The synthesis and the bulk rheological properties of the highly-branched block polyethers

Several kinds of highly-branched block polyethers were synthesized via anion ring-opening polymerization of propylene oxide (PO) and ethylene oxide (EO), using phenol-amine resin (PA) as the initiator. The rheological properties determined by rotational rheometer all followed the regular rules of polymer systems: under a certain conditions, the bulk polyethers were pseudoplastic and non-Newtonian fluid, and with the increasing of the shear rate and temperature, the apparent viscosity of the block copolymers were reduced. In addition, modulus determination showed that such polyether molecules presented preferable viscosity compared to the elasticity, meanwhile, storage modulus, loss modulus and compound viscosity all decreased with the increasing of temperature. Storage modulus and loss modulus increased along with the scanning frequency increasing. But compared with the same kind of linear polymers, the significant difference was the low melt viscosity, which attributed to the special three-dimension space structure hindering the entanglement of chains. Furthermore, the rheological properties among the several block polyethers showed differences obviously. In other words, the number of block and the content of EO all have a significant effect on the rheological properties, specifically, the modulus will increase with the increasing of the block number and the EO content.     

差示扫描量热法测定比沙可啶的纯度

建立差示扫描量热法测定比沙可啶原料药样品纯度的方法。考察了炉体气氛、升温速率、称样量3个因素对差示扫描量热法测定结果的影响,确定差示扫描量热法最佳实验条件:升温速率为2.0 K/min,称样量为2.0~4.0 mg,炉内气体为静态空气。差示扫描量热法测定比沙可啶样品纯度为99.86%,测定结果的相对标准偏差为0.02%(n=6),差示扫描量热法测定比沙可啶样品纯度值与HPLC测定结果具有良好的一致性。该方法可以快速、准确地测定比沙可啶化学纯度,为比沙可啶纯度测定提供了一种新的分析方法。     

熵驱大分子胶体粒子的柱状受限结晶

熵是物理化学的基本状态参量,在统计力学和热力学中处于核心位置.按照玻尔兹曼的微观解释,熵可以由孤立系统微观状态的数目(W)给出,即S=kBlnW,这里kB为玻尔兹曼常数[1,2].根据此公式,微观状态数越多,系统越混乱,熵越大,所以熵常被视作体系无序程度的度量.但熵增仅对应体系微观状态数的增加,与可观测的结构有序程度无关[3~5].在一些典型的软物质体系中,结构越有序熵反而越大,如胶体硬球在随机密堆积点的有序结晶[6]及描述各向异性棒状分子从各向同性相到向列相转变的Onsager原理[7].     

Anisotropic charge carrier transport of optoelectronic functional selenium-containing organic semiconductor materials

Organic semiconductors (OSCs) materials are currently under intense investigation because of their potential applications such as organic field-effect transistors, organic photovoltaic devices, and organic light-emitting diodes. Inspired by the selenization strategy can promote anisotropic charge carrier migration, and selenium-containing compounds have been proved to be promising materials as OSCs both for hole and electron transfer. Herein, we now explore the anisotropic transport properties of the series of selenium-containing compounds. For the compound containing Se Se bond, the Se Se bond will break when attaching an electron, thus those compounds cannot act as n-type OSCs. About the different isomer compounds with conjugated structure, the charge transfer will be affected by the stacking of the conjugated structures. The analysis of chemical structure and charge transfer property indicates that Se-containing materials are promising high-performance OSCs and might be used as p-type, n-type, or ambipolar OSCs. Furthermore, the symmetry of the selenium-containing OSCs will affect the type of OSCs. In addition, there is no direct relationship between the R groups with their performance, whether it or not as p-type OSCs or n-types. This work demonstrates the relationship between the optoelectronic function and structure of selenium-containing OSCs materials and hence paves the way to design and improve optoelectronic function of OSCs materials.     

含二茂铁基荧光探针对H2S的识别

以乙酰二茂铁和蒽醛为原料,合成了一种新的反应型荧光探针1-二茂铁基-3-(9-蒽基)丙烯酮,经1H NM R,13C NM R,IR,LC-M S等手段表征确证。基于Michael加成引起的电子转移机制,利用硫化氢的强亲核性,以荧光滴定法考察了该化合物在生理条件下对硫化氢的识别作用,得出其最佳识别时间为50 min,最佳识别浓度为50μmol/L,且多数离子不会对其识别作用产生干扰。这种能稳定检测的,具有高选择性、高灵敏度的反应型荧光探针化合物,可用于生物医药领域。     

基于氮掺杂碳载铁复合物的锌空电池氧阴极催化剂

迫在眉睫的环境和能源问题推动人类探索可行、可靠和可再生的能源技术.锌-空气电池和氢氧燃料电池等器件显示出高能量转换效率,但是仍有许多难题有待克服,例如阴极侧上缓慢的氧还原反应(ORR),以及高昂的成本极大地限制了铂基催化剂在商业上的广泛应用.因此,开发高性能的廉价ORR催化剂具有重要意义.过渡金属碳氮化合物(M-N-C, M=Co, Fe等)成为最有希望替代铂基催化剂的一类材料, M-N-C催化剂可以通过直接热解含有过渡金属、氮和碳物种的前驱体合成.然而热解时金属原子易团聚,多孔结构不能被有效地控制,导致相对较差的催化活性.目前, MOF衍生的催化剂在能源转化和储存技术中得到了广泛的关注,其具有丰富的氮含量、高比表面积和可调的孔道结构等特点.本文报道了一种简便可靠可控的合成铁氮共掺杂碳十二面体纳米结构催化剂的方法,并作为阴极电催化剂用于锌空气电池中,测试结果证实,合成的铁氮共掺杂的纳米碳具有与铂基材料相当的活性和更加优异的稳定性.表面吸附了的邻菲罗啉铁的ZIF-8在碳化过程中,氮基团能够结合铁形成Fe Nx结构单元,因此可得到铁氮共掺杂的电催化剂.粉末X射线衍射,扫描电镜证实ZIF-8的成功合成.经过热解得到的催化剂中Fe Nx或Fe Cx衍射峰较弱,表明样品中铁含量较低,存在部分无定型铁.通过拉曼光谱分析发现,引入的邻菲罗啉在热解过程中诱导了缺陷的形成,所以Fe-NCDNA-0的ID/IG比值明显高于NC.同时ID/IG随着铁含量的增加而减少,这是因为铁可以诱导石墨化,诱导效应随着铁含量的增加而增加.分析氮气吸附-脱附等温线得出,引入邻菲罗啉之后,比表面积增加;而铁的引入因其占据了微孔结构,导致比表面积下降.同时电镜证实Fe-NCDNA-2具有较大的形貌扭曲,使得该材料具有较大的比表面积.系统的电化学研究表明,氮掺杂有利于增强ORR活性,在引入铁之后形成高效的活性中心会进一步提高催化性能.因此, Fe-NCDNA-2在碱性条件下表现出优异的ORR性能.线性扫描伏安法曲线表明,铁氮共掺杂的材料表现出与Pt/C相似的性能,其中Fe-NCDNA-2的半波电位(E1/2)为0.863 V,比商业Pt/C的电位更正(E1/2=0.841 V).同时, Fe-NCDNA-2具有更加优异的稳定性,测试30000 s后的电流保持率为80%(Pt/C:64%).在中性介质中,合成的材料也展示了较高的ORR活性.Fe-NCDNA-2的E1/2=0.715 V,催化30000 s后电流保持率77%,均优于商业Pt/C催化剂.组装的锌空气电池进一步验证其作为氧还原催化剂实际应用的可行性.相比于以Pt/C为催化剂做空气阴极的电池,以Fe-NCDNA-2组装的电池表现出更高的开路电压,更高的功率密度(184 m Wcm^-2),以及更加优异的充放电循环稳定性.该工作也有利于启发研究人员探索类似的氮掺杂过渡金属碳材料在各种催化上的应用.     

基于窄内径多孔层毛细管开管柱的纳流高效液相色谱用于N-衍生化氨基酸对映体的分离

窄内径多孔层毛细管开管柱（NPLOT柱）在生命科学领域,特别是单细胞分析领域具有较好的应用前景。本研究采用原位热引发聚合法来制备窄内径奎尼丁类手性固定相多孔层开管柱,在6 μ m i.d.的毛细管中制备有机聚合物多孔层,考察了不同热聚合时间（3、6和9 h）对NPLOT柱形貌的影响,热聚3 h和6 h制备的NPLOT柱形貌均一,多孔层厚度分别为103±51 nm和210±51 nm。将热聚合3 h制备的NPLOT柱用于纳流高效液相色谱分离N-衍生化氨基酸对映体,在2 min内即可实现基本分离,消耗的样品量仅为皮升级别。该研究将为单细胞分析提供研究手段。     

聚合物前驱体3D打印制备高性能陶瓷

3D打印制备陶瓷可以实现结构-材料设计一体化,为复杂形状陶瓷材料快速成型提供了新途径。但是传统的3D打印制备陶瓷是以陶瓷粉末或陶瓷颗粒为打印材料,存在陶瓷构件尺寸精度差、表面光洁度低和力学性能不佳等问题。近年来,以聚合物前驱体为打印材料,通过3D打印成型、高温裂解等工艺制备高性能陶瓷技术的出现为改善这些不足提供了新方法,成为3D打印陶瓷领域的研究热点。本文概述了聚合物前驱体3D打印制备高性能陶瓷的研究进展,重点阐述了本体聚合物前驱体、聚合物前驱体/光敏化合物、聚合物前驱体/巯基化合物、光敏基团改性聚合物前驱体、增强体/聚合物前驱体五种典型材料体系的研究现状,并对其今后的发展方向进行了展望。     

Analysis of hybrid donor layer in organic solar cells based on SubPc and rubrene

In this paper, photovoltaic characteristics of ITO/PEDOT:PSS/SubPc:Rubrene (mixed ratio R by weight)/C₆₀/Bphen/Ag organic solar cells (OSCs) are analyzed in detail. The intrinsic properties of a SubPc:rubrene doped layer on device performance were discussed based on theoretical analysis of the experimental OSCs. The ratio R was 0, 0.25, 0.5, and 0.75,1, respectively. The results showed that when R was 0.75 performing the best, which owned the highest short circuit current (J _sc ) 6.61 mA/cm² and highest power conversion efficiency (PCE) 2.44%, the FF was 41% and the open circuit current (V _oc ) was 0.905 V. The suitable HOMO level, absorption capacity, carrier transport ability and exciton diffusion length (L _D ) of organic material are very important for the performance of the device.     

锁相环的相位模型与实验电路

讨论了锁相环的相位数学模型,给出了一种适合于数学的锁相环实验电路．