Ce0.6Zr0.35Y0.05O2和Pr0.6Zr0.35Y0.05O2催化剂表面上CO氧化和18O-16O交换反应的研究

测定了在Ce0.6Zr0.4O2,Ce0.6Zr0.35Y0.05O2,Pr0.6Zr0.4O2和Pr0.6Zr0.35Y0.05O2 (分别表示为CZ,CYZ,PZ和PYZ)样品表面上的CO氧化反应和18O-16O 同位素交换反应.结果表明: 在CZ和PZ系列固熔中掺杂Y3 离子可以改善晶格氧的迁移速度;PZ和PZY的晶格氧比CZ 和CZY 的晶格氧具有更高的氧化反应活性.其原因是将Y3 掺杂到Ce0.6Zr0.4O2 或Pr0.6Zr0.4O2晶格中,增加了样品的氧空位浓度,从而提高了晶格氧的迁移性质,而PrOx比CeO2具有更低温度的氧化还原性质,因此PZ和PZY的晶格氧比CZ 和CZY 的晶格氧具有更高的氧化反应活性.     

牛血清白蛋白与有机小分子偶氮磺Ⅲ、溴偶氮磺Ⅲ相互作用的研究

本文研究了在不同酸度下．偶氮磺、溴偶氮磺Ⅲ与牛血清白蛋白的作用情况，用光度法求出了不同条件下偶氮磺Ⅲ、溴偶氮磺Ⅲ与牛血清白蛋白的结合个数，并用三种不同的方法相互对照．证明偶氮磺Ⅲ、溴偶氮磺Ⅲ在牛血清白蛋白上有两类不同接合部位。利用Forster非幅射转移理论确定了有机小分子在牛血清白蛋白上的结合位置并对反应机理作了初步讨论。     

Light- and temperature-assisted spin state annealing: accessing the hidden multistability

Among responsive multistable materials, spin crossover (SCO) systems are of particular interest for stabilizing multiple spin states with various stimulus inputs and physical outputs. Here, in a 2D Hofmann-type coordination polymer, [Fe(isoq)₂{Au(CN)₂}₂] (isoq = isoquinoline), a medium-temperature annealing process is introduced after light/temperature stimulation, which accesses the hidden multistability of the spin state. With the combined effort of magnetic, crystallographic and Mössbauer spectral investigation, these distinct spin states are identified and the light- and temperature-assisted transition pathways are clarified. Such excitation-relaxation and trapping-relaxation joint mechanisms, as ingenious interplays between the kinetic and thermodynamic effects, uncover hidden possibilities for the discovery of multistable materials and the development of multistate intelligent devices.

Two new two-stage manipulation protocols, namely light- and temperature-assisted spin state annealing (LASSA/TASSA), are applied to a spin crossover coordination polymer, [Fe(isoq)₂{Au(CN)₂}₂], revealing the hidden multistability of spin states.     

Spectrophotometric study of the interaction of tetraphenylporphyrin tetrasulfonate (TPPS4) with proteins

The interaction of water-soluble porphyrin TPPS(4) (tetraphenylporphyrin tetrasulfonate) with proteins in acidic solution was studied by spectrophotometry. The absorption spectra of TPPS(4)-protein complexes, the aggregation of TPPS(4) in acidic solution, and comparison of the absorption spectra of TPPS(4)-protein conjugate with that of the TPPS(4)-protein complex was investigated in detail. The effects of denaturants including urea and SDS were also examined. A mechanism was proposed that TPPS(4) would be distributed between microphase of protein and the aqueous solution and then aggregated in the microphase.     

Investigation of efflorescence of inorganic aerosols using fluorescence spectroscopy

The phase transition is one of the most fundamental phenomena affecting the physical and chemical properties of atmospheric aerosols. Efflorescence, in particular, is not well understood, partly because the molecular interactions between the solute and water molecules of saturated or supersaturated solution droplets have not been well characterized. Recently, we developed a technique that combines the use of an electrodynamic balance and a fluorescence dye, 8-hydroxyl-1,3,6-pyrenetrisulfonate (pyranine), to study the distributions of solvated and free water in aqueous droplets (Choi, M. Y.; Chan, C. K.; Zhang, Y. H. J. Phys. Chem. A 2004, 108, 1133). We found that the equality of the amounts of solvated and free water is a necessary but not sufficient condition for efflorescence. For efflorescing compounds such as Na2SO4, (NH4)2SO4, and a mixture of NaCl and Na2SO4, the amount of free water decreases, while that of solvated water is roughly constant in bulk measurements and decreases less dramatically than that of free water in single-particle measurements as the relative humidity (RH) decreases. Efflorescence of the supersaturated droplets of these solutions occurs when the amounts of free and solvated water are equal, which is consistent with our previous observation for NaCl. For nonefflorescing compounds in single-particle levitation experiments such as MgSO4 and Mg(NO3)2, the amounts of free and solvated water are equal at a water-to-solute molar ratio of about 6, at which spectral changes due to the formation of contact ion pairs between magnesium and the anions occur as shown by Raman spectroscopy. Fluorescence imaging shows that the droplets of diluted Mg(NO3)2 (at 80% RH) and MgSO4 are homogeneous but those of NaCl, Na2SO4, (NH4)2SO4, and supersaturated Mg(NO3)2 (at 10% RH) are heterogeneous in terms of the solvated-to-free water distribution. The solvated-to-free water ratios in NaCl, Na2SO4, and (NH4)2SO4 droplets are higher in the outer regions by about half a radius deep than at the center of the droplets.     

Systematic quantification of the dynamics of newly synthesized proteins unveiling their degradation pathways in human cells

Proteins are continuously synthesized during cell growth and proliferation. At the same time, excessive and misfolded proteins have to be degraded, otherwise they are a burden to cells. Protein degradation is essential to maintain proteostasis in cells, and dysfunction of protein degradation systems results in numerous diseases such as cancer and neurodegenerative diseases. Despite the importance of protein degradation, the degradation pathways of many proteins remain to be explored. Here, we comprehensively investigated the degradation of newly synthesized proteins in human cells by integrating metabolic labeling, click chemistry, and multiplexed proteomics, and systematic and quantitative analysis of newly synthesized proteins first revealed the degradation pathways of many proteins. Bioinformatic analysis demonstrates that proteins degraded through two major pathways have distinct properties and functions. Proteins degraded through the ubiquitin-proteasome pathway contain more disordered structures, whereas those through the autophagy-lysosome pathway have significantly higher hydrophobicity. Systematic and quantitative investigation of the dynamics of newly synthesized proteins provides unprecedented and valuable information about protein degradation, which leads to a better understanding of protein properties and cellular activities.

Systematic quantification of the dynamics of newly synthesized proteins first reveals the degradation pathways of many proteins in human cells, and proteins degraded through each of the two major pathways have distinct properties and functions.     

Limits of One-dimensional Interacting Particle Systems with Two-scale Interaction*

This paper characterizes the limits of a large system of interacting particles distributed on the real line. The interaction occurring among neighbors involves two kinds of independent actions with different rates. This system is a generalization of the voter process, of which each particle is of type A or a. Under suitable scaling, the local proportion functions of A particles converge to continuous functions which solve a class of stochastic partial differential equations driven by Fisher-Wrig...     

An identification of the connections of Quillen and Beilinson-Schechtman

Given a family of Riemann surfaces and a holomorphic vector bundle Beilinson and Schechtman construct a canonical connection on the associated determinant bundle. We prove the conjecture which states that their connection coincides with the Quillen connection. This is done by reducing to the case where along fibers are invertible. Both connection forms become more accessible in this case.Supported in part by N.S.F. Grant No. DMS-9201022Supported in part by National Science Council of Republic of China Grant No. NSC 82-0208-M-002-125-T, and NSERC of Canada Grant No. OGP 0121883