Multi-scale dynamics at the glassy silica surface.

Silica-based glass is a household name, providing insulation for windows to microelectronics. The debate over the types of motions thought to occur in or on SiO2 glass well below the glass transition temperature continues. Here, we form glassy silica films by oxidizing the Si(100) surface (from 0.5 to 1.5 nm thick, to allow tunneling). We then employ scanning tunneling microscopy in situ to image and classify these motions at room temperature on a millisecond to hour time scale and 50-pm to 5-nm length scale. We observe two phenomena on different time scales. Within minutes, compact clusters with an average diameter of several SiO2 glass-forming units (GFUs) hop between a few (mostly two) configurations, hop cooperatively (facilitation), and merge into larger clusters (aging) or split into smaller clusters (rejuvenation). Within seconds, Si-O-Si bridges connect two GFUs within a single cluster flip, providing a vibrational fine structure to the energy landscape. We assign the vibrational fine structure using electronic structure calculations. Calculations also show that our measured barrier height for whole cluster hopping at the glass surface (configurational dynamics) is consistent with the configurational entropy predicted by thermodynamic models of the glass transition and that the vibrational entropy for GFU flipping and configurational entropy for cluster hopping are comparable (on a per GFU basis).

Plasmonic support-mediated activation of 1 nm platinum clusters for catalysis.

Nanometer-sized metal clusters are prime candidates for photoactivated catalysis, based on their unique tunable optical and electronic properties, combined with a large surface-to-volume ratio. Due to the very small optical cross sections of such nanoclusters, support-mediated plasmonic activation could potentially make activation more efficient. Our support is a semi-transparent gold film, optimized to work in a back-illumination geometry. It has a surface plasmon resonance excitable in the 510-540 nm wavelength range. Ptn clusters (size distribution peaked at n = 46 atoms) have been deposited onto this support and investigated for photoactivated catalytic performance in the oxidative decomposition of methylene blue. The Pt cluster catalytic activity under illumination exceeds that of the gold support by more than an order of magnitude per active surface area. To further investigate the underlying mechanism of plasmon-induced catalysis, the clusters have been imaged with optically-assisted scanning tunneling microscopy under illumination. The photoactivation of the Pt clusters via plasmonic excitation of the support and subsequential electronic excitation of the clusters can be imaged with nanometer resolution. The light-induced tunneling current on the clusters is enhanced relative to the gold film support.

Temperature-dependent two-state dynamics of individual cooperatively rearranging regions on a glass surface.

Cooperatively rearranging regions (CRRs) play a central role in the temperature dependence of glass dynamics. We record real-time atomic resolution movies of individual CRRs, while ramping their temperature. Between 295 and 326 K, well below the bulk glass transition temperature T(g), the rate coefficient for two-state hopping of CRRs increases over tenfold, yielding an Arrhenius activation barrier of ≈10k(B)T(g). By time resolving the dynamics of many individual CRRs, we show that highly stretched dynamics of the CRR ensemble results mainly from spatial heterogeneity, less from temporal heterogeneity of individual CRRs.

Communication: An obligatory glass surface.

Theory predicts, and experiments have shown, that dynamics is faster at glass surfaces than in the bulk, allowing the glass to settle into deeper energy landscape minima, or "age more." Is it possible that a glass surface could survive at temperatures where the bulk crystallizes, or that it could remain glassy after the bulk is heated all the way to its melting temperature and re-cooled? We image in real-time and with sub-nanometer resolution the two-state surface dynamics on a cerium-based glass surface, from deep within the glassy regime to above the crystallization temperature. Unlike other surfaces that we have studied, this glass surface remains amorphous even after the bulk re-crystallizes. The surface retains non-crystalline structure and two state dynamics of cooperatively rearranging regions even after heat annealing to just below the bulk melting temperature. The heat-annealed cooperatively rearranging regions are larger than originally, a sign that the surface is well aged. The surface dynamics depends weakly on temperature, showing no sign of the superexponential increase in bulk dynamics expected near T(g).

Field-directed sputter sharpening for tailored probe materials and atomic-scale lithography.

Fabrication of ultrasharp probes is of interest for many applications, including scanning probe microscopy and electron-stimulated patterning of surfaces. These techniques require reproducible ultrasharp metallic tips, yet the efficient and reproducible fabrication of these consumable items has remained an elusive goal. Here we describe a novel biased-probe field-directed sputter sharpening technique applicable to conductive materials, which produces nanometer and sub-nanometer sharp W, Pt-Ir and W-HfB(2) tips able to perform atomic-scale lithography on Si. Compared with traditional probes fabricated by etching or conventional sputter erosion, field-directed sputter sharpened probes have smaller radii and produce lithographic patterns 18-26% sharper with atomic-scale lithographic fidelity.

Direct imaging of two-state dynamics on the amorphous silicon surface.

Amorphous silicon is an important material, amidst a debate whether or not it is a glass. We produce amorphous Si surfaces by ion bombardment and vapor growth, and image discrete Si clusters which hop by two-state dynamics at 295 K. Independent of surface preparation, these clusters have an average diameter of ∼5 atoms. Given prior results for metallic glasses, we suggest that this cluster size is a universal feature. The hopping activation free energy of 0.93±0.15 eV is rather small, in agreement with a previously untested surface glass model. Hydrogenation quenches the two-state dynamics, apparently by increasing surface crystallinity.

Inducing electronic changes in graphene through silicon (100) substrate modification.

We have performed scanning tunneling microscopy and spectroscopy (STM/STS) measurements as well as ab initio calculations for graphene monolayers on clean and hydrogen(H)-passivated silicon (100) (Si(100)/H) surfaces. In order to experimentally study the same graphene piece on both substrates, we develop a method to depassivate hydrogen from under graphene monolayers on the Si(100)/H surface. Our work represents the first demonstration of successful and reproducible depassivation of hydrogen from beneath monolayer graphene flakes on Si(100)/H by electron-stimulated desorption. Ab initio simulations combined with STS taken before and after hydrogen desorption demonstrate that graphene interacts differently with the clean and H-passivated Si(100) surfaces. The Si(100)/H surface does not perturb the electronic properties of graphene, whereas the interaction between the clean Si(100) surface and graphene changes the electronic states of graphene significantly. This effect results from the covalent bonding between C and surface Si atoms, modifying the π-orbital network of the graphene layer. The local density of states shows that the bonded C and Si surface states are highly disturbed near the Fermi energy.

Atomic-scale desorption through electronic and vibrational excitation mechanisms.

The scanning tunneling microscope has been used to desorb hydrogen from hydrogen-terminated silicon (100) surfaces. As a result of control of the dose of incident electrons, a countable number of desorption sites can be created and the yield and cross section are thereby obtained. Two distinct desorption mechanisms are observed: (i) direct electronic excitation of the Si-H bond by field-emitted electrons and (ii) an atomic resolution mechanism that involves multiple-vibrational excitation by tunneling electrons at low applied voltages. This vibrational heating effect offers significant potential for controlling surface reactions involving adsorbed individual atoms and molecules.

Activation of class I HLA expression by TNF-alpha and gamma-interferon is mediated through protein kinase C-dependent pathway in CML cell lines.

The combination of tumour necrosis factor alpha (TNF alpha) and gamma-interferon induced transcription of class I HLA genes in chronic myelogenous leukaemia (CML) cell lines through the formation of a complex between nuclear proteins and the transcriptional enhancers associated with these genes. Although gamma-interferon or TNF-alpha stimulated expression of class I HLA antigens in the EM2 and K562 CML cell lines when used alone, the effect of the combination of TNF-alpha and gamma-interferon was greater than that observed with either agent alone. The induction of class I HLA expression by gamma-interferon and TNF-alpha was inhibited completely by the isoquinoline sulfonamide H7, an inhibitor of protein kinase C. We conclude that the enhancement of the gamma-interferon induced transcriptional activation of class I HLA gene expression by TNF-alpha involves a protein kinase C-dependent pathway.

Absent or rare human immunodeficiency virus infection of bone marrow stem/progenitor cells in vivo.

An important question in human immunodeficiency virus (HIV) pathogenesis is whether HIV-infected bone marrow CD34+ stem/progenitor cells serve as a significant reservoir of virus in HIV-infected individuals. Our data indicate that infection of bone marrow stem/progenitor cells with HIV occurs rarely, if ever, in vivo. In the present study, CD34+ cells were immunomagnetically purified from the bone marrow of HIV-seropositive individuals, and purified cells or colony-forming cells of the granulocyte/macrophage lineage were analyzed for HIV proviral DNA by the polymerase chain reaction. No HIV DNA was detected in colony-forming cells of the granulocyte/macrophage lineage from HIV-positive patients. Furthermore, no virus was found in CD34(+)-enriched cells from six of seven samples from asymptomatic HIV-infected individuals and four of four samples from patients with AIDS-related complex or AIDS. Thus, infected stem cells are not a major source of persistent HIV and do not account for hematopoietic suppression. These findings have positive implications for the concept of marrow reconstitution with autologous stem cells, genetically engineered for HIV resistance, following marrow-ablative antiviral therapy.

Transplantation with blood stem cells.

Peripheral blood stem cell transplantation (PBSCT) offers an alternative to autologous bone marrow transplants (A-BMT), especially in malignant diseases with bone marrow contamination. The presence of hemopoietic precursors in peripheral blood has been documented in several animal models and in humans. While many of these precursors might be committed cells with finite renewal capacity, ample evidence suggests that true pluripotent stem cells are circulating in a number sufficient to enable sustained trilineage engraftment after transplantation. Stem cell mobilization is markedly increased in the early recovery phase after intensive chemotherapy and can be promoted by the administration of various cytokines or polyanionic substances. These effects are used to optimize stem cell harvesting by leukapheresis. Clinical trials of PBSCT have been performed in several hundred patients with various hematological and nonhematological malignancies. Recovery was generally more rapid than after A-BMT. However, the envisioned advantage concerning disease control has not been documented so far.

Red cell aplasia due to host type isohemagglutinins with exuberant red cell progenitor production of donor type in an ABO-mismatched allogeneic bone marrow transplant recipient.

ABO-mismatched bone marrow transplants have resulted in delayed red cell production in patients who have persistently elevated anti-ABO isohemagglutinin titers. We present a patient with chronic myelogenous leukemia who received an HLA-matched, ABO-incompatible bone marrow transplant from his sister. Post-transplant, he developed pure red cell aplasia with exuberant production of donor red cell precursors by in vitro BFU-E assay. Restriction fragment length polymorphism (RFLP) analysis of bone marrow, peripheral blood and BFU-E colonies demonstrated only donor type DNA post-transplant. However, the patient had persistently elevated isohemagglutinin titer and Ph1 chromosome-positive metaphases on chromosome analysis, indicating the presence of persistent host lymphocytes. With onset of acute graft vs. host disease (GVHD), the isohemagglutinin titer dropped, Ph1 chromosome-positive metaphases disappeared, and full hematopoietic recovery ensued. Longitudinal analysis of RFLP's, isohemagglutinin titers and chromosomes may be helpful in understanding the immunological interplay following allogeneic bone marrow transplantation.

Regulation of adult and embryonic genes in human leukemia cells.

In this article, we have reviewed studies showing that altered expression of regulatory genes results in activation of embryonic genes in human leukemia cells. These data have led to important new insights as to how mutations in regulatory genes can lead to disease states in man.

Intramedullary spinal cord metastasis in Hodgkin's disease. Rapid diagnosis and treatment resulting in neurologic recovery.

Intramedullary spinal cord metastases are uncommon in Hodgkin's disease and have a poor prognosis. This prognosis reflects the refractory or widely disseminated status of the disease at the time of development of neurological symptoms and difficulties in diagnosis. Computerized tomography and magnetic resonance imaging have enabled more rapid and specific diagnosis of spinal cord diseases. The authors report a patient who presented with Brown-Sequard syndrome due to intramedullary spinal cord infiltration from Hodgkin's disease. This patient was diagnosed promptly and with rapid initiation of radiation and chemotherapy, she has had neurologic recovery.