Intermolecular Pauli repulsion: a QMC study of molecules in ground and excited state in free space and in solution

In this work we present a method to compute the Pauli repulsion interaction energy between two molecules and for a molecule solvated by a discrete medium. The method of Amovilli and Mennucci, that has been developed within a continuum solvent model approach, is here revised in order to treat the solvation environment with a discrete number of solvent molecules. In our model, one of the two interacting systems, and the solvent in the case of solvation, acts as ‘probe’. A probe has a volume domain defined by the atomic spheres centred on the nuclei of the relevant molecule. The probe measures the fraction of electrons of the solute molecule falling in its domain leading to the evaluation of Pauli repulsion energy. To this end, Quantum Monte Carlo calculations are used to sample the electronic configurations of the solute. The method has been designed to be applied also to excited states. We show results for test systems in the ground state and for the ground and the (Formula presented.) excited states of acetone in a cluster with 14 water molecules

Shannon Entropy in Atoms: A Test for the Assessment of Density Functionals in Kohn-Sham Theory

Electron density is used to compute Shannon entropy. The deviation from the Hartree-Fock (HF) of this quantity has been observed to be related to correlation energy. Thus, Shannon entropy is here proposed as a valid quantity to assess the quality of an energy density functional developed within Kohn-Sham theory. To this purpose, results from eight different functionals, representative of Jacob's ladder, are compared with accurate results obtained from diffusion quantum Monte Carlo (DMC) computations. For three series of atomic ions, our results show that the revTPSS and the PBE0 functionals are the best, whereas those based on local density approximation give the largest discrepancy from DMC Shannon entropy

Emergence of quasiparticle Bloch states in artificial crystals crafted atom-by-atom

The interaction of electrons with a periodic potential of atoms in crystalline solids gives rise to band structure. The band structure of existing materials can be measured by photoemission spectroscopy and accurately understood in terms of the tight-binding model, however not many experimental approaches exist that allow to tailor artificial crystal lattices using a bottom-up approach. The ability to engineer and study atomically crafted designer materials by scanning tunnelling microscopy and spectroscopy (STM/STS) helps to understand the emergence of material properties. Here, we use atom manipulation of individual vacancies in a chlorine monolayer on Cu(100) to construct one- and two-dimensional structures of various densities and sizes. Local STS measurements reveal the emergence of quasiparticle bands, evidenced by standing Bloch waves, with tuneable dispersion. The experimental data are understood in terms of a tight-binding model combined with an additional broadening term that allows an estimation of the coupling to the underlying substrate.Comment: 7 figures, 12 pages, main text and supplementary materia

Expression analysis of HLA-E and NKG2A and NKG2C receptors points at a role for natural killer function in ankylosing spondylitis

Background. Ankylosing Spondylitis (AS) is a complex chronic inflammatory disease strongly associated with the majority of HLA-B27 alleles. HLA-E are non-classical MHC class I molecules that specifically interact with the natural killer receptors NKG2A (inhibitory) and NKG2C (activating), and have been recently proposed to be involved in AS pathogenesis. Objectives: To analyze the expression of HLA-E and the CD94/NKG2 pair of receptors in HLA-B27 positive AS patients and healthy controls (HC) bearing the AS-associated, B*2705 and the non-AS-associated, B*2709 allele. Methods: The level of surface expression of HLA-E molecules on CD14 positive peripheral blood mononuclear cell was evaluated in 21 HLA-B*2705 patients with AS, 12 HLA-B*2705 HC, 12 HLA-B*2709 HC and 6 HLA-B27 negative HC, using the monoclonal antibody MEM-E/08 by quantitative cytofluorimetric analysis. The percentage and density of expression of HLA-E ligands NKG2A and NKG2C were also measured on CD3-CD56+ NK cells. Results. HLA-E expression in CD14 positive cells was significantly higher in AS patients (587.0 IQR 424-830) compared to B*2705 HC (389 IQR 251.3-440.5, p=0.0007), B*2709 HC (294.5 IQR 209.5-422, p=0.0004) and HLA-B27 negative HC (380 IQR 197.3-515.0, p=0.01). A higher number of NK cells expressing NKG2A compared to NKG2C was found in all cohort analysed as well as a higher cell surface density. Conclusion: The higher surface level of HLA-E molecules in AS patients compared to HC, concurrently with a prevalent expression of NKG2A, suggests that the crosstalk between these two molecules might play a role in AS pathogenesis accounting for the previously reported association between HLA-E and AS

Detection of interstellar H_2D^+ emission

We report the detection of the 1_{10}-1_{11} ground state transition of ortho-H_2D^+ at 372.421 GHz in emission from the young stellar object NGC 1333 IRAS 4A. Detailed excitation models with a power-law temperature and density structure yield a beam-averaged H_2D^+ abundance of 3 x 10^{-12} with an uncertainty of a factor of two. The line was not detected toward W 33A, GL 2591, and NGC 2264 IRS, in the latter source at a level which is 3-8 times lower than previous observations. The H_2D^+ data provide direct evidence in support of low-temperature chemical models in which H_2D^+ is enhanced by the reaction of H_3^+ and HD. The H_2D^+ enhancement toward NGC 1333 IRAS 4A is also reflected in the high DCO^+/HCO^+ abundance ratio. Simultaneous observations of the N_2H^+ 4-3 line show that its abundance is about 50-100 times lower in NGC 1333 IRAS 4A than in the other sources, suggesting significant depletion of N_2. The N_2H^+ data provide independent lower limits on the H_3^+ abundance which are consistent with the abundances derived from H_2D^+. The corresponding limits on the H_3^+$ column density agree with recent near-infrared absorption measurements of H_3^+ toward W 33A and GL 2591.Comment: Standard AAS LaTeX format (15 pages + 2 figures

BAT2 and BAT3 polymorphisms as novel genetic risk factors for rejection after HLA-related SCT.

The genetic background of donor and recipient is an important factor determining the outcome of allogeneic hematopoietic SCT (allo-HSCT). We applied whole-genome analysis to investigate genetic variants - other than HLA class I and II - associated with negative outcome after HLA-identical sibling allo-HSCT in a cohort of 110 β-Thalassemic patients. We identified two single-nucleotide polymorphisms (SNPs) in BAT2 (A/G) and BAT3 (T/C) genes, SNP rs11538264 and SNP rs10484558, both located in the HLA class III region, in strong linkage disequilibrium between each other (R2 =0.92). When considered as single SNP, none of them reached a significant association with graft rejection (nominal P<0.00001 for BAT2 SNP rs11538264, and P<0.0001 for BAT3 SNP rs10484558), whereas the BAT2/BAT3 A/C haplotype was present at significantly higher frequency in patients who rejected as compared to those with functional graft (30.0% vs 2.6%, nominal P=1.15 × 10-8; and adjusted P=0.0071). The BAT2/BAT3 polymorphisms and specifically the A/C haplotype may represent a novel immunogenetic factor associated with graft rejection in patients undergoing allo-HSCT

AIF-1 gene does not confer susceptibility to Behçet's disease: Analysis of extended haplotypes in Sardinian population

Background BehcEet's disease (BD) is a polygenic immune-mediated disorder characterized by a close association with the HLA-B∗51 allele. The HLA region has a strong linkage disequilibrium (LD) and carries several genetic variants (e.g. MIC-A, TNF-α genes) identified as associated to BD because of their LD with HLA-B∗51. In fact, the HLA-B∗51 is inherited as part of extended HLA haplotypes which are well preserved in patients with BD. Sardinian population is highly differentiated from other Mediterranean populations because of a distinctive genetic structure with very highly preserved HLA haplotypes. Patients and methods In order to identify other genes of susceptibility to BD within the HLA region we investigated the distribution of human Allograft Inflammatory Factor-1 (AIF-1) gene variants among BD patients and healthy controls from Sardinia. Six (rs2736182; rs2259571; rs2269475; rs2857597; rs13195276; rs4711274) AIF-1 single nucleotide polymorphisms (SNPs) and related extended haplotypes have been investigated as well as their LD within the HLA region and with HLA-B∗51. Overall, 64 BD patients, 43 HLA-B∗51 positive healthy controls (HC) and 70 random HC were enrolled in the study. Results HLA-B∗51 was the only allele with significantly higher frequency (pc = 0.0021) in BD patients (40.6%) than in HC (9.8%). The rs2259571TAIF-1 variant had a significantly reduced phenotypic, but not allelic frequency in BD patients (72.1%; pc = 0.014) compared to healthy population (91.3%). That was likely due to the LD between HLA-B∗51 and rs2259571G(pc= 9E-5), even though the rs2259571Gdistribution did not significantly differ between BD patients and HC. Conclusion No significant difference in distribution of AIF-1 SNPs haplotypes was observed between BD patients and HC and between HLA-B∗51 positive BD patients and HLA-B∗51 positive HC. Taken together, these results suggest that AIF-1 gene is not associated with susceptibility to BD in Sardinia

Differential Kinetics of Aspergillus nidulans and Aspergillus fumigatus Phagocytosis

Acknowledgements: The authors would like to acknowledge Fraser P. Coxon and Ian Ganley for providing LC3-GFP-mCherry BMDMs. M.S.G. was supported by an FEMS research grant and F.L.v.d.V. was supported by ZonMW under the name EURO-CMC frame of E-Rare-2, the ERA-Net for Research on Rare Diseases.Peer reviewedPublisher PD

Single-hole tunneling through a two-dimensional hole gas in intrinsic silicon

In this letter we report single-hole tunneling through a quantum dot in a two-dimensional hole gas, situated in a narrow-channel field-effect transistor in intrinsic silicon. Two layers of aluminum gate electrodes are defined on Si/SiO$_2$ using electron-beam lithography. Fabrication and subsequent electrical characterization of different devices yield reproducible results, such as typical MOSFET turn-on and pinch-off characteristics. Additionally, linear transport measurements at 4 K result in regularly spaced Coulomb oscillations, corresponding to single-hole tunneling through individual Coulomb islands. These Coulomb peaks are visible over a broad range in gate voltage, indicating very stable device operation. Energy spectroscopy measurements show closed Coulomb diamonds with single-hole charging energies of 5--10 meV, and lines of increased conductance as a result of resonant tunneling through additional available hole states.Comment: 4 pages, 4 figures. This article has been submitted to Applied Physics Letter