Synthesis and Spectroscopic Characterization of Fluorophore‐Labeled Oligospiroketal Rods

Fluorescence probes consisting of well‐established fluorophores in combination with rigid molecular rods based on spirane‐type structures were investigated with respect to their fluorescence properties under different solvent conditions. The attachment of the dyes was accomplished by 1,3‐dipolar cycloaddition between alkynes and azides (‘click’ reaction) and is a prime example for a novel class of sensor constructs. Especially, the attachment of two (different) fluorophores on opposite sides of the molecular rods paves the way to new sensor systems with less bulky (compared to the conventional DNA‐ or protein‐based concepts), nevertheless rigid spacer constructs, e.g., for FRET‐based sensing applications. A detailed photophysical characterization was performed in MeOH (and in basic H₂O/MeOH mixtures) for i) rod constructs containing carboxyfluorescein, ii) rod constructs containing carboxyrhodamine, iii) rod constructs containing both carboxyfluorescein and carboxyrhodamine, and iv) rod constructs containing both pyrene and perylene parts. For each dye (pair), two rod lengths with different numbers of spirane units were synthesized and investigated. The rod constructs were characterized in ensemble as well as single‐molecule fluorescence experiments with respect to i) specific rod? dye and ii) dye? dye interactions. In addition to MeOH and MeOH/NaOH, the rod constructs were also investigated in micellar systems, which were chosen as a simplified model for membranes.     

The Effect of Sample Age and Neutron Radiation to Dynamic Nuclear Polarization Parameters in Some Asphaltene Suspensions

Nuclear magnetic resonance and the Overhauser effect type dynamic nuclear polarization experiments were performed to study suspensions of asphaltene in the xylene isomers at a low magnetic field of 1.44 mT at room temperature. Intermolecular spin-spin interactions occur between nuclear spins of hydrogen in the solvent medium and the free electron spins in the asphaltene micelles. The samples were prepared in three different asphaltene concentrations at vacuum. The samples were waited for four years and dynamic nuclear polarization parameters were found via dynamic nuclear polarization experiments performed again. Thus, it was investigated the effect of sample age to dynamic nuclear polarization parameters. In addition, the medium concentrations of each sample were exposed to radiation for 48 hours and neutron radiation effects to the dynamic nuclear polarization parameters were investigated. The results are discussed.     

纳米金标记抗体增强SPR检测大肠杆菌O157∶H7

将金纳米粒子(AuNPs)标记的大肠杆菌O157∶H7(E.coli O157∶H7)的多克隆抗体(PAb)作为二抗,采用氨基偶联法将PAb固定在传感器表面作为一抗,通过三明治方法用双通道表面等离子体子共振(SPR)传感器对E.coli O157∶H7进行检测,并与SPR直接法检测进行了比较.结果表明,直接法的检出限为103cfu/mL,线性范围为103～109cfu/mL;AuNPs增强三明治法的检出限为10 cfu/mL,线性范围为10～1010cfu/mL,灵敏度比直接法提高了100倍,且具有更宽的检测范围.本方法不仅检测时间短,而且具有良好的选择性和重现性.     

The effect of ethanol on the phase behaviour and micro-rheology of liquid crystals

The effect of ethanol on the phase behaviour and micro-rheology of lyotropic liquid crystals (LC) has been studied using a binary mixture of monoglyceride (MG) and aqueous ethanol. The phase behaviour study reveals the structural modulation of surfactant aggregates with increasing ethanol concentration, namely a bicontinuous cubic phase (Ia3d) transitions to the lamellar phase (L_α), at a fixed MG concentration. This behaviour is explained by considering the critical packing parameter (CPP) of the surfactant molecule. Because ethanol dehydrates the surfactant head group (a _s), the CPP values increase (decreasing a _s) and thus the formation of larger CPP aggregates is favoured (i.e., the Ia3d–L_α transition occurs). Cross-polarised images and X-ray scattering data support this conclusion. The structural modulation of the LC has further been investigated using a diffusing wave spectroscopy technique. The correlation and relaxation times, determined from the intersection point at short and long time scales of the mean square displacement (MSD), decrease with increasing concentrations of ethanol, indicating structural modulation of the LC. The micro-viscoelastic moduli (G′ and G′′) derived from the Laplace transformation of the MSD decrease with increasing ethanol concentrations, due to the LC modulation. The thermal effects on the micro-rheology of the LC have also been studied.     

Determination of 1-hydroxypyrene in human urine by a multi-wall carbon nanotubes-modified glassy carbon electrode

A multi-walled carbon nanotubes (MWNTs) modified glassy carbon electrode (MWNT-GCE) was used to study the electrochemical behaviour of1-hydroxypyrene (1-OHP) and applied to its determination. The results showed that the modified electrode had a strong adsorptive ability to 1-OHP and enhances its electrochemical signal. By square wave voltammetry, the linear relationship of 1-OHP was 6?×?10^?9???8?×?10^?7?mol?L^?1 with a linear correlation coefficient of 0.996, and the detection limit was 1?×?10^?10?mol?L^?1. Compared with other published methods, this newly proposed method possesses many advantages such as very low detection limit, fast response, low cost and simplicity. And this method was applied successfully in the determination of 1‐OHP in real human urine samples.     

Nanosilver‐Decorated TiO2 Nanofibers Coated with a SiO2 Layer for Enhanced Light Scattering and Localized Surface Plasmons in Dye‐Sensitized Solar Cells

Enhanced harvesting of visible light is vital to the development of highly efficient dye‐sensitized solar cells (DSSCs). Nanosilver‐decorated TiO₂ nanofibers (Ag@TiO₂ NFs) were synthesized by depositing chemically reduced Ag ions onto the surface of electrospun TiO₂ nanofibers (TiO₂ NFs). The prepared Ag@TiO₂ NFs were coated with SiO₂ (SiO₂@Ag@TiO₂ NFs) by using PVP as coupling agent for protecting corrosion of Ag nanoparticle by I^?/${{\rm I}{{- \hfill \atop 3\hfill}}}$ solution. The fabricated SiO₂@Ag@TiO₂ NFs demonstrated a synergistic effect of light scattering and surface plasmons, leading to an enhanced light absorption. Moreover, an anode consisting of SiO₂@Ag@TiO₂ NFs incorporating TiO₂ nanoparticles (NPs) increased light harvesting without substantially sacrificing dye attachment. The power conversion efficiency increased from 6.8 to 8.7 % for a thick film (10 μm), that is, 28 %. These results suggest that SiO₂@Ag@TiO₂ NFs are promising materials for enhanced light absorption in dye‐sensitized solar cells.     

Enhanced Magneto‐optical Properties of Semiconductor EuS Nanocrystals Assisted by Surface Plasmon Resonance of Gold Nanoparticles

Remarkable magneto‐optical properties of a new isolator material, that is, europium sulfide nanocrystals with gold (EuS–Au nanosystem), has been demonstrated for a future photo‐information technology. Attachment of gold particles that exhibit surface plasmon resonance leads to amplification of the magneto‐optical properties of the EuS nanocrystals. To construct the EuS–Au nanosystems, cubic EuS and spherical Au nanocrystals have been joined by a variety of organic linkers, that is, 1,2‐ethanedithiol (EDT), 1,6‐hexanedithiol (HDT), 1,10‐decanedithiol (DDT), 1,4‐bisethanethionaphthalene (NpEDT), or 1,4‐bisdecanethionaphthalene (NpDDT) . Formation of these systems was observed by XRD, TEM, and absorption spectra measurements. The magneto‐optical properties of the EuS–Au nanosystem have been characterized by using Faraday rotation spectroscopy. The Faraday rotation angle of the EuS–Au nanosystem is dependent on the Au particle size and interparticle distance between EuS and Au nanocrystals. Enhancement of the Faraday rotation of EuS–Au nanosystems was observed. The spin configuration in the excited state of the EuS–Au nanosystem was also investigated using photo‐assisted electron paramagnetic resonance.     

Longitudinal Relaxation Enhancement in 1H NMR Spectroscopy of Tissue Metabolites via Spectrally Selective Excitation

Nuclear magnetic resonance spectroscopy is governed by longitudinal (T₁) relaxation. For protein and nucleic acid experiments in solutions, it is well established that apparent T₁ values can be enhanced by selective excitation of targeted resonances. The present study explores such longitudinal relaxation enhancement (LRE) effects for molecules residing in biological tissues. The longitudinal relaxation recovery of tissue resonances positioned both down‐ and upfield of the water peak were measured by spectrally selective excitation/refocusing pulses, and compared with conventional water‐suppressed, broadband‐excited counterparts at 9.4 T. Marked LRE effects with up to threefold reductions in apparent T₁ values were observed as expected for resonances in the 6–9 ppm region; remarkably, statistically significant LRE effects were also found for several non‐exchanging metabolite resonances in the 1–4 ppm region, encompassing 30–50 % decreases in apparent T₁ values. These LRE effects suggest a novel means of increasing the sensitivity of tissue‐oriented experiments, and open new vistas to investigate the nature of interactions among metabolites, water and macromolecules at a molecular level.     

Pt 含量对Co@Pt/C核壳结构催化剂性能的影响

采用两步还原法制得Co@Pt/C核壳结构催化剂, 其中Co与Pt 的总质量分数为20%. 通过改变金属前驱体的用量, 制备了不同Co:Pt 原子比的Co@Pt/C 催化剂, 以20% (w) Co@Pt(1:1)/C 与20% (w) Co@Pt(1:3)/C 表示. 采用透射电镜(TEM)、光电子射线能谱分析(XPS)、循环伏安(CV)、线性扫描伏安(LSV)等方法考察了其结构与性能, 并与实验室早先制备的40% (w) Co@Pt/C 催化剂进行了比较. 自制20% Co@Pt(1:1)/C 与20% Co@Pt(1:3)/C 催化剂的金属颗粒直径约为2.2-2.3 nm, 在碳载体上分散均匀, 粒径分布范围较窄, 电化学活性比表面积(ECSA)分别为56 和60 m²·g^-1, 均超过商用催化剂20% Pt/C(E-tek) (ECSA=54 m²·g^-1). 20%Co@Pt(1:1)/C 与20% Co@Pt(1:3)/C 的半波电位相较于40% Co@Pt(1:1)/C 和40% Co@Pt(1:3)/C 均向正向移动, 表现出更好的氧还原(ORR)催化活性, 并有望降低催化剂的成本, 在质子交换膜燃料电池领域表现出良好的应用前景.     

基于ARM的嵌入式超声传播时间测量装置

应用超声波检测技术进行检测时,通常需对超声波在介质中的传播时间进行精准的测量,为精准测量超声波的传播时间,设计了一套基于ARM的嵌入式超声传播时间测量装置。该装置电路运行稳定,成本低廉,采用多次测量结果取算数平均值的方法以减小随机干扰,采用参比方法放置接收探头以消减电路中电子器件的延时。通过对实验结果进行分析,得出该装置可精准测量超声波在实验试块中的传播时间且满足设计要求,分辨率可达一纳秒。