The structure and the electronic properties of a sodium tetrasilicate (Na2Si4O9) glass were studied by combined Car-Parrinello and classical molecular-dynamics simulations. The glass sample was prepared using a method employed recently in a study of a silica glass [M. Benoit et al, Euro. Phys. J. B 13, 631 (2000)]. First we generated a NS4 glass by classical molecular-dynamics and then we took ...

In this work, we present an innovative approach to investigate the structure and the reactivity of a molecularly dispersed organometallic compound. The poly(4-ethylstyrene-co-divinylbenzene) microporous system (PS) is used as "solid solvent" able to molecularly disperse CrCp2, allowing: (i) its full characterization by means of spectroscopic techniques; (ii) the pressure and temperature depende...

ALCL: anaplastic large cell lymphoma CTCL: cutaneous T-cell lymphoma LyP: lymphomatoid papulosis PCALCL: primary cutaneous anaplastic large cell lymphoma RA: rheumatoid arthritis TNF: tumor necrosis factor INTRODUCTION Antietumor necrosis factor (TNF) agents, such as etanercept, infliximab, and adalimumab, are increasingly used in the treatment of many chronic inflammatory diseases, including p...

We report an implementation of the spin-flip (SF) variant of time-dependent density functional theory (TD-DFT) within the Tamm-Dancoff approximation and non-collinear (NC) formalism for local, generalized gradient approximation, hybrid, and range-separated functionals. The performance of different functionals is evaluated by extensive benchmark calculations of energy gaps in a variety of diradi...

Three SHOP-type catalysts, in which the C=C(O) double bond was substituted by electron-withdrawing substituents, [Ni{Ph2PC(R1)=C(R2)O}Ph(PPh3)] (2: R1,R2 = -C(Me)=NN(Ph)-; 3: R1 = CO2Et, R2 = Ph; 4: R1 = CO2Et, R2 = CF3), were assessed as ethylene-oligomerisation and -polymerisation catalysts and compared to Keim's complex, [Ni{Ph2PCH=C(Ph)O}Ph(PPh3)] (1). A rationale for the influence of the d...

A single nucleotide polymorphism in PTPN22 (R620W), which encodes the Lyp tyrosine phosphatase, has been linked to a number of autoimmune diseases including type 1 diabetes, rheumatoid arthritis, and systemic lupus erythematosus. Studies in PTPN22 knockout (KO) mice and in mice expressing the mouse homolog of the pro-autoimmune allele, PEP(R619W), have reported increased germinal center activit...

We present a systematic density functional investigation on the prediction of the 13C, 15N, 17O, and 19F NMR properties of 23 molecules with 21 density functionals. Extensive comparisons are made for both 13C magnetic shieldings and chemical shifts with respect to the gas phase experimental data and the best CCSD(T) results. We find that the OPBE and OPW91 exchange-correlation functionals perfo...

Most membrane-enveloped viruses depend on host proteins of the endosomal sorting complex required for transport (ESCRT) machinery for their release. HIV-1 is the prototypic ESCRT-dependent virus. The direct interactions between HIV-1 and the early ESCRT factors TSG101 and ALIX have been mapped in detail. However, the full pathway of ESCRT recruitment to HIV-1 budding sites, which culminates wit...

Free energies for the homolysis of the NO-C and N-OC bonds were compared for a large number of alkoxyamines at 298 and 393 K, both in the gas phase and in toluene solution. On this basis, the scope of the N-OC homolysis side reaction in nitroxide-mediated polymerization was determined. It was found that the free energies of NO-C and N-OC homolysis are not correlated, with NO-C homolysis being m...

The recently proposed new family of "double-hybrid" density functionals [Grimme, S. J. Chem. Phys. 2006, 124, 34108] replaces a fraction of the semi-local correlation energy by a non-local correlation energy expression that employs the Kohn-Sham orbitals in second-order many-body perturbation theory. These functionals have provided results of high accuracy over a wide range of properties but fa...