Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safet...Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-Ⅱresponsive organic PTMs was explored, and their photothermal conversion efficiencies(PCEs) still remain relatively low. Herein, donor–acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-Ⅱ window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-Ⅱ absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-Ⅱ light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-Ⅱ window, without any side-effect. Moreover, by combining with PD-1 antibody,the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-Ⅱ window, offering a new horizon in developing radical-characteristic NIR-Ⅱ photothermal materials.展开更多
Super high molecular weight copolymers of AM/NaA/AMPS were prepared by oxidation–reduction[OR-P(AM/NaA/AMPS)]and controlled radical polymerization[CR-P(AM/NaA/AMPS)].The resulting copolymers were fully characterized,...Super high molecular weight copolymers of AM/NaA/AMPS were prepared by oxidation–reduction[OR-P(AM/NaA/AMPS)]and controlled radical polymerization[CR-P(AM/NaA/AMPS)].The resulting copolymers were fully characterized,and the reaction conditions for their preparation were optimized.OR-P(AM/NaA/AMPS),CR-P(AM/NaA/AMPS),and conventional partially hydrolyzed polyacrylamide(HPAM)in brine solution were comprehensively characterized by thermogravimetric analysis,scanning electron microscopy,atomic force microscopy,and dynamic light scattering.ORP(AM/NaA/AMPS)and CR-P(AM/NaA/AMPS)containing AMPS monomer showed better salt resistance,temperature tolerance,and viscosification property than the conventional HPAM polymer,making them more promising for enhanced oil recovery.Through comprehensive comparison and analysis,it was found that OR-P(AM/NaA/AMPS)was more conducive for high-temperature condition due to the existence of xanthone in OR-P(AM/NaA/AMPS).On the other hand,CR-P(AM/NaA/AMPS)was more suitable for high-mineral atmosphere,which could be attributed to its higher intrinsic viscosity.展开更多
The 2,2-dinitropropyl methacrylate（DNPMA） was synthesized by esterification of α-methacrylic acid with 2,2-dinitropropanol.The free-radical bulk polymerization of DNPMA in the presence of 2,2-azobisisobutyronitrile...The 2,2-dinitropropyl methacrylate（DNPMA） was synthesized by esterification of α-methacrylic acid with 2,2-dinitropropanol.The free-radical bulk polymerization of DNPMA in the presence of 2,2-azobisisobutyronitrile（AIBN） was investigated by differential scanning calorimetry（DSC） in the nonisothermal mode.Kissinger,Ozawa and Barrett methods were applied to determine the activation energy（Ea） and the reaction order of the free-radical polymerization.The results showed that the temperature of exothermic polymerization peaks increased with increasing heating rate.With increasing the molar ratio of monomer/initiator and the heating rate,the reaction order of nonisothermal polymerization was approximately equal to 1.The average Ea value from Kissinger and Ozawa methods（77.74±1.07 kJ/mol） was smaller than the value from the Barrett method（Ea=102.36 kJ/mol）.展开更多
Plasma initiated polymerization is a kind of well-known radical polymerization mechanism, but it has the ＇living＇ polymerization feature and produces ultra-high molecular weight polymer. In order to explain such phe...Plasma initiated polymerization is a kind of well-known radical polymerization mechanism, but it has the ＇living＇ polymerization feature and produces ultra-high molecular weight polymer. In order to explain such phenomena, we calculate the basic data of plasma initiated polymerization of methylmethacrylate （MMA） according to the principle of polymer physics and chemistry. It results in that the radical concentration ranges from 10^-12mol/L to 10^-16mol/L corresponding to the radical life in 10^4s to 10^8s, which means the radicals have a long lifetime. Moreover because of the long lifetime radicals it causes a unique feature rather than the common radical polymerization, and also shows no ＂living polymerization＂. It is noticed in experiments that there are two key factors playing important roles. One is the effective radical amount produced during the plasma discharging while the another is the diffusion factor.展开更多
以玉米芯为原料,利用原子转移自由基聚合(atomic transfer radical polymerization,ATRP)技术在其表面引发丙烯酸甲酯发生聚合反应,再利用NaOH将嫁接在玉米芯表面的聚丙烯酸甲酯水解成聚丙烯酸钠,得到羧基化玉米芯吸附材料(C-C-A)。通...以玉米芯为原料,利用原子转移自由基聚合(atomic transfer radical polymerization,ATRP)技术在其表面引发丙烯酸甲酯发生聚合反应,再利用NaOH将嫁接在玉米芯表面的聚丙烯酸甲酯水解成聚丙烯酸钠,得到羧基化玉米芯吸附材料(C-C-A)。通过单因素试验和正交试验优化得到C-C-A最佳制备条件,同时采用FTIR、SEM-EDS和XPS对C-C-A进行表征,结果表明其表面凹凸不平,存在大量羧基。C-C-A对Pb^(2+)、Cd^(2+)、Cu^(2+)和Ni^(2+)的去除率均可达到98%以上,说明其可以有效去除重金属离子。C-C-A吸附重金属离子的过程既符合Pseudo-second-order动力学模型,又符合Langmuir等温线模型,属于单分子层化学吸附,且吸附较快。展开更多
为了研究植物乳杆菌材料对黄曲霉毒素去除新方法,为黄曲霉毒素B_(1)的高效生物去除提供了新思路。本文采用基于聚多巴胺的原子转移自由基聚合方法(Polydopamine-based Atom Transfer Radical Polymerization,p-ATRP)和细胞自催化的无铜...为了研究植物乳杆菌材料对黄曲霉毒素去除新方法,为黄曲霉毒素B_(1)的高效生物去除提供了新思路。本文采用基于聚多巴胺的原子转移自由基聚合方法(Polydopamine-based Atom Transfer Radical Polymerization,p-ATRP)和细胞自催化的无铜添加原子转移自由基聚合方法(Cell-catalyzed Copper-free Atom Transfer Radical Polymerization,c-ATRP)对植物乳杆菌活细胞表面进行修饰,引导原子转移自由基聚合(Atom Transfer Radical Polymerization,ATRP)体系自组装聚合反应形成聚合物材料,对修饰后的植物乳杆菌进行表征,并比较修饰前后植物乳杆菌对黄曲霉毒素B_(1)吸附脱附能力。结果表明,未修饰的植物乳杆菌,细胞表面圆润光滑,经过p-ATRP修饰后的植物乳杆菌,细胞表面变得极为粗糙,经过c-ATRP修饰后的植物乳杆菌,细胞表面出现褶皱;未修饰的植物乳杆菌的Zeta点位为-8.43 mV,经过Dopamine和PNIPAAm修饰后的植物乳杆菌点位分别为1.791和13.767 mV;植物乳杆菌在0.1~100μg/mL黄曲霉毒素B_(1)吸附率为75.3%,p-ATRP和c-ATRP修饰的植物乳杆菌比未修饰的植物乳杆菌吸附能力分别提高了7.8%和6.4%。在相同黄曲霉毒素B_(1)浓度下,植物乳杆菌脱附率为6.1%,p-ATRP和c-ATRP修饰的植物乳杆菌脱附能力分别提高了14.4%和42%。经过修饰后的植物乳杆菌显著提升了植物乳杆菌对黄曲霉毒素的吸附和脱附能力。展开更多
文章通过两步反应简单高效地制备出目标多孔有机笼RCC3,将其作为配体和CuBr_(2)配位构建多孔有机笼配合物RCC3@Cu。采用X-射线衍射(X-ray diffraction,XRD)和电喷雾电离质谱(electrospray ionization mass spectrometry,ESI-MS)表征RCC3...文章通过两步反应简单高效地制备出目标多孔有机笼RCC3,将其作为配体和CuBr_(2)配位构建多孔有机笼配合物RCC3@Cu。采用X-射线衍射(X-ray diffraction,XRD)和电喷雾电离质谱(electrospray ionization mass spectrometry,ESI-MS)表征RCC3@Cu的结构与组成,结果表明,RCC3@Cu配位稳定,有望用于介导原子转移自由基聚合(atom transfer radical polymerization,ATRP)。采用RCC3配体介导甲基丙烯酸甲酯(MMA)的ATRP,2 h其转化率达到80%,聚合物分散性指数(polymer dispersity index,PDI)为1.15;最终转化率为98.5%,PDI为1.16。聚合动力学显示RCC3介导的ATRP为近似一级反应动力学,符合活性聚合特征。该文研究RCC3配体介导不同类型单体的聚合,验证了RCC3配体具有单体泛用性。研究结果表明,RCC3体可有效应用于ATRP催化,有进一步研究价值。展开更多
基金The work was financially supported by the National Natural Science Foundation of China(No.52173135,22207024)Jiangsu Specially Appointed Professorship,Leading Talents of Innovation and Entrepreneurship of Gusu(ZXL2022496)the Suzhou Science and Technology Program(SKY2022039).
文摘Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-Ⅱresponsive organic PTMs was explored, and their photothermal conversion efficiencies(PCEs) still remain relatively low. Herein, donor–acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-Ⅱ window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-Ⅱ absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-Ⅱ light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-Ⅱ window, without any side-effect. Moreover, by combining with PD-1 antibody,the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-Ⅱ window, offering a new horizon in developing radical-characteristic NIR-Ⅱ photothermal materials.
基金supported by the National Science and Technology Major Project(No.2016ZX05011-003)The Certificate of China Postdoctoral Science Foundation(No.2016M592241).
文摘Super high molecular weight copolymers of AM/NaA/AMPS were prepared by oxidation–reduction[OR-P(AM/NaA/AMPS)]and controlled radical polymerization[CR-P(AM/NaA/AMPS)].The resulting copolymers were fully characterized,and the reaction conditions for their preparation were optimized.OR-P(AM/NaA/AMPS),CR-P(AM/NaA/AMPS),and conventional partially hydrolyzed polyacrylamide(HPAM)in brine solution were comprehensively characterized by thermogravimetric analysis,scanning electron microscopy,atomic force microscopy,and dynamic light scattering.ORP(AM/NaA/AMPS)and CR-P(AM/NaA/AMPS)containing AMPS monomer showed better salt resistance,temperature tolerance,and viscosification property than the conventional HPAM polymer,making them more promising for enhanced oil recovery.Through comprehensive comparison and analysis,it was found that OR-P(AM/NaA/AMPS)was more conducive for high-temperature condition due to the existence of xanthone in OR-P(AM/NaA/AMPS).On the other hand,CR-P(AM/NaA/AMPS)was more suitable for high-mineral atmosphere,which could be attributed to its higher intrinsic viscosity.
基金Sponsored by the National Science Foundation of China and CAEP(10676003)
文摘The 2,2-dinitropropyl methacrylate（DNPMA） was synthesized by esterification of α-methacrylic acid with 2,2-dinitropropanol.The free-radical bulk polymerization of DNPMA in the presence of 2,2-azobisisobutyronitrile（AIBN） was investigated by differential scanning calorimetry（DSC） in the nonisothermal mode.Kissinger,Ozawa and Barrett methods were applied to determine the activation energy（Ea） and the reaction order of the free-radical polymerization.The results showed that the temperature of exothermic polymerization peaks increased with increasing heating rate.With increasing the molar ratio of monomer/initiator and the heating rate,the reaction order of nonisothermal polymerization was approximately equal to 1.The average Ea value from Kissinger and Ozawa methods（77.74±1.07 kJ/mol） was smaller than the value from the Barrett method（Ea=102.36 kJ/mol）.
文摘Plasma initiated polymerization is a kind of well-known radical polymerization mechanism, but it has the ＇living＇ polymerization feature and produces ultra-high molecular weight polymer. In order to explain such phenomena, we calculate the basic data of plasma initiated polymerization of methylmethacrylate （MMA） according to the principle of polymer physics and chemistry. It results in that the radical concentration ranges from 10^-12mol/L to 10^-16mol/L corresponding to the radical life in 10^4s to 10^8s, which means the radicals have a long lifetime. Moreover because of the long lifetime radicals it causes a unique feature rather than the common radical polymerization, and also shows no ＂living polymerization＂. It is noticed in experiments that there are two key factors playing important roles. One is the effective radical amount produced during the plasma discharging while the another is the diffusion factor.
文摘以玉米芯为原料,利用原子转移自由基聚合(atomic transfer radical polymerization,ATRP)技术在其表面引发丙烯酸甲酯发生聚合反应,再利用NaOH将嫁接在玉米芯表面的聚丙烯酸甲酯水解成聚丙烯酸钠,得到羧基化玉米芯吸附材料(C-C-A)。通过单因素试验和正交试验优化得到C-C-A最佳制备条件,同时采用FTIR、SEM-EDS和XPS对C-C-A进行表征,结果表明其表面凹凸不平,存在大量羧基。C-C-A对Pb^(2+)、Cd^(2+)、Cu^(2+)和Ni^(2+)的去除率均可达到98%以上,说明其可以有效去除重金属离子。C-C-A吸附重金属离子的过程既符合Pseudo-second-order动力学模型,又符合Langmuir等温线模型,属于单分子层化学吸附,且吸附较快。
文摘为了研究植物乳杆菌材料对黄曲霉毒素去除新方法,为黄曲霉毒素B_(1)的高效生物去除提供了新思路。本文采用基于聚多巴胺的原子转移自由基聚合方法(Polydopamine-based Atom Transfer Radical Polymerization,p-ATRP)和细胞自催化的无铜添加原子转移自由基聚合方法(Cell-catalyzed Copper-free Atom Transfer Radical Polymerization,c-ATRP)对植物乳杆菌活细胞表面进行修饰,引导原子转移自由基聚合(Atom Transfer Radical Polymerization,ATRP)体系自组装聚合反应形成聚合物材料,对修饰后的植物乳杆菌进行表征,并比较修饰前后植物乳杆菌对黄曲霉毒素B_(1)吸附脱附能力。结果表明,未修饰的植物乳杆菌,细胞表面圆润光滑,经过p-ATRP修饰后的植物乳杆菌,细胞表面变得极为粗糙,经过c-ATRP修饰后的植物乳杆菌,细胞表面出现褶皱;未修饰的植物乳杆菌的Zeta点位为-8.43 mV,经过Dopamine和PNIPAAm修饰后的植物乳杆菌点位分别为1.791和13.767 mV;植物乳杆菌在0.1~100μg/mL黄曲霉毒素B_(1)吸附率为75.3%,p-ATRP和c-ATRP修饰的植物乳杆菌比未修饰的植物乳杆菌吸附能力分别提高了7.8%和6.4%。在相同黄曲霉毒素B_(1)浓度下,植物乳杆菌脱附率为6.1%,p-ATRP和c-ATRP修饰的植物乳杆菌脱附能力分别提高了14.4%和42%。经过修饰后的植物乳杆菌显著提升了植物乳杆菌对黄曲霉毒素的吸附和脱附能力。
