应用化学交流论坛举办第九期——发泡材料

3月25日，第九期应用化学交流论坛在图书馆三楼阅览室成功举办。本期论坛以“发泡材料”为主题，邀请中科院生态环境高分子材料重点实验室董丽松研究员、高分子物理与化学国家重点实验室唐涛研究员担任主讲嘉宾。景遐斌研究员、姬相玲研究员、姜伟研究员、栾世方研究员、李胜海研究员、科技发展处孙小红处长以及多位中青年科研骨干、来自东北师大的青年教师等参加了此次活动。论坛活动中大家回顾了应化所发泡材料研究历史，分析了领域的现状，展望了行业的发展前景。参会者介绍了各自所在课题组从事的相关工作及进展情况，在讨论了一些共性科学问题的同时，又从基础理论、应用拓展、产业化推进等方面提出了新的问题和设想。针对目前国家重点研发计划的组织模式，参会者表达了对整合力量组建更大团队的想法，规划与信息处、科技发展处也就所内相关政策做了解释和说明。为取得更好的交流效果，论坛积极尝试各种组织形式。此次论坛活动在资产处图书馆的大力支持下，在更和谐的交流氛围中获得了参会者的广泛好评。“应用化学交流论坛”由所学术委员会牵头，由规划与信息处负责组织实施。目的在于加强所内科研人员相互了解，增进沟通交流，推进相近领域方向人员展开合作，促进跨学科跨领域前沿探索，激发中青年人才创新活力。2016年论坛活动将更加关注材料领域，注重产学研结合，加大“请进来、走出去”力度，打造东北地区最具影响力的学术活动品牌

Controllable synthesis of a narrow polydispersity CO2-based oligo(carbonate-ether) tetraol

A CO2-based oligo(carbonate-ether) tetraol was synthesized in a controlled manner by immortal copolymerization of carbon dioxide (CO2) and propylene oxide (PO) in the presence of 1,2,4,5-benzenetetracarboxylic acid (btcH(4)) catalyzed by using a zinc-cobalt double metal cyanide (Zn-Co-DMC) catalyst. The number average molecular weight (M-n) of the tetraol was in a good linear relationship with the molar ratio of PO and btcH4 (PO/btcH(4)), and hence can be precisely controlled. Besides, the rapid chain transfer in immortal copolymerization afforded the tetraol with a narrow polydispersity index (PDI) of 1.08 at a Mn of 1400 g mol(-1). Notably, the weight fraction of the byproduct propylene carbonate (W-PC) was reduced to as low as 4.0 wt%, which is the lowest W-pc ever reported for the synthesis of branched polyols. The structure of the oligo(carbonate-ether) tetraol was confirmed, providing new evidence for the effect of the acidity (pK(a1) value) of the chain transfer agent (CTA) on the initial catalytic mechanism. The acid only acts as the CTA directly participating in the copolymerization via the chain transfer reaction when its pK(a1) value is higher than that of adipic acid (pK(a1) = 4.43). However, when its pK(a1) value is lower than that of succinic acid (pK(a1) = 4.2), it acts as the initiate-transfer agent, which first initiates PO homopolymerization to an oligo-ether polyol, and then the in situ formed polyol acts as a new CTA for the copolymerization

Superior catalytic performance of Ce1-xBixO2-delta solid solution and Au/Ce1-xBixO2-delta for 5-hydroxymethylfurfural conversion in alkaline aqueous solution

Porous Bi-doped ceria(Ce1-xBixO2-delta solid solution) was prepared by the easy citrate method and then used as a supporting material for Au nanoparticles (NPs) obtained by deposition-precipitation. In the presence of O-2, Ce1-xBixO2-delta (0.08 <= x <= 0.5) efficiently catalyzed the conversion of 5-hydroxymethylfurfural (HMF) to 5-hydroxymethyl-2-furancarboxylic acid (HFCA) and 2,5-bishydroxymethylfuran (BHMF) in alkaline aqueous solution without degradation of HMF. The excellent catalytic activity was attributed to the oxygen activation and hydride transfer enhanced by Bi doping and the large amount of oxygen vacancies. After Au NPs were supported on Ce1-xBixO2-delta (x <= 0.2), the presence of Au delta+ facilitated the activation of the C-H bond in the hydroxymethyl group and then the production of 2,5-furandicarboxylic acid (FDCA) as an end product, inhibiting the generation of BHMF

蓖麻毒素和相思子毒素快速检测方法的研究

蓖麻毒素（ricin）和相思子毒素（abrin）是两个结构和功能类似的植物毒素，具有毒性强、来源广、易制备的特点，是生物武器核查清单中仅有的两种植物蛋白毒素，也是重要的生物恐怖剂之一。面对防生物战和反生物恐怖的迫切需求，对蓖麻毒素和相思子毒素的快速检测和防治已成为一个重要的研究热点。为此，本论文开展了对蓖麻毒素和相思子毒素快速检测方法的研究。 1. 应用一种基于适配子和免修饰金纳米粒子的比色分析法来实现对蓖麻毒素的检测。检测时，当体系中不存在蓖麻毒素时，蓖麻毒素的适配子可以吸附在金纳米粒子的表面，从而保护金纳米粒子在NaCl存在的条件下不发生聚集，溶液呈红色；当体系中存在蓖麻毒素时，适配子优先结合蓖麻毒素并发生构象改变，适配子失去保护金纳米粒子的能力，使得金纳米粒子在NaCl存在的条件下发生聚集，溶液呈蓝色。根据溶液颜色的变化就能够得到蓖麻毒素的定量分析结果。本方法具有较高的灵敏度，对于蓖...Ricin and abrin are phytotoxins with similar structure and properties. Their high toxicity, wide distribution and easy preparation make them the important phytotoxic bioterrorism agents listed in the checklist for biological weapons. The rapid test and prevention of both toxins have been a research hotspot in order to meet the urgent needs of defending against biological war and bioterrorism. Therefore, the study on the rapid detection method of ricin and abrin was carried out and detailed in this thesis. 1. We report a colorimetric detection method of ricin using ricin binding aptamer (RBA) as recognition element and unmodified gold nanoparticles as probe. In the absence of ricin, RBA could be adsorbed onto the surface of AuNPs and protect the AuNPs from NaCl-induced aggregation. The colo..

弱外延生长红荧烯薄膜

有机半导体材料由于具有分子结构多样性，丰富的物理、化学性质，并且容易实现功能的多样化，与生物亲和性好，可实现柔性器件的制备，易于大面积加工，成本低廉等优势特性，使其成为制备下一代电子器件的有力竞争体系。近几十年来，随着研究的不断深入，有机半导体材料发展迅速，以其为有源材料制备的器件性能得到了大幅度提高。尤其是在晶体管器件方面，已经超越了非晶硅的水平，具有广阔的应用前景。在有机半导体材料中，红荧烯是具有较高晶体管器件性能的一种小分子材料，单晶晶体管迁移率最优可达到40 cm2/Vs，但其薄膜晶体管器件性能却与之存在很大的差距，原因在于其在结晶薄膜的制备上存在困难，红荧烯容易在基底上形成非晶薄膜，进而限制了其薄膜晶体管器件的发展。因此如何制备出高有序的红荧烯结晶薄膜成为了研究热点，但是对于红荧烯结晶薄膜的成核机理还尚不清楚。因此，开展对于高有序红荧烯结晶薄膜成核规律以及特性的研究具有重要的意义...Organic semiconductor materials have become a powerful competitive material system for the preparation of next generation electronic devices duo to their special advantages such as diversity in molecular structures, rich in physical and chemical properties, easy to realize the device with multiple functions, good biological compatibility, realization of flexible device, easy for large-area processing and low cost. In recent decades, with the deepening of the research, organic semiconductor materials developed rapidly and their device performances were improved to a great extent. Especially in the field of transistor devices, the device performance has transcended the amorphous silicon level with a broad application prospect. In organic semiconductor materials, rubrene is a kind of small mo..

氢键增强的药物及基因载体

在使用小分子药物和基因药物对疾病进行治疗的过程中，为了提高治疗效果，降低毒副作用，均需要使用性能优异的载体。为了使载体具有更佳的药物和基因传递效果，我们需要对载体的性能进行调控，以满足不同治疗方法的需求。载体对药物和基因的担载离不开载体与药物、基因之间的相互作用。如化学键合作用、疏水相互作用或静电相互作用，等等。氢键是一种广泛存在于分子间和分子内的一种相互作用，它的存在对物质的理化性质有诸多影响。然而目前已有的报道中，鲜有研究去探索氢键对纳米药物载体和基因载体性能的影响。 本论文中，我们通过简单的材料设计和合成，向纳米药物载体和基因载体体系中引入了不同的氢键给体基团，试图探索氢键对于这些药物、基因载体的理化性能和生理性能的影响。 本论文的主要研究内容和主要结论如下： 1）通过氨基化聚乙二醇引发苄氧羰基保护的赖氨酸聚合，并在脱保护后对侧链氨基进行苄基（硫）脲改性，得到三种结构类似，但氢键结合...The demands for highly efficient drug/gene carriers are increased as time goes by, which could improve the therapeutic effect and decrease toxic or side effects during the treatment of diseases by small molecular drugs or theraputic genes. To achieve better drug/gene delivery efficiency, the performance of carriers should be adjusted so as to fullfil the different demands of different therapies. For the loading of durgs or genes, the interactions between the durg/gene and the carriers are always needed. In most of the existed drug/gene delivery systems, chemical bonds, hydrophobic interactions, electrostatic interactions etc. are used. Hydrogen bonds are a class of ubiquitous intermolecular or intramolecular interactions, and could affect many physicochemical properties of substances. Howe..

超声波制备可溶液加工半导体纳米晶界面材料研究

由于有机聚合物太阳能电池符合大规模低成本的辊对辊、喷涂、刮涂等溶液制膜加工方式的要求，同时其基底可以为有一定的机械强度柔性塑料基板，在过去的二十年一直是国际上的前沿研究领域和热点研究课题。随着窄带隙宽吸收的新型活性层给体材料的不断涌现，以及活性层中给受体纳米互穿网络结构的进一步优化，电池效率已经达到了10%。引入合适的电极界面层对提高有机光伏器件的能量转换效率和器件稳定性至关重要。常用的阳极界面材料PEDOT：PSS由于其弱酸性和吸湿特性影响器件的长期稳定性。可溶液加工的过渡金属氧化物纳米粒子作为电极界面材料在有机太阳能电池器件中得到了广泛研究, 但是目前采用溶胶-凝胶法制备的过渡金属氧化物纳米粒子通常需要高温后退火处理, 影响其在有机光伏器件中的实际应用。本论文以超声波制备可溶液加工无机半导体纳米晶界面材料为研究主题, 利用超声化学法合成出一系列可溶液加工的低温免退火的半导体纳米晶阳极和...Polymer solar cells (PSCs) have drawn intense investigation in the past decades due to their compatibility with large-scale thin film deposition technologies such as roll-to-roll processing, spray coating and inkjet printing, etc, and the combined merits of low cost, light weight and mechanical flexibility. Along with the advances of novel low bandgap polymer donors as well as the manipulation of bicontinuous nanoscale D/A phase separation, the power conversion efficiency (PCE) of PSCs has reached the so-called threshold of 10%. The interfacial layers play crucial roles in determining the photovoltaic performance and stability of PSCs. For example, the commonly used anode interfacial material PEDOT:PSS is considered to have a harmful effect on the device stability due to its acidic and hyg..

Immobilization of nattokinase-loaded red blood cells on the surface of superhydrophobic polypropylene targeting fibrinolytic performance

A platform for capture and release of drug-loaded red blood cells (RBCs) is demonstrated by utilizing polymer grafted superhydrophobic polypropylene (PP). Combined with micro/nanobinary structures, thermoresponsive polymers, and lectin-saccharides recognition, this platform enables highly efficient capture and release of RBCs loaded with nattokinase, which endows PP with potent fibrinolytic ability

Three-dimensional Fe- and N-incorporated carbon structures as peroxidase mimics for fluorescence detection of hydrogen peroxide and glucose

In this study, a simple and one-pot pyrolysis strategy is developed for the mass production of Fe, N-incorporated carbon nanotubes in situ grown on 3D porous carbon foam (denoted as Fe-Phen-CFs), which provides highly active Fe-N and doped-N species, and a large surface area with exposed active sites. The obtained composite exhibits intrinsic peroxidase-like catalytic activities. With the Fe-Phen-CFs as the catalyst, the peroxidase substrate of terephthalic acid (TA) can be oxidized to the fluorescent product of hydroxyterephthalate (HTA) by H2O2, which provides a unique strategy for fluorescence detection of H2O2. With such a process, as low as 68 nM H2O2 could be detected with a linear range from 0.1 to 100 mu M. Meanwhile, by integrating glucose oxidase on the Fe-Phen-CFs composite, sensitive detection of glucose is also achieved with a linear range from 0.5 to 200 mM and a limit of detection of 0.19 mM. Most importantly, such a novel TA/Fe-Phen-CFs system can be successfully applied to glucose determination in real human serum samples. The unique nature and 3D structure of the Fe-Phen-CFs composite makes it promising for the fabrication of low-cost, high-performance biosensors

Construction of D-alpha-tocopheryl polyethylene glycol succinate/PEO core-shell nanofibers on a blood-contacting surface to reduce the hemolysis of preserved erythrocytes

The hemolysis of erythrocytes is a big obstacle to the development of new non-plasticizer polymer containers for erythrocyte preservation. To construct a long-term anti-hemolytic surface of a plasticizer-free polymer, we coaxially electrospin core-shell structured D-alpha-tocopheryl polyethylene glycol 1000 succinate (TPGS)/poly(ethylene oxide) nanofibers on the surface of a styrene-b-(ethylene-co-butylene)-b-styrene (SEBS) elastomer that is covered with grafted poly(ethylene glycol) (PEG) chains. Our strategy is based on the fact that the grafted layers of PEG reduce mechanical damage to red blood cells (RBCs) while the TPGS released from the nanofibers on a blood-contacting surface can act as an antioxidant to protect RBCs from oxidative damage. We demonstrate that TPGS/PEO core-shell structured nanofibers have been well prepared on the surface of PEG modified SEBS; the controlled release of TPGS in distilled water is obtained and the release can last for almost 4 days at 4 degrees C; during RBC preservation, TPGS acts as the antioxidant to decrease the membrane oxidation and hemolysis of RBCs. Our work paves a new way for the development of non-plasticizer polymers for RBC preservation, which may be helpful for the fabrication of long-term anti-hemolytic biomaterials in vivo