Concatenation of electrochemical grafting with chemical or electrochemical modification for preparing electrodes with specific surface functionality

Surface modified electrodes are used in electro-analysis, electro-catalysis, sensors, biomedical applications, etc. and could also be used in batteries. The properties of modified electrodes are determined by the surface functionality. Therefore, the steps involved in the surface modification of the electrodes to obtain specific functionality are of prime importance. We illustrate here bridging of two routes of surface modifications namely electrochemical grafting, and chemical or electrochemical reduction. First, by electrochemical grafting an organic moiety is covalently immobilized on the surface. Then, either by chemical or by electrochemical route the terminal functional group of the grafted moiety is transformed. Using the former route we prepared lithium alkyl carbonate (–O(CH₂)₃OCO₂Li) modified carbon with potential applications in batteries, and employing the latter we prepared phenyl hydroxyl amine (–C₆H₄NHOH) modified carbon which may find application in biosensors. Benzyl alcohol (–C₆H₄CH₂OH) modified carbon was prepared by both chemical as well as electrochemical route. We report combinations of conjugating the two steps of surface modifications and show how the optimal route of terminal functional group modification depends on the chemical nature of the moiety attached to the surface in the electrochemical grafting step.     

Structural phase transitions of methane+ethane mixed-gas hydrate induced by 1,1-dimethylcyclohexane

Methane+ethane+1,1-dimethylcyclohexane+water system was investigated by using Raman spectroscopy and isothermal phase equilibrium measurements under four-phase (gas+aqueous+large guest species+hydrate phases) equilibrium conditions at 288.15 K. The results suggest that three kinds of hydrate structures emerge at 288.15 K in the methane+ethane+1,1-dimethylcyclohexane+water system. The hydrate structure for this system changed from structure-H to structure-I via structure-II with increase in the mole ratio of ethane to methane.     

Electrochemical performance of a mechanochemically prepared submicron-sized crystalline Nd1.8Ce0.2CuO4±δ cathode for intermediate temperature solid oxide fuel cells

To produce a Nd_1.8Ce_0.2CuO_4±δ solid solution, the oxide form of the reagents were milled for 36 h and sintered at 1173 K for 8 h in a microwave furnace. The transition from a negative temperature coefficient (NTC) of conductivity to a positive temperature coefficient (PTC) was suppressed due to the submicron size of the crystallites. The low-frequency response in the complex impedance plane fit the Gerischer element. At 973 K, the area specific resistance (ASR) of Nd_1.8Ce_0.2CuO_4±δ/GDC/Nd_1.8Ce_0.2CuO_4±δ sintered at 1073 K for 2 h was 1.92 ohm cm².     

Metastable zone determination of lipid systems: Ultrasound velocity versus optical back‐reflectance measurements

The metastable zone width (MZW) of a multi‐component system as influenced by the process parameters cooling rate, agitation speed, and additive concentration was determined via ultrasound velocity measurements. The results were compared with those obtained by optical back‐reflectance measurements (ORM) using coconut oil as a model substance. Increasing the cooling rate led to the shift of the nucleation point to lower temperatures. This tendency was better visualized by the ultrasonic curves while a significant disturbance of the ORM signal could be observed. Agitation led to an increase of the nucleation temperature and hence a narrower metastable zone. The influence of an additive on the MZW was found to strongly depend on its concentration. The MZW detected by the ultrasound technique was narrower compared to that obtained by the ORM method, indicating the faster response to the phase transition of the ultrasound technique. Another advantage of the ultrasound technique was the in situ evaluation of the experimental data, while ORM needed a linear fitting to estimate the saturation temperature. Furthermore, ultrasound velocity measurements are based on density determination of the medium whereas the ORM sensor is able to detect only particles that are located within the measuring zone and possess a well‐defined size. Practical applications: MZW is one of the most important parameters that determine the characteristics of crystalline products. However, a proper technique that can be used in MZW detection in fat systems has rarely been reported, due to the difficulties in dealing with natural fats. The findings of this study can greatly help those who are involved in the field of fat crystallization from both the academic and the practical point of view. This is due to the fact that new and promising techniques for the online and in situ determination of the MZW of fats, with high accuracy, and reproducibility, under most process conditions, were clarified in this work. The readers can easily follow the procedure developed in this paper. Also information about the influence of process parameters and additives on the MZW is included.     

Green synthesis of biocompatible gold nanoparticles using Fagopyrum esculentum leaf extract

This report describes the use of ethnolic extract of Fagopyrum esculentum leaves for the synthesis of gold nanoparticles. UV-visible spectroscopy analysis indicated the successful formation of gold nanoparticles. The synthesized nanoparticles were characterized by transmission electron microscopy (TEM), high resolution TEM (HRTEM) and were found to be spherical, hexagonal and triangular in shape with an average size of 8.3 nm. The crystalline nature of the gold nanoparticles was confirmed from X-ray diffraction (XRD) and selected-area electron diffraction (SAED) patterns. Fourier transform infrared (FT-IR) and energy-dispersive X-ray analysis (EDX) suggested the presence of organic biomolecules on the surface of the gold nanoparticles. Cytotoxicity tests against human HeLa, MCF-7 and IMR-32 cancer cell lines revealed that the gold nanoparticles were non-toxic and thus have potential for use in various biomedical applications.     

基于有效探测区域的频域内窥式漫射层析成像系统

内窥式漫射层析成像(EDOT)在内部器官癌症的早期诊断方面具有很大潜力,基于本课题组提出的有效探测区域(EDR)方法,发展了基于EDR的频域EDOT系统.首先,为了实现EDR测量模式并简化测量系统,研制了仅利用两根光纤的旋转探头;其次,研制了频域EDOT检测系统,发展了基于EDR的图像重构算法;最后,在固体仿体和管状生物组织上进行了实验验证.固体仿体重构结果表明:重构异质体的大小和位置均同固体仿体目标相同,双异质体可被清晰分开,且吸收和约化散射系数的量化率(QR)分别可达到25%和20%以上;管状生物组织的重构结果表明,重构异质体的位置正确,且重构出的吸收系数和约化散射系数的QR值分别可达到25.3%和18.7%.     

改进的Hough变换在校正汽车牌照倾斜中的应用

针对汽车牌照的自动识别中倾斜问题，对Hough变换提出了新的用法。首先，根据灰度确定汽车图像中车牌的位置和范围，取出包含车牌的子图像；然后对子图像中的点作二级Hough变换算法，计算出子图像中主要直线的角度，该角度被认为是车牌的倾斜角度；最后，用插值旋转的方法进行校正。仿真实验验证了本文算法的有效性。     

Impact of Solvent Additive on Carrier Transport in Polymer:Fullerene Bulk Heterojunction Photovoltaic Cells

The effects of a solvent additive, 1,8‐diiodooctane (DIO), on both hole and electron transport are investigated in a state‐of‐the‐art bulk‐heterojunction (BHJ) system, namely PTB7:PC₇₁BM. For a polymer:fullerene weight ratio of 1:1.5, the electron mobility in the blend film increases by two orders of magnitude with the DIO concentration while almost no change is found in the hole mobility. For lower DIO concentrations, the electron mobility is suppressed because of large, but poorly connected PC₇₁BM domains. For higher concentrations of DIO, the electron mobility is improved progressively and the hole mobility becomes the limiting factor. Between 1 and 5 vol%, the electron and hole mobilities are balanced. Using the Gaussian disorder model (GDM), we found that the DIO concentration modifies fundamentally the average hopping distances of the electrons. In addition, there exist alternative donor–acceptor ratios to achieve optimized PTB7:PC₇₁BM based solar cells. It is demonstrated that the fullerene content of the BHJ film can be significantly reduced from 1:1.5 to 1:1 while the optimized performance can still be preserved.     

Synthesis and performance of LiMn0.7Fe0.3PO4 cathode material for lithium ion batteries

Pure and carbon-containing olivine LiMn_0.7Fe_0.3O₄ were synthesized at 600 °C by the method of solid-state reaction. Structure, surface morphology and charge/discharge performance of LiMn_0.7Fe_0.3O₄ were characterized by X-ray diffraction, scanning electron microscopy, and electrochemical measurement, respectively. The prepared materials with and without carbon both show the single olivine structure. The morphologies of primary particles are greatly affected by the addition of carbon. Large particles (500-1000 nm) and densely sintered blocks were observed in pure LiMn_0.7Fe_0.3PO₄, which made the insertion and extraction of lithium ions difficult. Battery made from this sample can not charge and discharge effectively. The carbon-containing LiMn_0.7Fe_0.3PO₄ has a small particle size (100-200 nm) and a regular appearance. This material demonstrates high reversible capacity of about 120 mAh g⁻¹, perfect cycling performance, and excellent rate capability. It is obvious that the addition of carbon plays an important role in restricting the particle size of the material, which helps to prepare LiMn_0.7Fe_0.3PO₄ with excellent electrochemical performance. The electrochemical reaction resistance is much lower in the partly discharged state than in the fully charged or fully discharged state by the measurement of ac impedance for carbon-containing LiMn_0.7Fe_0.3PO₄. It is indicated that the mixed-valence of Fe³⁺/Fe²⁺ or Mn³⁺/Mn²⁺ is beneficial to the transfer of electron which happens between the interface.     

不同掺量碱集料的活性交流阻抗谱

本文以交流阻抗谱、膨胀率和MIP为研究方法,对不同掺量碱集料活性进行研究。结果表明:交流阻抗谱电化学参数与材料孔隙微观结构有着密切的联系。电阻Rs以及相角θ能表示碱集料活性的大小,可作为碱集料活性的评定方法;当混凝土中活性SiO2含量较高时,孔溶液中OH-离子会被活性SiO2颗粒大量吸附,导致参与碱硅酸反应的碱离子不足,碱硅酸反应生成的碱硅酸凝胶体数量减少。在碱硅酸反应中,活性碱集料与非活性集料之间的比值存在最劣点。