Solubility of polyethylene in n-pentane at high pressures

The high pressure solubility of polyethylene standards (M_w = 2100, 16400, 108000 and 420000 and M_w/M_n = 1.14, 1.16, 1.32 and 2.66, respectively) in n-pentane has been studied. Concentrations of up to 15 wt% polymer have been investigated. For each polymer sample and concentration, pressures that are required to achieve single-phase solutions have been determined over a range of temperatures. The solutions are found to all show lower critical solution temperatures. Demixing pressures are observed to depend strongly on the molecular weight of the polymer.     

荧光探针法研究结构明确的BzO-PDMAEMA均聚物水溶液性质

通过氧阴离子聚合合成了一系列不同相对分子质量的结构明确的BzO—PDMAEMA，用芘作为荧光探针研究了BzO—PDMAEMA在水溶液中的胶束化行为，发现CMC值与用表面张力法测得的结果相一致，即随BzO—PDMAEMA相对分子质量的增加而减小，但荧光探针法测得的CMC值稍大；LCST值则随相对分子质量的增加而增加。     

Tuning the thermoresponsive properties of poly(oligo(propylene glycol) methacrylate) hydrogels via gradient copolymerization with 2-hydroxyethyl methacrylate

Gamma radiation was used to prepare copolymer hydrogel libraries based on oligo(propylene glycol) methacrylate (OPGMA) and 2-hydroxyethyl methacrylate (HEMA); a complete screening in composition of P(OPGMA/HEMA) copolymers was elaborated from 0% to 100% of OPGMA. Determination of gel fraction was performed as the first step after radiation induced synthesis. Tuning of the volume phase transition temperature (VPTT) of P(OPGMA/HEMA) copolymeric hydrogels was investigated by swelling study. Additional characterization of structure and properties was conducted by FTIR, DSC, and UV-Vis spectroscopy. All results indicate that new P(OPGMA/HEMA) copolymeric hydrogels have wide diversity in thermoresponsive properties which strongly depend on their composition.     

Preparation of polymeric nanocapsules via nano-sized poly(methoxydiethyleneglycol methacrylate) colloidal templates

Polymeric nanocapsules are attractive devices with a number of potential applications. In the present contribution we describe a method for nanocapsule preparation which is based on the formation of nanosized templates (mesoglobules, prepared from thermo-responsive poly(methoxydiethyleneglycol methacrylate)s, PDEGMA). These mesoglobules were coated with a cross-linked shell formed by pseudo-seeded radical polymerization of either N-isopropylacrylamide or 2-hydroxyethylmethacrylate in the presence of a cross-linking agent. Dissolution and removal of templates were achieved by extensive dialysis against water at temperatures below the LCST of PDEGMA. The obtained nanocapsules were visualized by transmission electron microscopy and their dimensions were determined by dynamic light scattering. The differences in the morphology of the nanocapsules were attributed to the different structures of the cross-linked membranes.     

Micellar Growth in Cetylpyridinium Chloride/Alcohol System: Role of Long Chain Alcohol,Electrolyte and Surfactant Head Group

The microstructural transition of aqueous 0.1 M cetylpyridinium chloride (CPC) in the combined presence of salt KBr and long chain alcohol (C₉OH-C₁₂OH) has been studied as a function of alcohol concentration, electrolyte concentration and temperature. The viscosity of the CPC/KBr micellar system showed a peaked behavior with alcohol concentration (C ₀), due to alcohol induced structural transition, which was confirmed by dynamic light scattering (DLS) and rheological analysis. Besides C ₀, the chain length of alcohol (n) was found to show a remarkable effect on the micellization behavior of CPC/KBr system. It was observed that the ability of alcohol to induce micelle growth diminishes with n, which was well supported by viscosity, rheology and DLS measurements. To examine the effect of the electrolyte on the micellar growth, the salt concentration was varied from 0.05 to 0.15 M and it was observed that with increase in [KBr], the peak position shifts towards lower C ₀. The effect of temperature on the micellar system showed interesting phase behavior for CPC/KBr/Decanol. The system exhibited a closed solubility loop with an upper critical solution temperature (UCST) > the lower critical solution temperature (LCST), reminiscence of nicotine-water system. The role of surfactant head group on the structural evolution was revealed by comparing the present results with our previous report for similar micellar system, CTAB/KBr/long chain alcohol.     

Synthesis and characterization of NIR-responsive Aurod@pNIPAAm-PEGMA nanogels as vehicles for delivery of photodynamic therapy agents

A near-infrared (NIR)-responsive Au_rod@pNIPAAm-PEGMA nanogel was synthesized in two steps, growing a PEGMA monolayer on the surface of gold nanorods (AuNRs), followed by in situ polymerization and cross-linking of N-iso-propylacrylamide (NIPAAm) and poly-(ethylene glycol)-methacrylate (PEGMA). The AuNRs and Au_rod@pNIPAAm-PEGMA nanogel were characterized by UV–vis spectroscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy, respectively. The lower critical solution temperature of the Au_rod@pNIPAAm-PEGMA nanogel could be tuned by changing the molar ratio of NIPAAm/PEGMA. The NIR-mediated drug release behavior of the Au_rod@pNIPAAm-PEGMA nanogel was studied with zinc phthalocyanines (ZnPc₄) as a drug model. It was also demonstrated that the loaded ZnPc₄ could keep the capability of generating singlet oxygen, and the in vitro study showed a great photodynamic therapy (PDT) effect on Hela cells. It thus indicated the potential of this Au_rod@pNIPAAm-PEGMA nanogel for application as a drug carrier in PDT, which might make contributions to oncotherapy.     

温敏性微凝胶对蛋白质和酶的吸附性能

用微乳液聚合方法以N-异丙基丙烯酰胺为单体合成了温敏性微凝胶聚N-异丙基丙烯酰胺(PNIPAM),研究了其对两种蛋白质和两种酶的吸附性能,测定了吸附等温线和温度对吸附量的影响。结果表明,微凝胶在低临界溶解温度(LCST)附近吸附蛋白质和酶的量有一突跃,例如在LCST前后,1 g纳米颗粒吸附的酪蛋白的质量分别为225 mg和415 mg;吸附的枯草杆菌蛋白酶的质量分别为12 000U/mg和27 500 U/mg。蛋白质和酶是通过物理吸附作用结合到PNIPAM微凝胶上,可以用调节温度的方法,来控制温敏微凝胶对蛋白质和酶的吸附与脱附。     

Orthogonal ligation to spherical polymeric microparticles: Modular approaches for surface tailoring

Modular ligation strategies for the functionalization of polymeric microspheres provide new perspectives for their applications in material science. In the current trend article we highlight variable synthetic procedures for generating functional microspheres via orthogonal modular conjugation chemistries. An overview of the different surface chemistries available is provided, followed by surface-sensitive characterization techniques relevant for the microparticles. Finally, we explore future trends in modular orthogonal modification approaches on microparticles and provide an outlook on the perspectives that the field of surface-modification of polymeric microparticles holds.     

Heteroarm Star-Shaped Poly (N-isopropylacryamide-co-itaconic acid) Copolymer Prepared by Glucose Core as ATRP Initiator

Star-shaped temperature- and pH-sensitive poly (N-isopropylacryamide-co-itaconic acid) copolymer is synthesized by atom transfer radical polymerization (ATRP) using 1,2,3,4,6-penta-O-Isobutyrylbromide-α-D-glucose as 5-Arm ATRP Initiator. For ATRP of itaconic acid (IA), carboxylic groups of IA are protected via silylation by hexamethyldisilazane (HMDS) using Fe₃O₄ as a magnetic catalyst. The polymerization is carried out in 2-propanol/toluene 50:50 (v/v) mixed solvent at 90°C. Structure of copolymers is studied with FT-IR, ¹H NMR, glass transition temperature (Tg), and scanning electron microscopy (SEM). Results of temperature, pH, and percentage variation on polymer structure and the effects on lower critical solution temperature (LCST), which is investigated with potentiometery and conductometry, show that LCST of copolymer is around body temperature and demonstrate the ability of this polymer in the design of controlled drug delivery systems. According to the obtained results from naltrexone release, the investigated star-shaped copolymer may have potential applications in the controlled release of drugs.     

Non-linear PEG-based thermoresponsive polymer systems

Poly(ethylene glycol) (PEG) is one of the most used polymers in medical and biological applications. Its non-toxicity, non-immunogenicity, biocompatibility and solubility in a wide range of solvents offer various possibilities of utilization and explain the amount of studies dealing with this polymer. More recently, non-linear PEG-based monomers attracted much interest due to their thermal behavior. The present review aims at presenting many PEG-based thermoresponsive systems from structural and synthesis point of view and at highlighting all their fascinating properties from their behavior in solution, the fine-tuning of the transition temperature until the formation of smart materials.