聚丙烯酰胺/聚甲基丙烯酸(2-甲基氨基)乙酯高强度双网络水凝胶的制备及pH响应性

利用两步法合成了聚丙烯酰胺(PAM)/聚甲基丙烯酸(2-甲基氨基)乙酯(PDMAEMA)双网络水凝胶,第一网络为锂藻土(Laponite)物理交联的PAM纳米复合水凝胶,第二网络为化学交联剂N,N-亚甲基双丙烯酰胺(BIS)交联PDMAEMA。研究了2种网络相对含量、纳米黏土Laponite用量、化学交联剂BIS用量对水凝胶强度和pH响应性的影响。研究结果表明,PAM/PDMAEMA双网络水凝胶具有高强度,改变单体AM和DMAEMA的配比、交联剂的用量,其拉伸强度在36～91.9 kPa范围内可调。PAM/PDMAEMA双网络水凝胶还具有灵敏的pH刺激响应性,在pH=4时双网络水凝胶溶胀度急剧下降。     

聚合物智能纳米凝胶的反相微乳液聚合法合成与性能EI北大核心CSCD

以N,N-亚甲基双丙烯酰胺(MBA)为交联剂,过硫酸铵和亚硫酸氢钠为氧化还原引发剂,采用反相微乳液聚合将丙烯酰胺(AM)、衣康酸(IA)和N-异丙基丙烯酰胺(NIPAM)共聚制备pH/温度双重刺激响应性智能纳米凝胶;探讨了IA和NIPAM质量比对智能纳米凝胶吸水率、吸盐率以及对温度和pH敏感性的影响,并通过透射电镜、热重分析对智能纳米凝胶的形貌和热稳定性进行了表征。结果表明,随着IA和NIPAM质量比的增加,智能纳米凝胶的吸水率和pH敏感性增加,吸盐率和温度敏感性降低,智能纳米凝胶表现出较明显的pH/温度双重刺激响应性。当吸水溶胀时间从1 h增加到5 h,智能纳米凝胶的平均粒径从0.54μm增加到8.08μm,能够满足渗透率小于1×10-3μm2、孔喉半径小于8μm的特低渗透油藏调剖堵水的要求。透射电镜表明,智能纳米凝胶基本为球形,形状较规整,粒径范围为30 nm^75 nm,平均粒径为47 nm;热重分析表明,智能纳米凝胶具有良好的热稳定性。     

载银纳米颗粒多响应性复合水凝胶研究进展

近年来载银纳米颗粒多响应性复合水凝胶得到人们的广泛关注。该复合体系通过结合银纳米颗粒与水凝胶,不仅可以利用水凝胶的光学和电学特性,同时也表现出了对温度、pH、介质离子强度的轻微变化以及对某些生物物质浓度变化的快速响应。对近年来载银纳米颗粒多响应性复合水凝胶的性能和分类方法的研究进展进行了详述,介绍了该复合水凝胶在催化领域、生物医学领域、纳米技术和环境污染物质降解等方面的应用。     

α-CD/PAN纤维膜对Cu~(2+)、Zn~(2+)、Ni~(2+)和Pb~(2+)的吸附特性

应用静电纺丝技术制备α-环糊精(α-CD)/聚丙烯腈(PAN)纤维膜,采用SEM、FT-IR分别对纳米纤维膜进行表征。通过考察pH值、吸附时间、重金属离子初始浓度、温度几个因素,系统研究了α-CD/PAN纤维膜对重金属离子的吸附影响。结果表明:在溶液pH=6,吸附时间为2h,重金属离子初始浓度为10mg/L,温度为35℃的条件下,纳米纤维膜对铜离子(Cu~(2+))、锌离子(Zn~(2+))、镍离子(Ni~(2+))和铅离子(Pb~(2+))的吸附达到最佳,吸附容量分别为9.11、9.02、9.31和8.87mg/g。     

AOPAN/RC纳米纤维膜的制备及对金属离子吸附性能

采用静电纺丝技术制备聚丙烯腈/醋酸纤维素(PAN/CA)纳米纤维膜,通过化学改性制备偕胺肟化聚丙烯腈/再生纤维素(AOPAN/RC)纳米纤维膜,研究了纳米纤维膜对单一金属离子(Fe~(3+))和混合金属离子(Cu~(2+)、Cd~(2+)、Fe~(3+))的吸附性能。通过扫描电镜、红外光谱、X射线能谱仪等测试对纳米纤维膜进行了表征,并通过静态接触角测定纳米纤维膜亲水性能。研究表明,改性后制备的AOPAN/RC纳米纤维膜的亲水性能得到较大改善,同时纳米纤维膜能够高效吸附溶液中的金属离子,纳米纤维膜对单一组分Fe~(3+)的饱和吸附可达411.21mg/g,对于混合金属离子溶液,纳米纤维膜对其吸附能力顺序为Fe~(3+)Cu~(2+)Cd~(2+),而且纳米纤维膜具备优良的重复使用能力。     

前端聚合法制备聚丙烯酸/蒙脱土复合水凝胶及其性能测定

以丙三醇和水为混合溶剂,采用前端聚合法合成了聚丙烯酸(PAA)/蒙脱土(MMT)复合水凝胶,并对复合水凝胶的分子结构、微观形貌和热性能进行了表征;探究了MMT用量对聚合参数、复合水凝胶吸(盐)水及吸附碱性品红染料的影响。结果表明:丙三醇与水的质量比为3∶1时能有效抑制MMT聚沉;当MMT用量为3%时,复合水凝胶的吸水量达最大值632g/g;PAA/MMT复合水凝胶为pH敏感水凝胶;MMT的加入提高了水凝胶对碱性品红的吸附性能。     

PAM/AMPS/GO纳米复合水凝胶的制备及染料吸附性能研究

通过原位溶液聚合法制备聚丙烯酰胺/2-丙烯酰胺-2-甲基丙磺酸/氧化石墨烯(PAM/AMPS/GO)纳米复合水凝胶。采用X射线衍射和红外谱图对复合水凝胶的结构进行了表征,并研究pH对水凝胶的染料吸附性能的影响。结果表明:GO与聚合物基体间存在较强的相互作用,能够均匀的分散在基体中。另外,复合水凝胶在中性溶液中对亚甲基蓝染料的吸附效果最佳,且最快达到吸附平衡。     

高强度温敏性聚N-异丙基丙烯酰胺/SiO_2纳米复合水凝胶的制备表征及形状记忆行为

使用3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)对Si O2纳米粒子(SNPs)进行表面改性,获得带有双键的功能化Si O2纳米粒子(F-SNPs),然后将N-异丙基丙烯酰胺(NIPA)在F-SNPs分散液中原位自由基聚合,获得了高强度的PNIPA/Si O2纳米复合水凝胶(FS-NC gel)。力学性能测试与溶胀实验结果表明,与使用有机交联剂和未功能化的Si O2纳米粒子交联的水凝胶相比,FS-NC gel的力学性质明显提高,其拉伸强度和压缩强度最高可达205 k Pa和7.8 MPa,同时保持了PNIPA纳米复合水凝胶的快速响应性和温度敏感性。此外,水凝胶还表现出水驱动的形状记忆行为。     

聚丙烯酸/聚乳酸复合多孔pH响应水凝胶的制备及性能

利用电纺制备直径为(2.69±0.63)μm,孔径大小为150 nm×120 nm聚乳酸(PLLA)纳米孔超细纤维。以丙烯酸(AA)为单体,N,N-亚甲基双丙烯酰胺为交联剂,过硫酸钾为引发剂,通过自由基聚合制备聚丙烯酸(PAA)水凝胶。将PLLA纳米孔超细纤维浸泡在上述体系中,通过原位聚合制备PAA/PLLA复合水凝胶,并研究m(AA)∶m(PLLA)对复合水凝胶形貌的影响。致孔剂聚乙二醇(PEG)加入,明显提高纤维孔隙率。与PAA水凝胶相比,PAA/PLLA复合水凝胶pH响应时间大大缩短,且拉伸强度由1.9 MPa增加到5.2 MPa,弹性模量从90.4 MPa增加到108.2 MPa。     

交联方式对半乳糖基温敏凝胶结构和性能的影响

为改善传统化学交联水凝胶的低力学性能、透明度、溶胀度和生物相容性, 以无机纳米粒子硅酸镁锂(LMSH)作为物理交联剂, 半乳糖氨基化的丙烯酸衍生物(GAC)作为生物相容性单体, N-异丙基丙烯酰胺(NIPAM)为功能单体, 采用原位自由基聚合制备得到兼具温度敏感性和生物相容性的纳米复合水凝胶poly(NIPAM-LMSH-GAC)。结果表明: LMSH在水凝胶基体中被完全剥离, 并起到交联作用; 相比于传统化学交联剂制备的此类水凝胶, 所得物理交联的纳米复合水凝胶具有更高的溶胀度、良好的温敏性、优异的脉冲响应性, 但鼠成纤细胞(L929)在纳米复合水凝胶表面的细胞数量略低; 物理交联剂LMSH的使用和一定量的GAC的使用并没有明显改变水凝胶的体积相转变温度(VPTT), 仍保持在33℃左右。     

温度/pH敏感性Semi-IPN水凝胶的制备与性能

以N-乙烯基乙酰胺（NVA）、醋酸乙烯酯（VAc）和甲基丙烯酸-N,N′-二甲氨基乙酯（DMAEMA）为原料,通过自由基聚合制备了PDMAEMA/P（NVA-co-VAc）半互穿网络（Sem-iIPN）水凝胶。实验结果表明,该水凝胶具有较好的温度敏感性、pH敏感性、溶胀-退胀可逆性。随着温度的逐渐升高,凝胶的溶胀率随之...     

In situ controlled synthesis of thermosensitive poly(N-isopropylacrylamide)/Au nanocomposite hydrogels by gamma radiation for catalytic application

Thermosensitive poly(N‐isopropylacrylamide) (PNIPAM)/Au nanoparticle (NP) nanocomposite hydrogels are synthesized by in situ γ‐radiation‐assisted polymerization of N‐isopropylacrylamide monomer aqueous solution in the presence of HAuCl₄·4H₂O. In this reaction, the PNIPAM hydrogels and the Au NPs are formed simultaneously, thus demonstrating an easy and straightforward synthetic strategy for the preparation of a uniform nanocomposite. The results suggest that increasing the monomer content during the preparation of nanocomposite materials can increase the sizes of Au NPs. The effects of irradiation dose and concentration of HAuCl₄·4H₂O on the optical and thermal properties of the hydrogel are also investigated. The PNIPAM/Au nanocomposite hydrogels act as an excellent catalyst for the conversion of o‐nitroaniline to 1,2‐benzenediamine, and the catalytic activity of the composite hydrogel can be tuned by the volume transition of PNIPAM. The in situ polymerization of monomer and reduction of metal ions initiated by a “clean” and “green” γ‐radiation technique can be extended to the efficient synthesis of other nanocomposite materials.     

Nanocomposite synthesis by absorption of nanoparticles into macroporous hydrogels. Building a chemomechanical actuator driven by electromagnetic radiation

Macroporous hydrogels irreversibly absorb solid nanoparticles from aqueous dispersions. A nanocomposite is made using a macroporous thermosensitive hydrogel (poly(N-isopropylacrylamide-co-(2-acrylamido-2-methyl propane sulfonic acid)) (poly(NIPAm-co-AMPS)) and conductive polymer (polyaniline, PANI) nanoparticles (PANI NPs). Macroporous gels of poly(NIPAm-co-AMPS) were made by a cryogelation technique. NPs of PANI were produced by precipitation polymerization. It is found that PANI NPs are easily absorbed into the macroporous hydrogels while conventional non-porous hydrogels do not incorporate NPs. It is shown that PANI NPs, dispersed in water, absorb NIR laser light or microwave radiation, increasing their temperature. Upon irradiation of the nanocomposite with microwaves or NIR laser light, the PANI NPs heat up and induce the phase transition of the thermosensitive hydrogel matrix and the internal solution is released. Other nano-objects, such as gold nanorods and PANI nanofibers, are also easily incorporated into the macroporous gel. The resulting nanocomposites also suffer a phase transition upon irradiation with electromagnetic waves. The results suggest that, using a thermosensitive matrix and conducting nanoparticles, mechanical/chemical actuators driven at a distance by electromagnetic radiation can be built. The sensitivity of the nanocomposite to electromagnetic radiation can be modulated by the pH, depending on the nature of the incorporated nanoparticles. Additionally, it is possible to make systems which absorb either NIR or microwaves or both.     

多重响应性P(AAEA-co-DMAA)水凝胶的合成及其性能研究

以具有多重响应性的新型单体4-乙酰基丙烯酰乙酸乙酯(AAEA)和N,N′-二甲基丙烯酰胺(DMAA)为原料,采用溶液自由基聚合法合成了具有多重响应性的水凝胶,研究了凝胶的溶胀行为以及在不同离子强度、温度、pH值条件下共聚水凝胶的响应性能。结果表明,随凝胶中AAEA含量的增加,凝胶的溶胀方式由Fick型转变为非Fick型;凝胶对外界离子强度、温度、pH值的变化产生响应,当NaCl浓度约为0.1mol/L时,凝胶的离子响应性出现较大的突变;随温度的升高,凝胶疏水性增大,85℃时凝胶的保水率只有60%;低pH值时,凝胶收缩,随pH值的增大,凝胶内P-AAEA部分解离加剧,静电斥力使凝胶溶胀。     

Reduction of hexavalent chromium by Pannonibacter phragmitetus LSSE-09 coated with polyethylenimine-functionalized magnetic nanoparticles under alkaline conditions

A novel cell separation and immobilization method for Cr (VI)-reduction under alkaline conditions was developed by using superparamagnetic Fe(3)O(4) nanoparticles (NPs). The Fe(3)O(4) NPs were synthesized by coprecipitation followed by modification with sodium citrate and polyethyleneimine (PEI). The surface-modified NPs were monodispersed and the particle size was about 15 nm with a saturation magnetization of 62.3 emu/g and an isoelectric point (pI) of 11.5 at room temperature. PEI-modified Fe(3)O(4) NPs possess positive zeta potential at pH below 11.5, presumable because of the high density of amine groups in the long chains of PEI molecules on the surface. At initial pH 9.0, Pannonibacter phragmitetus LSSE-09 cells were immobilized by PEI-modified NPs via electrostatic attraction and then separated with an external magnetic field. Compared to free cells, the coated cells not only had the same Cr (VI)-reduction activity but could also be easily separated from reaction mixtures by magnetic force. In addition, the magnetically immobilized cells retained high specific Cr (VI)-reduction activity over six batch cycles. The results suggest that the magnetic cell separation technology has potential application for Cr (VI) detoxification in alkaline wastewater.     

Preparation,properties, and drug release of thermo- and pH-sensitive poly((2-dimethylamino)ethyl methacrylate)/poly(<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-diethylacrylamide) semi-IPN hydrogels

In this paper, a series of semi-interpenetrating polymer network (semi-IPN) hydrogels based on poly((2-dimethylamino)ethyl methacrylate)/poly (N,N-diethylacrylamide) (PDMAEMA/PDEA) were synthesized by changing the initial PDMAEMA/DEA molar ratio at room temperature. The influence of this additive on the property of resulting PDEA hydrogels was investigated and characterized. The interior morphology by scanning electron microscopy (SEM) revealed that the semi-IPN hydrogels have interconnected porous network structures. The glass transition temperature (T _g) of the semi-IPN hydrogels was observed by differential scanning calorimetry (DSC). Equilibrium swelling ratio (ESR), swelling and deswelling dynamics of the hydrogels responding to temperature and pH were investigated in detail. Compared to PDEA, the semi-IPN hydrogels exhibited excellent mutative values in response to an alternation of the temperature and pH, and showed fast swelling and deswelling rates in response to temperature and pH change. The release behaviors of the model drug, aminophylline, were found dependent on hydrogel compositions and environmental temperature. These results suggest that the stimuli semi-IPN hydrogel have potential application as intelligent drug carriers.     

聚丙烯酰胺/改性纳米纤维素晶体纳米复合水凝胶的光聚合制备与表征

先用马来酸酐对纳米纤维素晶体(NCC)进行表面改性得表面含碳-碳双键的改性NCC(mNCC),然后将丙烯酰胺(AM)和mNCC一起光聚合得PAM/mNCC纳米复合水凝胶;通过红外光谱、扫描电镜、热重分析、差热分析、溶胀实验和拉伸实验研究了水凝胶的结构和性能。结果表明,PAM/mNCC纳米复合水凝胶是一种物理/化学共交联水凝胶;与用质量分数0.25%N,N-亚甲基双丙烯酰胺交联的PAM水凝胶相比,PAM/mNCC纳米复合水凝胶中的微孔尺寸分布更宽,PAM分子链的起始分解温度和玻璃化转变温度升高;当mNCC的用量占AM质量的5%~10%时,PAM/mNCC纳米复合水凝胶的饱和溶胀率、拉伸强度、断裂伸长率分别为PAM水凝胶的2.1~2.7倍、0.45~1.1倍、3.8~7.1倍。     

温度敏感性聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)水凝胶的合成及性能研究

采用热化学聚合法制备了聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)水凝胶,并对其溶胀性能进行了研究.研究结果表明,PDMAEMA水凝胶具有温度敏感性,在去离子水中其ICST约为50℃;水凝胶的温度敏感性与介质的pH值有关,在碱性溶液中凝胶表现出典型的温度敏感性,而在酸性溶液中凝胶的溶胀率受温度的影响很小,没有温度敏感性.     

Synthesis and characterization of core∕shell Fe(3)O(4)∕ZnSe fluorescent magnetic nanoparticles

We report on the successful preparation and characterization of fluorescent magnetic core∕shell Fe(3)O(4)∕ZnSe nanoparticles (NPs) with a spherical shape by organometallic synthesis. The 7 nm core∕3 nm shell NPs show good magnetic and photoluminescence (PL) responses. The observed PL emission∕excitation spectra are shifted to shorter wavelengths, compared to a reference ZnSe NP sample. A dramatic reduction of PL quantum yield is also observed. The temperature dependence of the magnetization for the core∕shell NPs shows the characteristic features of two coexisting and interacting magnetic (Fe(3)O(4)) and nonmagnetic (ZnSe) phases. Compared to a reference Fe(3)O(4) NP sample, the room-temperature Néel relaxation time in core∕shell NPs is three times longer.     

Dynamic Coordination of Eu–Iminodiacetate to Control Fluorochromic Response of Polymer Hydrogels to Multistimuli

New fluorochromic materials that reversibly change their emission properties in response to their environment are of interest for the development of sensors and light‐emitting materials. A new design of Eu‐containing polymer hydrogels showing fast self‐healing and tunable fluorochromic properties in response to five different stimuli, including pH, temperature, metal ions, sonication, and force, is reported. The polymer hydrogels are fabricated using Eu–iminodiacetate (IDA) coordination in a hydrophilic poly(N,N‐dimethylacrylamide) matrix. Dynamic metal–ligand coordination allows reversible formation and disruption of hydrogel networks under various stimuli which makes hydrogels self‐healable and injectable. Such hydrogels show interesting switchable ON/OFF luminescence along with the sol–gel transition through the reversible formation and dissociation of Eu–IDA complexes upon various stimuli. It is demonstrated that Eu‐containing hydrogels display fast and reversible mechanochromic response as well in hydrogels having interpenetrating polymer network. Those multistimuli responsive fluorochromic hydrogels illustrate a new pathway to make smart optical materials, particularly for biological sensors where multistimuli response is required.