron microscopy studies demonstrated that polymeric aggregates formed from an aqueous solution of P2F‐b‐P1F at 60 °C were disrupted by cooling down to 20 °C and regenerated by heating to 60 °C. Temperature‐triggered release of a model hydrophobic drug, coumarin 102, was also demonstrated. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Temperature-dependent interfacial properties of hydrophobically end-modified poly(2-isopropyl-2-oxazoline)s assemblies at the air/water interface and on solid substrates

We describe herein the properties at the air/water (A/W) interface of hydrophobically end-modified (HM) poly(2-isopropyl-2-oxazoline)s (PiPrOx) bearing an n-octadecyl chain on both termini (telechelic HM-PiPrOx) or on one chain end (semitelechelic HM-PiPrOx) for different subphase temperatures and spreading solvents using the Langmuir film balance technique. The polymer interfacial properties revealed by the π–A isotherms depend markedly on the architecture and molecular weight of the polymer. On cold water subphases (14 °C), diffusion of PiPrOx chains onto water takes place for all polymers in the intermediate compressibility region (5 mN m⁻¹). At higher subphase temperatures (36 and 48 °C), the HM-PiPrOx film exhibited remarkable stability with time. Brewster angle microscopy (BAM) imaging of the A/W interface showed that the polymer assembly was not uniform and that large domains formed, either isolated grains or pearl necklaces, depending on the polymer structure, the concentration of the spreading solution and the subphase temperature. The Langmuir films were transferred onto hydrophilic substrates (silica) by the Langmuir–Blodgett (LB) technique and onto hydrophobic substrates (gold) by Langmuir–Schaefer (LS) film deposition, resulting in the formation of adsorbed particles ranging in size from 200 to 500 nm, depending on the polymer architecture and the substrate temperature. The particles presented “Janus”-like hydrophilic/hydrophobic characteristics.     

聚丙烯表面接枝PNIPAAm膜Ⅱ.表面特性和温度响应性研究

通过吸水率和接触角测定研究了聚N 异丙基丙烯酰胺 (PNIPAAm)接枝膜的温度敏感特性 .尽管非交联型接枝膜和交联型接枝膜的吸水特性没有显著差别 ,但是交联组分的引入确实在一定程度上延缓了接枝膜的失水趋势 ,同时也有利于接枝膜亲水性的提高 .对接枝膜进行接触角研究发现 ,在某临界温度以下 ,接触角随时间的变化表征了探测水滴与膜表面之间的相互作用过程 .为了消除接触角测定过程中水份蒸发造成的影响 ,建立了接触角修正算法和修正经验关系式 ,并发展了一种适合于温度敏感性接枝膜LCST测定的变温实时接触角测定方法 .提出了接枝膜与水滴相互作用过程分为两个阶段的模型 ,并得到交联型PP接枝膜表面性能发生明显变化的临界接枝率为 0 6mg cm2 左右     

Pegylated thermally responsive block copolymer micelles and nanogels via in situ RAFT aqueous dispersion polymerization

A very straightforward approach was developed to synthesize pegylated thermoresponsive core‐shell nanoparticles in a minimum of steps, directly in water. It is based on RAFT‐controlled radical crosslinking copolymerization of N,N‐diethylacrylamide (DEAAm) and N,N′‐methylene bisacrylamide (MBA) in aqueous dispersion polymerization. Because DEAAm is water‐soluble and poly(N,N‐diethylacrylamide) (PDEAAm) exhibits a lower critical solution temperature at 32 °C, the initial medium was homogeneous, whereas the polymer formed a separate phase at the reaction temperature. The first macroRAFT agent was a surface‐active trithiocarbonate based on a hydrophilic poly(ethylene oxide) block and a hydrophobic dodecyl chain. It was further extented with N,N‐dimethylacrylamide (DMAAm) to target macroRAFT agents with increasing chain length. All macroRAFT agents provided excellent control over the aqueous dispersion homopolymerization of DEAAm. When they were used in the radical crosslinking copolymerization of DEAAm and MBA, the stability and size of the resulting gel particles were found to depend strongly on the chain length of the macroRAFT agent, on the concentrations of both the monomer and the crosslinker, and on the process (one step or two steps). The best‐suited experimental conditions to reach thermosensitive hydrogels with nanometric size and well‐defined surface properties were determined. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2373–2390, 2009     

Thermodynamic cloud point assays

Analysis of cloud points and clouding curves by varying heating rates using a commercially available automated melting point apparatus is a method to obtain a corrected cloud point for polymers that have a lower critical solution temperature (LCST). Such assays also provide information about the effects of varying heating rates on LCSTs and similar stimuli‐responsive phase separation behavior. This melting point apparatus makes it experimentally simple to conduct such assays that probe the effect of varying heating rates, the effect of polymer structure, and the effect of solution components on the breadth and progress of the phase transition process over a wide temperature range. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 186–193, 2008     

荧光探光对N—异丙基丙烯酰胺—丙烯酰胺共聚物水溶液相变的研究

合成了多种不同配比的Ｎ－异丙基丙烯酰胺（ＮＩＰＡＭ）与丙烯酰胺（ＡＭ）的共聚物。用荧光探针法研究了共聚物溶液荧光光谱随温度升高而引起的变化,研究表明：共聚物的最低临界溶温度（ＬＣＳＴ）取决于ＡＭ与ＮＩＰＡＭ的组成比,ＡＭ的比例越大。ＬＣＳＴ就越高,且有较好的正比关系,通过以共价键连接于共聚物的荧光探针法（标记法）和以小分子探针混入共聚物水溶液的方法（混入法）测定上述体系ＬＣＳＴ的结果比较,发现标记探针法具有较高的灵敏度,更适宜用来研究共聚物水相体系的相变问题。