Interaction between pentacene molecules and monolayer transition metal dichalcogenides.

Using first-principles calculations based on density-functional theory, we investigated the adsorption of pentacene molecules on monolayer two-dimensional transition metal dichalcogenides (TMD). We considered the four most popular TMDs, namely, MoS2, MoSe2, WS2 and WSe2, and we examined the structural and electronic properties of pentacene/TMD systems. We discuss how monolayer pentacene interacts with the TMDs, and how this interaction affects the charge transfer and work function of the heterostructure. We also analyse the type of band alignment formed in the heterostructure and how it is affected by molecule-molecule and molecule-substrate interactions. Such analysis is valuable since pentacene/TMD heterostructures are considered to be promising for application in flexible, thin and lightweight photovoltaics and photodetectors.

Surface structural phase transition induced by the formation of metal-organic networks on the Si(111)--In surface.

We studied the adsorption of 7,7,8,8-tetracyanoquinodimethane (TCNQ) on the Si(111)- -In surface, a known surface superconductor. Scanning tunneling microscopy shows the development of a surface-confined metal-organic network (SMON) where TCNQ molecules coordinate with indium atoms from the underlying reconstruction. The formation of the SMON causes a surface structural phase transition from the reconstruction to a previously unknown 5 × 5 reconstruction of the Si(111)-In surface. Scanning tunneling spectroscopy measurements indicate that the 5 × 5 reconstruction has a stronger insulating character than the reconstruction. Density-functional-theory calculations are used to evaluate the atomic arrangement and stability of the 5 × 5 and reconstructions as a function of In coverage, and suggest that the structural phase transition is driven by a slight reduction of the In coverage, caused by the incorporation of indium atoms into the SMON.

Influence of the substrate lattice structure on the formation of quantum well states in thin In and Pb films on silicon.

The substrate lattice structure may have a considerable influence on the formation of quantum well states in a metal overlayer material. Here we study three model systems using angle resolved photoemission and low energy electron diffraction: indium films on Si(111) and indium and lead on Si(100). Data are compared with theoretical predictions based on density functional theory. We find that the interaction between the substrate and the overlayer strongly influences the formation of quantum well states; indium layers only exhibit well defined quantum well states when the layer relaxes from an initial face-centred cubic to the bulk body-centred tetragonal lattice structure. For Pb layers on Si(100) a change in growth orientation inhibits the formation of quantum well states in films thicker than 2 ML.

In adatom diffusion on In(x)Ga(1-x)As/GaAs(001): effects of strain, reconstruction and composition.

By using density functional theory (DFT) calculations of the potential energy surface in conjunction with the analytical solution of the master equation for the time evolution of the adatom site distribution, we study the diffusion properties of an isolated In adatom on In(x)Ga(1-x)As wetting layers (WL) deposited on the GaAs(001). The WL reconstructions considered in this study are, listed in the order of increasing In coverage: c(4 × 4), (1 × 3), (2 × 3), α(2)(2 × 4) and ß(2)(2 × 4). We analyze the dependence of the diffusion properties on WL reconstruction, composition and strain, and find that: (i) diffusion on the (2 × N) reconstructions is strongly anisotropic, owing to the presence of the low barrier potential in-dimer trench, favoring the diffusion along the [Formula: see text] direction over that along the [110] direction; (ii) In diffusion at a WL coverage θ = 2/3 monolayers (ML; with composition x = 2/3) is faster than on clean GaAs(001) c(4 × 4), and decreases at θ = 1.75 ML (x = 1; e.g. InAs/GaAs(001)); (iii) diffusion and nucleation on the (2 × 4) WL is affected by the presence of adsorption sites for indium inside the As dimers; (iv) the approximation used for the exchange-correlation potential within DFT has an important effect on the description of the diffusion properties.

Atomic structure of the GaAs(001)-c(4x4) surface: first-principles evidence for diversity of heterodimer motifs.

The GaAs(001)-c(4x4) surface was studied using ab initio atomistic thermodynamics based on density-functional theory calculations. We demonstrate that in a range of stoichiometries, between those of the conventional three As-dimer and the new three Ga-As-dimer models, there exists a diversity of atomic structures featuring Ga-As heterodimers. These results fully explain the experimental scanning tunneling microscopy images and are likely to be relevant also to the c(4x4)-reconstructed (001) surfaces of other III-V semiconductors.

Quantum Monte Carlo calculations of H2 dissociation on Si(001).

The dissociative adsorption of H2 on the Si(001) surface is theoretically investigated for several reaction pathways using quantum Monte Carlo methods. Our reaction energies and barriers are at large variance with those obtained with commonly used approximate exchange-correlation density functionals. Our results for adsorption support recent experimental findings, while, for desorption, the calculations give barriers in excess of the presently accepted experimental value, pinpointing the role of coverage effects and desorption from steps.

Reaction-limited island nucleation in molecular beam epitaxy of compound semiconductors.

Kinetic Monte Carlo simulations on the basis of rates derived from density-functional calculations are used to investigate the atomic processes in molecular beam epitaxy of GaAs. This approach puts us in a position to describe island nucleation and growth in all relevant atomistic detail by bridging the gap in length and time scales between the mesoscopic scale of growth morphology and the atomic scale. We observe a nonmonotonic dependence of the island density on growth temperature related to a reversible surface reaction of As2 with Ga adatoms.

Probing interface electronic structure with overlayer quantum-well resonances: Al/Si(111).

The dispersion of quantum-well resonances in ultrathin epitaxial Al films on Si(111) reveals energy- and wave vector-dependent reflection properties at the Al/Si interface. The substrate electronic structure strongly influences the phase shift of the electron waves upon reflection at the interface. Thus the details of the substrate electronic structure need to be taken into account for a complete analysis of metallic quantum-well resonances. Furthermore, the assumption of loss of parallel wave vector information upon reflection or transmission through a lattice-mismatched interface is challenged. The changes induced in the electronic structure of the overlayer can be used to probe the ground-state substrate band edges.

Role of electronic correlation in the Si(100) reconstruction: a quantum Monte Carlo study.

Recent low-temperature scanning tunneling experiments have questioned the generally accepted picture of buckled silicon dimers as the ground state reconstruction of the Si(100) surface, undermining the ability of density functional theory to accurately describe electronic correlations at surfaces. We present quantum Monte Carlo calculations on large cluster models of the surface, and conclude that buckling remains energetically favorable even when the present-day best treatment of electronic correlation is employed. The implications for experimental interpretation are discussed.

GaAs(2 5 11): a new stable surface within the stereographic triangle.

The atomic structure of GaAs(2 5 11), a hitherto unknown stable surface, has been determined by in situ scanning tunneling microscopy and first-principles electronic structure calculations. This orientation is located within the stereographic triangle, i.e., far away from all low-index surfaces. A low-energy ( 1x1) reconstruction containing arsenic dimers forms on the surface. The analysis of the surface structure shows that, for semiconductor surfaces, the gain in stability due to minimization of the number of dangling bonds is more important than the gain from rendering a semiconducting ground state.

Atomic Structure of the Stoichiometric GaAs(114) Surface.

The stoichiometric GaAs(114) surface has been prepared using molecular beam epitaxy followed by annealing in ultrahigh vacuum. Based on in situ scanning tunneling microscopy measurements and first-principles electronic-structure calculations, we determine the surface reconstruction which we call alpha2(2x1). Contrary to what is expected for a high-index surface, it is surprisingly elementary. The (2x1) unit cell contains two As dimers and two rebonded Ga atoms. The surface energy is calculated as 53 meV/Å(2), which falls well within the range of low-index GaAs surface energies.

Cytogenetic evidence for enhanced selective miscarriage of trisomy 21 pregnancies with advancing maternal age.

The effect of advancing maternal age on the risk of death of fetuses with certain chromosome abnormalities has been tested by comparing their frequency at the time of chorionic villus sampling (CVS) with that at amniocentesis. The frequency of chromosome abnormalities among women whose sole risk factor for a chromosome abnormality was advanced maternal age (> or = 35 years old) was determined in a pooled group of 15,147 CVS cases, of whom > 1/3 were from the initial 7,500 CVS cases at the University of California, San Francisco, and compared with a pooled group of 74,851 amniocentesis cases collected from the literature. The frequency of trisomy 21 not only increased with advancing maternal age as expected, but the slope of the increase was about 25% greater in the CVS group than in the amniocentesis group (P = 0.08 for the difference in slopes by a logistic statistical model and P = 0.04 by a normit model). Similar patterns were seen for trisomies 18 and 13, but the P values for the differences in slopes were much higher. These results suggest that the miscarriage rate of trisomy 21 during the gestational interval studied is selectively greater with advancing maternal age. The basis for the enhanced selective loss of trisomy 21 with maternal age may be a reduced ability of the ageing "maternal compartment" to compensate for abnormal conceptuses.

First-trimester aneuploidy screening using serum human chorionic gonadotropin (hCG), free ahCG, and progesterone.

Immunochemical serum assays for human chorionic gonadotropin (hCG), the free ahCG subunit, and progesterone (P) were considered separately and in combination for their ability to screen for chromosomally abnormal pregnancies in the first trimester. Maternal serum was collected from 141 women undergoing chorionic villus sampling at 9-12 menstrual weeks. Trisomy 21 pregnancies had significantly higher hCG levels, while trisomy 18 and 13 pregnancies had markedly lower hCG and progesterone levels than those of chromosomally normal pregnancies. However, the discrimination of normal from aneuploid pregnancies was poor with either hCG alone, progesterone alone, or free ahCG alone. Much improved discrimination was obtained by combining hCG, free ahCG, and P into an aneuploidy index [(P/hCG)(free ahCG/hCG)]. This index distinguished 9 out of 17 (53 per cent) of the trisomy 21 pregnancies, while only misidentifying 5 out of 112 (4.5 per cent) of the normal pregnancies. The aneuploidy index thus appears promising as a first-trimester biochemical screen for aneuploid pregnancies.

Trisomic pregnancies have normal human chorionic gonadotropin bioactivity.

Sera from women carrying either chromosomally normal or aneuploid fetuses in the first half of pregnancy were assayed for human chorionic gonadotropin (hCG) bioactivity in order to determine whether differences might provide the basis for a useful antenatal screen for aneuploidy. A mouse uterine weight assay was used to assess hCG bioactivity in sera from 35 patients undergoing chorionic villus sampling (12 normal pregnancies and 23 trisomic pregnancies) and in sera from 18 patients undergoing elective second-trimester abortion (12 presumed normal pregnancies, 3 trisomic pregnancies, and 3 pregnancies with neural tube defects). The hCG bioactivity to immunoactivity (B:I) ratio of normal pregnancies progressively decreased from 7.7 +/- 1.3 at 4-5 menstrual weeks, to 4.7 +/- 0.4 at 9-12 menstrual weeks, to 3.3 +/- 0.5 at 16-20 menstrual weeks. There were no significant differences in the B:I ratios between normal and aneuploid pregnancies in either the first-trimester (4.7 +/- 0.4 versus 5.2 +/- 0.3) or the second-trimester samples (3.3 +/- 0.5 versus 2.6 +/- 0.3), despite significantly greater hCG concentrations in the trisomic pregnancies. We conclude that while aneuploid pregnancies display dysfunctional regulation of hCG expression, the bioactivity of their hCG is normal and does not appear to form the basis for a useful screen for aneuploidy.

Corpus luteum function in early pregnancies is primarily determined by the rate of change of human chorionic gonadotropin levels.

Regulation of human corpus luteum activity was studied with radioimmunoassays and bioassays of sera drawn serially from women suspected of having ectopic pregnancies. Progesterone values exhibited considerable overlap in pregnancies that were subsequently classified as normal intrauterine (n = 21), ectopic (n = 35), or spontaneous abortion (n = 14). The rate of change of human chorionic gonadotropin concentration was significantly correlated with progesterone levels in ectopic (r = 0.64) and all pregnancies (r = 0.70). There was no correlation (r = -0.18) between the rate of change of human chorionic gonadotropin and the bioactivity produced per volume of serum. Ectopic pregnancies and normal intrauterine pregnancies did not differ in their ratio of in vivo bioactivity to immunoactivity. From these data we conclude that corpus luteum activity is primarily regulated by the rate of change of human chorionic gonadotropin concentration, without the involvement of other serum factors. We also conclude that reduced corpus luteum function in ectopic pregnancies is not a result of biochemical modification of the human chorionic gonadotropin molecule. Finally, we discourage the use of single progesterone values in screening for ectopic pregnancies because of the considerable overlap in progesterone values among these and normal intrauterine pregnancies.

Patients' expectations from renal grafting and transplantation outcome.

Prevailing reports on psychological prediction of renal graft integration are rare, mostly based on case studies. Focusing on patients' expectations from the transplantation process before grafting, we investigate the influence of psychological data and statements on the final transplantation results. In the whole group (n = 83) the attitude toward transplantation was very optimistic. Comparing the features of patients with successful graft outcome (n = 23) and graft failure or patient's death (n = 10) the latter group shows: lower scale values of optimistic attitude toward transplantation outcome, higher level of fear concerning surgical treatment, less willingness to agree preoperatively to second transplantation in case of first graft failure. Psychological data indicate a greater tendency toward more submissive, rigid, and depressive behavior. It is assumed that the patient's attitude and expectation on grafting is a part of the conditions influencing the final transplantation result. Further studies should prove this concept.

Expression of maternally and embryonically derived hypoxanthine phosphoribosyl transferase (HPRT) activity in mouse eggs and early embryos.

X-chromosome activity in early mouse development has been studied by a gene dosage method that involves measuring the activity level of the X-linked enzyme hypoxanthine phosphoribosyl transferase (HPRT) in single eggs and embryos from XO females and from females heterozygous for In(X)1H, a paracentric inversion of the X chromosome. The HPRT activity in oocytes increased threefold over a 24-hr period beginning after ovulation. Afterward, the activity plateaued in unfertilized eggs but continued to increase for at least 66 hr in presumed OY embryos. Both before and after ovulation, the level of activity in unfertilized eggs from In(X)/X females was twice that from XO females, and the distributions of activity in eggs for both sets of females remained unimodal. Beginning with the two-cell stage, distributions of activity for embryos from In(X)/X females were trimodal, which is evidence for embryonic activity. It is proposed that activation of a maternal mRNA or proenzyme is responsible for the HPRT activity increase in oocytes and early embryos and is supplemented by dosage-dependent activity of the embryonic Hprt gene as early as the two-cell stage.