Orthogonal solubility in fully conjugated donor-acceptor block copolymers: Compatibilizers for polymer/fullerene bulk-heterojunction solar cells

Donor-acceptor (D-A) type fully conjugated block copolymer systems have been rarely reported due to the challenges in synthetic approaches to prepare well-defined low-polydispersity products. In this work, fully conjugated block copolymers are synthesized in a one-pot reaction through Stille coupling polycondensation, by utilizing the end-functional polymer copolymerization method. End-functional P3HT are copolymerized with AA (2,7-dibromo-9-(heptadecan-9-yl)-9H-carbazole) and BB (4,7-bis(5-(trimethylstannyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole, TBT) type monomers, respectively. The orthogonal solubility between the very soluble P3HT donor and the insoluble PCDTBT acceptor block improves the purity of block copolymers as well as distinct nano-scale phase-separation compared with other reports on miscibility of donor and acceptor polymer block. Further purification via preparative GPC is carried out to remove the excess of unreacted P3HT and free PCDTBT as well as to achieve low polydispersity of block copolymers. The chemical structure of the P3HT-b-PCDTBT block copolymers are verified via ¹H-NMR, and further confirmed by FTIR spectra. The block copolymer shows broad absorption and moderate optical band gap of 1.8 eV. Furthermore, the fully conjugated block copolymer films exhibit significant fine structures, much smoother film morphology compared to P3HT/PCDTBT polymer blends. By adding a small amount of block copolymer P3HT-b-PCDTBT as a compatibilizer into the bulk-heterojunction of P3HT:PC₆₁BM blends, polymer solar cells with an 8% increase of short circuit current (J _sc and 10% increase of power conversion efficiency (PCE) are achieved owing to the improvement of the active-layer film morphology. To the best of our knowledge, this is the first report on donor-acceptor type fully conjugated block copolymer as an effective ternary additive in polymer: fullerene bulk heterojunction solar cells.     

非富勒烯聚合物太阳电池研究进展

综述了以p-型共轭聚合物为给体、n-型有机半导体为受体的非富勒烯聚合物太阳电池光伏材料最新研究进展,包括n-型共轭聚合物和可溶液加工小分子n-型有机半导体(n-OS)受体光伏材料,以及与之匹配的p-型共轭聚合物给体光伏材料.介绍的n-型共轭聚合物受体光伏材料包括基于苝酰亚胺(BDI)、萘酰亚胺(NDI)以及新型硼氮键连受体单元的D-A共聚物受体光伏材料,目前基于聚合物给体(J51)和聚合物受体(N2200)的全聚合物太阳电池的能量转换效率最高达到8.26%.n-OS小分子受体光伏材料包括基于BDI和NDI单元的有机分子、基于稠环中心给体单元的A-D-A型窄带隙有机小分子受体材料等.给体光伏材料包括基于齐聚噻吩和苯并二噻吩(BDT)给体单元的D-A共聚物,重点介绍与窄带隙A-D-A结构小分子受体吸收互补的、基于噻吩取代BDT单元的中间带隙二维共轭聚合物给体光伏材料.使用中间带隙的p-型共轭聚合物为给体、窄带隙A-D-A结构有机小分子为受体的非富勒烯聚合物太阳电池能量转换效率已经突破12%,展示了光明的前景.最后对非富勒烯聚合物太阳电池将来的发展进行了展望.     

Simultaneous determination of tyramine and tryptamine and their precursor amino acids by micellar liquid chromatography and pulsed amperometric detection in wines

Two biogenic amines, tryptamine and tyramine, and their precursors, tryptophan and tyrosine, were determined by a liquid chromatographic procedure. A hybrid micellar mobile phase of sodium dodecyl sulphate (SDS) and 1-propanol, a C18 column and electrochemical detection were used. A pH study in the range of 3-9 was performed and pH 3 was finally selected in accordance with resolution and analysis time. Oxidation potential was also checked in the range 0.6-0.9V: the maximum area obtained in all those potentials was at 0.8V, which was selected to carry out the analysis using a sequence of pulsed amperometric detection waveform. The four compounds were resolved using a mobile phase of 0.15M SDS-5% 1-propanol with an analysis time of 16 min. Repeatabilities and intermediate precision were evaluated at three different concentrations for each compound with RSD values lower than 2.6 and 4.8%, respectively. Limits of detection and quantification were also obtained within the 10-40 and 33-135 ng/ml ranges, respectively. Finally, the applicability of the procedure was tested in several types of wine and no matrix effect was observed. The possibility of direct sample introduction simplifies and greatly expedites the treatments with reduced cost, improving the accuracy of the procedures.     

Multiresidue pesticide analysis of fruits by ultra-performance liquid chromatography tandem mass spectrometry

Ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC–MS–MS) has been used for screening and quantification of 32 pesticides and metabolites in two fruit matrices. The compounds investigated belonged to different chemical families of insecticides, acaricides, fungicides, and herbicides; several metabolites were also included. Quantification was conducted using matrix-matched standards calibration; response was a linear function of concentration in the range tested (10–500 ng mL⁻¹). The method was validated with blank samples of lemon and raisin spiked at 0.01 and 0.1 mg kg⁻¹, and recoveries were satisfactory, between 70 and 110%, for most of the pesticides tested and relative standard deviations were below 15% (n = 5 at each spiking level). Excellent sensitivity resulted in limits of detection for all compounds well below 0.01 mg kg⁻¹, with the limit of quantification being validated at 0.01 mg kg⁻¹. The UPLC system generates narrow peaks (approx. 5 s), thus increasing peak height and improving sensitivity. This improved separation efficiency facilitates adequate resolution not only of the analytes but also of matrix interferences compared with conventional HPLC. The method developed could also resolve some geometric isomers. The main advantage of this approach is the high sample throughput achieved because of the short analysis time, which enables satisfactory separation of all the compounds in less than 5 min per sample.     

四元体系CsCl-PrCl3-13%HCl-H2O(25℃)和CsCl-Prcl3-42%HAc-H2O(30℃)的相平衡研究

测定了四元体系CsCl-PrCl₃-13%HCl-H₂O(25℃)和CsCl-PrCl₃-42%HAc-H₂O(30℃)的稳定平衡态的溶度数据,绘制了相应的溶度图.两个体系中皆有4种固相:CsCl、PrCL₃·6H₂O₂种原始盐和CsCl·PrCl·6H₂O、3CsCl·PrCl₃·7H₂O2种复盐.证实了文献中对Meyer反应1机理的解释,并对新相进行了热分析、X射线粉末衍射及偏光显微镜测定.     

11B NMR study of the tautomeric transformations of the 7,8-dicarba-nido-und ecaborane(11) adducts with pyridine derivatives

The tautomeric transformations of o-carborane(12) 7,8-C₂B₉H₁₁-Py(X), where Py(X) = 4-picoline (4-CH₃-C₅H₄N), 3-picoline (3-CH₃-C₅H₄N 4-stilbazole (4-C₆H_5-C₂H₂-C₅H₄N, or 3-bromopyridine (3-Br-C₅H₄N), and the iodo derivative 7,8-C₂B₉H₁₀I C₅H₅N were studied by¹¹B NMR spectroscopy in solution. The tautomeric transformations found are caused by migration of the bridging hydrogen cluster C₂B₉H₁₁ which is present in the structures. In the¹¹B NMR spectra, the boron signal is observed in the high-field region of the spectrum if the nearest two boron atoms are additionally bound by the bridging hydrogen. This enables the recording of the dynamic structural transformations of the adducts. It was found that the tautomeric equilibrium depends on the nature of substituents introduced in the heterocyclic ligand and the carborane cluster. Substituents with greater electron-accepting ability induce a shift of equilibrium toward the tautomer in which the bridging hydrogen is farther from the boron atom bonded to the substituent.     

Soil radon levels measured with SSNTD's and the soil radium content

The source of the radon gas ²²²Rn in the ground air is the soil and the bedrock underneath. The potential radon level in the ground is given by the content of ²²⁶Ra in the ground. The presence of ²²⁶Ra is in turn dependent on the amount of ²³⁸U in the ground, and these two isotopes are not always found to be in equilibrium in a sample of soil or bedrock. Especially if the soil is washed out, the radium content may be reduced. When the soil is the relevant source of the radon gas, it is interesting to look for a possible relation between the radon level and the radium content of the soil.

In this paper we report on measurements of soil radon level carried out with SSNTDs at several European sites. Soil samples were collected at these sites and analysed with gamma spectrometry to determine their radium content. A comparison of the different degree of disequilibrium of radon, defined as the ratio between the actual and the secular equilibrium-with-radium soil radon concentration, found at the different sites and depths is presented. The influence on the result of soil type and climate is briefly discussed.     

一维位势透射系数的计算与谐振隧穿现象的研究

使用具有不同有效质量的一维多阶梯势透射系数的递推计算公式,可以方便地计算任意形状的一维分区位势的透射系数。给出了几种位势的透射系数随入射粒子能量变化的曲线,研究了谐振隧穿现象。对半导体材料GaAlAs/GaAs/GaAlAs的谐振隧穿现象进行了较详细的讨论。计算结果表明,对于两对称方势垒夹一个任意形状势阱的位势,也可能存在谐振隧穿现象。     

二甲基硅硼烷,o-(SiMe)_2B_(10)H_(10),振动光谱的理论研究

本文利用高斯 94从头计算程序在 6- 31 G基组下对二甲基硅硼烷 ,o- (Si Me) 2 B1 0 H1 0 ,进行几何优化及振动光谱的理论计算 ,并对主要谱带特性进行指认 ,结果与实验基本符合。振动模式分析表明 450 cm-1 以下的两个强带中 32 6cm-1 (计算值为 369cm-1 )似乎是两个 Si原子相对笼骨架中其余 B原子整体的伸缩振动 ,而 399cm-1 (计算值为 42 1 cm-1 )则为 Si- Si(及其联带的 C原子一起参与的 )对称伸缩振动。优化几何及振动光谱的研究表明重的杂原子硅占据二十面体硼笼骨架位置后使笼结构的刚性弱化     

用丹磺酰氯定性鉴定吡咯喹啉醌

建立了用丹磺酰氯定性鉴定吡咯喹啉醌的薄层色谱法. 甲基营养菌 No.2 培养液经二乙氨基乙基交联葡聚糖凝胶 A-25离子交换剂、 Sep-Pak C18 Cartridge 纯化后,可获得纯度92%以上的吡咯喹啉醌(PQQ)粉末. 在碱性条件下丹磺酰氯(DNS-Cl)可与 PQQ 生成具有特征性的 DNS-N-PQQ 荧光衍生物, 将其点样于聚酰胺薄膜上, 经正庚烷-正丁醇-醋酸(体积比3∶3∶1)系统展开, Rf值为0.73.