Dye-sensitized solar cells based on composite solid polymer electrolytes

The ionic conductivity of polymer electrolytes and their interfacial contact with dye-attached TiO2 particles were enhanced markedly by the addition of amorphous oligomer into polymer electrolytes, resulting in very high overall energy conversion efficiency.     

K对Mn—Co—O的结构及氧化活性的影响

利用XRD,TPD,TFD-MS及催化氧化反应等实验技术,研究了K对Mn-Co-O的结构及氧化活性的影响。XRD结果表明,Mn-Co-O系已形成反尖晶石型的MnCo_2O_4结构;K-Mn-Co-O系中除MnCo_2O_4型结构外,还有新相KMnO_2存在。根据O_2的TPD-MS及吡啶的TPD结果,Mn-Co-O中添加适量的K能提高供氧活性和增加供氧数目,但酸中心数目减少,强度降低。K对Mn-Co—O催化剂氧化活性的影响随反应物分子结构的不同而异,对乙酸乙脂、苯甲酰氯等极性有机物的完全氧化反应,K能提高氧化活性,但对苯、正己烷等非极性有机物的完全氧化反应,K使其活性降低。     

新型重整催化剂的研究—Pt／BaKL型沸石中钡的作用

本文采用XRD,NH_3-TPD,IR以及TEM等方法考察了Pt/BaKL沸石中Ba~(2+)的作用。NH_3-TPD结果表明,交换Ba~(2+)后的L型沸石的酸性,由于阳离子的作用仅在弱酸范围内有些改变,但与载铂的沸石的催化活性无明显的对应关系。IR及XRD谱线表明,BaKL沸石中Ba~(2+)在最佳交换度(26.3%)时,随预培烧温度的提高,使Ba~(2+)处于沸石孔道中B、C、D位置,接近于最佳分布,此时IR谱线上1421cm~(-1)处有一新峰。当沸石负载铂后,因铂与Ba~(2+)的相互作用,新峰消失,导致铂粒在沸石上分布更加均匀;铂粒在1.5—3.0nm之间占有最大比例,使得Pt/BaKL沸石呈现芳构化活性及选择性高于Pt/KL沸石,分别为～98%和～95%。     

Fibrous crystalline hydrogels formed from polymers possessing a linear poly(ethyleneimine) backbone

Novel thermoreversible physical hydrogels formed from polymers with linear and star architectures possessing a linear poly(ethyleneimine) (PEI) backbone have been investigated. The hydrogelation occurred simply upon natural cooling of hot aqueous solutions of PEIs to room temperature. The X-ray diffraction and differential scanning calorimetry measurements for the resultant hydrogels unambiguously indicated that the hydrogelation originated from the formation of dihydrate crystalline structures of PEI. These crystalline hydrogels are structurally unique and hierarchical. Microscopic images revealed that the morphologies of the crystalline hydrogels depend on their molecular architectures. The linear PEI resulted in branched fibrous bundles organized by unit crystalline nanofibers with a width of ca. 5-7 nm. The six-armed star with benzene ring core produced fanlike fibrous bundles while the four-armed star with porphyrin core assembled into asterlike aggregates. The critical concentration of gelation (C(G)) was low (about 0.2 approximately 0.3%) and the thermoreversible gel-sol transition temperatures (T(G)) were controllable from approximately 43 to approximately 79 degrees C. The hydrogels formed in the presence of the various aqueous additives including organic solvents, hydrophilic polymers, physical cross-linker, chemical cross-linker, and base enabling modification and functionalization during synthesis. The mechanical properties of the hydrogels could be improved by chemical cross-linking of preformed hydrogels by glutaraldehyde. Physically and physical/chemical cross-linked hydrogels served as excellent template roles in biomimetic silicification, which produced silica-PEI hybrid powder or monolith constructed by nanofibers.     

What controls the melting properties of DNA-linked gold nanoparticle assemblies?

We report a series of experiments and a theoretical model designed to systematically define and evaluate the relative importance of nanoparticle, oligonucleotide, and environmental variables that contribute to the observed sharp melting transitions associated with DNA-linked nanoparticle structures. These variables include the size of the nanoparticles, the surface density of the oligonucleotides on the nanoparticles, the dielectric constant of the surrounding medium, target concentration, and the position of the nanoparticles with respect to one another within the aggregate. The experimental data may be understood in terms of a thermodynamic model that attributes the sharp melting to a cooperative mechanism that results from two key factors: the presence of multiple DNA linkers between each pair of nanoparticles and a decrease in the melting temperature as DNA strands melt due to a concomitant reduction in local salt concentration. The cooperative melting effect, originating from short-range duplex-to-duplex interactions, is independent of DNA base sequences studied and should be universal for any type of nanostructured probe that is heavily functionalized with oligonucleotides. Understanding the fundamental origins of the melting properties of DNA-linked nanoparticle aggregates (or monolayers) is of paramount importance because these properties directly impact one's ability to formulate high sensitivity and selectivity DNA detection systems and construct materials from these novel nanoparticle materials.     

Quantitative determination of glutathione in single human erythrocytes by capillary zone electrophoresis with electrochemical detection

Glutathione (GSH) in single human erythrocytes is determined by capillary zone electrophoresis with end-column amperometric detection at a gold/mercury amalgam microelectrode. A capillary of 10 microm inner diameter is suitable for determination of GSH in an individual erythrocyte with a good signal-to-noise ratio. The limit of detection is 1 x 10(-7) mol/L or 26 amol and the linear dynamic range is 2 x 10(-7) to 2 X 10(-5) mol/L for the capillary. In this method, the calibration line is obtained with a capillary adsorbed before a certain amount of hemoglobin can be used for the quantification of GSH in the external standardization. The whole cell injection and the lack of necessity of a derivatization reaction lead to more accurate and precise results, which are closer to the macroscopic values of glutathione in human red blood cell (i.e., hemolysate) than those determined by indirect laser-induced fluorescence detection.     

Sorption of 241Am by Aspergillus nigerspore and hyphae

Biosorption of ²⁴¹Am by a fungus A. niger, including the spore and hyphae, was investigated. The preliminary results showed that the adsorption of ²⁴¹Am by the microorganism was efficient. More than 96% of the total ²⁴¹Am could be removed from ²⁴¹Am solutions of 5.6-111 MBq/l (C _o) by spore and hyphaeof A. niger, with adsorbed ²⁴¹Am metal (Q) of 7.2-142.4 MBq/g biomass, and 5.2-106.5 MBq/g, respectively. The biosorption equilibrium was achieved within 1 hour and the optimum pH range was pH 1-3. No obvious effects on ²⁴¹Am adsorption by the fungus were observed at 10-45 °C, or in solutions containing Au³⁺ or Ag⁺, even 2000 times above the ²⁴¹Am concentration. The ²⁴¹Am biosorption by the fungus obeys the Freundlich adsorption equation. There was no significant difference between the adsorption behavior of A. nigerspore and hyphae. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dispersion state of CuO on CeO2

XRD and XPS are used to study the dispersion state of CuO on ceria surface. The dispersion capacity values of CuO measured by the two methods are consistent, which are of 1.20 mmol CuO/100 m² CeO₂. In addition, the results reveal that highly dispersed Cu²⁺ ions are formed at low CuO loadings and that increasing the CuO content to a value higher than its dispersion capacity produces crystalline CuO after the surface vacant sites on CeO₂ are filled. The atomic composition of the outermost layer of the CuO/CeO₂ samples has been probed by using static secondary ion mass spectroscopy (SSIMS), and the ratim of Cu/Ce are found to be 0.93 and 0.46 for the 1.22 and 0.61 mmol CuO/CeO₂ samples respectively. Temperature-programmed reduction (TPR) profile with two reduction peaks at 156 and 165°C suggests that the reduction of highly dispersed Cu²⁺ ions consists of two steps and is easier than that of CuO crystallites, in which the TPR profile has only one reduction peak at about 249°C. The above experimental results are in good agreement with the prediction of the incorporation model. Project supported by the National Natural Science Foundation of China.     

Biosorption of americium-241 by Saccharomyces cerevisiae

The biosorption of radionuclide ²⁴¹Am from solution by Saccharomyces cerevisiae (S. cerevisiae), and the effects of experimental conditions on the adsorption were investigated. The preliminary results showed thatS. cerevisiae is a very efficient biosorbent. An average of more than 99% of the total ²⁴¹Am could be removed by S. cerevisiae of 2.1 g/l (dry weight) from ²⁴¹Am solutions of 17.54–4386.0 mg/l (2.22 MBq/l–555 MBq/l) with adsorption capacities of 7.45–1880.0 mg/g biomass (dry weight) (0.94 MBq/g–237.9 MBq/g). The adsorption equilibrium was achieved within 1 hour and the optimum pH ranged 1–3. No significant differences on ²⁴¹Am adsorption were observed at 10–45 °C, or in solutions containing Au³⁺ or Ag⁺, even 2000 times above ²⁴¹Am concentration. The relationship between concentrations and adsorption capacities of ²⁴¹Am indicated the biosorption process should be described by the Freundlich adsorption isotherm.     

Ruthenium-based Conjugated Polymer and Metal-organic Framework Nanocomposites for Glucose Sensing

Many studies have focused on effective ways to exploit enzyme immobilization on an electrode surface to help improve the performance of enzymatic electrochemical biosensors. Herein, a novel glucose sensor was fabricated by immobilizing glucose oxidase (GOx) onruthenium-based conjugated polymer (CP) and metal-organic framework (MOF) nanocomposites. This has not only reduced the applied potential to 0.2 V (vs. Ag/AgCl), but also improved the effective surface area for enzyme immobilization.PPG@Ru@UiO-66-NH₂ was tailored by controlled chemical synthesis from a pre-synthesized water-soluble conjugated polymer (poly(N-phenylglycine)) and metal-organic framework (UiO-66-NH₂). The resulting nanocomposites were characterized using Fourier transform infrared spectroscopy, X-ray fluorescence, scanning electron microscopy, and cyclic voltammetry. The PPG@Ru@UiO-66-NH₂/GOx coated electrodedisplayed a linear measurementrange for glucose from 1 mM to 10 mM, with a sensitivity of 45.92 μA ⋅ mM⁻¹cm⁻¹ and limit of detection of5 μM( ). Furthermore, the practical application of the fabricatedglucosesensor was tested in simulative blood samples with satisfactoryaccuracy. This approach alsoopens a new door for applications regarding both enzymatic electrochemical biosensors and enzymatic biofuel cells (EBFCs).