Homogeneous tandem catalysis of the bis‐(diphenylphosphino)‐amine/chromium tetramerization catalyst with metallocene catalysts

Homogeneous tandem catalysis of the bis(diphenylphoshino)amine‐chromium oligomerization catalyst with the metallocenes Ph₂C(Cp)(9‐Flu)ZrCl₂ and rac‐EtIn₂ZrCl₂, is discussed. GC, CRYSTAF, and ¹³C NMR analysis of the products obtained from reactions at constant temperatures show that during tandem catalysis, α‐olefins, mainly 1‐hexene and 1‐octene, are produced from ethylene by the oligomerization catalyst and subsequently built into the polyethylene chain. At 40 °C the Cr/PNP catalyst acts as a tetramerization catalyst while the polymerization catalyst activity is low. Copolymerization of ethylene and the in situ produced α‐olefins have also been carried out by increasing the temperature from 40 °C, where primarily oligomerization takes place, to above 100 °C, where polymerization becomes dominant. The melting temperature of the polymer is dependent on the catalyst and cocatalyst ratios as well as on the temperature gradient followed during the reaction, while the presence of the oligomerization catalyst reduces the activity of the polymerization catalyst. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6847–6856, 2006     

Primer preactivation of peptidoglycan polymerases

Peptidoglycan glycosyltransferases are highly conserved bacterial enzymes that catalyze glycan strand polymerization to build the cell wall. Because the cell wall is essential for bacterial cell survival, these glycosyltransferases are potential antibiotic targets, but a detailed understanding of their mechanisms is lacking. Here we show that a synthetic peptidoglycan fragment that mimics the elongating polymer chain activates peptidoglycan glycosyltransferases by bypassing the rate-limiting initiation step.     

稳态实验考察经模拟道路老化的全配方稀燃Nox捕集催化剂上的Nox还原

Fully formulated lean NOx trap(LNT)catalysts of the type Pt/Rh/BaO/Al2O3 were prepared with and without incorporation of CeO2-ZrO2 in the washcoat,and their NOx reduction behavior was evaluated in steady-state,continuous flow experiments.In the fresh state, the CeO2-ZrO2 addition was found to exert little effect on NOx reduction activity using H2,CO,and NH3 as the reductants.However,after simulated road aging,NOx reduction activity was significantly impaired for the CeO2-ZrO2-free catalyst,whereas the perfo...     

How the Asymmetric Nature of IP Traffic Influences the Cost of the Underlying Optical Layer

In this article the influence of the asymmetric nature of (IP) traffic on the cost of the underlying optical transport network is investigated over a time frame of six years using a realistic traffic forecast for a European fiber-optic network. The currently deployed transport networks contain bidirectional optical line systems and are thus inherently symmetric, although the traffic that has to be conveyed over those networks is asymmetric. This article shows that a cost reduction of up to 38% can be obtained if the bidirectional line systems are replaced by unidirectional ones.     

Orbital contributions to relativistic corrections of the NMR nuclear magnetic shielding tensor originated in scalar field-dependent operators

In this work relativistic corrections to the magnetic shielding constant (σM), which arise from scalar field-dependent operators (both linear and bilinear), are calculated and decomposed into contributions from molecular orbitals (MOs). Numerical results for the magnetic shielding constant of the heavy nucleus X in closed shell atomic ions X^? and HX compounds (X = F, Cl, Br, I) are presented. The relative importance of inner-shell and valence electrons in the definition of each one of these terms is thus assessed and its relation with their sensitivity to changes in a chemical environment is discussed.     

Quantum coherent control of the vibrational dynamics of a polyatomic molecule using adaptive feedback control of a femtosecond laser

We simulate adaptive feedback control to coherently shape a femtosecond infrared laser pulse by means of a 4f-spatial light modulator in order to selectively excite the rovibrational modes of a polyatomic molecule. We preferentially populate an arbitrarily chosen upper rovibrational level by only employing these tailored temporally shaped pulses. A second laser would then allow for mode selective chemistry to interact selectively with the excited population. Alternatively the excited molecules enhanced reactivity could be exploited for selective chemistry.     

S-matrix approach to the equation of state of dilute nuclear matter

Based on the general analysis of the grand canonical partition function in the S-matrix framework, a method is presented to calculate the equation of state of dilute warm nuclear matter. The result is a model-independent virial series for the pressure and density that systematically includes contributions from all the ground and excited states of all the stable nuclear species and their scattering channels. The multiplicity distribution of these species to keep the matter in statistical equilibrium is found out and then the pressure, incompressibility and the symmetry energy of the system are evaluated. The calculated symmetry energy coefficients are found to be in fair agreement with the recent experimental data.