Two new metal–organic framework structures derived from terephthalate and linear trimetallic zinc building units

Two new zinc-terephthalate MOFs, (H2NEt2)[Zn3(BDC)3(HCO2)]1.5DEF (1) and Zn4(BDC)3(HCO2)2(DEF)4(2), based on trinuclear zinc secondary building units have been solvothermally synthesized from the well-studied MOF-5 system Zn–H2BDC–DEF (H2BDC = 1,4-benzenedicarboxylic acid or terephthalic acid; DEF = N,N-diethylformamide). It is shown that adding small amounts of formic acid to this system has a great influence on the formation of 3D networks based upon trimetallic zinc building units Zn3(O2CR)6. The structures of 1 and 2 comprise stacked 36 tessellated 2D zinc-terephthalate layers which are linked into 3D frameworks either by bridging formate monoanions (1) or by in situ generated neutral bridging units Zn(HCO2)2(DEF)4 (2). Flowing supercritical-CO2 activation of 1 led to a partially (80%) desolvated and probably collapsed structure (1-SC) with a measured BET (Brunauer–Emmett–Teller) surface area of 38 m2 g-1

The XMM-LSS survey. Survey design and first results

We have designed a medium deep large area X-ray survey with XMM - the XMM Large Scale Structure survey, XMM-LSS - with the scope of extending the cosmological tests attempted using ROSAT cluster samples to two redshift bins between 0<z<1 while maintaining the precision of earlier studies. Two main goals have constrained the survey design: the evolutionary study of the cluster-cluster correlation function and of the cluster number density. The results are promising and, so far, in accordance with our predictions as to the survey sensitivity and cluster number density. The feasibility of the programme is demonstrated and further X-ray coverage is awaited in order to proceed with a truly significant statistical analysis. (Abridged)Comment: Published in Journal of Cosmology and Astroparticle Physic

Localized Surface Plasmon Resonance of Metallic Nanoparticles--Optical Property Characterization for Rational Applications

在光的激发下金属纳米结构中的自由电子能够发生群体性的振荡，进而产生表面等离激元（SPP）。发生等离激元共振时，金属纳米结构会将光束缚在表面，并在表面产生极强的电场增强。表面等离激元有两种类型：一类具有传播的特点，其表面等离激元能够在表面传播，称之为propagatingSPP；另一类不具有传播性，共振局域在一个很小的金属结构中，称之为localizedSPP，即局域表面等离激元共振（LSPR）。金属纳米颗粒就具有很强的表面等离激元共振的（LSPR）性质，使其对光产生增强的吸收和增强的散射，并表现出相关的热、光电场增强和热电子等效应。近年，随着纳米科技的发展，金属纳米粒子的LSPR效应已经成为一...The collective oscillation of free electrons in metal nanostructures excited with light is called surface plasmon polaritons (SPP). The light will be confined to a small area on the surface under the resonance condition (SPR), thus a giant enhancement in the electric field will be produced. There are two kinds of surface plasmon polaritons (SPP): one is propagating plasmon polaritons (PSPP), which...学位：理学博士院系专业：化学化工学院_物理化学(含化学物理)学号：2052010015366

Etude théorique de l'hydrolyse acide des monoesters de phosphate

TOULOUSE3-BU Sciences (315552104) / SudocSudocFranceF

Etude théorique des mécanismes d'hydrolyse des esters de phosphate

TOULOUSE3-BU Sciences (315552104) / SudocSudocFranceF

Crystal structure of a two-dimensional coordination polymer of formula [Zn(NDC)(DEF)] (H 2 NDC is naphthalene-2,6-dicarboxylic acid and DEF is N , N -diethylformamide)

International audienc

Theoretical Studies of the Hydroxide-Catalyzed P−O Cleavage Reactions of Neutral Phosphate Triesters and Diesters in Aqueous Solution: Examination of the Changes Induced by H/Me Substitution

International audienceDFT calculations and dielectric continuum methods have been employed to map out the lowest activation free-energy profiles for the alkaline hydrolysis of representative phosphate triesters and diesters, including trimethyl phosphate (TMP), dimethyl 4-nitrophenyl phosphate (DMNPP), dimethyl hydrogen phosphate (DMHP), and the dimethyl phosphate anion (DMP-). The reliability of the calculations is supported by the excellent agreement observed between the calculated and the experimentally determined activation enthalpies for phosphate triesters with poor (TMP) and good (DMNPP) leaving groups. The results obtained for the OH- + DMHP and OH- + DMP- reactions are also consistent with all the available experimental information concerning the hydrolysis reaction of dimethyl phosphate anion at pH > 5. By performing geometry optimizations in the dielectric field (ε = 78.39), we found that OH- can attack the phosphorus atom of DMHP without capturing its proton only if the O−H bond of DMHP is oriented opposite the attacking OH- group. In these conditions, the rate for OH- attack on DMHP was found to be ∼103-fold faster than that for OH- attack on TMP. The calculated rate acceleration induced by the phosphoryl proton corresponds to the maximum rate effect expected from kinetic studies. Overall, our calculations performed on the dimethyl phosphate ester predict that, contrary to what is generally observed for RNA and aryl phosphodiesters, the water-promoted P−O cleavage reaction of DNA should dominate the base-catalyzed reaction at pH 7. These results are suggestive that nucleases may be less proficient as catalysts than has recently been suspected