Influence of ethyl methacrylate content on the volume‐phase transition of temperature‐sensitive poly[(N‐isopropylacrylamide)‐co‐(ethyl methacrylate)] microgels

A novel series of temperature‐sensitive poly[(N‐isopropylacrylamide)‐co‐(ethyl methacrylate)] (p(NIPAM‐co‐EMA)) microgels was prepared by the surfactant‐free radical polymerization of N‐isopropylacrylamide (NIPAM) with ethyl methacrylate (EMA). The shape, size dispersity and volume‐phase transition behavior of the microgels were investigated by transmission electron microscopy (TEM), ultraviolet–visible (UV–Vis) spectroscopy, dynamic light scattering (DLS) and differential scanning calorimetry (DSC). The transmission electron micrographs and DLS results showed that microgels with narrow distributions were prepared. It was shown from UV–Vis, DLS and DSC measurements that the volume‐phase transition temperature (VPTT) of the p(NIPAM‐co‐EMA) microgels decreased with increasing incorporation of EMA, but the temperature‐sensitivity was impaired when more EMA was incorporated, causing the volume‐phase transition of the microgels to become more continuous. It is noteworthy that incorporation of moderate amounts of EMA could not only lower the VPTT but also enhance the temperature‐sensitivity of the microgels. The reason for this phenomenon could be attributed to changes in the complicated interactions between the various molecules. Copyright © 2004 Society of Chemical Industry     

Enzyme catalyzed durable and authentic oriental lacquer: a natural microgel-printable coating by polysaccharide–glycoprotein–phenolic lipid complexes

The chemistry and technology of oriental lacquer, proof of long-term durability by a laboratory test, and morphological features of the closely packed shell (polysaccharides–glycoproteins)–core (polymerized urushiol) microgel particles, which are chiefly responsible for degradation due to efflorescence outdoors, are described. The dimerization mechanism of urushiol was demonstrated by separation of over 20 urushiol dimer derivatives. Physiological dimerization of urushiol in the lacquer is very much influenced by the humidity in drying, and the interaction of semiquinone radicals with metal ions, hydrophilic polysaccharides and amphipathic glycoproteins contained in the lacquer. A mechanism for renewable oriental lacquer is proposed, involving harmony of technology and nature within the lacquer tree plantations in south-east Asia. A brief review of studies of lacquer chemistry and synthetic coatings is given.     

Glass and Jamming Rheology in Soft Particles Made of PNIPAM and Polyacrylic Acid

The phase behaviour of soft colloids has attracted great attention due to the large variety of new phenomenologies emerging from their ability to pack at very high volume fractions. Here we report rheological measurements on interpenetrated polymer network microgels composed of poly(N-isopropylacrylamide) (PNIPAM) and polyacrylic acid (PAAc) at fixed PAAc content as a function of weight concentration. We found three different rheological regimes characteristic of three different states: a Newtonian shear-thinning fluid, an attractive glass characterized by a yield stress, and a jamming state. We discuss the possible molecular mechanisms driving the formation of these states.     

Very fast H2 production from the methanolysis of NaBH4 by metal‐free poly(ethylene imine) microgel catalysts

The polyethyleneimine (PEI) microgels prepared via microemulsion polymerization are protonated by hydrochloric acid treatment (p‐PEI) and quaternized (q‐PEI) via modification reaction with methyl iodide and with bromo alkanes of different alkyl chain lengths such as 1‐bromoethane, 1‐bromobutane, 1‐bromohexane, and 1‐bromooctane. The bare p‐PEI and q‐PEI microgels are used as catalysts directly without any metal nanoparticles for the methanolysis reaction of sodium borohydride (NaBH₄). Various parameters such as the protonation/quaternization reaction on PEI microgels, the amount of catalyst, the amount of NaBH₄, and temperature are investigated for their effects on the hydrogen (H₂) production rate. The reaction of self‐methanolysis of NaBH₄ finishes in about 32.5 min, whereas the bare PEI microgel as catalyst finishes the methanolysis of NaBH₄ in 22 min. Surprisingly, it is found that when the protonated PEI microgels are used as catalyst, the same methanolysis of NaBH₄ is finished in 1.5 min. The highest H₂ generation rate value is observed for protonated PEI microgels (10 mg) with 8013 mL of H₂/(g of catalyst.min) for the methanolysis of NaBH₄. Moreover, activation parameters are also calculated with activation energy value of 23.7 kJ/mol, enthalpy 20.9 kJ/mol, and entropy ?158 J/K.mol. Copyright © 2016 John Wiley & Sons, Ltd.     

Alginate gel particles–A review of production techniques and physical properties

The application of hydrocolloid gel particles is potentially useful in food, chemical, and pharmaceutical industries. Alginate gel particles are one of the more commonly used hydrocolloid gel particles due to them being biocompatible, nontoxic, biodegradable, cheap, and simple to produce. They are particularly valued for their application in encapsulation. Encapsulation in alginate gel particles confers protective benefits to cells, DNA, nutrients, and microbes. Slow release of flavors, minerals, and drugs can also be achieved by encapsulation in gel particles. The particle size and shape of the gel particles are crucial for specific applications. In this review, current methods of producing alginate gel particles will be discussed, taking into account their advantages, disadvantages, scalability, and impact on particle size. The physical properties of alginate gel particles will determine the effectiveness in different application conditions. This review will cover the current understanding of the alginate biopolymer, gelation mechanisms and factors affecting release properties, gel strength, and rheology of the alginate gel particle systems.     

The effects of thermoresponsive microgel density on cell adhesion,proliferation, and detachment

In recent years, poly(N-isopropylacrylamide)-based microgels have been emerged as a new thermoresponsive coating for cell/cell sheet harvesting, yet few work reports their effect on cell attachment, morphology, activity, and proliferation in details. In this work, poly(N-isopropylacrylamide-co-styrene) (pNIPAAmSt) microgel was selected as the model to study its density on NIH3T3 cell adhesion, morphology, activity, and detachment. Results showed that 0.5 wt % pNIPAAmSt microgel density leads to more cells adhesion, higher cell activity yet lower cell proliferation. Moreover, cell adhesion location can be well controlled either by manipulating the sub-cellular scale distances between microgels or by fabricating large scale surface patterns of the microgels on higher microgel density. By temperature stimuli, similar ratio cells detached from the microgel density surface from 0.5 to 1.5 wt %. The results in this article are worthy for the application of thermoresponsive microgels in cell regulation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48773.     

聚合物微凝胶的制备及其在不饱和聚酯改性中的应用

以苯乙烯和丙烯酸丁酯为单体，二乙烯基苯（ＤＶＢ）为交联剂利用乳液聚合法制备出聚合物微凝胶并研究了ＤＶＢ及乳化剂用量对聚合反应的影响，将所得到的微凝胶用于增进不饱和聚酯（ＵＰ）的流变性。试验证明聚合物微凝胶对提高ＵＰ的触变指数具有良好的效果。     

次氯酸钠催化交联的非水解聚丙烯酰胺微凝胶的研制

在次氯酸钠作用下水溶液中非水解聚丙烯酰胺的酰胺基经由异氰酸酯基转变为氨基 ,后二种基团反应生成二价碳酰二胺基 ,将聚合物分子交联而形成水基凝胶。将次氯酸钠用量与使一半酰胺基转变为氨基所需的次氯酸钠量之比定为交联度。实验微凝胶由 6 g/LPAM水溶液形成的凝胶稀释而成。配液用水有清水 (自来水 )、盐水 (2g/LNaCl水溶液 )和高矿化水 (矿化度 80 g/L ,含Ca2 + 、Mg2 + 各 1g/L)。用红外光谱表征了交联聚合物的结构。当PAM浓度为 2 g/L ,交联度为 11.4 %时 ,在宽剪切速率范围内清水微凝胶的粘度低于而盐水微凝胶的粘度则高于相应的 2 g/LHPAM溶液 ,高矿化水微凝胶 7s-1下的粘度 ,2 0℃时略低于而 4 5℃和 6 0℃时则高于清水微凝胶。在渗透率～ 1μm2 的填砂模型上 ,注入～ 0 .3PV的PAM浓度 1.0～ 3.0 g/L、交联度 11.4 %的微凝胶 ,在水驱基础上清水微凝胶提高采收率的幅度随PAM浓度增大而增大 (17.6 %～ 2 4 .2 %) ,盐水微凝胶在PAM浓度为 1.5 g/L时提高采收率的幅度最大 (2 5 .3%)。用于驱油的PAM微凝胶的最佳交联度为 11.4 %,PAM浓度为 2 .0 g/L时粘度为 2 1.0mPa·s ,在水驱基础上提高采收率 2 2 .3%。图 4表 3参 5。     

Ultrastrong Anchoring Yet Barrier‐Free Adsorption of Composite Microgels at Liquid Interfaces

Microgel particles display an interesting duality with properties attributed typically both to polymeric and colloidal systems. When adsorbed at a liquid‐liquid interface, this duality becomes particularly apparent as the various phenomena at play are governed by different aspects of these soft and responsive particles. The introduction of a solid, fluorescently labeled, polystyrene core into the microgels allows direct and accurate visualization without the necessity of potential perturbing sample preparation techniques. By combining in‐situ imaging and tensiometry, we determine that composite microgels at a wide variety of oil‐water interfaces anchor strongly, with adsorption energies of approximately 10⁶ k_BT, typical for particle adsorption, yet accumulate at the interface spontaneously without any energy barrier, which is more typical for polymers. The high adsorption energies allow the particle to spontaneously form very dense crystalline packings at the liquid interface in which the microgels are significantly compressed with respect to their swollen state in bulk solutions. Finally, we demonstrate the unique nature of these particles by producing highly stable and monodisperse microgel‐stabilized droplets using microfluidics.     

Fe3O4-nanoparticle-functionalized 3D-printed injectable microgel

Magnetic Fe₃O₄ nanoparticles have attached attention in bone tissue engineering because of their superior magnetism and great biocompatibility. However, some disadvantages such as the potential risk of agglomeration impair their applications. Here, we proposed a hybrid magnetic nanocomposite microgel by the integration of Fe₃O₄ nanoparticles and digital lighting processing (DLP) three-dimensional (3D) printing technology. The 3D-printed microgels could be precisely customized by printing the mixture of gelatin methacryloyl (GelMA) solution and polydopamine-coated Fe₃O₄ nanoparticles, in which polydopamine decoration improved the hydrophilicity and distribution of the incorporated Fe₃O₄. The degradable microgels could be injected through a 22-G needle while retaining their original shape after injection. Interestingly, the addition of Fe₃O₄ nanoparticles into GelMA solution displayed improved printing accuracy. Moreover, these magnetic microgels were biocompatible in vitro and in vivo. After induction within osteogenic medium, addition of nanoparticles upregulated the osteogenic gene expression of rat bone mesenchymal stem cells (BMSCs). In a word, this work provides a magnetic microplatform, which shows great potential in bone tissue engineering.