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Sample records for adlay coix lachryma-jobi

  1. Postharvest strategies for deoxynivalenol and zearalenone reduction in stored adlay (Coix lachryma-jobi L.) grains.

    PubMed

    Choi, Hye Jin; An, Tae-Jin; Kim, Juil; Park, Seong-Hwan; Kim, Dongwook; Ahn, Young-Sup; Moon, Yuseok

    2014-03-01

    Improperly practiced postharvest procedures can pose mycotoxin-related risks in the production of medicinal herbs. As a health food with pharmacological supplements, cereal-based adlay has been broadly used in oriental medical practice. Compared with the standard production protocol, three provisional critical control points (CCPs) in the conventional procedure were identified and assessed for mycotoxin contamination in the adlay from small farms in Korea. Although various mycotoxins were present, the prevalence of deoxynivalenol (DON) or zearalenone (ZEN) was relatively high in the adlay. In terms of drying conditions, field drying in the conventional pathway was associated with more exposure to DON than heated-air drying. Moreover, the DON or ZEN levels in chaff were higher than the levels in the inner grain, suggesting that the hulling process as another CCP would reduce the DON or ZEN exposure. In particular, the DON or ZEN levels in adlay stored for protracted periods without dehulling were very high, but a lower storage temperature of 12°C was not effective at significantly reducing these mycotoxins. In this case, the inner grain was more contaminated with DON or ZEN than the chaff after protracted storage because surface fungi, which produce mycotoxins, can penetrate deep into grain with time. Heated-air drying and nonprotracted storage limited DON contamination in adlay. More importantly, an early dehulling process should be adopted as an easy preventive action to reduce the risk of exposure to DON or ZEN in adlay postharvest. This is monitored as a central CCP for safer production of adlay from local farms. PMID:24674439

  2. Biological activities of fructooligosaccharide (FOS)-containing Coix lachryma-jobi Linn. extract.

    PubMed

    Manosroi, Jiradej; Khositsuntiwong, Narinthorn; Manosroi, Aranya

    2014-02-01

    Fructooligosaccharide (FOS), a prebiotic was extracted from the grain of Coix lachryma-jobi Linn. (Job's tears) by hot water extraction at 60 °C for 1 h. The resulting dried powder extract was assayed for FOS content of 1-kestose (GF2), nystose (GF3) and 1-β-D-fructofuranosylnystose (GF4) using HPLC equipped with RI detector. Total FOS content of the extract was 24.98 ± 7.48% (g/100 g crude extract). The biological activity including antioxidant and cytotoxicity of the FOS-containing extract was determined. The antioxidant activity by DPPH free radical scavenging of FOS-containing extract was comparable to vitamin C (0.97 fold of vitamin C) with a slight lipid peroxidation inhibition activity. The extract exhibited no cytotoxic effect on normal human skin fibroblast. These results have confirmed not only the source of FOS from Job's tears extract but also its potential application as antioxidant in food or cosmetic products. PMID:24493893

  3. Structural characterization of phenolic compounds and antioxidant activity of the phenolic-rich fraction from defatted adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) seed meal.

    PubMed

    Wang, Lifeng; Chen, Chao; Su, Anxiang; Zhang, Yiyi; Yuan, Jian; Ju, Xingrong

    2016-04-01

    The current study aims to investigate the antioxidant activities of various extracts from defatted adlay seed meal (DASM) based on the oxygen radical absorbance capacity (ORAC) assay, peroxyl radical scavenging capacity (PSC) assay and cellular antioxidant activity (CAA) assay. Of all the fractions, the n-butanol fraction exhibited the highest antioxidant activity, followed by crude acetone extract and aqueous fractions. Of the three sub-fractions obtained by Sephadex LH-20 chromatography, sub-fraction 3 possessed the highest antioxidant activity and total phenolic content. There was a strong positive correlation between the total phenolic content and the antioxidant activity. Based on HPLC-DAD-ESI-MS/MS analysis, the most abundant phenolic acid in sub-fraction 3 of DASM was ferulic acid at 67.28 mg/g, whereas the predominant flavonoid was rutin at 41.11 mg/g. Of the major individual compounds in sub-fraction 3, p-coumaric acid exhibited the highest ORAC values, and quercetin exhibited the highest PSC values and CAA values. PMID:26593521

  4. The amino acid sequence of a cereal Bowman-Birk type trypsin inhibitor from seeds of Jobs' tears (Coix lachryma-jobi L.).

    PubMed

    Ary, M B; Shewry, P R; Richardson, M

    1988-02-29

    The major trypsin inhibitor from seeds of Jobs' tears (Coix lachryma-jobi) was purified by heat treatment, fractional precipitation with (NH4)2SO4, ion-exchange chromatography on DEAE-Sepharose, gel-filtration on Sephadex G-75 and preparative reverse-phase HPLC. The complete amino acid sequence was determined by analysis of peptides derived from the reduced and S-carboxymethylated protein by digestion with trypsin, chymotrypsin and the S. aureus V8 protease. The polypeptide contained 64 amino acids with a high content of cysteine. The sequence exhibited strong homology with a number of Bowman-Birk inhibitors from legume seeds and similar proteins recently isolated from wheat and rice. PMID:3162215

  5. A polysaccharide fraction of adlay seed (Coixlachryma-jobi L.) induces apoptosis in human non-small cell lung cancer A549 cells

    SciTech Connect

    Lu, Xiangyi; Liu, Wei; Wu, Junhua; Li, Mengxian; Wang, Juncheng; Wu, Jihui; Luo, Cheng

    2013-01-11

    Highlights: Black-Right-Pointing-Pointer A polysaccharide from adlay seed, its molecular mass, optical rotation and sugars was determined. Black-Right-Pointing-Pointer We demonstrated that a polysaccharide from adlay can induce apoptosis in cancer cells. Black-Right-Pointing-Pointer The polysaccharide inhibited the metabolism and proliferation of NSCLC A549 cells. Black-Right-Pointing-Pointer The polysaccharide may trigger apoptosis via the mitochondria-dependent pathway. -- Abstract: Different seed extracts from Coix lachryma-jobi (adlay seed) have been used for the treatment of various cancers in China, and clinical data support the use of these extracts for cancer therapy; however, their underlying molecular mechanisms have not been well defined. A polysaccharide fraction, designated as CP-1, was extracted from the C.lachryma-jobi L. var. using the ethanol subsiding method. CP-1 induced apoptosis in A549 cells in a dose-dependent manner, as determined by MTT assay. Apoptotic bodies were observed in the cells by scanning electronic microscopy. Apoptosis and DNA accumulation during S-phase of the cell cycle were determined by annexin V-FITC and PI staining, respectively, and measured by flow cytometry. CP-1 also extended the comet tail length on single cell gel electrophoresis, and disrupted the mitochondrial membrane potential. Further analysis by western blotting showed that the expression of caspase-3 and caspase-9 proteins was increased. Taken together, our results demonstrate that CP-1 is capable of inhibiting A549 cell proliferation and inducing apoptosis via a mechanism primarily involving the activation of the intrinsic mitochondrial pathway. The assay data suggest that in addition to its nutritional properties, CP-1 is a very promising candidate polysaccharide for the development of anti-cancer medicines.

  6. Gibberella moniliformis AH13 with antitumor activity, an endophytic fungus strain producing triolein isolated from Adlay (Coix lacryma-jobi: poaceae).

    PubMed

    Jia, Min; Ming, Qian-Liang; Zhang, Qiao-Yan; Chen, Yu; Cheng, Nuo; Wu, Wen-wen; Han, Ting; Qin, Lu-Ping

    2014-09-01

    In this study, the isolation of an endophytic fungus from the leaves of the medicinal herb adlay (Coix lacryma-jobi L. var. ma-yuen Stapf) is reported for the first time. The fungus produced Triolein (trioleoylglycerol), a major constituent of triacylglycerols (TAGs) of adlay, in rice medium under shake-flask and bench-scale fermentation conditions. The fungus was identified as Gibberella moniliformis (Fusarium verticillioides) by its morphology and authenticated by ITS analysis (ITS1 and ITS2 regions and the intervening 5.8S rDNA region). Triolein was identified by HPLC-ELSD coupled with APCI-MS and confirmed through comparison with authentic standard. The concentration of triolein produced by G. moniliformis AH13 reached 2.536 ± 0.006 mg/g dry weight of mycelium. Moreover, the EtOAc extract of G. moniliformis AH13 showed strong antitumor activity against four types of tumor cells (A549, HCT116, MDA-MB-231, and SW1990). These results suggest that G. moniliformis AH13 in adlay has significant scientific and industrial potential to meet the pharmaceutical demands and sustainable energy requirements for TAGs in a cost-effective, easily accessible, and reproducible way and is also a potential novel source of natural antitumor bioactive agents. PMID:24810291

  7. Assessment of the Genetic Diversity of Different Job's Tears (Coix lacryma-jobi L.) Accessions and the Active Composition and Anticancer Effect of Its Seed Oil

    PubMed Central

    Xi, Xiu-Jie; Zhu, Yun-Guo; Tong, Ying-Peng; Yang, Xiao-Ling; Tang, Nan-Nan; Ma, Shu-Min; Li, Shan; Cheng, Zhou

    2016-01-01

    Job’s tears (Coix lachryma-jobi L.) is an important crop used as food and herbal medicine in Asian countries. A drug made of Job’s tears seed oil has been clinically applied to treat multiple cancers. In this study, the genetic diversity of Job’s tears accessions and the fatty acid composition, triglyceride composition, and anti-proliferative effect of Job’s tears seed oil were analyzed using morphological characteristics and ISSR markers, GC-MS, HPLC-ELSD, and the MTT method. ISSR analysis demonstrated low genetic diversity of Job’s tears at the species level (h = 0.21, I = 0.33) and the accession level (h = 0.07, I = 0.10), and strong genetic differentiation (GST = 0.6702) among all accessions. It also clustered the 11 accessions into three cultivated clades corresponding with geographical locations and two evidently divergent wild clades. The grouping patterns based on morphological characteristics and chemical profiles were in accordance with those clustered by ISSR analysis. Significant differences in morphological characteristics, fatty acid composition, triglyceride composition, and inhibition rates of seed oil were detected among different accessions, which showed a highly significant positive correlation with genetic variation. These results suggest that the seed morphological characteristics, fatty acid composition, and triglyceride composition may be mainly attributed to genetic factors. The proportion of palmitic acid and linoleic acid to oleic acid displayed a highly significant positive correlation with the inhibition rates of Job’s tears seed oil for T24 cells, and thus can be an important indicator for quality control for Job’s tears. PMID:27070310

  8. Triterpene-loaded microemulsion using Coix lacryma-jobi seed extract as oil phase for enhanced antitumor efficacy: preparation and in vivo evaluation.

    PubMed

    Qu, Ding; He, Junjie; Liu, Congyan; Zhou, Jing; Chen, Yan

    2014-01-01

    Ganoderma lucidum triterpene-loaded microemulsions (TMEs) using Coix lacryma-jobi (adlay) seed oil as oil phase were prepared, characterized, and evaluated for enhanced antitumor activity. Ternary phase diagrams for the TMEs were constructed and the optimal preparation was developed. Transmission electron microscopy and dynamic light scattering showed that this formulation had a well defined spherical shape, a homogeneous distribution, a small size, and a narrow polydispersity index. The drug-loading rate was determined to be 9.87% by ultraviolet spectrophotometry, and acceptable stability under various stimulations in vitro was confirmed. Importantly, the TME formulation showed a significantly greater antiproliferative effect towards human lung carcinoma (A549) cells and murine lung tumor (Lewis) cells in comparison with suspension formulations containing triterpene and adlay seed oil as a positive control. The half-maximal inhibitory concentration of the TMEs was about 0.62 mg crude drug per mL, being 2.5-fold improved relative to that of the corresponding suspension formulation, but no significant cytotoxicity was observed for the bare microemulsion in A549 cells and Lewis cells. In vivo, the TME formulation showed markedly enhanced antitumor efficacy in a xenograft model of Lewis lung cancer after intragastric administration. Compared with cyclophosphamide, the TME formulation showed similar antitumor activity but less general toxicity. These results indicate the feasibility of using a microemulsion to increase the solubility of triterpene and adlay. TMEs hold promise as an efficient drug delivery system for the treatment of lung cancer. PMID:24379669

  9. Triterpene-loaded microemulsion using Coix lacryma-jobi seed extract as oil phase for enhanced antitumor efficacy: preparation and in vivo evaluation

    PubMed Central

    Qu, Ding; He, Junjie; Liu, Congyan; Zhou, Jing; Chen, Yan

    2014-01-01

    Ganoderma lucidum triterpene-loaded microemulsions (TMEs) using Coix lacryma-jobi (adlay) seed oil as oil phase were prepared, characterized, and evaluated for enhanced antitumor activity. Ternary phase diagrams for the TMEs were constructed and the optimal preparation was developed. Transmission electron microscopy and dynamic light scattering showed that this formulation had a well defined spherical shape, a homogeneous distribution, a small size, and a narrow polydispersity index. The drug-loading rate was determined to be 9.87% by ultraviolet spectrophotometry, and acceptable stability under various stimulations in vitro was confirmed. Importantly, the TME formulation showed a significantly greater antiproliferative effect towards human lung carcinoma (A549) cells and murine lung tumor (Lewis) cells in comparison with suspension formulations containing triterpene and adlay seed oil as a positive control. The half-maximal inhibitory concentration of the TMEs was about 0.62 mg crude drug per mL, being 2.5-fold improved relative to that of the corresponding suspension formulation, but no significant cytotoxicity was observed for the bare microemulsion in A549 cells and Lewis cells. In vivo, the TME formulation showed markedly enhanced antitumor efficacy in a xenograft model of Lewis lung cancer after intragastric administration. Compared with cyclophosphamide, the TME formulation showed similar antitumor activity but less general toxicity. These results indicate the feasibility of using a microemulsion to increase the solubility of triterpene and adlay. TMEs hold promise as an efficient drug delivery system for the treatment of lung cancer. PMID:24379669

  10. [Study on porous maize starch preparation and powdering coix seed oil].

    PubMed

    Jiang, Yan-Rong; Zhang, Zhen-Hai; Ding, Dong-Mei; Sun, E; Wang, Jing; Jia, Xiao-Bin

    2013-07-01

    To optimize the preparation conditions of porous starch The porous starch was used to powder coix seed oil. Porous starch was made of maize starch by using compound enzymes of glucoamylase and alpha-amylase. The preparation process was optimized through orthogonal test design with oil absorption rate to salad oil as indexes. The effect of different dosages of porous starch on yield of triglyceride by powdering coix seed oil was studied. The triglyceride release behaviors and fluidity of powdered coix seed oil were also studied. The results showed that the optimum conditions for preparation of porous maize starch were as follows, the mass radio of glucoamylase to a-amylase was 3:1, the temperatures was 55 degrees C, pH was 5.0, and hydrolysis time was 12 h. Under these conditions, the oil absorption rate to salad oil was 98.5% for porous maize starch. Porous starch was used to power coix seed oil. When porous starch to coix seed oil was 4:1, the triglyceride yield of powering coix seed oil was up to 97.02%. The fluidity of powdered coix seed oil was favorable and control released. The preparation of powdered liquid oil with porous starch had many advantages such as simple production technology, convenient operation, low cost and was worth generalizing. PMID:24199556

  11. Molecular Conduction through Adlayers: Cooperative Effects can Help or Hamper Electron Transport

    SciTech Connect

    Reuter, Matthew G; Seideman, Tamar; Ratner, Mark A.

    2011-01-01

    We use a one-electron, tight-binding model of a molecular adlayer sandwiched between two metal electrodes to explore how cooperative effects between molecular wires influence electron transport through the adlayer. When compared to an isolated molecular wire, an adlayer exhibits cooperative effects that generally enhance conduction away from an isolated wire s resonance and diminish conductance near such a resonance. We also find that the interwire distance (related to the adlayer density) is a key quantity. Substrate-mediated coupling induces most of the cooperative effects in dense adlayers, whereas direct, interwire coupling (if present) dominates in sparser adlayers. In this manner, cooperative effects through dense adlayers cannot be removed, suggesting an optimal adlayer density for maximizing conduction.

  12. Adenine adlayers on Cu(111): XPS and NEXAFS study.

    PubMed

    Tsud, Nataliya; Bercha, Sofiia; Ševčíková, Klára; Acres, Robert G; Prince, Kevin C; Matolín, Vladimír

    2015-11-01

    The adsorption of adenine on Cu(111) was studied by photoelectron and near edge x-ray absorption fine structure spectroscopy. Disordered molecular films were deposited by means of physical vapor deposition on the substrate at room temperature. Adenine chemisorbs on the Cu(111) surface with strong rehybridization of the molecular orbitals and the Cu 3d states. Annealing at 150 °C caused the desorption of weakly bonded molecules accompanied by formation of a short-range ordered molecular adlayer. The interface is characterized by the formation of new states in the valence band at 1.5, 7, and 9 eV. The present work complements and refines existing knowledge of adenine interaction with this surface. The coverage is not the main parameter that defines the adenine geometry and adsorption properties on Cu(111). Excess thermal energy can further rearrange the molecular adlayer and, independent of the initial coverage, the flat lying stable molecular adlayer is formed. PMID:26547179

  13. Adenine adlayers on Cu(111): XPS and NEXAFS study

    SciTech Connect

    Tsud, Nataliya; Bercha, Sofiia; Ševčíková, Klára; Matolín, Vladimír; Acres, Robert G.; Prince, Kevin C.

    2015-11-07

    The adsorption of adenine on Cu(111) was studied by photoelectron and near edge x-ray absorption fine structure spectroscopy. Disordered molecular films were deposited by means of physical vapor deposition on the substrate at room temperature. Adenine chemisorbs on the Cu(111) surface with strong rehybridization of the molecular orbitals and the Cu 3d states. Annealing at 150 °C caused the desorption of weakly bonded molecules accompanied by formation of a short-range ordered molecular adlayer. The interface is characterized by the formation of new states in the valence band at 1.5, 7, and 9 eV. The present work complements and refines existing knowledge of adenine interaction with this surface. The coverage is not the main parameter that defines the adenine geometry and adsorption properties on Cu(111). Excess thermal energy can further rearrange the molecular adlayer and, independent of the initial coverage, the flat lying stable molecular adlayer is formed.

  14. Physicochemical characterization of fish protein adlayers with bacteria repelling properties.

    PubMed

    Meyer, R L; Arpanaei, A; Pillai, S; Bernbom, N; Enghild, J J; Ng, Y Y; Gram, L; Besenbacher, F; Kingshott, P

    2013-02-01

    Materials coated with aqueous fish protein extracts can reduce bacterial adhesion, but the mechanism behind the observed effect is not fully understood. In this study we explore the physicochemical properties of fish muscle protein adlayers on four substrates: gold, stainless steel, polystyrene and silicon dioxide. The aims were (i) to determine if the anti-adhesive effect is independent of the underlying substrate chemistry, (ii) to link the physicochemical properties of the adlayer to its ability to repel bacteria, and (iii) to elucidate the mechanism behind this effect. The main proteins on all surfaces were the muscle proteins troponin, tropomyosin, and myosin, and the lipid binding protein apolipoprotein. The quantity, viscoelasticity, and hydration of the protein adlayers varied greatly on the different substrates, but this variation did not affect the bacterial repelling properties. Our results imply that these proteins adsorb to all substrates and provide a steric barrier towards bacterial adhesion, potentially providing a universal antifouling solution. PMID:23104021

  15. Two Dimensional Epitaxial Water Adlayer on Mica with Graphene Coating: An ab Initio Molecular Dynamics Study.

    PubMed

    Li, Hui; Zeng, Xiao Cheng

    2012-09-11

    Motivated by a recent atomic-force-microscopy (AFM) study of water adlayers on mica by Heath and co-workers (Graphene Visualizes the First Water Adlayers on Mica at Ambient Conditions. Science2010, 329, 1188), we performed an ab initio molecular dynamics study of structural and dynamic properties of monolayer, bilayer, and trilayer water adlayers on the muscovite mica (001) surface with and without a graphene coating. We find that in the first epitaxial water adlayer, water molecules that form strong hydrogen bonds with the oxygen on the mica surface show little motions, thereby solid-like, while those "bridging" water molecules on top of the first water adlayer exhibit "itinerant" behavior, thereby liquid-like. Overall, the Born-Oppenheim molecular dynamics (BOMD) simulations (based on the BLYP-D functional) show that the first water adlayer on mica exhibits a unique hybrid solid-liquid-like behavior with a very low diffusion coefficient at ambient conditions. In particular, no dangling hydrogen bonds are found in the first water adlayer on mica. Moreover, the bilayer and trilayer water adlayers show slightly higher structural stability than the first water adlayer. A graphene coating on the water adlayer further enhances stability of the water adlayers. Most importantly, the bilayer water adlayer on mica with the graphene coating becomes fully solid-like, the structure of which is the same as the bilayer slice of ice-Ih with a thickness of 7.4 Å, consistent with the AFM measurement. PMID:26605715

  16. Administration of Herbal Complexes, Dangguijakyak-san (TJ-23) and Coix Seeds, for Treating Verruca Planae: A Case Report.

    PubMed

    Byun, A Ri; Kwon, Seungwon; Kim, Sewha

    2016-01-01

    Verruca planae (VP) are warts caused by the human papillomavirus. Many patients develop resistance to the conventional therapy for these lesions. Therefore, alternative therapies are needed. We encountered a patient with VP who showed resistance to conventional therapy and was subsequently treated with Dangguijakyak-san (TJ-23; Tsumura, Japan; and Tokishakuyakusan in Japanese) and coix seed tablets with favorable outcomes. A 29-year-old woman had typical VP on her left upper extremity for >11 years. She had been receiving conventional therapies such as immunotherapy with diphenylcyclopropenone, and tretinoin and imiquimod ointments. However, her VP symptoms persisted. Therefore, she was given herbal medication therapy consisting of Dangguijakyak-san (TJ-23) and coix seeds (500mg coix seed extract; Kracie, Japan). At the four-month follow-up, the papules were found to have disappeared. Therefore, we stopped the TJ-23 + coix seed therapy. Until September 2014, the patient has had no recurrence. We believe that Dangguijakyak-san with coix seeds remedy can have an effect on the immune system and consequently treat VP. PMID:26701790

  17. Bitargeted microemulsions based on coix seed ingredients for enhanced hepatic tumor delivery and synergistic therapy.

    PubMed

    Qu, Ding; Sun, Wenjie; Liu, Mingjian; Liu, Yuping; Zhou, Jing; Chen, Yan

    2016-04-30

    A hepatic tumor bitargeted microemulsions drug delivery system using coix seed oil and coix seed polysaccharide (CP) acting as anticancer components, as well as functional excipients, was developed for enhanced tumor-specific accumulation by CP-mediated enhancement on passive tumor targeting and modification of galactose stearate (tumor-targeted ligand). In the physicochemical characteristics studies, galactose stearate-modified coix seed multicomponent microemulsions containing 30% CP (w%) (Gal-C-MEs) had a well-defined spherical shape with a small size (47.63 ± 1.41 nm), a narrow polydispersity index (PDI, 0.101 ± 0.002), and a nearly neutral surface charge (-4.37 ± 1.76 mV). The half-maximal inhibitory concentration (IC50) of Gal-C-MEs against HepG2 cells was 70.2 μg/mL, which decreased by 1.8-fold in comparison with that of coix seed multicomponent microemulsions (C-MEs). The fluorescence intensity of fluorescein isothiocyanate (FITC)-loaded Gal-C-MEs (FITC-Gal-C-MEs) internalized by HepG2 cells was 1.8-fold higher than that of FITC-loaded C-MEs (FIT C-C-MEs), but the cellular uptake of the latter became reduce by 1.6-fold when the weight ratio of CP decreased up to 10%. In the cell apoptosis studies, C-MEs (containing 30% CP) did not show a significant difference with Gal-C-MEs, but exhibited 3.3-fold and 1.5-fold increase relative to C-MEs containing 10% CP and 20% CP, respectively. In the in vivo tumor targeting studies, Cy5-loaded Gal-C-MEs (Cy5-Gal-C-MEs), notably distributed in the tumor sites and still found even at 48 h post-administration, displayed the strongest capability of tumor tissue accumulation and retention among all the test groups. Most importantly, Gal-C-MEs had stronger inhibition of tumor growth, prolonged survival time and more effectively tumor cell apoptosis induction in comparison with C-MEs containing different amounts of CP, which further confirmed that a certain amount of CP and tumor-targeted ligand were of great importance to

  18. Platinum adlayered ruthenium nanoparticles, method for preparing, and uses thereof

    DOEpatents

    Tong, YuYe; Du, Bingchen

    2015-08-11

    A superior, industrially scalable one-pot ethylene glycol-based wet chemistry method to prepare platinum-adlayered ruthenium nanoparticles has been developed that offers an exquisite control of the platinum packing density of the adlayers and effectively prevents sintering of the nanoparticles during the deposition process. The wet chemistry based method for the controlled deposition of submonolayer platinum is advantageous in terms of processing and maximizing the use of platinum and can, in principle, be scaled up straightforwardly to an industrial level. The reactivity of the Pt(31)-Ru sample was about 150% higher than that of the industrial benchmark PtRu (1:1) alloy sample but with 3.5 times less platinum loading. Using the Pt(31)-Ru nanoparticles would lower the electrode material cost compared to using the industrial benchmark alloy nanoparticles for direct methanol fuel cell applications.

  19. Coix seed emulsion synergistically enhances the antitumor activity of gemcitabine in pancreatic cancer through abrogation of NF-κB signaling.

    PubMed

    Qian, Yafang; Yang, Bo; Xiong, Yang; Gu, Mancang

    2016-09-01

    Clinical outcomes in patients with pancreatic cancer (PC) continue to be dismal, in part due to de novo and acquired chemoresistance. In the present study, we provide preclinical evidence that pre-treatment with coix seed emulsion, an injectable agent extracted from coix seeds, synergistically sensitized PC cell lines (BxPC-3, PANC-1 and AsPC-1) to gemcitabine, both in vitro and in vivo. Such pretreatment led to significant induction of pro-apoptosis proteins, including caspase-3, cleaved-PARP and Bax (P<0.05), after lower doses of gemcitabine compared to monotherapy. We also showed that coix seed emulsion suppressed the constitutive and gemcitabine-induced activation of nuclear factor-κB (NF-κB), as shown with the use of electrophoretic mobility shift, reporter and immunoblotting analyses. Coix seed emulsion pretreatment also downregulated the NF-κB-dependent anti‑apoptotic molecules Bcl-2, survivin and cyclooxygenase-2. In vivo, coix seed emulsion combined with gemcitabine had a much greater antitumor effect than the effect of either agent alone, consistent with the downregulation of the proliferation index, and the results of immunostaining for Ki-67, or for the NF-κB subunit p65. Overall, our data demonstrated that coix seed emulsion abrogated gemcitabine-induced activation of NF-κB, and synergistically sensitized PC cells to gemcitabine therapy. PMID:27459907

  20. Investigations of the Host Range of the Corn Cyst Nematode, Heterodera zeae, from Maryland

    PubMed Central

    Ringer, Chloe E.; Sardanelli, Sandra; Krusberg, Lorin R.

    1987-01-01

    The host range of the corn cyst nematode, Heterodera zeae, recently detected in Maryland, was investigated. A total of 269 plant entries, representing 68 families, 172 genera, and 204 species, was inoculated with cysts or a mixture of eggs and second-stage juveniles of H. zeae. The host range of the Maryland population of H. zeae was limited to plants of the Gramineae and included 11 tribes, 33 genera, 42 species, and 77 entries. All 22 corn (Zea mays) cultivars tested were hosts. Other economic hosts included certain cultivars of barley (Hordeum vulgare), oat (Arena sativa), rice (Oryza sativa), sorghum (Sorghum bicolor), sugar cane (Saccharum interspecific hybrid), and wheat (Triticum aestivum). Fall panicum (Panicum dichotomiflorum), a weed species common to cultivated fields in Maryland, was also a host for H. zeae. Other hosts included meadow foxtail (Alopecurus pratensis), Calamagrostis eipgeios, Job's tears (Coix Lachryma-Jobi), green sprangletop (Leptochloa dubia), witchgrass (Panicum capillare), broomcorn (Panicum miliaceum), fountain grass (Pennisetum rueppeli), reed canary grass (Phalaris arundinacea), common reed (Phragmites australis), eastern gamagrass (Tripsacum dactyloides), corn (Zea mays), and teosinte (Zea mexicana). PMID:19290286

  1. Removal of copper ions from aqueous solution by adlai shell (Coix lacryma-jobi L.) adsorbents.

    PubMed

    de Luna, Mark Daniel G; Flores, Edgar D; Cenia, Marie Chela B; Lu, Ming-Chun

    2015-09-01

    Adlai shell (Coix lacryma-jobi L.) adsorbents (ASA) were used to remove copper ions from aqueous solutions under batch conditions. The effect of physical and chemical modification of ASA on Cu(II) removal was evaluated. Results showed that the high coefficients of determination for the pseudo-second order (R(2) > 0.9999) and for the intraparticle diffusion (R(2) > 0.9843) equations indicate that the rate-determining step is a combination of pore diffusion and chemisorption at low Cu(II) concentration and boundary layer, pore diffusion and chemisorption at high Cu(II) concentration. At 298K and 100 mg L(-1) Cu(II), the computed qe and k2 values were 17.2 mg g(-1) and 0.012 g mg(-1) min(-1), respectively. The Freundlich model (R(2) > 0.9636) adequately describes the experimental data indicating heterogeneous adsorption. Overall, the results of the study demonstrate the potential of adlai shell adsorbents for the removal of heavy metals from aqueous solutions. PMID:26081160

  2. Probing the hydration of ultrathin antifouling organosilane adlayers using neutron reflectometry.

    PubMed

    Pawlowska, Natalia M; Fritzsche, Helmut; Blaszykowski, Christophe; Sheikh, Sonia; Vezvaie, Mansoor; Thompson, Michael

    2014-02-11

    Neutron reflectometry data and modeling support the existence of a relatively thick, continuous phase of water stemming from within an antifouling monoethylene glycol silane adlayer prepared on oxidized silicon wafers. In contrast, this physically distinct (from bulk) interphase is much thinner and only interfacial in nature for the less effective adlayer lacking internal ether oxygen atoms. These results provide further insight into the link between antifouling and surface hydration. PMID:24471689

  3. Complete supramolecular self-assembled adlayer on a silicon surface at room temperature.

    PubMed

    Makoudi, Younes; Palmino, Frank; Arab, Madjid; Duverger, Eric; Chérioux, Frédéric

    2008-05-28

    The engineering of a complete adlayer of organic nanolines by supramolecular self-assembly has been achieved for the first time on a silicon-based surface at room temperature and has been studied by scanning tunneling microscopy. This complete adlayer has been successfully obtained thanks to the combination of a specific Si(111)-B square root 3x square root 3R30 degrees semiconductive surface and of strong hydrogen bonds between a pair of dipolar molecules. PMID:18459775

  4. Surface reactions, solvation and adsorption phenomena of electrolytic adlayers on metal surfaces

    NASA Astrophysics Data System (ADS)

    Lim, Seng Woon

    Fundamental understandings of electrolytic adlayers are important to areas like: batteries, ultra-capacitors, fuel cells, corrosion and atmospheric chemistry. In this dissertation, interactions of electrolytic adlayers are systematically examined using ultra-high vacuum surface analytical techniques. In particular, interactions of water with constituents of electrolytic adlayers are closely followed. On clean Ag(110), water desorbs at 165 K and adsorbs as crystalline ice at 145 K. During continuous adsorption, water initially adsorbs with its molecular plane parallel to the surface, and then gradually tilts towards the surface normal as more water adsorbs. A layer-by-layer adsorption model is proposed for crystalline ice growth on Ag(110). When water is separately coadsorbed with hydroxyl and carbonate, water is stabilized to temperatures as high as 220 and 300 K, respectively. Both anions exhibit great surface solvation. An extended bilayer model is proposed for OH interactions with water, and isotopic exchange experiments have illustrated that (1) the extent of proton mobility in the adlayers, and (2) the migration of hydroxide ion into the water-ice multilayer. On Pt(111), mutual displacement of water and methanol occurs in electrolytic adlayers. Adsorbed methanol monolayer is destabilized when it is co-adsorbed with hydrogen. However, methanol monolayer can be restabilized when water is introduced to the adlayer system. With addition of excess water, destabilization induced by hydrogen can be completely removed and methanol behaves as if it interacts only with water. Interactions of Ru-modified Pt(111) with electrolytic adlayer has been studied. Ru adlayers were deposited with a low power electron beam heated evaporation source, and Ru can be probed with molecular nitrogen. Optimum activity of Ru/Pt(111) surfaces occurs when they are thermally activated to 573 K. Water can be stabilized to temperatures as high as 250 K on these surfaces, and partial

  5. Unequal-sphere packing model for simulation of the uniaxially compressed iodine adlayer on Au(111).

    PubMed

    Tkatchenko, Alexandre; Batina, Nikola

    2005-11-24

    A simple unequal-sphere packing (USP) model, based on pure geometrical principles, was applied to study the centered-rectangular iodine c(px radical3)R30 degrees adlayer on the Au(111) surface, well-known from surface X-ray structure (SXS), low energy electron diffraction (LEED), and scanning tunneling microscopy (STM) experiments. To reproduce the exact patterns observed in experiments, two selective conditions-minimum average adsorbate height and minimum adlayer roughness-were imposed. As a result, a series of adlayer patterns with c(px radical3)R30 degrees symmetry (2.3 < p < 3), with precise structural details, including atomic registry and identification of the p-bisector as the most likely trajectory for the iodine adatom movement during the so-called uniaxial compression phenomenon, were identified. In addition, using the same model, the difference between the iodine adlayer arranged in hexagonal and centered-rectangular c(px radical3)R30 degrees patterns, as in the case of Pt(111) and Au(111) surfaces, was investigated. Qualitative and quantitative comparison shows that iodine adatoms in these two arrangements differ significantly in atomic registry, distance from the substrate, and the adlayer corrugation. Our findings could be of special interest in the study of the nature of the iodine adatom bonding to different substrates (i.e., Au vs Pt). PMID:16853820

  6. Substitution effect on the adlayer formation of tetrachloroperylene bisimides on HOPG surface

    NASA Astrophysics Data System (ADS)

    Chen, Qing; Zhang, Xu; Chen, Ting; Wang, Dong; Qian, Hua-Lei; Wang, Zhao-Hui; Wan, Li-Jun

    2010-11-01

    Di-perylene-3,4,9,10-tetracarboxylic acid bisimides (diPBI) is an n-type graphene molecule with nonplanar conformation. The controllable assembly and molecular adlayer structures of tetrachlorinated diPBI derivatives with different alkyl chains substitutions on highly oriented pyrolytic graphite were studied by scanning tunneling microscopy. When the molecule was substituted by butyl, the formation of multilayer or monolayer can be regulated by the solution concentration. When the molecule was substituted by 2-ethylhexyl, however, it can only form monolayer assembly. The unit cell of 2-ethylhexyl substituted diPBI adlayer was expanded to a rectangular shape compared to that of the butyl substituted diPBI. The steric repulsion of the alkyl chains (straight or branched) substitution is proposed as the key factor to control the adlayer structures of diPBI derivatives. The result is helpful to the design and fabrication of the organic film of chemically synthesized graphene type materials.

  7. Triazatriangulenium adlayers on Au(111): Superstructure as a function of alkyl side chain length

    NASA Astrophysics Data System (ADS)

    Lemke, Sonja; Ulrich, Sandra; Claußen, Frauke; Bloedorn, Andreas; Jung, Ulrich; Herges, Rainer; Magnussen, Olaf M.

    2015-02-01

    The structure of organic adlayers, formed by self-assembly of molecular platforms of triazatriangulenium ions on Au(111), was systematically studied by scanning tunneling microscopy as a function of the length of the lateral ligands for alkyl side chains from propyl to dodecyl. A series of hexagonally-ordered adlayers with spacings from 10.7 Å (propyl) to 13.6 Å (dodecyl) was found which are commensurate to the Au(111) substrate lattice, indicating localized bonding of the molecules to the metal.

  8. In vitro and in vivo studies on adlay-derived seed extracts: phenolic profiles, antioxidant activities, serum uric acid suppression, and xanthine oxidase inhibitory effects.

    PubMed

    Zhao, Mouming; Zhu, Dashuai; Sun-Waterhouse, Dongxiao; Su, Guowan; Lin, Lianzhu; Wang, Xiao; Dong, Yi

    2014-08-01

    This study aimed to explore the potential of polished adlay, brown adlay, adlay bran, and adlay hull to prevent and treat hyperuricemia. Brown adlay extract effectively decreased the serum uric acid levels of oxonate-induced hyperuricemic rats. Free and bound phenolic extracts from these materials contained significant amounts of phenolics, with free phenolics dominated by chlorogenic acid and p-coumaric acid while bound phenolics dominated by p-coumaric acid and ferulic acid. Free and bound phenolics of adlay bran exhibited significant xanthine oxidase inhibition activities, 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activities, oxygen radical absorbance capacities, and superoxide radical scavenging activities. Adlay bran phenolics could be effective xanthine oxidase inhibitors and radical scavengers. p-Coumaric acid is a xanthine oxidase inhibitor with strong superoxide radical scavenging activity. However, ferulic acid is a xanthine oxidase inhibitor with weak superoxide radical scavenging activity. Chlorogenic acid is a superoxide radical scavenger with weak xanthine oxidase inhibitory activity. PMID:25029106

  9. Inhibitory Effects of Adlay Extract on Melanin Production and Cellular Oxygen Stress in B16F10 Melanoma Cells

    PubMed Central

    Huang, Huey-Chun; Hsieh, Wan-Yu; Niu, Yu-Lin; Chang, Tsong-Min

    2014-01-01

    The aim of this study was to determine the effects of adlay extract on melanin production and the antioxidant characteristics of the extract. The seeds were extracted by the supercritical fluid CO2 extraction (SFE) method. The effect of adlay extract on melanin production was evaluated using mushroom tyrosinase activity assay, intracellular tyrosinase activity, antioxidant properties and melanin content. Those assays were performed spectrophotometrically. In addition, the expression of melanogenesis-related proteins was determined by western blotting. The results revealed that the adlay extract suppressed intracellular tyrosinase activity and decreased the amount of melanin in B16F10 cells. The adlay extract decreased the expression of microphthalmia-associated transcription factor (MITF), tyrosinase, tyrosinase related protein-1 (TRP-1) and tyrosinase related protein-2 (TRP-2). The extract also exhibited antioxidant characteristics such as free radical scavenging capacity and reducing power. It effectively decreased intracellular reactive oxygen species (ROS) levels in B16F10 cells. We concluded that the adlay extract inhibits melanin production by down-regulation of MITF, tyrosinase, TRP-1 and TRP-2. The antioxidant properties of the extract may also contribute to the inhibition of melanogenesis. The adlay extract can therefore be applied as an inhibitor of melanogenesis and could also act as a natural antioxidant in skin care products. PMID:25244016

  10. Electron-stimulated desorption of cesium atoms from adlayers on a gold surface

    NASA Astrophysics Data System (ADS)

    Kuznetsov, Yu. A.; Lapushkin, M. N.; Potekhina, N. D.

    2016-06-01

    We have studied the process of electron-stimulated desorption (ESD) of Cs atoms from a Cs/CsAu/Au/W system. It is established that ESD takes place from a Cs adlayer and the adjacent CsAu layer of this system. A model of Cs atom desorption from the Cs/CsAu/Au/W system is proposed. The results confirm the semiconductor nature of CsAu compounds.

  11. Adsorption and desorption characteristics of adlay bran free phenolics on macroporous resins.

    PubMed

    Yang, Qingyun; Zhao, Mouming; Lin, Lianzhu

    2016-03-01

    In this study, the adsorption and desorption characteristics of six macroporous resins including XAD-7HP, XAD-16, HP-20, HP-2MGL, SP-207 and SP-825 for enrichment of adlay bran free phenolics were studied. XAD-16, SP-207 and SP-825 were chosen for further study due to their strong adsorption and desorption capacities. XAD-16, SP-207 and SP-825 had similar phenolics adsorption/desorption behaviors. Pseudo-second-order kinetics model and Freundlich isotherm model were suitable for describing the whole exothermic and physical adsorption processes of adlay bran free phenolics on XAD-16, SP-207 and SP-825. After treatment with gradient elution on XAD-16 resin column, the free phenolics were mostly enriched (from 89.61 to 1015.26mg/100g) in 50% ethanol fraction. The oxygen radical absorbance capacity of 50% ethanol fraction was eight times higher than that of the crude extract. Therefore, the production of highly concentrated phenolics might expand the application of adlay bran used as a bioactive ingredient in functional food. PMID:26471633

  12. Development of a sensitive and reliable high performance liquid chromatography method with fluorescence detection for high-throughput analysis of multi-class mycotoxins in Coix seed.

    PubMed

    Kong, Wei-Jun; Li, Jun-Yuan; Qiu, Feng; Wei, Jian-He; Xiao, Xiao-He; Zheng, Yuguo; Yang, Mei-Hua

    2013-10-17

    As an edible and medicinal plant, Coix seed is readily contaminated by more than one group of mycotoxins resulting in potential risk to human health. A reliable and sensitive method has been developed to determine seven mycotoxins (aflatoxins B1, B2, G1, G2, zearalenone, α-zearalenol, and β-zearalenol) simultaneously in 10 batches of Coix seed marketed in China. The method is based on a rapid ultrasound-assisted solid-liquid extraction (USLE) using methanol/water (80/20) followed by immunoaffinity column (IAC) clean-up, on-line photochemical derivatization (PCD), and high performance liquid chromatography coupled with fluorescence detection (HPLC-FLD). Careful optimization of extraction, clean-up, separation and detection conditions was accomplished to increase sample throughput and to attain rapid separation and sensitive detection. Method validation was performed by analyzing samples spiked at three different concentrations for the seven mycotoxins. Recoveries were from 73.5% to 107.3%, with relative standard deviations (RSDs) lower than 7.7%. The intra- and inter-day precisions, expressed as RSDs, were lower than 4% for all studied analytes. Limits of detection and quantification ranged from 0.01 to 50.2 μg kg(-1), and from 0.04 to 125.5 μg kg(-1), respectively, which were below the tolerance levels for mycotoxins set by the European Union. Samples that tested positive were further analyzed by HPLC tandem electrospray ionization mass spectrometry for confirmatory purposes. This is the first application of USLE-IAC-HPLC-PCD-FLD for detecting the occurrence of multi-class mycotoxins in Coix seed. PMID:24091376

  13. Chemical diffusion of CO in mixed CO + O adlayers and reaction-front propagation in CO oxidation on Pd(100).

    PubMed

    Liu, Da-Jiang; Evans, J W

    2006-08-01

    Within the framework of a realistic atomistic lattice-gas model, we present the theoretical formulation and simulation procedures for precise analysis of the chemical diffusion flux of highly mobile CO within a nonuniform interacting mixed CO + O adlayer on a Pd(100) surface. The approach applies in both regimes of relatively immobile unequilibrated and fairly mobile near-equilibrated O adlayer distributions. Spatiotemporal behavior in surface reactions is controlled by chemical diffusion in mixed adlayers. Thus, we naturally integrate the above analysis with a previously developed multiscale modeling strategy to describe mesoscale reaction front propagation in CO oxidation on Pd(100). This treatment avoids using a simplified prescription of chemical diffusion and reaction kinetics as in traditional mean-field reaction-diffusion equation approaches. PMID:16942243

  14. Glycerol-Induced Membrane Stiffening: The Role of Viscous Fluid Adlayers

    PubMed Central

    Pocivavsek, Luka; Gavrilov, Kseniya; Cao, Kathleen D.; Chi, Eva Y.; Li, Dongxu; Lin, Binhua; Meron, Mati; Majewski, Jaroslaw; Lee, Ka Yee C.

    2011-01-01

    Lipid interfaces, ranging from cell membranes to thin surfactant layers that stabilize lung alveoli, are integral to living systems. Such interfaces are often subjected to mechanical forces, and because of their membrane-like geometry, they can easily deform by bending into localized folds. In this work, we explore the role of small molecules (i.e., glycerol) on the mechanical stability of model lung surfactant monolayers. We demonstrate that the presence of glycerol increases local monolayer bending stiffness by orders of magnitude. Our x-ray and neutron reflectivity measurements indicate that water is preferentially depleted, or glycerol is preferentially enriched, at the lipid headgroup/solvent interface, and that this glycerol-enriched layer extends O(10Å) beneath the monolayer with an adsorption free energy of −2.5 to −4.6 kJ/mol. The dramatic change in membrane bending stiffness in the presence of the sugar adlayer is understood in terms of two models: 1), lipid antiplasticization by glycerol; and 2), a continuum mechanical model of the viscous adlayer. PMID:21723821

  15. Conditioning materials with biomacromolecules: composition of the adlayer and influence on cleanability.

    PubMed

    Touré, Yetioman; Genet, Michel J; Dupont-Gillain, Christine C; Sindic, Marianne; Rouxhet, Paul G

    2014-10-15

    The influence of substrate hydrophobicity and biomacromolecules (dextran, bovine serum albumin - BSA) adsorption on the cleanability of surfaces soiled by spraying aqueous suspensions of quartz particles (10-30μm size), then dried, was investigated using glass and polystyrene as substrates. The cleanability was evaluated using radial flow cell (RFC). The surface composition was determined by X-ray photoelectron spectroscopy (XPS). The interpretation of XPS data allowed the complexity due to the ubiquitous presence of organic contaminants to be coped with, and the surface composition to be expressed in terms of both the amount of adlayer and the mass concentration of adlayer constituents. When soiled with a suspension of particles in water, glass was much less cleanable than polystyrene, which was attributed to its much lower water contact angle, in agreement with previous observations on starch soil. Dextran was easily desorbed and did not affect the cleanability. The presence of BSA at the interface strongly improved the cleanability of glass while the contact angle did not change appreciably. In contrast, soiling polystyrene with quartz particles suspended in a BSA solution instead of water did not change markedly the cleanability, while the contact angle was much lower and the aggregates of soiling particles were more flat. These observations are explained by the major role of capillary forces developed upon drying, which influence the closeness of the contact between the soiling particles and the substrate and, thereby, the adherence of particles. The capillary forces are proportional to the liquid surface tension and depend in a more complex way on contact angles of the particles and of the substrate. The dependence of cleanability on capillary forces, and in particular on the liquid surface tension, is predominant as compared with its dependence on the size and shape of the soiling aggregates, which influence the efficiency of shear forces exerted by the

  16. Prophylactic Treatment with Adlay Bran Extract Reduces the Risk of Severe Acute Radiation Dermatitis: A Prospective, Randomized, Double-Blind Study

    PubMed Central

    Huang, Chih-Jen; Hou, Ming-Feng; Kan, Jung-Yu; Juan, Chiung-Hui; Yuan, Shyng-Shiou F.; Luo, Kuei-Hau; Chuang, Hung-Yi; Hu, Stephen Chu-Sung

    2015-01-01

    Acute radiation dermatitis is a frequent adverse effect in patients with breast cancer undergoing radiotherapy, but there are only a small number of studies providing evidence-based interventions for this clinical condition. Adlay is a cereal crop that has been previously shown to have anti-inflammatory and antioxidant properties. In this study, we seek to evaluate the effectiveness of oral prophylactic treatment with adlay bran extract in reducing the risk of severe acute radiation dermatitis. A total of 110 patients with breast cancer undergoing radiotherapy were analyzed. Using a prospective, randomized, double-blind design, 73 patients received oral treatment with adlay bran extract and 37 patients received olive oil (placebo). Treatment was started at the beginning of radiation therapy and continued until the termination of radiation treatment. Our results showed that the occurrence of severe acute radiation dermatitis (RTOG grade 2 or higher) was significantly lower in patients treated with oral adlay bran extract compared to placebo (45.2% versus 75.7%, adjusted odds ratio 0.24). No serious adverse effects from adlay bran treatment were noted. In conclusion, prophylactic oral treatment with adlay bran extract reduces the risk of severe acute radiation dermatitis and may have potential use in patients with breast cancer undergoing radiotherapy. PMID:26495009

  17. Investigating the Self-Assembly and Nanopatterning Characteristics of Organic Molecular Adlayers on Silicon and Graphene via Scanning Tunneling Microscopy

    NASA Astrophysics Data System (ADS)

    Karmel, Hunter Jason

    The controlled nanostructuring of matter on the atomic and molecular scale requires deep insight into the complex physical and chemical interactions that occur between adsorbates and surfaces. This dissertation examines the self assembly of molecularly thin organic adlayers on technologically significant nanoelectronic substrates using ultra high vacuum (UHV) scanning tunneling microscopy (STM). The three material systems considered in this work are cyclopentene monolayers on silicon, perylenetetracarboxylic diimide (PTCDI) adlayers on epitaxial graphene, and PTCDI melamine nanoporous molecular arrays on epitaxial graphene. The nanolithographic properties of each of these organic inorganic hybrid interfaces are extensively characterized at the molecular level. First, the molecularly precise desorption of individual cyclopentene molecules from a saturated organic passivation layer is demonstrated using feedback controlled lithography (FCL), thus achieving sub nanometer patterning resolution and the possibility of generating molecularly abrupt nanostructures on the silicon (100) surface. Second, the exceptional structural and thermal stability of PTCDI adlayers on epitaxial graphene is established using a combination of STM and X ray reflectivity (XRR) measurements. The enhanced stability of the PTCDI adlayer allows it to accommodate sub 5 nanometer voids with molecularly defined boundaries in addition to isolated molecular vacancies at room temperature. Third, a hydrogen bonded molecularly thin organic heteromolecular nanoporous network is generated on epitaxial graphene, formed by the intermixing of PTCDI and melamine. This molecular array exhibits a sub 5 nanometer two dimensional periodicity with hexagonal symmetry and is in atomic registry with the underlying graphene lattice. Overall this thesis explores the richly diverse physical and chemical interactions that promote molecularly precise lithography on nanoelectronic surfaces. In conclusion, the key insights

  18. Alkyl-Nitrile Adlayers as Probes of Plasmonically Induced Electric Fields

    PubMed Central

    Kwasnieski, Daniel T.; Wang, Hao; Schultz, Zachary D.

    2015-01-01

    Vibrational Stark shifts observed from mercaptoalkyl monolayers on surface enhanced Raman (SERS) active materials are reported to provide a direct measurement of the local electric field around plasmonic nanostructures. Adlayers of CN−, p-mercaptobenzonitrile, and n-mercaptobutylnitrile were adsorbed to a heterogeneous nanostructured Ag surface. The frequency of the CN moiety was observed to shift in a correlated fashion with the SERS intensity. These shifts are attributed to a vibrational Stark shift arising from rectification of the optical field, which gives rise to a DC potential on the surface. All three molecules showed CN Stark shifts on the plasmonic surfaces. P-mercaptobenzonitrile is observed to be a well-behaved probe of the electric field, providing a narrow spectral line, suggesting a more uniform orientation on the surface. The utility of p-mercaptobenzonitrile was demonstrated by successfully assessing the electric field between gold nanoparticles adsorbed to a monolayer of the nitrile on a flat gold surface. A model is presented where the Stark shift of the alkyl-nitrile probe can be correlated to optical field, providing an intensity independent measurement of the local electric field environment. PMID:26213606

  19. Anti-fouling properties of Fab' fragments immobilized on silane-based adlayers

    NASA Astrophysics Data System (ADS)

    Crivianu-Gaita, Victor; Romaschin, Alexander; Thompson, Michael

    2015-12-01

    Biosensors require surfaces that are highly specific towards the target analyte and that are minimally fouling. However, surface tuning to minimize fouling is a difficult task. The last decade has seen an increase in the use of immobilized antigen-binding antibody fragments (Fab') in biosensors. One Fab' linker compound S-(11-trichlorosilyl-undecanyl)-benzothiosulfonate (TUBTS) and three spacers were used to create the silane-based adlayers. The ultra-high frequency electromagnetic piezoelectric acoustic sensor (EMPAS) was used to gauge the fouling properties of the various surfaces using bovine serum albumin (BSA), goat IgG, and mouse serum. X-ray photoelectron spectroscopy (XPS), contact angle, and atomic force microscopy (AFM) were employed to characterize the surfaces. It was discovered that immobilized oriented Fab' fragments reduced the fouling levels of surfaces up to 80% compared to the surfaces without fragments. An explanation for this phenomenon is that the antibody fragments increase the hydration of the surfaces and aid in the formation of an anti-fouling water barrier. The anti-fouling effect of the Fab' fragments is at its maximum when there is an even distribution of fragments across the surfaces. Finally, using Fab'-covered surfaces, a cancer biomarker was detected from serum, showing the applicability of this work to the field of biodetection.

  20. The formation and activity of platinum adlayers on diamond electrodes for electrocatalysis

    NASA Astrophysics Data System (ADS)

    Bennett, Jason Alan

    The research described in this dissertation evaluates the potential of diamond as an advanced carbon electrocatalyst support material. This includes both assessing the physical and electrochemical properties of the material as well as a comprehensive investigation into the nature of metal adlayer formation on the material. The physical and electrochemical properties of boron-doped polycrystalline diamond thin films, prepared with varying levels of sp2-bonded nondiamond carbon impurity, were systematically investigated. This impurity was introduced through adjustment of the methane-to-hydrogen source gas ratio used for the deposition. Increasing the methane-to-hydrogen ratio resulted in an increase in the fraction of grain boundary, the extent of secondary nucleation, and the amount of sp2-bonded nondiamond carbon impurity. The effect of the source gas ratio on the electrochemical response towards several well known redox analytes and the oxygen reduction reaction in both acidic and alkaline media was also investigated. The results demonstrate that the grain boundaries, and the sp2-bonded nondiamond carbon impurity presumably residing there, can have a significant impact on the electrode reaction kinetics for certain redox systems and little influence for others. The morphological and microstructural stability of microcrystalline and nanocrystalline boron-doped diamond thin film electrodes under conditions observed in phosphoric acid fuel cells was investigated. The electrodes were exposed to a 2 h period of anodic polarization in 85% H3PO 4 at ˜180°C and 0.1 A/cm2. Catastrophic degradation was not observed for either type of diamond. The oxidation of the microcrystalline diamond was limited to the surface, and the effects could be reversed upon exposure to a hydrogen plasma. The nanocrystalline diamond exhibited similar responses to well known redox analytes after anodic polarization, however an irreversible increase in the film capacitance was also observed

  1. Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111).

    PubMed

    Hong, Sung-Young; Xu, Pan; Camillone, Nina R; White, Michael G; Camillone, Nicholas

    2016-07-01

    We report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate-adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probability increases roughly two orders magnitude, and (ii) the adsorbate-substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate-substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, ηel, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of ηel largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors. PMID:27394118

  2. Nonreversible immobilization of water-borne plutonium onto self-assembled adlayers of silanized humic materials.

    PubMed

    Shcherbina, Natalia S; Kalmykov, Stepan S; Karpiouk, Leonid A; Ponomarenko, Sergey A; Hatfield, Kirk; Haire, Richard; Perminova, Irina V

    2014-02-18

    The objective was to study plutonium partitioning between immobile and mobile humic materials at the water-solid interfaces. Immobilization of the humic materials on solid supports was performed in situ using self-adhesive silanized humic derivatives. The presence of the humic adlayers on solid supports was shown to significantly enhance Pu sorption and its retention under both steady state and dynamic conditions. While plutonium may exist in multiple oxidations states plus colloidal forms, the major thrust in this work was to study the behavior of most mobile--the PuO2(+) form in dilute solutions. The values of the plutonium partition coefficients (Kd) between water and humics-coated silica gels after 10 days exposure reached 1.6 × 10(4) L · kg(-1) at pH 7.5 under anaerobic conditions with a total plutonium concentration of 1.2 × 10(-8) M exceeding those for the uncoated SiO2 (6.3 × 10(2) L · kg(-1)). Column tests showed substantial sequestration of water-borne plutonium (up to 73%) on the humics-coated silica gels. Remobilization experiments conducted under batch conditions at different pH values (3.5, 4.5, 7.5) showed that no more than 3% of the sequestered Pu was remobilized from the humics-coated silica gels by treatment with dissolved humic materials at environmentally relevant pH of 7.5. Consequently, silanized humic materialas can be seen as both molecular probes and as potent candidate materials for scavenging mobile Pu from an aqueous phase. PMID:24533599

  3. Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

    NASA Astrophysics Data System (ADS)

    Hong, Sung-Young; Xu, Pan; Camillone, Nina R.; White, Michael G.; Camillone, Nicholas

    2016-07-01

    We report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate-adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probability increases roughly two orders magnitude, and (ii) the adsorbate-substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate-substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, ηel, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of ηel largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.

  4. In situ X-ray studies of adlayer-induced crystal nucleation at the liquid–liquid interface

    PubMed Central

    Elsen, Annika; Festersen, Sven; Runge, Benjamin; Koops, Christian T.; Ocko, Benjamin M.; Deutsch, Moshe; Seeck, Oliver H.; Murphy, Bridget M.; Magnussen, Olaf M.

    2013-01-01

    Crystal nucleation and growth at a liquid–liquid interface is studied on the atomic scale by in situ Å-resolution X-ray scattering methods for the case of liquid Hg and an electrochemical dilute electrolyte containing Pb2+, F−, and Br− ions. In the regime negative of the Pb amalgamation potential V, no change is observed from the surface-layered structure of pure Hg. Upon potential-induced release of Pb2+ from the Hg bulk at , the formation of an intriguing interface structure is observed, comprising a well-defined 7.6-Å–thick adlayer, decorated with structurally related 3D crystallites. Both are identified by their diffraction peaks as PbFBr, preferentially aligned with their axis along the interface normal. X-ray reflectivity shows the adlayer to consist of a stack of five ionic layers, forming a single-unit-cell–thick crystalline PbFBr precursor film, which acts as a template for the subsequent quasiepitaxial 3D crystal growth. This growth behavior is assigned to the combined action of electrostatic and short-range chemical interactions. PMID:23553838

  5. Probing Surface-Adlayer Conjugation on Organic-Modified Si(111) Surfaces with Microscopy, Scattering, Spectroscopy, and Density Functional Theory

    SciTech Connect

    Kellar, Joshua A.; Lin, Jui-Ching; Kim, Jun-Hyun; Yoder, Nathan L.; Bevan, Kirk H.; Stokes, Grace Y.; Geiger, Franz M.; Nguyen, SonBinh T.; Bedzyk, Michael J.; Hersam, Mark C.

    2009-03-24

    Highly conjugated molecules bound to silicon are promising candidates for organosilicon electronic devices and sensors. In this study, 1-bromo-4-ethynylbenzene was synthesized and reacted with a hydrogen-passivated Si(111) surface via ultraviolet irradiation. Through an array of characterization and modeling tools, the binding configuration and morphology of the reacted molecule were thoroughly analyzed. Atomic force microscopy confirmed an atomically flat surface morphology following reaction, while X-ray photoelectron spectroscopy verified reaction to the surface via the terminal alkyne moiety. In addition, synchrotron X-ray characterization, including X-ray reflectivity, X-ray fluorescence, and X-ray standing wave measurements, enabled sub-angstrom determination of the position of the bromine atom with respect to the silicon lattice. This structural characterization was quantitatively compared with density functional theory (DFT) calculations, thus enabling the {pi}-conjugation of the terminal carbon atoms to be deduced. The X-ray and DFT results were additionally corroborated with the vibrational spectrum of the organic adlayer, which was measured with sum frequency generation. Overall, these results illustrate that the terminal carbon atoms in 1-bromo-4-ethynylbenzene adlayers on Si(111) retain {pi}-conjugation, thus revealing alkyne molecules as promising candidates for organosilicon electronics and sensing.

  6. In situ X-ray studies of adlayer-induced crystal nucleation at the liquid-liquid interface

    SciTech Connect

    Elsen, Annika; Festersen, Sven; Runge, Benjamin; Koops, Christian T.; Ocko, Benjamin M.; Deutsch, Moshe; Seeck, Oliver H.; Murphy, Bridget M.; Magnussen, Olaf M.

    2013-05-29

    Crystal nucleation and growth at a liquid–liquid interface is studied on the atomic scale by in situ Å-resolution X-ray scattering methods for the case of liquid Hg and an electrochemical dilute electrolyte containing Pb2+, F-, and Br- ions. In the regime negative of the Pb amalgamation potential Φrp = -0.70 V, no change is observed from the surface-layered structure of pure Hg. Upon potential-induced release of Pb2+ from the Hg bulk at Graphic, the formation of an intriguing interface structure is observed, comprising a well-defined 7.6-Å–thick adlayer, decorated with structurally related 3D crystallites. Both are identified by their diffraction peaks as PbFBr, preferentially aligned with their Graphic axis along the interface normal. X-ray reflectivity shows the adlayer to consist of a stack of five ionic layers, forming a single-unit-cell–thick crystalline PbFBr precursor film, which acts as a template for the subsequent quasiepitaxial 3D crystal growth. This growth behavior is assigned to the combined action of electrostatic and short-range chemical interactions.

  7. Controlling the relative rates of adlayer formation and removal during etching in inductively coupled plasmas

    NASA Astrophysics Data System (ADS)

    Fuller, Nicholas Colvin Masi

    Laser desorption (LD) of the adlayer coupled with laser induced fluorescence (LIF) and plasma induced emission (PIE) of desorbed adsorbates is used to investigate the relative rates of chlorination and sputtering during the etching of Si in inductively coupled Cl2-Ar plasmas. Such an analysis is a two-fold process: surface analysis and plasma characterization. Surface analysis of Si etching using LD-LIF and LD-PIE techniques combined with etch rate measurements have revealed that the coverage of SiCl2 and etch rate increases and coverage of Si decreases abruptly for a chlorine fraction of 75% and ion energy of 80 eV. The precise Cl2 fraction for which these abrupt changes occur increases with an increase in ion energy. These changes may be caused by local chemisorption-induced reconstruction of Si <100>. Furthermore, the chlorination and sputtering rates are increased by ˜ an order of magnitude as the plasma is changed from Ar-dominant to Cl-dominant. Characterization of the plasma included determination of the dominant ion in Cl2 plasmas using LIF and a Langmuir probe and measurement of the absolute densities of Cl2, Cl, Cl+, and At + in Cl2-Ar discharges using optical emission actinometry. These studies reveal that Cl+ is the dominant positive ion in the H-mode and the dissociation of Cl2 to Cl increases with an increase in Ar fraction due to an increase in electron temperature. Furthermore, for powers exceeding 600 W, the neutral to ion flux ratio is strongly dependent on Cl2 fraction and is attributed mostly to the decrease in Cl density. Such dependence of the flux ratio on Cl2 fraction is significant in controlling chlorination and sputtering rates not only for Si etching, but for etching other key technological materials. ICP O2 discharges were also studied for low-kappa polymeric etch applications. These studies reveal that the electron temperature is weakly dependent on rf power and O2 dissociation is low (˜2%) at the maximum rf power density of 5.7 Wcm

  8. Collision-induced desorption in 193-nm photoinduced reactions in (O{sub 2}+CO) adlayers on Pt(112)

    SciTech Connect

    Han Song; Ma Yunsheng; Matsushima, Tatsuo

    2005-09-01

    The spatial distribution of desorbing O{sub 2} and CO{sub 2} was examined in 193-nm photoinduced reactions in O{sub 2}+CO adlayers on stepped Pt (112)=[(s)3(111)x(001)]. The O{sub 2} desorption collimated in inclined ways in the plane along the surface trough, confirming the hot-atom collision mechanism. In the presence of CO(a), the product CO{sub 2} desorption also collimated in an inclined way, whereas the inclined O{sub 2} desorption was suppressed. The inclined O{sub 2} and CO{sub 2} desorption is explained by a common collision-induced desorption model. At high O{sub 2} coverage, the CO{sub 2} desorption collimated closely along the (111) terrace normal.

  9. Temperature-Switchable Control of Ligand Display on Adlayers of Mixed Poly(lysine)-g-(PEO) and Poly(lysine)-g-(ligand-modified poly-N-isopropylacrylamide).

    PubMed

    Dalier, F; Eghiaian, F; Scheuring, S; Marie, E; Tribet, C

    2016-05-01

    Adlayers of poly(lysine)-g-PEG comblike copolymer are extensively used to prepare cell-repellant and protein-repellent surfaces by a straightforward coulomb-driven adsorption that is compatible with diverse substrates (glass, Petri dish, etc.). To endow surfaces with functional properties, namely, controlled ligand-protein binding, comblike poly(lysine) derivatives were used to deposit temperature-responsive poly(NIPAM) macrografts mixed with PEG ones on glass surfaces. Simple surface immersion in mixed solutions of biotin-modified poly(lysine)-g-poly(N-isopropylacrylamide) and poly(lysine)-g-poly(ethylene oxide) yielded robust adlayers whose composition reflected the ratio between the two polymers in solution. We show by fluorescence imaging, and comparison with repellent 100% PEGylated patterns, that specific binding of model avidin/particle conjugates (diameters of ca. 10 or 200 nm) was controlled by temperature switch. The biotin ligand was displayed and accessible at low T, or hidden at T > LCST. Topography and mechanical mapping measurements by AFM confirmed the swelling/collapse status of PNIPAM macrografts in the adlayer at low/high T, respectively. Temperature-responsive comblike PLL derivative that can spontaneously cover anionic interfaces is a promising platform enabling good control on the deposition and accessibility of biofunctional groups on various solid surfaces. PMID:27011022

  10. Structure of Tl adlayers on the Pt(111) electrode surface: Effects of solution pH and bisulfate coadsorption

    SciTech Connect

    Adzic, R.R.; Wang, J.X.; Magnussen, O.M.; Ocko, B.M.

    1996-08-29

    The structure of Tl adlayers deposited at underpotentials on Pt(111) has been investigated in four different electrolyte solutions (HClO{sub 4}, NaClO{sub 4}, NaOH, and H{sub 2}SO{sub 4}) with surface X-ray scattering (SXS) techniques. In all solutions investigated, Tl forms an incommensurate, aligned-hexagonal phase at the most negative potentials prior to its bulk deposition or hydrogen evolution. With decreasing potential the monolayer compresses and thus the Tl coverage increases. Under hydrogen evolution, the close-packed hexagonal Tl monolayer also exists and this reaction causes a slight lowering of the Tl coverage and a significant decrease of the in-plane ordering of the monolayer. In sulfuric acid solution, besides the close-packed hexagonal phase, a commensurate ({radical}3 x {radical}3)R30{degree} phase with a Tl coverage of 1/3 monolayer is formed in coadsorption with bisulfates over a 0.22 V wide potential range. 21 refs., 8 figs.

  11. Scanning tunneling microscopy study of α,ω-dihexylsexithiophene adlayers on Au(111): a chiral separation induced by a surface.

    PubMed

    Song, Yonghai; Wang, Yu; Wan, Lingli; Ye, Shuhong; Hou, Haoqing; Wang, Li

    2012-08-01

    The self-assembly of α,ω-dihexylsexithiophene molecules on an Au(111) surface was examined by using scanning tunneling microscopy at room temperature, revealing the internal molecular structures of the sexithiophene backbones and the hexyl side chains. The α,ω-dihexylsexithiophene formed a large and well-ordered monolayer in which the molecule lay flatly on the Au(111) surface and was separated into two chiral domains. A detailed observation reveals that the admolecules were packed in one lamellae with their molecular axis aligned along the main axis of the Au(111) substrate with their hexyl chains deviated from <110> direction of the Au(111) substrate by 12 ± 0.5°. In contrast to the behavior in the three-dimensional bulk structure, flat-lying adsorption introduced molecular chirality: right- and left-handed molecules separate into domains of two different orientations, which are mirror symmetric with respect to the <121> direction of the Au(111) substrate. Details of the adlayer structure and the chiral self-assembly were discussed here. PMID:22849803

  12. Composition and Permeability of Oleate Adlayers of CdS Quantum Dots upon Dilution to Photoluminescence-Relevant Concentrations.

    PubMed

    Nepomnyashchii, Alexander B; Harris, Rachel D; Weiss, Emily A

    2016-03-15

    This paper describes the changes in surface chemistry that occur in oleate-capped CdS quantum dots (QDs) upon dilution from NMR-relevant concentrations (10 μM) to photoluminescence (PL)-relevant concentrations (0.1 μM) and the consequences these changes have on the relative probabilities of radiative and nonradiative decay of the QD exciton. Characterization of the QD surface by nuclear magnetic resonance (NMR) spectroscopy reveals that upon dilution in three solvents, C6D6, C6D12, and CDCl3, oleate ligands, in the form of cadmium oleate and Cd(x)OA(y) clusters, desorb. Changes in the ligand coverage by 30-40% do not impact the solubility of the QDs, do not have measurable influence on the absorption or PL line widths, produce small (±0.05), nonmonotonic changes in the relative PL quantum yield, and produce small, nonmonotonic changes the relative partitioning between band-edge and "trapped" exciton emission. Desorption of surface ligands as a result of dilution of the QDs does, however, make the QDs more redox-active with respect to a small-molecule photooxidant, benzoquinone (BQ), because less dense organic adlayers allow a greater number of BQs to permeate the ligand shell and adsorb to the QD surface. Unlike previous studies, in which the QD concentrations used for NMR characterization were more than a factor of 10 higher than those used for optical measurements, this study directly correlates the surface composition of the QDs to their photophysical properties. PMID:26901485

  13. Effects of the surface mobility on the oxidation of adsorbed CO on platinum electrodes in alkaline media. The role of the adlayer and surface defects.

    PubMed

    Herrero, Enrique; Chen, Qing-Song; Hernández, Javier; Sun, Shi-Gang; Feliu, Juan M

    2011-10-01

    The oxidation of adsorbed CO on Pt single crystal electrodes has been studied in alkaline media. The surfaces used in this study were the Pt(111) electrode and vicinal stepped and kinked surfaces with (111) terraces. The kinked surfaces have either (110) steps broken by (100) kinks or (100) steps broken by (110) kinks and different kink densities. The voltammetric profiles for the CO stripping on those electrodes show peaks corresponding to the oxidation of CO on the (111) terraces, on the (100) steps/kinks and on the (110) steps/kinks at very distinctive potentials. Additionally, the stripping voltammograms always present a prewave. The analysis of the results with the different stepped and kinked surfaces indicates that the presence of the prewave is not associated with defects or kinks in the electrode surface. Also, the clear separation of the CO stripping process in different peak contributions indicates that the mobility of CO on the surface is very low. Using partial CO stripping experiments and studies at different pH, it has been proposed that the low mobility is a consequence of the negative absolute potential at which the adlayers are formed in alkaline media. Also, the surface diffusion coefficient for CO in these media has been estimated from the dependence of the stripping charge of the peaks with the scan rate of the voltammetry. PMID:21863178

  14. Conductance control at the LaAlO{sub 3}/SrTiO{sub 3}-interface by a multiferroic BiFeO{sub 3} ad-layer

    SciTech Connect

    Mix, Christian; Finizio, Simone; Kläui, Mathias; Jakob, Gerhard

    2014-06-30

    Multilayered BiFeO{sub 3} (BFO)/LaAlO{sub 3} (LAO) thin film samples were fabricated on SrTiO{sub 3} (STO) substrates by pulsed laser deposition. In this work, the ferroelectric polarization of a multiferroic BFO ad-layer on top of the quasi-two-dimensional electron gas (2DEG) at the LAO/STO interface is used to manipulate the conductivity of the quasi-2DEG. By microstructuring the conductive area of the LAO/STO-interface, a four-point geometry for the measurement of the resistivity was achieved. Piezo force microscopy allows for imaging and poling the spontaneous ferroelectric polarization of the multiferroic layer. The resistance changes showed a linear dependence on the area scanned and a hysteretic behavior with respect to the voltages applied in the scanning process. This is evidence for the ferroelectric polarization of the multiferroic causing the resistance changes. Coupling the antiferromagnetic BFO layer to another ferromagnetic layer could enable a magnetic field control of the conductance of the quasi-2DEG at the LAO/STO interface.

  15. Redox-switching in a viologen-type adlayer: an electrochemical shell-isolated nanoparticle enhanced Raman spectroscopy study on Au(111)-(1×1) single crystal electrodes.

    PubMed

    Liu, Bo; Blaszczyk, Alfred; Mayor, Marcel; Wandlowski, Thomas

    2011-07-26

    We reported the first application of in situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) to an interfacial redox reaction under electrochemical conditions. We construct gap-mode sandwich structures composed of a thiol-terminated HS-6V6H viologen adlayer immobilized on a single crystal Au(111)-(1×1) electrode and covered by Au(60 nm)@SiO(2) core-shell nanoparticles acting as plasmonic antennas. We observed high-quality, potential-dependent Raman spectra of the three viologen species V(2+), V(+●), and V(0) on a well-defined Au(111) substrate surface and could map their potential-dependent evolution. Comparison with experiments on powder samples revealed an enhancement factor of the nonresonant Raman modes of ∼3 × 10(5), and up to 9 × 10(7) for the resonance modes. The study illustrates the unique capability of SHINERS and its potential in the entire field of electrochemical surface science to explore structures and reaction pathways on well-defined substrate surfaces, such as single crystals, for molecular, (electro-)catalytic, bioelectrochemical systems up to fundamental double layer studies at electrified solid/liquid interfaces. PMID:21634391

  16. The growth of sulfur adlayers on Au(100).

    PubMed

    Jiang, Yue; Liang, Xihui; Ren, Shendong; Chen, Chi-Lu; Fan, Liang-Jen; Yang, Yaw-Wen; Tang, Jian-Ming; Luh, Dah-An

    2015-02-14

    We have studied the growth of S layers adsorbed on Au(100) with low-energy electron diffraction (LEED), X-ray photoemission spectra (XPS), and scanning tunneling microscope (STM). Three phases of S/Au(100)-(2 × 2), trimer, and c(2 × 4)-are identified; the latter two are not previously reported. A dose of S2 at 300 K transformed Au(100)-(5 × 20) initially into the (2 × 2) phase and formed the c(2 × 4) phase at a saturation coverage. The STM results show that monolayer Au islands formed during the initial S dose and remained throughout the growth, resulting in a rough c(2 × 4) surface. We show that a highly ordered c(2 × 4) phase can be obtained with a flat (2 × 2) phase as an intermediate step during growth. Based on the evolution of XPS and STM images with varied S2 dose, the components of S 2p are assigned and structural models for the various S/Au(100) phases are proposed. In the (2 × 2) phase, one S atom resides on a four-fold hollow site in each (2 × 2) unit cell, corresponding to a S coverage of 0.25 ML; in the trimer phase, three S atoms form a trimer residing on a four-fold hollow site in each (2 × 2) unit cell, corresponding to a S coverage of 0.75 ML; in the c(2 × 4) phase, there are five S atoms in each primitive unit cell of c(2 × 4); three of them form a trimer residing on a four-fold hollow site, and the other two form a dimer located on the top of the trimer, corresponding to a nominal S coverage of 1.25 ML. With the proposed structural models, the growth of S on Au(100) at 300 K is described in detail. PMID:25681936

  17. The growth of sulfur adlayers on Au(100)

    SciTech Connect

    Jiang, Yue; Ren, Shendong; Chen, Chi-Lu; Liang, Xihui; Fan, Liang-Jen; Yang, Yaw-Wen; Tang, Jian-Ming; Luh, Dah-An

    2015-02-14

    We have studied the growth of S layers adsorbed on Au(100) with low-energy electron diffraction (LEED), X-ray photoemission spectra (XPS), and scanning tunneling microscope (STM). Three phases of S/Au(100)—(2 × 2), trimer, and c(2 × 4)—are identified; the latter two are not previously reported. A dose of S{sub 2} at 300 K transformed Au(100)-(5 × 20) initially into the (2 × 2) phase and formed the c(2 × 4) phase at a saturation coverage. The STM results show that monolayer Au islands formed during the initial S dose and remained throughout the growth, resulting in a rough c(2 × 4) surface. We show that a highly ordered c(2 × 4) phase can be obtained with a flat (2 × 2) phase as an intermediate step during growth. Based on the evolution of XPS and STM images with varied S{sub 2} dose, the components of S 2p are assigned and structural models for the various S/Au(100) phases are proposed. In the (2 × 2) phase, one S atom resides on a four-fold hollow site in each (2 × 2) unit cell, corresponding to a S coverage of 0.25 ML; in the trimer phase, three S atoms form a trimer residing on a four-fold hollow site in each (2 × 2) unit cell, corresponding to a S coverage of 0.75 ML; in the c(2 × 4) phase, there are five S atoms in each primitive unit cell of c(2 × 4); three of them form a trimer residing on a four-fold hollow site, and the other two form a dimer located on the top of the trimer, corresponding to a nominal S coverage of 1.25 ML. With the proposed structural models, the growth of S on Au(100) at 300 K is described in detail.

  18. Electrodes synthesized from carbon nanostructures coated with a smooth and conformal metal adlayer

    DOEpatents

    Adzic, Radoslav; Harris, Alexander

    2014-04-15

    High-surface-area carbon nanostructures coated with a smooth and conformal submonolayer-to-multilayer thin metal films and their method of manufacture are described. The preferred manufacturing process involves the initial oxidation of the carbon nanostructures followed by a surface preparation process involving immersion in a solution with the desired pH to create negative surface dipoles. The nanostructures are subsequently immersed in an alkaline solution containing a suitable quantity of non-noble metal ions which adsorb at surface reaction sites. The metal ions are then reduced via chemical or electrical means. The nanostructures are exposed to a solution containing a salt of one or more noble metals which replace adsorbed non-noble surface metal atoms by galvanic displacement. The process can be controlled and repeated to obtain a desired film coverage. The resulting coated nanostructures may be used, for example, as high-performance electrodes in supercapacitors, batteries, or other electric storage devices.

  19. Platinum-based electrocatalysts synthesized by depositing contiguous adlayers on carbon nanostructures

    DOEpatents

    Adzic, Radoslav R.; Harris, Alexander

    2015-10-06

    High-surface-area carbon nanostructures coated with a smooth and conformal submonolayer-to-multilayer thin metal films and their method of manufacture are described. The manufacturing process may involve initial oxidation of the carbon nanostructures followed by immersion in a solution with the desired pH to create negative surface dipoles. The nanostructures are subsequently immersed in an alkaline solution containing non-noble metal ions which adsorb at surface reaction sites. The metal ions are then reduced via chemical or electrical means and the nanostructures are exposed to a solution containing a salt of one or more noble metals which replace adsorbed non-noble surface metal atoms by galvanic displacement. Subsequent film growth may be performed via the initial quasi-underpotential deposition of a non-noble metal followed by immersion in a solution comprising a more noble metal. The resulting coated nanostructures may be used, for example, as high-performance electrodes in supercapacitors, batteries, or other electric storage devices.

  20. Platinum-based electrocatalysts synthesized by depositing contiguous adlayers on carbon nanostructures

    DOEpatents

    Adzic, Radoslav; Harris, Alexander

    2013-03-26

    High-surface-area carbon nanostructures coated with a smooth and conformal submonolayer-to-multilayer thin metal films and their method of manufacture are described. The preferred manufacturing process involves the initial oxidation of the carbon nanostructures followed by immersion in a solution with the desired pH to create negative surface dipoles. The nanostructures are subsequently immersed in an alkaline solution containing non-noble metal ions which adsorb at surface reaction sites. The metal ions are then reduced via chemical or electrical means and the nanostructures are exposed to a solution containing a salt of one or more noble metals which replace adsorbed non-noble surface metal atoms by galvanic displacement. Subsequent film growth may be performed via the initial quasi-underpotential deposition of a non-noble metal followed by immersion in a solution comprising a more noble metal. The resulting coated nanostructures may be used, for example, as high-performance electrodes in supercapacitors, batteries, or other electric storage devices.

  1. Adlayer structures of anthracenthiol on Au(111) after removal of covering multilayers with probe scan

    NASA Astrophysics Data System (ADS)

    Azzam, Waleed

    2016-05-01

    Self-assembled monolayers (SAMs) of anthracene-2-thiol (AnT) on Au(111) have been investigated using scanning tunneling microscopy (STM). A preparation of AnT-SAMs from ethanolic solutions results in a deposition of multilayer films. As a result, the general features that have been frequently observed for different systems of thiol-modified gold surfaces are hidden in AnT-SAMs. The thin overlayers on top of the chemisorbed anthracenethiolate monolayer are removed by the STM-tip after a repetitive scanning over the same part of the SAM at nondestructive imaging conditions. After ∼2 h of consecutive and continuous STM scanning, smooth AnT-SAM surfaces were formed. The polished surfaces contain vacancy depressions rather than the elevated gold islands which are typically formed after the adsorption of purely aromatic thiols such as AnT on Au(111). The STM data showed the coexistence of two distinct stable commensurate phases, namely, α and β. High-resolution STM images revealed a (√{ 3 } × 8) structure for the α phase and a (√{ 7 } × 4) R11° structure for the β phase whose unit cells contain, respectively, four and two molecules. The β phase was found to be 50% less densely packed than the α phase. The lower molecular density of the β phase should be correlated with a significantly larger tilt angle of the AnT molecular backbone with respect to the surface normal.

  2. A green chemistry of graphene: photochemical reduction towards monolayer graphene sheets and the role of water adlayers.

    PubMed

    Li, Xin-Hao; Chen, Jie-Sheng; Wang, Xinchen; Schuster, Manfred E; Schlögl, Robert; Antonietti, Markus

    2012-04-01

    Clean sheets: Stable aqueous dispersions of graphene sheets (GSs) are obtained by exposing graphene oxide to irradiation with light at room temperature, without using any chemical additives. The photochemical reduction method is sustainable and scalable, repairs a majority of defects in the graphene layers, and can be used to fine-tune surface functional groups. Interestingly, the aqueous GS dispersions are stable without any added surfactant. The existence of a water layer that is strongly bound to GS is evidenced. PMID:22415902

  3. Submonolayer Ag films on Fe(100): A first-principles analysis of energetics controlling adlayer thermodynamics and kinetics

    NASA Astrophysics Data System (ADS)

    Li, Wei; Huang, Li; Evans, James W.; Han, Yong

    2016-04-01

    Epitaxial growth of Ag on Fe(100) and postdeposition relaxation have been studied in several experiments. We provide a first-principles density functional theory analysis of key adatom interaction energies and diffusion barriers controlling growth and relaxation kinetics for the submonolayer regime, as these have not been assessed previously. A cluster expansion approach is used to obtain an extensive set of conventional lateral interactions between adatoms on fourfold hollow adsorption sites. We find robust oscillatory decay of pair interactions with increasing separation, and of trio interactions with increasing perimeter length. First- and second-nearest-neighbor pair interactions, as well as compact linear and bent trio interactions, dominate. The adatom terrace diffusion barrier is estimated to be Ed≈0.39 eV. We also provide a limited analysis of unconventional interactions for which one adatom is at the bridge-site transition state for hopping and one or more others are at fourfold hollow sites. Energy barriers for diffusion along island edges can be determined with the aid of both conventional and unconventional interactions.

  4. Probing the Properties of the Molecular Adlayers on Metal Substrates: Scanning Tunneling Microscopy Study of Amine Adsorption on Gold(111) and Graphene Nanoislands on Cobalt(0001)

    NASA Astrophysics Data System (ADS)

    Zhou, Hui

    In this thesis, we present our findings on two major topics, both of which are studies of molecules on metal surfaces by scanning tunneling microscopy (STM). The first topic is on adsorption of a model amine compound, 1,4-benzenediamine (BDA), on the reconstructed Au(111) surface, chosen for its potential application as a molecular electronic device. The molecules were deposited in the gas phase onto the substrate in the vacuum chamber. Five different patterns of BDA molecules on the surface at different coverages, and the preferred adsorption sites of BDA molecules on reconstructed Au(111) surface, were observed. In addition, BDA molecules were susceptible to tip-induced movement, suggesting that BDA molecules on metal surfaces can be a potential candidate in STM molecular manipulations. We also studied graphene nanoislands on Co(0001) in the hope of understanding interaction of expitaxially grown graphene and metal substrates. This topic can shed a light on the potential application of graphene as an electronic device, especially in spintronics. The graphene nanoislands were formed by annealing contorted hexabenzocoronene (HBC) on the Co(0001) surface. In our experiments, we have determined atop registry of graphene atoms with respect to the underlying Co surface. We also investigated the low-energy electronic structures of graphene nanoislands by scanning tunneling spectroscopy. The result was compared with a first-principle calculation using density functional theory (DFT) which suggested strong coupling between graphene pi-bands and cobalt d-electrons. We also observed that the islands exhibit zigzag edges, which exhibits unique electronic structures compared with the center areas of the islands.

  5. Quantum oscillation of Rashba spin splitting in topological insulator Bi2Se3 induced by the quantum size effects of Pb adlayers

    SciTech Connect

    Yang, Hong; Peng, Xiangyang; Wei, Xiaolin; Liu, Wenliang; Zhu, Wenguang; Xiao, Di; Stocks, George Malcolm; Zhong, Jianxin

    2012-01-01

    Basedon rst-principlescalculationswithindensityfunctionaltheory,we ndthatPbadlayerscaninduceagiantRashbaspinsplittinginthequantumwellstatesofanunderlyingBi2Se3 lm.AsthethicknessofthePbadlayersvaries,thedistancebetweenthePbadlayerandtheBi2Se3 lm,thechargedensityattheinterface,andthebindingbetweenthePbadlayersexhibitanoscillatorybehaviorduetothequantumsizeeffects,whichinturnmodulatesthemagnitudeoftheRashbaspinsplittingofthequantumwellstatesintheBi2Se3 lm.

  6. Relationship between interfacial forces measured by colloid-probe atomic force microscopy and protein resistance of poly(ethylene glycol)-grafted poly(L-lysine) adlayers on niobia surfaces.

    PubMed

    Pasche, Stéphanie; Textor, Marcus; Meagher, Laurence; Spencer, Nicholas D; Griesser, Hans J

    2005-07-01

    Adsorbed layers of "comb-type" copolymers consisting of PEG chains grafted onto a poly(l-lysine) (PLL) backbone on niobium oxide substrates were studied by colloid-probe AFM in order to characterize the interfacial forces associated with coatings of varying architectures (PEG/PLL ratios and PEG chain lengths) and their relevance to protein resistance. The steric and electrostatic forces measured varied substantially with the architecture of the PLL-g-PEG copolymers. Varying the ionic strength of the buffer solutions enabled discrimination between electrostatic and steric-entropic contributions to the net interfacial force. For high PEG grafting densities the steric component was most prominent, but at low ionic strengths and high grafting densities, a repulsive electrostatic surface force was also observed; its origin was assigned to the niobia charges beneath the copolymer, as insufficient protonated amine groups in the PLL backbone were available for compensation of the oxide surface charges. For lower grafting densities and lower ionic strengths there was a substantial attractive electrostatic contribution arising from interaction of the electrical double layer arising from the protonated amine groups, with that of the silica probe surface (as under low ionic strength conditions, the electrical double layer was thicker than the PEG layer). For these PLL-g-PEG coatings the net interfacial force can thus be a markedly varying superposition of electrostatic and steric-entropic contributions, depending on various factors. The force curves correlate with protein adsorption data, demonstrating the utility of AFM colloid-probe force measurements for quantitative analysis of surface forces and how they determine interfacial interactions with proteins. Such characterization of the net interfacial forces is essential to elucidate the multiple types of interfacial forces relevant to the interactions between PLL-g-PEG coatings and proteins and to advance interpretation of protein adsorption or repellence beyond the oversimplified steric barrier model; in particular, our data demonstrate the importance of an ionic-strength-dependent minimum PEG layer thickness to screen the electrostatic interactions of charged interfaces. PMID:15982060

  7. Evidence for multi-polymorphic islands during epitaxial growth of ZnO on Ag(1 1 1)

    NASA Astrophysics Data System (ADS)

    Demiroglu, Ilker; Bromley, Stefan T.

    2016-06-01

    A range of models of free standing and Ag(1 1 1)-supported stoichiometric ZnO films with coverages between 2-3 monolayers are studied using density functional calculations. Following experimental observations we focus on stoichiometric hexagonal and triangular ad-layer islands grown on top of two complete ZnO monolayers. The adlayer islands display distinct edge and corner reconstructions and are found to induce a structural transition extending from the island core to the layered phase below. Based on our results we propose a general model of ad-layer triangular island structure based on seven regions exhibiting four distinct polymorphs.

  8. Evidence for multi-polymorphic islands during epitaxial growth of ZnO on Ag(1 1 1).

    PubMed

    Demiroglu, Ilker; Bromley, Stefan T

    2016-06-01

    A range of models of free standing and Ag(1 1 1)-supported stoichiometric ZnO films with coverages between 2-3 monolayers are studied using density functional calculations. Following experimental observations we focus on stoichiometric hexagonal and triangular ad-layer islands grown on top of two complete ZnO monolayers. The adlayer islands display distinct edge and corner reconstructions and are found to induce a structural transition extending from the island core to the layered phase below. Based on our results we propose a general model of ad-layer triangular island structure based on seven regions exhibiting four distinct polymorphs. PMID:26979335

  9. In-situ X-ray diffraction and STM studies of bromide adsorption on Au(111) electrodes

    SciTech Connect

    Magnussen, O.M.; Ocko, B.M; Wang, J.X.; Adzic, R.R.

    1996-03-28

    The structure of bromide adlayers at the Au(111)-aqueous solution interface has been studied by in-situ surface X-ray scattering (SXS) and scanning tunneling microscopy (STM). Both techniques show the existence of a hexagonal close-packed adlayer phase above a critical potential and are in good quantitative agreement on the adlayer structural parameters. The bromide-bromide spacing changes continuously between 4.24 A at the critical potential and 4.03 A at a potential 300 mV more positive. The adlayer is rotated relative to the substrate by an angle dependent on potential and bromide concentration. The potential- dependent adlayer density corresponding to these structural results agrees well with Br surface excess densities from published electrochemical measurements. At very positive potentials a bromide-induced step-flow etching of the Au substrate is observed. The results are used to compare the different techniques and to discuss the adlayer structure, the phase behavior, and the halide-gold chemical interaction. 49 refs., 8 figs.

  10. The ultrasonic-enhanced factor of mass-transfer coefficient in the supercritical carbon dioxide extraction

    NASA Astrophysics Data System (ADS)

    Luo, Benyi; Lu, Yigang

    2008-10-01

    Based on several hypotheses about the process of supercritical carbon dioxide extraction, the onflow around the solute granule is figured out by the Navier-Stocks equation. In combination with the Higbie’s solute infiltration model, the link between the mass-transfer coefficient and the velocity of flow is found. The mass-transfer coefficient with the ultrasonical effect is compared with that without the ultrasonical effect, and then a new parameter named the ultrasonic-enhanced factor of mass-transfer coefficient is brought forward, which describes the mathematical model of the supercritical carbon dioxide extraction process enhanced by ultrasonic. The model gives out the relationships among the ultrasonical power, the ultrasonical frequency, the radius of solute granule and the ultrasonic-enhanced factor of mass-transfer coefficient. The results calculated by this model fit well with the experimental data, including the extraction of Coix Lacryma-jobi Seed Oil (CLSO) and Coix Lacryma-jobi Seed Ester (CLSE) from coix seeds and the extraction of Eicosapentaenoic Acid (EPA) and Docosahexaenoic Acid (DHA) from the alga by means of the ultrasonic-enhanced supercritical carbon dioxide extraction (USFE) and the supercritical carbon dioxide extraction (SFE) respectively. This proves the rationality of the ultrasonic-enhanced factor model. The model provides a theoretical basis for the application of ultrasonic-enhanced supercritical fluid extraction technique.

  11. Kinetic energy barriers on the GaN(0001) surface: A nucleation study by scanning tunneling microscopy

    SciTech Connect

    Zheng Hao; Xie, M. H.; Wu, H. S.; Xue, Q. K.

    2008-01-15

    Island nucleation of GaN on its (0001) surface is studied by scanning tunneling microscopy. A comparison is made between surfaces with and without excess Ga and among surfaces with different excess Ga coverages. Evidence is provided for the change of step characteristics of GaN(0001) by excess Ga adlayers, where the Ehrlich-Schwoebel effect is seen to be mediated by excess Ga coverage. For single Ga adlayer covered GaN(0001) surfaces, nucleation island densities are evaluated, which are used to derive the kinetic barriers of adatom diffusion on a terrace. A barrier of less than 1 eV is obtained for the system, and the Ga adlayers make GaN growth surfactant mediated.

  12. Gas phase versus surface contributions to photolytic laser chemical vapor deposition rates

    NASA Astrophysics Data System (ADS)

    Braichotte, D.; van den Bergh, H.

    1988-04-01

    The rate of cw photolytic laser chemical vapor deposition (LCVD) of platinum is measured for λ≈350 nm as a function of the light intensity and the metalorganic vapor pressure. The growth of the metal films is studied in situ and in real time by monitoring their optical transmission. At low intensities the transmitted light decreases monotonically with time, and the LCVD process is photolytic with its rate limiting step in the surface adlayer. At higher intensities we observe two distinct time domains: Relatively slow initial photolytic deposition with its rate limiting step in the gas phase, which is followed by much faster pyrolytic LCVD. An improved method for distinguishing between adlayer and gas-phase limiting processes is demonstrated. These observations are confirmed by studying the photolytic deposition rates while varying the thickness of the adlayer.

  13. Mobility of indium on the ZnO(0001) surface

    SciTech Connect

    Heinhold, R.; Reeves, R. J.; Allen, M. W.; Williams, G. T.; Evans, D. A.

    2015-02-02

    The mobility of indium on the Zn-polar (0001) surface of single crystal ZnO wafers was investigated using real-time x-ray photoelectron spectroscopy. A sudden transition in the wettability of the ZnO(0001) surface was observed at ∼520 °C, with indium migrating from the (0001{sup ¯}) underside of the wafer, around the non-polar (11{sup ¯}00) and (112{sup ¯}0) sidewalls, to form a uniform self-organized (∼20 Å) adlayer. The In adlayer was oxidized, in agreement with the first principles calculations of Northrup and Neugebauer that In{sub 2}O{sub 3} precipitation can only be avoided under a combination of In-rich and Zn-rich conditions. These findings suggest that unintentional In adlayers may form during the epitaxial growth of ZnO on indium-bonded substrates.

  14. Mobility of indium on the ZnO(0001) surface

    NASA Astrophysics Data System (ADS)

    Heinhold, R.; Reeves, R. J.; Williams, G. T.; Evans, D. A.; Allen, M. W.

    2015-02-01

    The mobility of indium on the Zn-polar (0001) surface of single crystal ZnO wafers was investigated using real-time x-ray photoelectron spectroscopy. A sudden transition in the wettability of the ZnO(0001) surface was observed at ˜520 °C, with indium migrating from the ( 000 1 ¯ ) underside of the wafer, around the non-polar ( 1 1 ¯ 00 ) and ( 11 2 ¯ 0 ) sidewalls, to form a uniform self-organized (˜20 Å) adlayer. The In adlayer was oxidized, in agreement with the first principles calculations of Northrup and Neugebauer that In2O3 precipitation can only be avoided under a combination of In-rich and Zn-rich conditions. These findings suggest that unintentional In adlayers may form during the epitaxial growth of ZnO on indium-bonded substrates.

  15. The effect of adsorption on static conductivity of epitaxial graphene

    NASA Astrophysics Data System (ADS)

    Davydov, S. Yu.

    2014-12-01

    An analytical expression for adsorption-induced changes in the static conductivity of the adlayer-single-sheet-graphene-substrate system has been obtained using the Kubo-Greenwood formalism with allowance for the dipole-dipole repulsion in the adlayer. The cases of both metal and semiconductor substrates have been considered. The results are applied to description of the hydrogen monolayer-single-sheet-graphene-tungsten substrate system. Numerical estimations show that the magnitude of the effect of the adsorbed hydrogen monolayer on the static conductivity σeg of epitaxial graphene on tungsten is on the order of the σeg value.

  16. Antioxidative Dietary Compounds Modulate Gene Expression Associated with Apoptosis, DNA Repair, Inhibition of Cell Proliferation and Migration

    PubMed Central

    Wang, Likui; Gao, Shijuan; Jiang, Wei; Luo, Cheng; Xu, Maonian; Bohlin, Lars; Rosendahl, Markus; Huang, Wenlin

    2014-01-01

    Many dietary compounds are known to have health benefits owing to their antioxidative and anti-inflammatory properties. To determine the molecular mechanism of these food-derived compounds, we analyzed their effect on various genes related to cell apoptosis, DNA damage and repair, oxidation and inflammation using in vitro cell culture assays. This review further tests the hypothesis proposed previously that downstream products of COX-2 (cyclooxygenase-2) called electrophilic oxo-derivatives induce antioxidant responsive elements (ARE), which leads to cell proliferation under antioxidative conditions. Our findings support this hypothesis and show that cell proliferation was inhibited when COX-2 was down-regulated by polyphenols and polysaccharides. Flattened macrophage morphology was also observed following the induction of cytokine production by polysaccharides extracted from viili, a traditional Nordic fermented dairy product. Coix lacryma-jobi (coix) polysaccharides were found to reduce mitochondrial membrane potential and induce caspase-3- and 9-mediated apoptosis. In contrast, polyphenols from blueberries were involved in the ultraviolet-activated p53/Gadd45/MDM2 DNA repair system by restoring the cell membrane potential. Inhibition of hypoxia-inducible factor-1 by saponin extracts of ginsenoside (Ginsen) and Gynostemma and inhibition of S100A4 by coix polysaccharides inhibited cancer cell migration and invasion. These observations suggest that antioxidants and changes in cell membrane potential are the major driving forces that transfer signals through the cell membrane into the cytosol and nucleus, triggering gene expression, changes in cell proliferation and the induction of apoptosis or DNA repair. PMID:25226533

  17. Self-assembled monolayer and multilayer formation using redox-active Ru complex with phosphonic acids on silicon oxide surface

    NASA Astrophysics Data System (ADS)

    Ishida, Takao; Terada, Kei-ichi; Hasegawa, Kiichi; Kuwahata, Hironao; Kusama, Kazunori; Sato, Ryo; Nakano, Miki; Naitoh, Yasuhisa; Haga, Masa-aki

    2009-08-01

    The formation of self-assembled monolayer and multilayer using redox-active Ru complex molecules with phosphonic acids on SiO 2 surface has been examined using X-ray photoelectron spectroscopy (XPS), ellipsometry, and time of flight secondary mass-ion spectroscopy (TOF-SIMS). We found that an introduction of a Zr adlayer leads to higher surface molecular density of Ru complex SAMs on the SiO 2 surface, compared to that of obtained from the direct adsorption of Ru complex monolayer on the SiO 2 surface. We further tried to fabricate a multilayer film using this molecule with Zr(IV) ion acting as a chemical glue by a successive immersion process. The XPS data revealed that the molecular densities of the multilayers were also higher for the immobilization with Zr adlayer between Ru complex and SiO 2 surface than those without the Zr adlayer, suggesting that Zr adlayer is effective in forming highly packed molecular layer of phosphonic acids on SiO 2 surface. We found the film growth reached a saturation point after 6 layers on the SiO 2 surface. The film growth saturation can be explained by a molecular domain boundary effect encountered due to the large tilt angle of the molecular layer.

  18. Protein-based integrated optical switching and modulation

    NASA Astrophysics Data System (ADS)

    Ormos, Pál; Fábián, László; Oroszi, László; Wolff, Elmar K.; Ramsden, Jeremy J.; Dér, András

    2002-05-01

    The static and dynamic response of optical waveguides coated with a thin protein film of bacteriorhodopsin was investigated. The size and kinetics of the light-induced refractive index changes of the adlayer were determined under different conditions of illumination. The results demonstrate the applicability of this protein as an active, programmable nonlinear optical material in all-optical integrated circuits.

  19. The role of hydrogen in oxygen-assisted chemical vapor deposition growth of millimeter-sized graphene single crystals

    NASA Astrophysics Data System (ADS)

    Zhao, Pei; Cheng, Yu; Zhao, Dongchen; Yin, Kun; Zhang, Xuewei; Song, Meng; Yin, Shaoqian; Song, Yenan; Wang, Peng; Wang, Miao; Xia, Yang; Wang, Hongtao

    2016-03-01

    Involving oxygen in the traditional chemical vapor deposition (CVD) process has proven a promising approach to achieve large-scale graphene single crystals (GSCs), but its many relevant fundamental aspects are still not fully understood. Here we report a systematic study on the role of hydrogen in the growth of millimeter-sized GSCs using enclosure-like Cu structures via the oxygen-assisted CVD process. Results show that GSCs have different first layer growth behaviors on the inside and outside surfaces of a Cu enclosure when the H2 environment is varied, and these behaviors will consequently and strongly influence the adlayer formation in these GSCs, leading to two entirely different growth modes. Low H2 partial pressure (PH2) tends to result in fast growth of dendritically shaped GSCs with multiple small adlayers, but high PH2 can modify the GSC shape into hexagons with single large adlayer nuclei. This difference of adlayers is attributed to the different C diffusion paths determined by the shapes of their host GSCs. On the basis of these observations, we developed an isothermal two-step method to obtain GSCs with significantly improved growth rate and sample quality, in which low PH2 is first set to accelerate the growth rate followed by high PH2 to restrict the adlayer nuclei. Our results prove that the growth of GSCs can reach a reasonable optimization between their growth rates and sample quality by simply adjusting the CVD H2 environment, which we believe will lead to more improvements in graphene synthesis and fundamental insight into the related growth mechanisms.Involving oxygen in the traditional chemical vapor deposition (CVD) process has proven a promising approach to achieve large-scale graphene single crystals (GSCs), but its many relevant fundamental aspects are still not fully understood. Here we report a systematic study on the role of hydrogen in the growth of millimeter-sized GSCs using enclosure-like Cu structures via the oxygen-assisted CVD

  20. Hybridization behavior of mixed DNA/alkylthiol monolayers on gold: characterization by surface plasmon resonance and 32P radiometric assay.

    PubMed

    Gong, Ping; Lee, Chi-Ying; Gamble, Lara J; Castner, David G; Grainger, David W

    2006-05-15

    Nucleic acid assay from a complex biological milieu is attractive but currently difficult and far from routine. In this study, DNA hybridization from serum dilutions into mixed DNA/mercaptoundecanol (MCU) adlayers on gold was monitored by surface plasmon resonance (SPR). Immobilized DNA probe and hybridized target densities on these surfaces were quantified using 32P-radiometric assays as a function of MCU diluent exposure. SPR surface capture results correlated with radiometric analysis for hybridization performance, demonstrating a maximum DNA hybridization on DNA/MCU mixed adlayers. The maximum target surface capture produced by MCU addition to the DNA probe layer correlates with structural and conformational data on identical mixed DNA/MCU adlayers on gold derived from XPS, NEXAFS, and fluorescence intensity measurements reported in a related study (Lee, C.-Y.; Gong, P.; Harbers, G. M.; Grainger, D. W.; Castner, D. G.; Gamble, L. J. Anal. Chem. 2006, 78, 3316-3325.). MCU addition into the DNA adlayer on gold also improved surface resistance to both nonspecific DNA and serum protein adsorption. Target DNA hybridization from serum dilutions was monitored with SPR on the optimally mixed DNA/MCU adlayers. Both hybridization kinetics and efficiency were strongly affected by nonspecific protein adsorption from a complex milieu even at a minimal serum concentration (e.g., 1%). No target hybridization was detected in SPR assays from serum concentrations above 30%, indicating nonspecific protein adsorption interference of DNA capture and hybridization from complex milieu. Removal of nonsignal proteins from nucleic acid targets prior to assay represents a significant issue for direct sample-to-assay nucleic acid diagnostics from food, blood, tissue, PCR mixtures, and many other biologically complex sample formats. PMID:16689533

  1. The role of hydrogen in oxygen-assisted chemical vapor deposition growth of millimeter-sized graphene single crystals.

    PubMed

    Zhao, Pei; Cheng, Yu; Zhao, Dongchen; Yin, Kun; Zhang, Xuewei; Song, Meng; Yin, Shaoqian; Song, Yenan; Wang, Peng; Wang, Miao; Xia, Yang; Wang, Hongtao

    2016-04-14

    Involving oxygen in the traditional chemical vapor deposition (CVD) process has proven a promising approach to achieve large-scale graphene single crystals (GSCs), but its many relevant fundamental aspects are still not fully understood. Here we report a systematic study on the role of hydrogen in the growth of millimeter-sized GSCs using enclosure-like Cu structures via the oxygen-assisted CVD process. Results show that GSCs have different first layer growth behaviors on the inside and outside surfaces of a Cu enclosure when the H2 environment is varied, and these behaviors will consequently and strongly influence the adlayer formation in these GSCs, leading to two entirely different growth modes. Low H2 partial pressure (PH2) tends to result in fast growth of dendritically shaped GSCs with multiple small adlayers, but high PH2 can modify the GSC shape into hexagons with single large adlayer nuclei. This difference of adlayers is attributed to the different C diffusion paths determined by the shapes of their host GSCs. On the basis of these observations, we developed an isothermal two-step method to obtain GSCs with significantly improved growth rate and sample quality, in which low PH2 is first set to accelerate the growth rate followed by high PH2 to restrict the adlayer nuclei. Our results prove that the growth of GSCs can reach a reasonable optimization between their growth rates and sample quality by simply adjusting the CVD H2 environment, which we believe will lead to more improvements in graphene synthesis and fundamental insight into the related growth mechanisms. PMID:26987665

  2. Interplay between electronic and structural properties in the Pb/Ag(1 0 0) interface.

    PubMed

    Crepaldi, A; Zhan, R R; Moser, S; Sheverdyaeva, P M; Carbone, C; Papagno, M; Moras, P; Baraldi, A; Grioni, M

    2015-11-18

    We report an investigation of the structural and electronic properties of a Pb monolayer (ML) grown on Ag(1 0 0), by combining x-ray photoelectron diffraction (XPD) and angle resolved photoelectron spectroscopy (ARPES). The Pb atoms are found to arrange in a pseudo-hexagonal adlayer commensurate to the underlying square Ag substrate, resulting in a coincidence cell with c([Formula: see text]) periodicity. The electronic structure of the Pb ML in proximity of the Fermi level consists in three p-derived bands, which show different degrees of hybridization with the substrate for their different orbital characters. In particular, we report that the p xy states disperse without forming energy gap, in contrast to previous ARPES studies of the Pb ML on different metallic substrates. We attribute the absence of energy gap to the commensurability between substrate and adlayer, resulting in a higher two-dimensionality of the Pb ML. PMID:26490303

  3. Dissociative adsorption of O2 on unreconstructed metal (100) surfaces: Pathways, energetics, and sticking kinetics

    SciTech Connect

    Liu, Da-Jiang; Evans, James W.

    2014-05-06

    An accurate description of oxygen dissociation pathways and kinetics for various local adlayer environments is key for an understanding not just of the coverage dependence of oxygen sticking, but also of reactive steady states in oxidation reactions. Density functional theory analysis for M(100) surfaces with M=Pd, Rh, and Ni, where O prefers the fourfold hollow adsorption site, does not support the traditional Brundle-Behm-Barker picture of dissociative adsorption onto second-nearest-neighbor hollow sites with an additional blocking constraint. Rather adsorption via neighboring vicinal bridge sites dominates, although other pathways can be active. The same conclusion also applies for M=Pt and Ir, where oxygen prefers the bridge adsorption site. Statistical mechanical analysis is performed based on kinetic Monte Carlo simulation of a multisite lattice-gas model consistent with our revised picture of adsorption. This analysis determines the coverage and temperature dependence of sticking for a realistic treatment of the oxygen adlayer structure.

  4. High-speed integrated optical logic based on the protein bacteriorhodopsin.

    PubMed

    Mathesz, Anna; Fábián, László; Valkai, Sándor; Alexandre, Daniel; Marques, Paulo V S; Ormos, Pál; Wolff, Elmar K; Dér, András

    2013-08-15

    The principle of all-optical logical operations utilizing the unique nonlinear optical properties of a protein was demonstrated by a logic gate constructed from an integrated optical Mach-Zehnder interferometer as a passive structure, covered by a bacteriorhodopsin (bR) adlayer as the active element. Logical operations were based on a reversible change of the refractive index of the bR adlayer over one or both arms of the interferometer. Depending on the operating point of the interferometer, we demonstrated binary and ternary logical modes of operation. Using an ultrafast transition of the bR photocycle (BR-K), we achieved high-speed (nanosecond) logical switching. This is the fastest operation of a protein-based integrated optical logic gate that has been demonstrated so far. The results are expected to have important implications for finding novel, alternative solutions in all-optical data processing research. PMID:23500476

  5. Proteins dominate in the surface layers formed on materials exposed to extracellular polymeric substances from bacterial cultures.

    PubMed

    Yang, Yi; Wikieł, Agata J; Dall'Agnol, Leonardo T; Eloy, Pierre; Genet, Michel J; Moura, José J G; Sand, Wolfgang; Dupont-Gillain, Christine C; Rouxhet, Paul G

    2016-01-01

    The chemical compositions of the surface conditioning layers formed by different types of solutions (from isolated EPS to whole culture media), involving different bacterial strains relevant for biocorrosion were compared, as they may influence the initial step in biofilm formation. Different substrata (polystyrene, glass, steel) were conditioned and analyzed by X-ray photoelectron spectroscopy. Peak decomposition and assignment were validated by correlations between independent spectral data and the ubiquitous presence of organic contaminants on inorganic substrata was taken into account. Proteins or peptides were found to be a major constituent of all conditioning layers and polysaccharides were not present in appreciable concentrations; the proportion of nitrogen which may be due to DNA was lower than 15%. There was no significant difference between the compositions of the adlayers formed from different conditioning solutions, except for the adlayers produced with tightly bound EPS extracted from D. alaskensis. PMID:26769222

  6. Carbon adsorption on tungsten and electronic field emission

    NASA Astrophysics Data System (ADS)

    Márquez-Mijares, Maykel; Lepetit, Bruno; Lemoine, Didier

    2016-03-01

    Electronic emission taking place at the electrodes of high voltage systems and responsible for detrimental breakdown processes is known to be strongly dependent on the cathode surface state and in particular on the presence of carbon contamination. To understand better the effect of carbon adsorption on cathode electronic emission, density functional theory calculations are reported for bulk bcc tungsten as well as for clean and carbon-covered W(100) surfaces for several coverages up to 2 ML. Adsorption geometries and energies, work functions and electronic densities of states are analyzed to assess the effect of the presence of adlayers on surface electronic field emission properties. It is shown that flat carbon adlayer deposition on clean W(100) surfaces induces an increase of the surface work function and a decrease of electronic density near the Fermi level. Both factors contribute to reducing electronic field emission levels.

  7. Elucidation of the low coverage chiral adsorption assembly of L-lysine on Cu(1 1 0) surface: A theoretical study

    NASA Astrophysics Data System (ADS)

    Tielens, Frederik; Humblot, Vincent; Pradier, Claire-Marie

    2008-03-01

    The adsorption of L-lysine on Cu(1 1 0) surface was studied using periodic DFT. The geometry is discussed in terms of the molecular electrostatic interactions, and electronic properties such as DOS. An STM image was simulated and compared with our recently obtained experimental results. Compelling evidence of the μ3 adsorption geometry and the open row adsorption pattern of the adlayer is provided. The stability of the geometry of the adlayer is explained in terms of a subtle interplay between inter-molecular repulsive interactions, inter-molecular H-bonds, and surface tension of the copper surface. The relative orientation of the L-lysine molecules is discussed using the electrostatic potential, explaining the formation of chiral adsorption assemblies.

  8. Luminescence from 3,4,9,10-perylenetetracarboxylic dianhydride on Ag(111) surface excited by tunneling electrons in scanning tunneling microscopy.

    PubMed

    Ino, Daisuke; Yamada, Taro; Kawai, Maki

    2008-07-01

    The electronic excitations induced with tunneling electrons into adlayers of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on Ag(111) have been investigated by in situ fluorescence spectroscopy in scanning tunneling microscopy (STM). A minute area of the surface is excited by an electron tunneling process in STM. Fluorescence spectra strongly depend on the coverage of PTCDA on Ag(111). The adsorption of the first PTCDA layer quenches the intrinsic surface plasmon originated from the clean Ag(111). When the second layer is formed, fluorescence spectra are dominated by the signals from PTCDA, which are interpreted as the radiative decay from the manifold of first singlet excited state (S(1)) of adsorbed PTCDA. The fluorescence of PTCDA is independent of the bias polarity. In addition, the fluorescence excitation spectrum agrees with that by optical excitation. Both results indicate that S(1) is directly excited by the inelastic impact scattering of electrons tunneling within the PTCDA adlayer. PMID:18624490

  9. Monolithically integrated broad-band Mach-Zehnder interferometers for highly sensitive label-free detection of biomolecules through dual polarization optics

    PubMed Central

    Psarouli, A.; Salapatas, A.; Botsialas, A.; Petrou, P. S.; Raptis, I.; Makarona, E.; Jobst, G.; Tukkiniemi, K.; Sopanen, M.; Stoffer, R.; Kakabakos, S. E.; Misiakos, K.

    2015-01-01

    Protein detection and characterization based on Broad-band Mach-Zehnder Interferometry is analytically outlined and demonstrated through a monolithic silicon microphotonic transducer. Arrays of silicon light emitting diodes and monomodal silicon nitride waveguides forming Mach-Zehnder interferometers were integrated on a silicon chip. Broad-band light enters the interferometers and exits sinusoidally modulated with two distinct spectral frequencies characteristic of the two polarizations. Deconvolution in the Fourier transform domain makes possible the separation of the two polarizations and the simultaneous monitoring of the TE and the TM signals. The dual polarization analysis over a broad spectral band makes possible the refractive index calculation of the binding adlayers as well as the distinction of effective medium changes into cover medium or adlayer ones. At the same time, multi-analyte detection at concentrations in the pM range is demonstrated. PMID:26825114

  10. Monolithically integrated broad-band Mach-Zehnder interferometers for highly sensitive label-free detection of biomolecules through dual polarization optics.

    PubMed

    Psarouli, A; Salapatas, A; Botsialas, A; Petrou, P S; Raptis, I; Makarona, E; Jobst, G; Tukkiniemi, K; Sopanen, M; Stoffer, R; Kakabakos, S E; Misiakos, K

    2016-01-01

    Protein detection and characterization based on Broad-band Mach-Zehnder Interferometry is analytically outlined and demonstrated through a monolithic silicon microphotonic transducer. Arrays of silicon light emitting diodes and monomodal silicon nitride waveguides forming Mach-Zehnder interferometers were integrated on a silicon chip. Broad-band light enters the interferometers and exits sinusoidally modulated with two distinct spectral frequencies characteristic of the two polarizations. Deconvolution in the Fourier transform domain makes possible the separation of the two polarizations and the simultaneous monitoring of the TE and the TM signals. The dual polarization analysis over a broad spectral band makes possible the refractive index calculation of the binding adlayers as well as the distinction of effective medium changes into cover medium or adlayer ones. At the same time, multi-analyte detection at concentrations in the pM range is demonstrated. PMID:26825114

  11. Mass transport and alloying during InN growth on GaN by molecular-beam epitaxy

    SciTech Connect

    Liu, Y.; Xie, M.H.; Wu, H.S.; Tong, S.Y.

    2006-05-29

    During Stranski-Krastanov (SK) growth of InN on GaN by molecular-beam epitaxy, a mass transport is noted from the two-dimensional wetting layer and/or the surface excess metal adlayers to the SK islands when the excess nitrogen flux is used for deposition. The extent of mass transport depends on the material coverage. For growth under the excess indium flux condition, no such mass transport is observed.

  12. First-principles investigation of graphene-metal interfaces

    NASA Astrophysics Data System (ADS)

    Ross, Andrew; Adamska, Lyudmyla; Lin, You; Oleynik, Ivan

    2011-03-01

    Epitaxial growth of graphene on Ni(111) substrates is one promising method of large-scale, high-quality graphene wafer production, due to the small lattice mismatch between these two materials. We present results of first-principles density functional theory (DFT) investigation of thestructural, electronic, and magnetic properties of graphene/Ni(111) interfaces relevant to experimental studies of graphene growth on nickel substrates. DFT calculations were performed to identify the favored interface geometries and binding sites for different interface configurations. Additional adlayers of Ni and Cu were either adsorbed on top of the graphene/metal interface, or placed between the graphene and substrate to model processes of metal intercalation. It was also found that the interaction between graphene/Ni(111) and the top Cu adlayer is much weaker compared to that for Ni adlayer. The atomic, electronic, and magnetic properties of these interfaces, including induced magnetic moments in graphene/Ni(111) and Cu,Ni/graphene/Ni(111) systems are also discussed. This work was supported by NSF REU supplement to the award CCF-0726842.

  13. X-ray Absorption Spectroscopy Characterization of Zn Underpotential Deposition on Au(111) from Phosphate Supporting Electrolyte

    SciTech Connect

    Lee, J R; O'Malley, R L; O'Connell, T J; Vollmer, A; Rayment, T

    2009-12-11

    Zn K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the structure of Zn monolayers prepared on Au(111) electrodes via underpotential deposition (UPD) from phosphate supporting electrolyte. Theoretical modeling of the XAS data indicates that the Zn adatoms adopt a commensurate ({radical}3x{radical}3)R30{sup o} ({mu}{sub sc} = 0.33) adlayer structure and reside within the 3-fold hollow sites of the Au(111) surface. Meanwhile, phosphate counter-ions co-adsorb on the UPD adlayer and bridge between the Zn adatoms in a ({radical}3x{radical}3)R30{sup o} ({mu}{sub sc} = 0.33) configuration, with each phosphorous atom residing above a vacant 3-fold hollow site of the Au(111). Significantly, this surface structure is invariant between the electrochemical potential for UPD adlayer formation and the onset of bulk Zn electrodeposition. Analysis of the Zn K-edge absorption onset also presents the possibility that the Zn adatoms do not fully discharge during the process of UPD, which had been proposed in prior voltammetric studies of the phosphate/Zn(UPD)/Au(111) system.

  14. Density functional theory screening of gas-treatment strategies for stabilization of high energy-density lithium metal anodes

    NASA Astrophysics Data System (ADS)

    Koch, Stephan L.; Morgan, Benjamin J.; Passerini, Stefano; Teobaldi, Gilberto

    2015-11-01

    To explore the potential of molecular gas treatment of freshly cut lithium foils in non-electrolyte-based passivation of high-energy-density Li anodes, density functional theory (DFT) has been used to study the decomposition of molecular gases on metallic lithium surfaces. By combining DFT geometry optimization and Molecular Dynamics, the effects of atmospheric (N2, O2, CO2) and hazardous (F2, SO2) gas decomposition on Li(bcc) (100), (110), and (111) surfaces on relative surface energies, work functions, and emerging electronic and elastic properties are investigated. The simulations suggest that exposure to different molecular gases can be used to induce and control reconstructions of the metal Li surface and substantial changes (up to over 1 eV) in the work function of the passivated system. Contrary to the other considered gases, which form metallic adlayers, SO2 treatment emerges as the most effective in creating an insulating passivation layer for dosages ≤1 mono-layer. The substantial Li → adsorbate charge transfer and adlayer relaxation produce marked elastic stiffening of the interface, with the smallest change shown by nitrogen-treated adlayers.

  15. A growth diagram for plasma-assisted molecular beam epitaxy of In-face InN

    SciTech Connect

    Gallinat, C. S.; Koblmueller, G.; Brown, J. S.; Speck, J. S.

    2007-09-15

    We investigated the role of temperature and In/N flux ratios to determine suitable growth windows for the plasma-assisted molecular beam epitaxy of In-face (0001) InN. Under vacuum, InN starts decomposing at 435 deg. C as defined by the release of N{sub 2} from the InN crystal and a buildup of an In adlayer and liquid In droplets on the sample surface. At temperatures greater than 470 deg. C, InN decomposition was characterized by a release of both In vapor and N{sub 2} in the absence of a significant accumulation of an In adlayer. No growth was observed at substrate temperatures above 500 deg. C or at temperatures in which the decomposition rates were higher than the growth rates. A growth diagram was then constructed consisting of two growth regimes: the 'In-droplet regime' characterized by step-flow growth and relatively flat surfaces and the ''N-rich regime'' characterized by rough, three-dimensional surfaces. The growth diagram can then be used to predict the surface structure of films grown at varying substrate temperatures and In fluxes. A 2.5 monolayer In adlayer was observed during In-droplet growth, suggesting that an In wetting layer was necessary for step-flow growth.

  16. Selective growth of graphene in layer-by-layer via chemical vapor deposition.

    PubMed

    Park, Jaehyun; An, Hyosub; Choi, Dong-Chul; Hussain, Sajjad; Song, Wooseok; An, Ki-Seok; Lee, Won-Jun; Lee, Naesung; Lee, Wan-Gyu; Jung, Jongwan

    2016-08-14

    Selective and precise control of the layer number of graphene remains a critical issue for the practical applications of graphene. First, it is highly challenging to grow a continuous and uniform few-layer graphene since once the monolayer graphene fully covers a copper (Cu) surface, the growth of the second layer stops, resulting in mostly nonhomogeneous films. Second, from the selective adlayer growth point of view, there is no clear pathway for achieving this. We have developed the selective growth of a graphene adlayer in layer-by-layer via chemical vapor deposition (CVD) which makes it possible to stack graphene on a specific position. The key idea is to deposit a thin Cu layer (∼40 nm thick) on pre-grown monolayer graphene and to apply additional growth. The thin Cu atop the graphene/Cu substrate acts as a catalyst to decompose methane (CH4) gas during the additional growth. The adlayer is grown selectively on the pre-grown graphene, and the thin Cu is removed through evaporation during CVD, eventually forming large-area and uniform double layer graphene. With this technology, highly uniform graphene films with precise thicknesses of 1 to 5 layers and graphene check patterns with 1 to 3 layers were successfully demonstrated. This method provides precise LBL growth for a uniform graphene film and a technique for the design of new graphene devices. PMID:27436358

  17. Interaction of ionic liquids with noble metal surfaces: structure formation and stability of [OMIM][TFSA] and [EMIM][TFSA] on Au(111) and Ag(111).

    PubMed

    Uhl, Benedikt; Huang, Hsinhui; Alwast, Dorothea; Buchner, Florian; Behm, R Jürgen

    2015-10-01

    Aiming at a comprehensive understanding of the interaction of ionic liquids (ILs) with metal surfaces we have investigated the adsorption of two closely related ILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][TFSA] and 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide [OMIM][TFSA], with two noble metal surfaces, Au(111) and Ag(111), under ultrahigh vacuum (UHV) conditions using scanning tunneling microscopy (STM). At room temperature, the ILs form a 2D liquid on either of the two surfaces, while at lower temperatures they condense into two-dimensional (2D) islands which exhibit ordered structures or a short-range ordered 2D glass structure. Comparison of the adlayer structures formed in the different adsorption systems and also with those determined recently for n-butyl-n-methylpyrrolidinium [TFSA](-) adlayers on Ag(111) and Au(111) (B. Uhl et al., Beilstein J. Nanotechnol., 2013, 4, 903) gains detailed insight into the adsorption geometry of the IL ions on the surface. The close similarity of the adlayer structures indicates that (i) the structure formation is dominated by the tendency to optimize the anion adsorption geometry, and that (ii) also in the present systems the cation adsorbs with the alkyl chain pointing up from the surface. PMID:26305417

  18. Revealing a 5,000-y-old beer recipe in China.

    PubMed

    Wang, Jiajing; Liu, Li; Ball, Terry; Yu, Linjie; Li, Yuanqing; Xing, Fulai

    2016-06-01

    The pottery vessels from the Mijiaya site reveal, to our knowledge, the first direct evidence of in situ beer making in China, based on the analyses of starch, phytolith, and chemical residues. Our data reveal a surprising beer recipe in which broomcorn millet (Panicum miliaceum), barley (Hordeum vulgare), Job's tears (Coix lacryma-jobi), and tubers were fermented together. The results indicate that people in China established advanced beer-brewing technology by using specialized tools and creating favorable fermentation conditions around 5,000 y ago. Our findings imply that early beer making may have motivated the initial translocation of barley from the Western Eurasia into the Central Plain of China before the crop became a part of agricultural subsistence in the region 3,000 y later. PMID:27217567

  19. Ultrastructure and phylogeny of Ustilago coicis *

    PubMed Central

    Zhang, Jing-ze; Guan, Pei-gang; Tao, Gang; Ojaghian, Mohammad Reza; Hyde, Kevin David

    2013-01-01

    Ustilago coicis causes serious smut on Coix lacryma-jobi in Dayang Town, Jinyun County, Zhejiang Province of China. In this paper, ultrastructural assessments on fungus-host interactions and teliospore development are presented, and molecular phylogenetic analyses have been done to elucidate the phylogenetic placement of the taxon. Hyphal growth within infected tissues was both intracellular and intercellular and on the surface of fungus-host interaction, and the fungal cell wall and the invaginated host plasma membrane were separated by a sheath comprising two distinct layers between the fungal cell wall and the invaginated host plasma membrane. Ornamentation development of teliospore walls was unique as they appeared to be originated from the exosporium. In addition, internal transcribed spacer (ITS) and large subunit (LSU) sequence data showed that U. coicis is closely related to Ustilago trichophora which infects grass species of the genus Echinochloa (Poaceae). PMID:23549851

  20. Hypoglycemic effect of plants used in Mexico as antidiabetics.

    PubMed

    Román Ramos, R; Alarcón-Aguilar, F; Lara-Lemus, A; Flores-Saenz, J L

    1992-01-01

    The objective of this work is to investigate the hypoglycemic effect of 12 "antidiabetic" plants used in Mexico. The studies were performed using 27 healthy rabbits with the gastric administration of water, tolbutamide or decoction of the "antidiabetic" plant before the induction of temporary hyperglycemia by subcutaneous injection of 50% dextrose solution (4 ml/kg of weight) at the beginning of the experiment and after 60 min. Blood glucose was determined every 60 min for a period of 5 h. Tolbutamide and eight of the studied plants decreased significantly the hyperglycemia as compared with control test (water) (p < 0.05). The strongest effect was yielded by Guaiacum coulteri, followed by Marrubium vulgare, Crataegus pubescens, Cynodon dactylon, Calea zacatechichi, Buddleia americana, Bauhinia divaricata and Coix lachryma. The decrease of hyperglycemia caused by Physalis phyladelphyca, Pavonia schiedeana and Eucaliptus globulus was not significant (p > 0.05). Urtica dioica increased glycemia slightly. PMID:1308793

  1. Kanglaite attenuates UVB-induced down-regulation of aquaporin-3 in cultured human skin keratinocytes

    PubMed Central

    SHAN, SHI-JUN; XIAO, TING; CHEN, JOHN; GENG, SHI-LING; LI, CHANG-PING; XU, XUEGANG; HONG, YUXIAO; JI, CHAO; GUO, YING; WEI, HUACHEN; LIU, WEI; LI, DAPENG; CHEN, HONG-DUO

    2012-01-01

    Ultraviolet (UV) radiation plays an important role in the pathogenesis of skin photoaging. Depending on the wavelength of UV, the epidermis is affected primarily by UVB. One major characteristic of photoaging is the dehydration of the skin. Membrane-inserted water channels (aquaporins) are involved in this process. In this study we demonstrated that UVB radiation induced aquaporin-3 (AQP3) down-regulation in cultured human skin keratinocytes. Kanglaite is a mixture consisting of extractions of Coix Seed, which is an effective anti-neoplastic agent and can inhibit the activities of protein kinase C and NF-κB. We demonstrated that Kanglaite inhibited UVB-induced AQP3 down-regulation of cultured human skin keratinocytes. Our findings provide a potential new agent for anti-photoaging. The related molecular mechanisms remain to be further elucidated. PMID:22211241

  2. Surface-Bound Intermediates in Low-Temperature Methanol Synthesis on Copper. Participants and Spectators

    SciTech Connect

    Yang, Yong; Mei, Donghai; Peden, Charles H.F.; Campbell, Charles T.; Mims, Charles A.

    2015-11-03

    The reactivity of surface adsorbed species present on copper catalysts during methanol synthesis at low temperatures was studied by simultaneous infrared spectroscopy (IR) and mass spectroscopy (MS) measurements during “titration” (transient surface reaction) experiments with isotopic tracing. The results show that adsorbed formate is a major bystander species present on the surface under steady-state methanol synthesis reaction conditions, but it cannot be converted to methanol by reaction with pure H2, nor with H2 plus added water. Formate-containing surface adlayers for these experiments were produced during steady state catalysis in (a) H2:CO2 (with substantial formate coverage) and (b) moist H2:CO (with no IR visible formate species). Both these reaction conditions produce methanol at steady state with relatively high rates. Adlayers containing formate were also produced by (c) formic acid adsorption. Various "titration" gases were used to probe these adlayers at modest temperatures (T = 410-450K) and 6 bar total pressure. Methanol gas (up to ~1% monolayer equivalent) was produced in "titration" from the H2:CO2 catalytic adlayers by H2 plus water, but not by dry hydrogen. The decay in the formate IR features accelerated in the presence of added water vapor. The H2:CO:H2O catalytic adlayer produced similar methanol titration yields in H2 plus water but showed no surface formate features in IR (less than 0.2% monolayer coverage). Finally, formate from formic acid chemisorption produced no methanol under any titration conditions. Even under (H2:CO2) catalytic reaction conditions, isotope tracing showed that pre-adsorbed formate from formic acid did not contribute to the methanol produced. Although non-formate intermediates exist during low temperature methanol synthesis on copper which can be converted to methanol gas

  3. (Non) formation of methanol by direct hydrogenation of formate on copper catalysts

    SciTech Connect

    Yang, Yong; Mims, Charles A.; Disselkamp, Robert S.; Kwak, Ja Hun; Peden, Charles HF; Campbell, C. T.

    2010-10-14

    We have attempted to hydrogenate adsorbed formate species on copper catalysts to probe the importance of this postulated mechanistic step in methanol synthesis. Surface formate coverages up to 0.25 were produced at temperatures between 413K and 453K on supported (Cu/SiO2) copper and unsupported copper catalysts. The adlayers were produced by various methods including (1) steady state catalytic conditions in CO2-H2 (3:1, 6 bar) atmospheres, and (2) by exposure of the catalysts to formic acid. As reported in earlier work, the catalytic surface at steady state contains bidentate formate species with coverages up to saturation levels of ~ 0.25 at the low temperatures of this study. The reactivity of these formate adlayers was investigated at relevant reaction temperatures in atmospheres containing up to 6 bar H2 partial pressure by simultaneous mass spectrometry (MS) and infrared (IR) spectroscopy measurements. The yield of methanol during the attempted hydrogenation (“titration”) of these adlayers was insignificant (<0.2 mol % of the formate adlayer) even in dry hydrogen partial pressures up to 6 bar. Hydrogen titration of formate species produced from formic acid also failed to produce significant quantities of methanol, and attempted titration in gases consisting of CO-hydrogen mixtures or dry CO2 were also unproductive. The formate decomposition kinetics, measured by IR, were also unaffected by these changes in the gas composition. Similar experiments on unsupported copper also failed to show any methanol. From these results, we conclude that methanol synthesis on copper cannot result from the direct hydrogenation of (bidentate) formate species in simple steps involving adsorbed H species alone. Furthermore, experiments performed on both supported (Cu/SiO2) and unsupported copper catalysts gave similar results implying that the methanol synthesis reaction mechanism only involves metal surface chemistry. Pre-exposure of the bidentate formate adlayer to oxidation

  4. Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (1 0 0) surfaces

    NASA Astrophysics Data System (ADS)

    Liu, Da-Jiang; Evans, James W.

    2013-12-01

    A realistic molecular-level description of catalytic reactions on single-crystal metal surfaces can be provided by stochastic multisite lattice-gas (msLG) models. This approach has general applicability, although in this report, we will focus on the example of CO-oxidation on the unreconstructed fcc metal (1 0 0) or M(1 0 0) surfaces of common catalyst metals M = Pd, Rh, Pt and Ir (i.e., avoiding regimes where Pt and Ir reconstruct). These models can capture the thermodynamics and kinetics of adsorbed layers for the individual reactants species, such as CO/M(1 0 0) and O/M(1 0 0), as well as the interaction and reaction between different reactant species in mixed adlayers, such as (CO + O)/M(1 0 0). The msLG models allow population of any of hollow, bridge, and top sites. This enables a more flexible and realistic description of adsorption and adlayer ordering, as well as of reaction configurations and configuration-dependent barriers. Adspecies adsorption and interaction energies, as well as barriers for various processes, constitute key model input. The choice of these energies is guided by experimental observations, as well as by extensive Density Functional Theory analysis. Model behavior is assessed via Kinetic Monte Carlo (KMC) simulation. We also address the simulation challenges and theoretical ramifications associated with very rapid diffusion and local equilibration of reactant adspecies such as CO. These msLG models are applied to describe adsorption, ordering, and temperature programmed desorption (TPD) for individual CO/M(1 0 0) and O/M(1 0 0) reactant adlayers. In addition, they are also applied to predict mixed (CO + O)/M(1 0 0) adlayer structure on the nanoscale, the complete bifurcation diagram for reactive steady-states under continuous flow conditions, temperature programmed reaction (TPR) spectra, and titration reactions for the CO-oxidation reaction. Extensive and reasonably successful comparison of model predictions is made with experimental

  5. Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (100) surfaces

    SciTech Connect

    Liu, Dajiang; Evans, James W.

    2013-12-01

    A realistic molecular-level description of catalytic reactions on single-crystal metal surfaces can be provided by stochastic multisite lattice-gas (msLG) models. This approach has general applicability, although in this report, we will focus on the example of CO-oxidation on the unreconstructed fcc metal (100) or M(100) surfaces of common catalyst metals M = Pd, Rh, Pt and Ir (i.e., avoiding regimes where Pt and Ir reconstruct). These models can capture the thermodynamics and kinetics of adsorbed layers for the individual reactants species, such as CO/M(100) and O/M(100), as well as the interaction and reaction between different reactant species in mixed adlayers, such as (CO + O)/M(100). The msLG models allow population of any of hollow, bridge, and top sites. This enables a more flexible and realistic description of adsorption and adlayer ordering, as well as of reaction configurations and configuration-dependent barriers. Adspecies adsorption and interaction energies, as well as barriers for various processes, constitute key model input. The choice of these energies is guided by experimental observations, as well as by extensive Density Functional Theory analysis. Model behavior is assessed via Kinetic Monte Carlo (KMC) simulation. We also address the simulation challenges and theoretical ramifications associated with very rapid diffusion and local equilibration of reactant adspecies such as CO. These msLG models are applied to describe adsorption, ordering, and temperature programmed desorption (TPD) for individual CO/M(100) and O/M(100) reactant adlayers. In addition, they are also applied to predict mixed (CO + O)/M(100) adlayer structure on the nanoscale, the complete bifurcation diagram for reactive steady-states under continuous flow conditions, temperature programmed reaction (TPR) spectra, and titration reactions for the CO-oxidation reaction. Extensive and reasonably successful comparison of model predictions is made with experimental data. Furthermore

  6. Indium arsenide as a material for biological applications: Assessment of surface modifications, toxicity, and biocompatibility

    NASA Astrophysics Data System (ADS)

    Jewett, Scott A.

    III-V semiconductors such as InAs have recently been employed in a variety of applications where the electronic and optical characteristics of traditional, silicon-based materials are inadequate. InAs has a narrow band gap and very high electron mobility in the near-surface region, which makes it very attractive for high performance transistors, optical applications, and chemical sensing. However, InAs forms an unstable surface oxide layer in ambient conditions, which can corrode over time and leach toxic indium and arsenic components. Current research has gone into making InAs more attractive for biological applications through passivation of the surface by adlayer adsorption. In particular, wet-chemical methods are current routes of exploration due to their simplicity, low cost, and flexibility in the type of passivating molecule. This dissertation focuses on surface modifications of InAs using wet-chemical methods in order to further its use in biological applications. First, the adsorption of collagen binding peptides and mixed peptide/thiol adlayers onto InAs was assessed. X-ray photoelectron spectroscopy (XPS) along with atomic force microscopy (AFM) data suggested that the peptides successfully adsorbed onto InAs, but were only able to block oxide regrowth to a relatively low extent. This low passivation ability is due to the lack of covalent bonds of the peptide to InAs, which are necessary to effectively block oxide regrowth. The addition of a thiol, in the form of mixed peptide/thiol adlayers greatly enhanced passivation of InAs while maintaining peptide presence on the surface. Thiols form tight, covalent bonds with InAs, which prevents oxide regrowth. The presence of the collagen-binding peptide on the surface opens the door to subsequent modification with collagen or polyelectrolyte-based adlayers. Next, the stability and toxicity of modified InAs substrates were determined using inductively coupled plasma mass spectrometry (ICP-MS) and zebrafish

  7. Selective growth of graphene in layer-by-layer via chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Park, Jaehyun; An, Hyosub; Choi, Dong-Chul; Hussain, Sajjad; Song, Wooseok; An, Ki-Seok; Lee, Won-Jun; Lee, Naesung; Lee, Wan-Gyu; Jung, Jongwan

    2016-07-01

    Selective and precise control of the layer number of graphene remains a critical issue for the practical applications of graphene. First, it is highly challenging to grow a continuous and uniform few-layer graphene since once the monolayer graphene fully covers a copper (Cu) surface, the growth of the second layer stops, resulting in mostly nonhomogeneous films. Second, from the selective adlayer growth point of view, there is no clear pathway for achieving this. We have developed the selective growth of a graphene adlayer in layer-by-layer via chemical vapor deposition (CVD) which makes it possible to stack graphene on a specific position. The key idea is to deposit a thin Cu layer (~40 nm thick) on pre-grown monolayer graphene and to apply additional growth. The thin Cu atop the graphene/Cu substrate acts as a catalyst to decompose methane (CH4) gas during the additional growth. The adlayer is grown selectively on the pre-grown graphene, and the thin Cu is removed through evaporation during CVD, eventually forming large-area and uniform double layer graphene. With this technology, highly uniform graphene films with precise thicknesses of 1 to 5 layers and graphene check patterns with 1 to 3 layers were successfully demonstrated. This method provides precise LBL growth for a uniform graphene film and a technique for the design of new graphene devices.Selective and precise control of the layer number of graphene remains a critical issue for the practical applications of graphene. First, it is highly challenging to grow a continuous and uniform few-layer graphene since once the monolayer graphene fully covers a copper (Cu) surface, the growth of the second layer stops, resulting in mostly nonhomogeneous films. Second, from the selective adlayer growth point of view, there is no clear pathway for achieving this. We have developed the selective growth of a graphene adlayer in layer-by-layer via chemical vapor deposition (CVD) which makes it possible to stack graphene

  8. Glycemic index, glycemic load and insulinemic index of Chinese starchy foods

    PubMed Central

    Lin, Meng-Hsueh Amanda; Wu, Ming-Chang; Lu, Shin; Lin, Jenshinn

    2010-01-01

    AIM: To determine the glycemic index (GI), glycemic load (GL) and insulinemic index (II) of five starchy foods that are commonly used in Chinese diets. METHODS: Ten healthy subjects aged between 20-30 years were recruited. Each subject was asked to consume 50 g of available carbohydrate portions of test foods and reference food. Finger capillary blood samples were collected at the start of eating and 15, 30, 45, 60, 90 and 120 min after consumption. The GI and II of foods were calculated from the ratio of incremental area under the glucose/insulin response curves of test and reference foods. The GL for each test food was determined from its GI value and carbohydrate content. RESULTS: The results showed that brown rice elicited the highest postprandial glucose and insulin responses, followed by taro, adlay, yam and mung bean noodles, which produced the lowest. Among the five starchy foods, brown rice evoked the highest GI and GL at 82 ± 0.2 and 18 ± 0.2, followed by taro (69 ± 0.4, 12 ± 0.2), adlay (55 ± 0.4, 10 ± 0.2), yam (52 ± 0.3, 9 ± 0.0) and mung bean noodles (28 ± 0.5, 7 ± 0.2), respectively. The II values of the test foods corresponded with GI values. Similarly, brown rice gave the highest II at 81 ± 0.1, followed by taro (73 ± 0.3), adlay (67 ± 0.3), yam (64 ± 0.5) and mung bean noodles (38 ± 0.3). All five starchy foods had lower GI, GL and II than reference bread (P < 0.05). CONCLUSION: The GI, GL and II values of starchy foods provide important information for the public to manage their diet and could be useful for the prevention of lifestyle-related diseases such as diabetes mellitus. PMID:20954285

  9. Preconditioning of model biocarriers by soluble pollutants: a QCM-D study.

    PubMed

    Huang, Hui; Ding, Li-li; Ren, Hong-qiang; Geng, Jin-ju; Xu, Ke; Zhang, Yan

    2015-04-01

    Preconditioning of a biocarrier surface is the first step in triggering biofilm formation in attached-growth bioreactors. However, the quantification and control of this step as influenced by solution conditions and biocarrier properties have been rarely explored. In this paper, deposition behaviors of soluble pollutants on the model biocarriers polystyrene (PS) and polyamide (PA) were performed using a quartz crystal microbalance with dissipation monitoring (QCM-D). Three types of wastewater from municipal and industrial wastewater treatment plants and 12 synthetic wastewaters with different configurations of model macromolecules (bovine serum albumin and sodium alginate) and ionic compositions (Na(+) and Ca(2+)) were prepared. Results showed that high organic contents (protein and humic acid) in real wastewater increased deposition compared to the impact of ions on the two types of carriers. For synthetic wastewater, an interesting phenomenon was observed in that the presence of Ca(2+) can transform a thin and rigid adlayer into a denser and viscoelastic one on the surface of PS with low organic contents, yet a viscoelastic adlayer can directly form on PS and an increase in the ionic strength hinders deposition in the presence of high organic contents. The deposition of solutes on PA produces a thicker and viscoelastic adlayer that is strengthened an elevated concentration of organic materials. Additionally, a weakening effect of Ca(2+) on deposition was revealed under high ionic strength. This is the first demonstration of control strategies for preconditioning hydrophilic and hydrophobic biocarriers under different water quality conditions and has important implications for the design of a start-up process for biofilm formation in attached-growth bioreactors. PMID:25785553

  10. Vibrational dynamics and band structure of methyl-terminated Ge(111)

    NASA Astrophysics Data System (ADS)

    Hund, Zachary M.; Nihill, Kevin J.; Campi, Davide; Wong, Keith T.; Lewis, Nathan S.; Bernasconi, M.; Benedek, G.; Sibener, S. J.

    2015-09-01

    A combined synthesis, experiment, and theory approach, using elastic and inelastic helium atom scattering along with ab initio density functional perturbation theory, has been used to investigate the vibrational dynamics and band structure of a recently synthesized organic-functionalized semiconductor interface. Specifically, the thermal properties and lattice dynamics of the underlying Ge(111) semiconductor crystal in the presence of a commensurate (1 × 1) methyl adlayer were defined for atomically flat methylated Ge(111) surfaces. The mean-square atomic displacements were evaluated by analysis of the thermal attenuation of the elastic He diffraction intensities using the Debye-Waller model, revealing an interface with hybrid characteristics. The methyl adlayer vibrational modes are coupled with the Ge(111) substrate, resulting in significantly softer in-plane motion relative to rigid motion in the surface normal. Inelastic helium time-of-flight measurements revealed the excitations of the Rayleigh wave across the surface Brillouin zone, and such measurements were in agreement with the dispersion curves that were produced using density functional perturbation theory. The dispersion relations for H-Ge(111) indicated that a deviation in energy and lineshape for the Rayleigh wave was present along the nearest-neighbor direction. The effects of mass loading, as determined by calculations for CD3-Ge(111), as well as by force constants, were less significant than the hybridization between the Rayleigh wave and methyl adlayer librations. The presence of mutually similar hybridization effects for CH3-Ge(111) and CH3-Si(111) surfaces extends the understanding of the relationship between the vibrational dynamics and the band structure of various semiconductor surfaces that have been functionalized with organic overlayers.

  11. Vibrational dynamics and band structure of methyl-terminated Ge(111).

    PubMed

    Hund, Zachary M; Nihill, Kevin J; Campi, Davide; Wong, Keith T; Lewis, Nathan S; Bernasconi, M; Benedek, G; Sibener, S J

    2015-09-28

    A combined synthesis, experiment, and theory approach, using elastic and inelastic helium atom scattering along with ab initio density functional perturbation theory, has been used to investigate the vibrational dynamics and band structure of a recently synthesized organic-functionalized semiconductor interface. Specifically, the thermal properties and lattice dynamics of the underlying Ge(111) semiconductor crystal in the presence of a commensurate (1 × 1) methyl adlayer were defined for atomically flat methylated Ge(111) surfaces. The mean-square atomic displacements were evaluated by analysis of the thermal attenuation of the elastic He diffraction intensities using the Debye-Waller model, revealing an interface with hybrid characteristics. The methyl adlayer vibrational modes are coupled with the Ge(111) substrate, resulting in significantly softer in-plane motion relative to rigid motion in the surface normal. Inelastic helium time-of-flight measurements revealed the excitations of the Rayleigh wave across the surface Brillouin zone, and such measurements were in agreement with the dispersion curves that were produced using density functional perturbation theory. The dispersion relations for H-Ge(111) indicated that a deviation in energy and lineshape for the Rayleigh wave was present along the nearest-neighbor direction. The effects of mass loading, as determined by calculations for CD3-Ge(111), as well as by force constants, were less significant than the hybridization between the Rayleigh wave and methyl adlayer librations. The presence of mutually similar hybridization effects for CH3-Ge(111) and CH3-Si(111) surfaces extends the understanding of the relationship between the vibrational dynamics and the band structure of various semiconductor surfaces that have been functionalized with organic overlayers. PMID:26429030

  12. Etching of hexagonal SiC surfaces in chlorine-containing gas media at ambient pressure

    NASA Astrophysics Data System (ADS)

    Zinovev, A. V.; Moore, J. F.; Hryn, J.; Pellin, M. J.

    2006-06-01

    The modification of the silicon carbide (4H-SiC) single-crystal surface in a chlorine-containing gas mixture at high temperature (800-1000 °C) and ambient pressure was investigated. The results of silicon carbide chlorination are found to strongly depend on the hexagonal surface orientation. Due to the thermodynamically more favorable reaction of chlorine with silicon rather than carbon, the C-terminated side (0 0 0 1¯) clearly undergoes considerable changes, resulting in coverage by a black-colored carbon film, whereas the Si-side (0 0 0 1) surprisingly remains visually untouched. With using X-ray photoelectron spectroscopy (XPS), angle-resolved XPS and SEM it is shown that this drastic change in behavior is associated with a different structure of oxicarbide/silicate adlayer formed on the C- and Si-terminated sides of silicon carbide surface during experimental pre-treatment and air exposure. The presence of oxygen bridges connecting the silicate adlayer with the bulk SiC in the case of Si-side inhibits the chlorination reaction and makes this surface strongly resistant to chlorine attack. Only some places on the Si-terminated side demonstrate traces of chlorine etching in the form of hexagonal-shaped voids, which are possibly initiated by distortion of the initial crystalline structure by micropipes. In contrast, a thin carbon layer resulted on the C-terminated side as a consequence of the chlorination process. XPS, ARXPS, SEM and Raman spectroscopy study of created film allows us to argue that it consists mainly of sp2-bonded carbon, mostly in the form of nanoscale graphene sheets. The absence of a protective oxygen bridge between the silicate adlayer and the bulk silicon carbide crystal leads to unlimited growth of carbon film on the SiC(0 0 0 1¯) side.

  13. Co-adsorbtion of Cu and Keggin type polytungstates on polycrystalline Pt: interplay of atomic and molecular UPD.

    PubMed

    Tsirlina, Galina; Mishina, Elena; Timofeeva, Elena; Tanimura, Nobuko; Sherstyuk, Nataliya; Borzenko, Marina; Nakabayashi, Seiichiro; Petrii, Oleg

    2008-01-01

    Second harmonic generation (SHG), electrochemical quartz microbalance (EQCM), and cyclic voltammetry are applied to clarify the structure and properties of Cu adlayers formed in the presence of Keggin polytungstate anions. For 0.02-10 mM CuSO4 solutions, no pronounced suppression of underpotential copper deposition (Cu UPD) by 0.1-10 mM H3PW12O40 (PW12) or H4SiW12O40 (SiW12) is observed in electrochemical experiments. Moreover, coadsorption with polyanions results in an increase of charge in the Cu UPD region. EQCM data demonstrate high surface coverage with polytungstate in the overall potential range and their pronounced co-adsorption with Cu2+ cations under open circuit. The unusual potential dependence of EQCM response of polytungstates is discovered and discussed in terms of anion interactions with adsorbed hydrogen. The SHG response of Cu UPD demonstrates a non-linear dependence on Cu surface coverage, which is interpreted in terms of discontinuous submonolayers consisting of 2D Cu islands. The additives of PW12 or SiW12 decrease copper SHG response at low and high CuSO4 concentrations, with minor effect for a mid range of concentrations. In all mixed solutions, the potential dependence of the SHG response remains typical for Cu UPD, not for polytungstates. SHG transients measured under potential step mode demonstrate that the initial non-steady-state SHG behavior of the adlayer is more close to the behavior of polytungstates, but typical copper features appear at longer wavelength. These facts favor the hypothesis of Cu adatom penetration through anionic adlayers and formation of a metal submonolayer at the vacant areas between large quasi-spherical polyanions, with subsequent transformation into a Pt/Cu/polytungstate layered structure. PMID:19213321

  14. Vibrational dynamics and band structure of methyl-terminated Ge(111)

    SciTech Connect

    Hund, Zachary M.; Nihill, Kevin J.; Sibener, S. J.; Campi, Davide; Bernasconi, M.; Wong, Keith T.; Lewis, Nathan S.; Benedek, G.

    2015-09-28

    A combined synthesis, experiment, and theory approach, using elastic and inelastic helium atom scattering along with ab initio density functional perturbation theory, has been used to investigate the vibrational dynamics and band structure of a recently synthesized organic-functionalized semiconductor interface. Specifically, the thermal properties and lattice dynamics of the underlying Ge(111) semiconductor crystal in the presence of a commensurate (1 × 1) methyl adlayer were defined for atomically flat methylated Ge(111) surfaces. The mean-square atomic displacements were evaluated by analysis of the thermal attenuation of the elastic He diffraction intensities using the Debye-Waller model, revealing an interface with hybrid characteristics. The methyl adlayer vibrational modes are coupled with the Ge(111) substrate, resulting in significantly softer in-plane motion relative to rigid motion in the surface normal. Inelastic helium time-of-flight measurements revealed the excitations of the Rayleigh wave across the surface Brillouin zone, and such measurements were in agreement with the dispersion curves that were produced using density functional perturbation theory. The dispersion relations for H-Ge(111) indicated that a deviation in energy and lineshape for the Rayleigh wave was present along the nearest-neighbor direction. The effects of mass loading, as determined by calculations for CD{sub 3}-Ge(111), as well as by force constants, were less significant than the hybridization between the Rayleigh wave and methyl adlayer librations. The presence of mutually similar hybridization effects for CH{sub 3}-Ge(111) and CH{sub 3}-Si(111) surfaces extends the understanding of the relationship between the vibrational dynamics and the band structure of various semiconductor surfaces that have been functionalized with organic overlayers.

  15. A sensitivity metric and software to guide the analysis of soft films measured by a quartz crystal microbalance.

    PubMed

    McNamara, Thomas P; Blanford, Christopher F

    2016-05-10

    This article introduces a set of mathematical and computational tools for use with a quartz crystal microbalance (QCM) to aid in experimental planning and data interpretation. The optimisation tools are based on a metric we term the total parameter matrix sensitivity (TPM-sensitivity). TPM-sensitivity is defined mathematically as the Jacobian determinant of a QCM's responses (e.g., frequency change or dissipation/bandwidth change for a given harmonic) with respect to changes in the physical properties of a soft film and surrounding solution (e.g., density or viscosity). Large TPM-sensitivity values denote conditions where the sensor responses are not only large but also allow the selected unknown physical properties to be mathematically decoupled. In some cases, the viscoelastic properties of an adlayer can be determined using only frequency responses. We validated this method using experimentally obtained data of an ageing adlayer of the enzyme bilirubin oxidase from Myrothecium verrucaria. Fits to these measurements produced more realistic film parameters when responses, including frequency-only combinations, were selected to maximise TPM sensitivity. We provide documented MATLAB code with a graphical user interface to enable other QCM users to employ this analysis. The current software can be applied to any single, homogeneous adlayer that obeys a Kelvin-Voigt viscoelastic model and sits under a semi-infinite Newtonian fluid. Only initial estimates of the film values are required, with the analysis providing guidance and predictions, allowing users to create testable hypothesis and determine the physical changes on the surface rather than have pre-existing values for them. PMID:27079276

  16. Relationship between the surface coverage of spectator species and the rate of electrocatalytic reactions.

    SciTech Connect

    Strmcnik, D. S.; Rebec, P.; Gaberscek, M.; Tripkovic, D.; Stamenkovic, V.; Lucas, C.; Markovic, N. M.; Materials Science Division; Univ. of Chicago; National Inst. of Chemistry; Univ. of Liverpool

    2007-12-20

    Relationships between the surface coverage of spectator (blocking) species and the rate of the hydrogen oxidation reaction (HOR), the oxygen reduction reaction (ORR), and the bulk oxidation of dissolved CO on Pt(100) and Pt(111) single crystals in acidic electrolytes has been probed by cyclic voltammetry, in situ surface X-ray scattering (SXS), and ex situ scanning tunneling microscopy (STM) techniques. It is shown that the surface coverage by spectator species during the HOR and the ORR are the same as for the corresponding coverage obtained in the inert (Ar-saturated) environment. This observation is consistent with the proposition that the availability of active sites for H{sub 2} and O{sub 2} is determined almost entirely by the coverage of adsorbates from the supporting electrolyte and not by the active intermediates. Related electrochemical-SXS studies undertaken for bulk CO oxidation reveal that the maximum rate above the ignition potential is reached on a surface that is covered by {approx}90% of an ordered CO adlayer. The nature of the active sites in this case is determined by a combination of electrochemical and STM results. It is found that the active sites in this potential region are steps, which appear to be active sites for OH adsorption. To get insight into the relationship between the diffusion-limiting current and the surface coverage by the inactive CO adlayer, we introduce the concept of a partially blocked electrode surface with active and inactive areas. On the basis of the calculations and experimental results, it is proposed that the active sites for given electrochemical reactions on Pt electrodes are arrays of adsorbate-free nanoscale patches embedded in an inactive adlayer of nonreactive molecular species.

  17. Self-organization of surfactant molecules on solid surface: an STM study of sodium alkyl sulfonates [rapid communication

    NASA Astrophysics Data System (ADS)

    Yin, Xiu-Li; Wan, Li-Jun; Yang, Zheng-Yu; Yu, Jia-Yong

    2005-02-01

    Adsorption and self-organization of sodium alkyl sulfonates (STS and SHS) on HOPG have been studied by using in situ scanning tunneling microscopy (STM). Both SHS and STS molecules adsorb on HOPG surface and form long-range well-ordered monolayers. The molecular rows and the axes of alkyl chain of the molecules cross each other at angles of 60° and 90° in the STS and SHS layers, respectively. Molecular details such as sulfonate functional group (head) and alkyl chain are clearly imaged. The neighboring molecules in different rows form a "head to head" configuration. Structural models for the molecular arrangement of the two adlayers are proposed.

  18. Synthesis and sensing application of large scale bilayer graphene

    NASA Astrophysics Data System (ADS)

    Hong, Sung Ju; Yoo, Jung Hoon; Baek, Seung Jae; Park, Yung Woo

    2012-02-01

    We have synthesized large scale bilayer graphene by using Chemical Vapor Deposition (CVD) in atmospheric pressure. Bilayer graphene was grown by using CH4, H2 and Ar gases. The growth temperature was 1050^o. Conventional FET measurement shows ambipolar transfer characteristics. Results of Raman spectroscopy, Atomic Force microscope (AFM) and Transmission Electron Microscope (TEM) indicate the film is bilayer graphene. Especially, adlayer structure which interrupt uniformity was reduced in low methane flow condition. Furthermore, large size CVD bilayer graphene film can be investigated to apply sensor devices. By using conventional photolithography process, we have fabricated device array structure and studied sensing behavior.

  19. Transverse thermal depinning and nonlinear sliding friction of an adsorbed monolayer.

    PubMed

    Granato, E; Ying, S C

    2000-12-18

    We study the response of an adsorbed monolayer under a driving force as a model of sliding friction phenomena between two crystalline surfaces with a boundary lubrication layer. Using Langevin-dynamics simulation, we determine the nonlinear response in the direction transverse to a high symmetry direction along which the layer is already sliding. We find that below a finite transition temperature there exist a critical depinning force and hysteresis effects in the transverse response in the dynamical state when the adlayer is sliding smoothly along the longitudinal direction. PMID:11135998

  20. The study of in situ scanning tunnelling microscope characterization on GaN thin film grown by plasma assisted molecular beam epitaxy

    SciTech Connect

    Yang, R.; Krzyzewski, T.; Jones, T.

    2013-03-18

    The epitaxial growth of GaN by Plasma Assisted Molecular Beam Epitaxy was investigated by Scanning Tunnelling Microscope (STM). The GaN film was grown on initial GaN (0001) and monitored by in situ Reflection High Energy Electron Diffraction and STM during the growth. The STM characterization was carried out on different sub-films with increased thickness. The growth of GaN was achieved in 3D mode, and the hexagonal edge of GaN layers and growth gradient were observed. The final GaN was of Ga polarity and kept as (0001) orientation, without excess Ga adlayers or droplets formed on the surface.

  1. Mono- and multilayers of molecular spoked carbazole wheels on graphite

    PubMed Central

    Aggarwal, A Vikas; Kalle, Daniel; Höger, Sigurd

    2014-01-01

    Summary Self-assembled monolayers of a molecular spoked wheel (a shape-persistent macrocycle with an intraannular spoke/hub system) and its synthetic precursor are investigated by scanning tunneling microscopy (STM) at the liquid/solid interface of 1-octanoic acid and highly oriented pyrolytic graphite. The submolecularly resolved STM images reveal that the molecules indeed behave as more or less rigid objects of certain sizes and shapes – depending on their chemical structures. In addition, the images provide insight into the multilayer growth of the molecular spoked wheels (MSWs), where the first adlayer acts as a template for the commensurate adsorption of molecules in the second layer. PMID:25550744

  2. Characterization of poly(L-lysine)-graft-poly(ethylene glycol) assembled monolayers on niobium pentoxide substrates using time-of-flight secondary ion mass spectrometry and multivariate analysis.

    PubMed

    Wagner, M S; Pasche, S; Castner, D G; Textor, M

    2004-03-01

    Control of protein adsorption onto solid surfaces is a critical area of biomaterials and biosensors research. Application of high performance surface analysis techniques to these problems can improve the rational design and understanding of coatings that control protein adsorption. We have used static time-of-flight secondary ion mass spectrometry (TOF-SIMS) to investigate several poly(L-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG) adlayers adsorbed electrostatically onto negatively charged niobium pentoxide (Nb(2)O(5)) substrates. By varying the PEG graft ratio (i.e., the number of lysine monomers per grafted PEG chain) and the molecular weights of the PLL and PEG polymers, the amount of protein adsorption can be tailored between 1 and 300 ng/cm(2). Detailed multivariate analysis using principal component analysis (PCA) of the positive and negative ion TOF-SIMS spectra showed changes in the outermost surface of the polymer films that were related to the density and molecular weight of the PEG chains on the surface. However, no significant differences were noted due to PLL molecular weight, despite observed differences in the serum adsorption characteristics for adlayers of PLL-g-PEG polymers with different PLL molecular weights. From the PCA results, multivariate peak intensity ratios were developed that correlated with the thickness of the adlayer and the enrichment of the PEG chains and the methoxy terminus of the PEG chains at the outermost surface of the adlayer. Furthermore, partial least squares regression was used to correlate the TOF-SIMS spectra with the amount of protein adsorption, resulting in a predictive model for determining the amount of protein adsorption on the basis of the TOF-SIMS spectra. The accuracy of the prediction of the amount of serum adsorption depended on the molecular weight of the PLL and PEG polymers and the PEG graft ratio. The combination of multivariate analysis and static TOF-SIMS provides detailed information on the surface

  3. Spin polarization of two-dimensional electronic gas decoupled from structural asymmetry environment

    NASA Astrophysics Data System (ADS)

    Pieczyrak, B.; Szary, M.; Jurczyszyn, L.; Radny, M. W.

    2016-05-01

    It is shown, using density functional theory, that a 2D electron gas induced in a monolayer of Pb or Tl adatoms on the Si (111 )-1 ×1 surface is insensitive to the structural asymmetry of the system and its spin polarization is governed by the interaction between the adlayer and the substrate. It is demonstrated that this interaction changes the in-plane inversion symmetry of the charge distribution within the monolayer and can either suppress [Pb/Si(111)] or enhance [Tl/Si(111)] the adatom intra-atomic spin-orbit effect on a Rashba-Bychkov-type spin splitting.

  4. Surface structures and phase transitions at the Au(100)-Br interface: pH and CO effects

    SciTech Connect

    Blizanac, Berislav B.; Lucas, Chris A.; Gallagher, Mark E.; Ross, Philip N.; Markovic, Nenad M.

    2004-07-29

    The surface reconstruction of Au(100) and the formation of an ordered commensurate c(sqrt 2 x 22 sqrt 2)R45o adlayer of Br (Brad) have been studied by a combination of electrochemical (EC) and surface X-ray scattering (SXS) measurements. Emphasis is placed on linking the microscopic structural information concerning the Brad adlayer to the voltammetric and other macroscopic electrochemical responses, including using the rotating ring disk electrode (RRDE) measurements for determining the surface coverage by Brad. It is found that the potential-induced hexagonal (''hex'') to (1 x 1) transition of the Au surface coincides with Br- adsorption and occurs faster in solutions containing Br- anions than in Br--free solutions. In agreement with previous SXS results, in acid solutions, Brad forms a c(sqrt 2 x sqrt 2)R45o structure at around 0.15 V. However, no ordered structures of Brad are observed in alkaline solution, although the cyclic voltammetry indicates that the order structure should be present at 0.12 V. Absence of an ordered Brad adlayer in alkaline solution is attributed to competitive adsorption between Brad and OHad. To probe the role of OHad on the ordering of the bromide adlayer, coadsorbed OHad is consumed in an electrochemical reaction in which strongly adsorbed OHad is removed from the surface by a relatively weakly adsorbed reactant, viz. COad. Under such experimental conditions, we found that (i) in acid solution the c(sqrt 2 x 2 sqrt 2)R45o structure develops/disappears more rapidly than in CO-free solution and (ii) in alkaline solution the c(sqrt 2 x 2 sqrt 2)R45o structure is formed in exactly the same potential region as in acid solution. We propose that the continuous removal of OHad in the Langmuir-Hinshelwood reaction (COad + OHad) CO2 + H+ + e- may stabilize the c(sqrt 2 x 2 sqrt 2)R45o structure in both acid as well as alkaline media.

  5. Adding Four Extra K-Regions to Hexa-peri-hexabenzocoronene.

    PubMed

    Dumslaff, Tim; Yang, Bo; Maghsoumi, Ali; Velpula, Gangamallaiah; Mali, Kunal S; Castiglioni, Chiara; De Feyter, Steven; Tommasini, Matteo; Narita, Akimitsu; Feng, Xinliang; Müllen, Klaus

    2016-04-13

    A multistep synthesis of hexa-peri-hexabenzocoronene (HBC) with four additional K-regions was developed through a precursor based on two benzotetraphene units bridged with p-phenylene, featuring preinstalled zigzag moieties. Characterization by laser desorption/ionization time-of-flight mass spectrometry, Raman and IR spectroscopy, and scanning tunneling microscopy unambiguously validated the successful formation of this novel zigzag edge-rich HBC derivative. STM imaging of its monolayers revealed large-area, defect-free adlayers. The optical properties of the modified HBC were investigated by UV/visible absorption spectroscopy. PMID:27007058

  6. Adsorption structure of water molecules on the Be(0001) surface

    SciTech Connect

    Yang, Yu; Li, Yanfang; Wang, Shuangxi; Zhang, Ping

    2014-06-07

    By using density functional theory calculations, we systematically investigate the adsorption of water molecules at different coverages on the Be(0001) surface. The coverage dependence of the prototype water structures and energetics for water adlayer growth are systematically studied. The structures, energetics, and electronic properties are calculated and compared with other available studies. Through our systematic investigations, we find that water molecules form clusters or chains on the Be(0001) surface at low coverages. When increasing the water coverage, water molecules tend to form a 2 × 2 hexagonal network on the Be(0001) surface.

  7. Layer-coupled plasmons in a sawtooth-type potassium double-layer model on Si(001)-2×1 surfaces

    NASA Astrophysics Data System (ADS)

    Huang, Danhong; Antoniewicz, P. R.

    1991-10-01

    Using a sawtooth-type potassium double-layer model, we have calculated the layer-coupled interband and intraband plasmon modes of alkali-metal adatoms on Si(001)-2×1 surfaces. For K adlayer on Si(001)-2×1 surfaces, our calculated plasmon dispersion curves successfully reproduce the diplike shape in the [100] direction of the overlayer-plasmon dispersion curves observed in an experiment by using angle-resolved electron-energy-loss spectroscopy. The agreement between our calculated results and the experimental results is found to be good.

  8. Mussel-inspired surface chemistry for multifunctional coatings.

    PubMed

    Lee, Haeshin; Dellatore, Shara M; Miller, William M; Messersmith, Phillip B

    2007-10-19

    We report a method to form multifunctional polymer coatings through simple dip-coating of objects in an aqueous solution of dopamine. Inspired by the composition of adhesive proteins in mussels, we used dopamine self-polymerization to form thin, surface-adherent polydopamine films onto a wide range of inorganic and organic materials, including noble metals, oxides, polymers, semiconductors, and ceramics. Secondary reactions can be used to create a variety of ad-layers, including self-assembled monolayers through deposition of long-chain molecular building blocks, metal films by electroless metallization, and bioinert and bioactive surfaces via grafting of macromolecules. PMID:17947576

  9. Platinum and Palladium Overlayers Dramatically Enhance the Activity of Ruthenium Nanotubes for Alkaline Hydrogen Oxidation

    DOE PAGESBeta

    St. John, Samuel; Atkinson, Robert W.; Unocic, Kinga A.; Unocic, Raymond R.; Zawodzinski, Thomas A.; Papandrew, Alexander B.

    2015-10-18

    Templated vapor synthesis and thermal annealing were used to synthesize unsupported metallic Ru nanotubes with Pt or Pd overlayers. By controlling the elemental composition and thickness of these overlayers, we obtain nanostructures with very high alkaline hydrogen oxidation activity. For nanotubes with a nominal atomic composition of Ru0.90Pt0.10 display a surface-specific activity (2.4 mA/cm2) that is 35 times greater than that of pure Ru nanotubes at a 50 mV overpotential and 2.5 times greater than that of pure Pt nanotubes (0.98 mA/cm2). The surface-segregated structure also confers dramatically increased Pt utilization efficiency. We find a platinum-mass-specific activity of 1240 A/gPtmore » for the optimized nanotube versus 280 A/gPt for carbon-supported Pt nanoparticles and 109 A/gPt for monometallic Pt nanotubes. Here, we attribute the enhancement of both area- and platinum-mass-specific activity to the atomic-scale homeomorphism of the nanotube form factor with adlayer-modified polycrystals. Subsurface ligand and bifunctional effects previously observed on segregated, adlayer-modified polycrystals are translated to nanoscale catalysts.« less

  10. QCM-D and reflectometry instrument: applications to supported lipid structures and their biomolecular interactions.

    PubMed

    Edvardsson, Malin; Svedhem, Sofia; Wang, Guoliang; Richter, Ralf; Rodahl, Michael; Kasemo, Bengt

    2009-01-01

    A novel setup was recently developed, combining quartz crystal microbalance with dissipation monitoring (QCM-D) and optical reflectometry for measurements on one and the same surface of, for example, biomolecular adlayers and interactions ( Rev. Sci. Instr. 2008 , 79 075107 ). This combination was chosen on the basis of prior experience of using QCM-D and optical techniques in separate instruments, which showed both the advantage of employing multiple techniques and the disadvantage of not working with the same surface and (flow) cell. The new instrument provides, for example, information about associated water and structural changes of the adlayers that would often pass unnoticed or be hard to interpret or quantify, using either technique alone. The triple response instrument (QCM-D frequency and dissipation and reflectometry) is here applied to four model systems: (A) formation of supported lipid bilayers (SLBs), (B) lipid exchange between a SLB and transiently adsorbed vesicles, (C) binding of a hydrated peptide on a functionalized SLB, and (D) streptavidin coupling to a biotinylated SLB, followed by attachment of biotinylated vesicles. The results demonstrate three major advantages of the combination instrument: (i) much faster data collection because the experiments are done on one surface for all signals, (ii) a common time axis and the same relative importance of surface kinetics and mass transport because the same liquid sample and the same transport conditions apply, and (iii) new features are discovered about the studied system that would be difficult to unravel in separate instruments. PMID:19035651

  11. Therapeutic Potential of Traditional Chinese Medicine on Inflammatory Diseases

    PubMed Central

    Tsai, Wen-Hsin; Yang, Chih-Ching; Li, Ping-Chia; Chen, Wang-Chuan; Chien, Chiang-Ting

    2013-01-01

    Increased oxidative stress induces inflammation to several tissues/organs leading to cell death and long-term injury. Traditional Chinese Medicine (TCM) with antioxidant, anti-inflammatory, anti-apoptotic, and autophagic regulatory functions has been widely used as preventive or therapeutic strategy in modern medicine. Oxidative stress and inflammation have been widely reported to contribute to cigarette smoke-induced lung inflammation, hepatotoxicity, or sympathetic activation-induced liver inflammation, lipopolysaccharide-induced renal inflammation, and substance P-mediated neurogenic hyperactive bladder based on clinical findings. In this review, we introduce several evidences for TCM treatment including Monascus adlay (MA) produced by inoculating adlay (Cois lachrymal-jobi L. var. ma-yuen Stapf) with Monascus purpureus on lung injury, Amla (Emblica officinalis Gaertn. of Euphorbiaceae family) on hepatotoxin-induced liver inflammation, Virgate Wormwood Decoction (Yīn Chén Hāo tāng) and its active component genipin on sympathetic activation–induced liver inflammation, and green tea extract and its active components, catechins, or a modified TCM formula Five Stranguries Powder (Wǔ Lén Sǎn) plus Crataegi Fructus (Shān Zhā) on hyperactive bladder. The pathophysiologic and molecular mechanisms of TCM on ameliorating inflammatory diseases are discussed in the review. PMID:24716170

  12. HCI Adsorption and Ionization on Amorphous and Crystalline H2O Films below 50 K

    SciTech Connect

    Ayotte, Patrick; Marchand, Patrick; Daschbach, John L.; Smith, R. Scott; Kay, Bruce D.

    2011-06-16

    Molecular beams were used to grow amorphous and crystalline H2O films and to dose HCl on their surface. The adsorption state of HCl on the films was probed with infrared spectroscopy. The spectral signature of hydronium ions was observed only when the HCl adlayer was in direct contact with the solid water films at temperatures as low as 20 K. The spectral signature of solid HCl (amorphous or crystalline) was identified only after saturation of the adsorption sites in the first layer or when deposited onto a rare gas spacer layer between the HCl and water film. The Zundel continuum is also clearly observed when the first HCl adlayer is in contact with the thin solid water films. These observations strongly support the spontaneous ionic dissociation of the first layer HCl adsorbed onto the ice surface, and the subsequent condensation of solid HCl, as observed by Parent and coworkers. [F. Bournel et al. Physical Review B 2002, 65, 2014041] using synchrotron-based electron spectroscopy

  13. Structure and Function Evolution of Thiolate Monolayers on Gold

    SciTech Connect

    Grant Alvin Edwards

    2006-05-01

    The use of n-alkanethiolate self-assembled monolayers on gold has blossomed in the past few years. These systems have functioned as models for common interfaces. Thiolate monolayers are ideal because they are easily modified before or after deposition. The works contained within this dissertation include interfacial characterization (inbred reflection absorption spectroscopy, ellipsometry, contact angle, scanning probe microscopy, and heterogeneous electron-transfer kinetics) and various modeling scenarios. The results of these characterizations present ground-breaking insights into the structure, function, and reproducible preparation of these monolayers. Surprisingly, three interfacial properties (electron-transfer, contact angle, and ellipsometry) were discovered to depend directly on the odd-even character of the monolayer components. Molecular modeling was utilized to investigate adlayer orientation, and suggests that these effects are adlayer structure specific. Finally, the electric force microscopy and theoretical modeling investigations of monolayer samples are presented, which show that the film dielectric constant, thickness, and dipole moment directly affect image contrast. In addition, the prospects for utilization of this emerging technique are outlined.

  14. Electrical detection of the biological interaction of a charged peptide via gallium arsenide junction-field-effect transistors

    NASA Astrophysics Data System (ADS)

    Lee, Kangho; Nair, Pradeep R.; Alam, Muhammad A.; Janes, David B.; Wampler, Heeyeon P.; Zemlyanov, Dmitry Y.; Ivanisevic, Albena

    2008-06-01

    GaAs junction-field-effect transistors (JFETs) are utilized to achieve label-free detection of biological interaction between a probe transactivating transcriptional activator (TAT) peptide and the target trans-activation-responsive (TAR) RNA. The TAT peptide is a short sequence derived from the human immunodeficiency virus-type 1 TAT protein. The GaAs JFETs are modified with a mixed adlayer of 1-octadecanethiol (ODT) and TAT peptide, with the ODT passivating the GaAs surface from polar ions in physiological solutions and the TAT peptide providing selective binding sites for TAR RNA. The devices modified with the mixed adlayer exhibit a negative pinch-off voltage (VP) shift, which is attributed to the fixed positive charges from the arginine-rich regions in the TAT peptide. Immersing the modified devices into a TAR RNA solution results in a large positive VP shift (>1 V) and a steeper subthreshold slope (˜80 mV/decade), whereas "dummy" RNA induced a small positive VP shift (˜0.3 V) without a significant change in subthreshold slopes (˜330 mV/decade). The observed modulation of device characteristics is analyzed with analytical modeling and two-dimensional numerical device simulations to investigate the electronic interactions between the GaAs JFETs and biological molecules.

  15. Platinum and Palladium Overlayers Dramatically Enhance the Activity of Ruthenium Nanotubes for Alkaline Hydrogen Oxidation

    SciTech Connect

    St. John, Samuel; Atkinson, Robert W.; Unocic, Kinga A.; Unocic, Raymond R.; Zawodzinski, Thomas A.; Papandrew, Alexander B.

    2015-10-18

    Templated vapor synthesis and thermal annealing were used to synthesize unsupported metallic Ru nanotubes with Pt or Pd overlayers. By controlling the elemental composition and thickness of these overlayers, we obtain nanostructures with very high alkaline hydrogen oxidation activity. For nanotubes with a nominal atomic composition of Ru0.90Pt0.10 display a surface-specific activity (2.4 mA/cm2) that is 35 times greater than that of pure Ru nanotubes at a 50 mV overpotential and 2.5 times greater than that of pure Pt nanotubes (0.98 mA/cm2). The surface-segregated structure also confers dramatically increased Pt utilization efficiency. We find a platinum-mass-specific activity of 1240 A/gPt for the optimized nanotube versus 280 A/gPt for carbon-supported Pt nanoparticles and 109 A/gPt for monometallic Pt nanotubes. Here, we attribute the enhancement of both area- and platinum-mass-specific activity to the atomic-scale homeomorphism of the nanotube form factor with adlayer-modified polycrystals. Subsurface ligand and bifunctional effects previously observed on segregated, adlayer-modified polycrystals are translated to nanoscale catalysts.

  16. High-resolution He-scattering apparatus for gas-surface interaction studies

    NASA Astrophysics Data System (ADS)

    David, Rudolf; Kern, Klaus; Zeppenfeld, Peter; Comsa, George

    1986-11-01

    A high-resolution apparatus designed for the study of elastic and inelastic scattering of thermal helium atoms from crystal surfaces is presented. The highly expanded He nozzle beam has an energy spread ΔE/E of about 1.4% and is collimated to 0.2°. The angle subtended by the detector opening as seen from the sample is also 0.2°. Beam intensities as low as 10-6 of the specular beam intensity from a low-temperature clean Pt(111) surface are detectable. Pseudorandom chopping with a resolution of 2.5 μs (flight path 790 mm) is used for time-of-flight (TOF) analysis of the scattered helium. The base pressure in the sample chamber is in the low 10-11 mbar. The capabilities of the apparatus are demonstrated for physisorbed Xe adlayers on Pt(111). The results presented are obtained by using He scattering in various modes: coherent inelastic, coherent elastic, and incoherent (diffuse) elastic. This technique allows for a nondestructive nearly exhaustive characterization of the thermodynamics, structure, and dynamics of physisorbed adlayers on arbitrary substrates.

  17. Cluster formation and distributions in field ionization of coadsorbed methanol and water on platinum

    NASA Astrophysics Data System (ADS)

    Rothfuss, C. J.; Medvedev, V. K.; Stuve, E. M.

    2016-08-01

    Pure and mixed clusters of methanol and water were examined with pulsed field desorption time-of-flight mass spectrometry (TOF-MS) as a function of adlayer composition varying from pure water to nominally pure methanol. The experiments were performed on a Pt tip at 165 K and total pressure of approximately 5 × 10-6 Torr. Protonated clusters of up 7 water molecules and up to 4 methanol molecules were detected. For mixed adlayers, mixed clusters involving 1 or 2 water and methanol molecules were observed. The hydronium cluster (H2O)H+ exhibited unusual behavior in that its maximum intensity occurred for an approximately equimolar mixture. This was attributed to direct ionization of a methanol monohydrate species, (CH3OH ṡ H2O). Water production was observed in methanol-rich layers and ascribed to scission of the C-O bond to produce CH3 and OH. The TOF-MS data exhibited significant time lags for most higher mass clusters. The time lags for pure H2O were analyzed in terms of a two-step mechanism involving a trade-off of ion cluster emission and growth, from which the rate constant for cluster growth was estimated as 9 × 10-6 s-1.

  18. Quartz crystal microbalance with dissipation monitoring: enabling real-time characterization of biological materials and their interactions.

    PubMed

    Dixon, Matthew C

    2008-07-01

    In recent years, there has been a rapid growth in the number of scientific reports in which the quartz crystal microbalance (QCM) technique has played a key role in elucidating various aspects of biological materials and their interactions. This article illustrates some key advances in the development of a special variation of this technique called quartz crystal microbalance with dissipation monitoring (QCM-D). The main feature and advantage of QCM-D, compared with the conventional QCM, is that it in addition to measuring changes in resonant frequency (Deltaf), a simultaneous parameter related to the energy loss or dissipation (DeltaD) of the system is also measured. Deltaf essentially measures changes in the mass attached to the sensor surface, while DeltaD measures properties related to the viscoelastic properties of the adlayer. Thus, QCM-D measures two totally independent properties of the adlayer. The focus of this review is an overview of the QCM-D technology and highlights of recent applications. Specifically, recent applications dealing with DNA, proteins, lipids, and cells will be detailed. This is not intended as a comprehensive review of all possible applications of the QCM-D technology, but rather a glimpse into a few highlighted application areas in the biomolecular field that were published in 2007. PMID:19137101

  19. Influence of pH and Surface Chemistry on Poly(L-lysine) Adsorption onto Solid Supports Investigated by Quartz Crystal Microbalance with Dissipation Monitoring.

    PubMed

    Choi, Jae-Hyeok; Kim, Seong-Oh; Linardy, Eric; Dreaden, Erik C; Zhdanov, Vladimir P; Hammond, Paula T; Cho, Nam-Joon

    2015-08-20

    Poly(L-lysine) (PLL) adsorption onto various materials has been widely applied as a surface modification strategy and layer-by-layer fabrication method. Considering the role of electrostatic charges, a detailed understanding of the influence of solution pH on PLL adsorption process is important for optimization of PLL coating protocols. Herein, PLL adsorption onto different polar and hydrophilic substrates—silica, an amine-terminated self-assembled monolayer (SAM) on gold, and a carboxyl-terminated SAM on gold—across a range of pH conditions was investigated using the quartz crystal microbalance with dissipation. The adsorption kinetics consisted of an initial rapid phase, followed by a second phase where adsorption rate gradually decelerated. These features were interpreted by applying a mean-field kinetic model implying diffusion-limited adsorption in the first phase and reconfiguration of adsorbed PLL molecules in the second phase. The adsorption kinetics and uptake were found to be sensitive to the pH condition, surface chemistry, and flow rate. The strongest PLL adsorption occurred at pH 11 on all three surfaces while weak PLL adsorption generally occurred under acidic conditions. The surface morphology and roughness of adsorbed PLL layers were investigated using atomic force microscopy, and strong PLL adsorption is found to produce a uniform and smooth adlayer while weak adsorption formed a nonuniform and rough adlayer. PMID:26061703

  20. Initial interaction of sulfur dioxide with water covered metal surfaces: An in situ IRAS study

    SciTech Connect

    Persson, D.; Leygraf, C.

    1995-05-01

    Sulfur dioxide is considered to be one of the most important stimulators of atmospheric corrosion in outdoor environments and numerous investigations have been made to understand its role. Despite clear evidence of the corrosion accelerating effect of SO{sub 2} there is still a lack in detailed knowledge on a molecular level of how SO{sub 2} interacts with metal surfaces during conditions of atmospheric corrosion. In situ infrared reflection absorption spectroscopy (IRAS) has been used to study the initial interaction of sulfur dioxide with water adlayer covered copper, nickel, and zinc surfaces. Each metal was exposed to 0.21 ppm SO{sub 2} in flowing air at 80% relative humidity and the formation of sulfite was followed from submonolayer thickness to layers of corrosion products of a few manometers thickness. From the positions of sulfite bonds in the experimentally obtained IRAS spectra and from considerations of optically induced band shifts in calculated IRAS spectra, it is suggested that the sulfite ions are coordinated with sulfur or sulfur and oxygen to the copper surface and with oxygen to the nickel and zinc surfaces. A fast initial growth rate was observed for the sulfite layer, which was followed by a slower growth rate after a few hours of exposure. A reaction sequence is suggested where bisulfite ions, formed by hydrolysis of sulfur dioxide in the water adlayer, generate surface metal-sulfite complexes at the oxide covered metal surface which subsequently detach from the surface and precipitate as thin layers of corrosion products.

  1. Sum-frequency generation of acetate adsorption on Au and Pt surfaces: Molecular structure effects

    NASA Astrophysics Data System (ADS)

    Braunschweig, Björn; Mukherjee, Prabuddha; Kutz, Robert B.; Wieckowski, Andrzej; Dlott, Dana D.

    2010-12-01

    The reversible adsorption of acetate on polycrystalline Au and Pt surfaces was investigated with broadband sum-frequency generation (SFG) and cyclic voltammetry. Specifically adsorbed acetate as well as coadsorbed sulfuric acid anions are observed for the first time with SFG and give rise to dramatically different SFG intensities on Au and Pt surfaces. While similar coverages of acetate adlayers on Au and Pt surfaces are well established by previous studies, an identification of the interfacial molecular structure has been elusive. However, we have applied the high sensitivity of SFG for interfacial polar ordering to identify different acetate structures at Au and Pt surfaces in contact with HClO4 and H2SO4 electrolytes. Acetate competes with the formation of surface oxides and shifts the oxidation threshold of both Au and Pt electrodes anodically. Effects of the supporting electrolyte on the formation of acetate adlayers are revealed by comparing SFG spectra in HClO4 and H2SO4 solutions: Sulfuric acid anions modify the potential-dependent acetate adsorption, compete with adsorbed acetate on Au and coadsorb with acetate on Pt surfaces.

  2. Therapeutic potential of traditional chinese medicine on inflammatory diseases.

    PubMed

    Tsai, Wen-Hsin; Yang, Chih-Ching; Li, Ping-Chia; Chen, Wang-Chuan; Chien, Chiang-Ting

    2013-07-01

    Increased oxidative stress induces inflammation to several tissues/organs leading to cell death and long-term injury. Traditional Chinese Medicine (TCM) with antioxidant, anti-inflammatory, anti-apoptotic, and autophagic regulatory functions has been widely used as preventive or therapeutic strategy in modern medicine. Oxidative stress and inflammation have been widely reported to contribute to cigarette smoke-induced lung inflammation, hepatotoxicity, or sympathetic activation-induced liver inflammation, lipopolysaccharide-induced renal inflammation, and substance P-mediated neurogenic hyperactive bladder based on clinical findings. In this review, we introduce several evidences for TCM treatment including Monascus adlay (MA) produced by inoculating adlay (Cois lachrymal-jobi L. var. ma-yuen Stapf) with Monascus purpureus on lung injury, Amla (Emblica officinalis Gaertn. of Euphorbiaceae family) on hepatotoxin-induced liver inflammation, Virgate Wormwood Decoction (Yīn Chén Hāo tāng) and its active component genipin on sympathetic activation-induced liver inflammation, and green tea extract and its active components, catechins, or a modified TCM formula Five Stranguries Powder (Wǔ Lén Sǎn) plus Crataegi Fructus (Shān Zhā) on hyperactive bladder. The pathophysiologic and molecular mechanisms of TCM on ameliorating inflammatory diseases are discussed in the review. PMID:24716170

  3. Competitive Coadsorption Dynamics of Viruses and Dissolved Organic Matter to Positively Charged Sorbent Surfaces.

    PubMed

    Armanious, Antonius; Münch, Melanie; Kohn, Tamar; Sander, Michael

    2016-04-01

    Adsorption onto solid-water interfaces is a key process governing the fate and transport of waterborne viruses. Although negatively charged viruses are known to extensively adsorb onto positively charged adsorbent surfaces, virus adsorption in such systems in the presence of negatively charged dissolved organic matter (DOM) as coadsorbate remains poorly studied and understood. This work provides a systematic assessment of the adsorption dynamics of negatively charged viruses (i.e., bacteriophages MS2, fr, GA, and Qβ) and polystyrene nanospheres onto a positively charged model sorbent surface in the presence of varying DOM concentrations. In all systems studied, DOM competitively suppressed the adsorption of the viruses and nanospheres onto the model surface. Electrostatic repulsion of the highly negatively charged MS2, fr, and the nanospheres impaired their adsorption onto DOM adlayers that formed during the coadsorption process. In contrast, the effect of competition on overall adsorption was attenuated for less-negatively charged GA and Qβ because these viruses also adsorbed onto DOM adlayer surfaces. Competition in MS2-DOM coadsorbate systems were accurately described by a random sequential adsorption model that explicitly accounts for the unfolding of adsorbed DOM. Consistent findings for viruses and nanospheres suggest that the coadsorbate effects described herein generally apply to systems containing negatively charged nanoparticles and DOM. PMID:26901121

  4. X-ray energy dependent photochemistry of the adamantane (C[sub 10]H[sub 16])/Si(111)-7[times]7 surface

    SciTech Connect

    Simons, J.K. ); Frigo, S.P. ); Taylor, J.W. ); Rosenberg, R.A. )

    1993-07-01

    We have studied the synchrotron radiation (SR) induced photochemistry of the adamantane (C[sub 10]H[sub 16]) dosed Si(111)-7[times]7 surface using photoelectron spectroscopy. The adamantane/Si surfaces were characterized before and after they were exposed to broadband SR of varying energies and then annealed. When annealed to 525 K, the unexposed adamantane layers desorbed leaving only a layer of Si--H and hydrated Si--C species on the surface. When the adamantane adlayer was irradiated with broadband SR that contained energies greater than the C(1[ital s]) binding energy (284 eV), the surface reacted to form a layer similar to SiC. In contrast, when the surface was irradiated with broadband SR with energies below 284 eV, only the adamantane in direct contact with the Si surface dissociated. The remaining adamantane adlayer reacted with the surface in a manner which left the molecular structure of the reacted adamantane intact. The reacted adamantane layer was stable up to temperatures of at least 675 K.

  5. Concentration-dependent structure and structural transition from chirality to nonchirality at the liquid-solid interface by coassembly.

    PubMed

    Xu, Li; Miao, Xinrui; Cui, Lihua; Liu, Pei; Chen, XiaoFeng; Deng, Wenli

    2015-07-21

    Understanding the formation and structural transition of the two-dimensional chirality of self-assembly is a subject which still gains significant interest in surface or interface chirality studies. Here, we present the solvent-induced chiral structural transition of a 2-hydroxy-7-pentadecyloxy-9-fluorenone (HPF) molecules' self-assembled adlayer through coassembly with achiral aliphatic solvents under different concentrations. Polymorphic chiral patterns are obtained at low concentrations of aliphatic solvents with different chain lengths. The HPF molecules form coassembled structures with these solvents through van der Waals interactions. At the same time, at high concentrations, HPF molecules uniformly form a nonchiral multimer structure without coadsorbed aliphatic solvent molecules. What is interesting is that these structures under different concentrations will finally change into a zigzag structure, which is the thermodynamically most stable configuration. Especially when using n-hexadecane as the solvent, the adlayer shows perfect steric matching due to the close chain length of HPF and n-hexadecane, which can maximize the molecule-solvent interactions. Thus, HPF molecules in n-hexadecane exhibit the most diversiform configuration. The distinct concentration-dependence has proven that the solvent molecules can act as a coadsorbed component through van der Waals interactions rather than simply a dispersant and further result in the probability and stability of chiral self-assembled monolayers by subtle tuning of the solvent-molecule and solvent-substrate interactions. This result provides a simple and alternative strategy to construct the 2D chiral assembled monolayer. PMID:26103009

  6. First-principles calculations: The elemental transition metals and their compounds

    SciTech Connect

    Watson, R.E.; Fernando, G.W.; Weinert, M.; Davenport, J.W.

    1991-01-01

    If done with sufficient care, present day a priori theory yields calculated enthalpies of formation whose agreement with experiment (when such data is available) is of the order of the experimental scatter. Comparisons will be made for the Pt-Ti systems for which such data exist and for which one crystal structure involves atomics sites of low symmetry. Two other cases will be considered for which there is no direct experimental heats data. The first of these will be the structural stabilities of the 4d elemental metals. Such structural stabilities have been an issue of contention between electronic structure theorists and those who construct phase diagrams for some twenty-five years. The second involves the energetics of forming metal adlayers and artificial multilayers. The distortion energies associated with the requirement that adlayers (or multilayers) conform to some given substrate are often the controlling factors in the fabrication of multilayer materials. This contribution is best understood by invoking a combination of elemental structural promotion energies plus elastic distortions from these structures. As will be seen, the fabrication of multilayers also involves a term not normally encountered in bulk phase diagram considerations, namely the difference in surface energies of the two multilayer constituents. 22 refs., 4 figs.

  7. Nanopatterning of Donor/Acceptor Hybrid Supramolecular Architectures on HOPG: An STM Study

    PubMed Central

    Wang, Ling; Chen, Qing; Pan, Ge-Bo; Wan, Li-Jun; Zhang, Shiming; Zhan, Xiaowei; Northrop, Brian H.; Stang, Peter J.

    2009-01-01

    Hybrid supramolecular architectures have been fabricated with acceptor 1,4-bis(4-pyridylethynyl)-2,3-bis-dodecyloxy-benzene (PBP) and donor 2,6-bis(3,4,5-tris-dodecyloxy-phenyl)dithieno[3,2-b:2′,3′-d]thiophene (DTT) compounds on highly oriented pyrolytic graphite (HOPG) surfaces and their structures and molecular conductance are characterized by scanning tunneling microscopy/spectroscopy (STM/STS). Stable, one-component adlayers of PBP and DTT are also investigated. The coadsorption of two-component mixtures of PBP and DTT results in a variety of hybrid nanopattern architectures that differ from those of their respective one-component surface assemblies. Adjusting the acceptor/donor molar ratio in mixed adlayer assemblies results in dramatic changes in the structure of the hybrid nanopatterns. STS measurements indicate that the HOMO and LUMO energy levels of PBP and DTT on an HOPG surface are relatively insensitive to changes in the hybrid supramolecular architectures. These results provide important insight into the design and fabrication of two-dimensional hybrid supramolecular architectures. PMID:18783221

  8. Adsorption and thermal decomposition of 2-octylthieno[3,4-b]thiophene on Au(111).

    PubMed

    Park, Joon B; Zong, Kyukwan; Jeon, Il Chul; Hahn, Jae Ryang; Stacchiola, Dario; Starr, David; Müller, Kathrin; Noh, Jaegeun

    2012-10-15

    The adsorption and thermal stability of 2-octylthieno[3,4-b]thiophene (OTTP) on the Au(111) surfaces have been studied using scanning tunneling microscopy (STM), temperature programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). UHV-STM studies revealed that the vapor-deposited OTTP on Au(111) generated disordered adlayers with monolayer thickness even at saturation coverage. XPS and TPD studies indicated that OTTP molecules on Au(111) are stable up to 450 K and further heating of the sample resulted in thermal decomposition to produce H(2) and H(2)S via C-S bond scission in the thieno-thiophene rings. Dehydrogenation continues to occur above 600 K and the molecules were ultimately transformed to carbon clusters at 900 K. Highly resolved air-STM images showed that OTTP adlayers on Au(111) prepared from solution are composed of a well-ordered and low-coverage phase where the molecules lie flat on the surface, which can be assigned as a (9×2√33)R5° structure. Finally, based on analysis of STM, TPD, and XPS results, we propose a thermal decomposition mechanism of OTTP on Au(111) as a function of annealing temperature. PMID:22818203

  9. Electrical detection of the biological interaction of a charged peptide via gallium arsenide junction-field-effect transistors

    PubMed Central

    Lee, Kangho; Nair, Pradeep R.; Alam, Muhammad A.; Janes, David B.; Wampler, Heeyeon P.; Zemlyanov, Dmitry Y.; Ivanisevic, Albena

    2008-01-01

    GaAs junction-field-effect transistors (JFETs) are utilized to achieve label-free detection of biological interaction between a probe transactivating transcriptional activator (TAT) peptide and the target trans-activation-responsive (TAR) RNA. The TAT peptide is a short sequence derived from the human immunodeficiency virus-type 1 TAT protein. The GaAs JFETs are modified with a mixed adlayer of 1-octadecanethiol (ODT) and TAT peptide, with the ODT passivating the GaAs surface from polar ions in physiological solutions and the TAT peptide providing selective binding sites for TAR RNA. The devices modified with the mixed adlayer exhibit a negative pinch-off voltage (VP) shift, which is attributed to the fixed positive charges from the arginine-rich regions in the TAT peptide. Immersing the modified devices into a TAR RNA solution results in a large positive VP shift (>1 V) and a steeper subthreshold slope (∼80 mV∕decade), whereas “dummy” RNA induced a small positive VP shift (∼0.3 V) without a significant change in subthreshold slopes (∼330 mV∕decade). The observed modulation of device characteristics is analyzed with analytical modeling and two-dimensional numerical device simulations to investigate the electronic interactions between the GaAs JFETs and biological molecules. PMID:19484151

  10. Quartz Crystal Microbalance with Dissipation Monitoring: Enabling Real-Time Characterization of Biological Materials and Their Interactions

    PubMed Central

    Dixon, Matthew C.

    2008-01-01

    In recent years, there has been a rapid growth in the number of scientific reports in which the quartz crystal microbalance (QCM) technique has played a key role in elucidating various aspects of biological materials and their interactions. This article illustrates some key advances in the development of a special variation of this technique called quartz crystal microbalance with dissipation monitoring (QCM-D). The main feature and advantage of QCM-D, compared with the conventional QCM, is that it in addition to measuring changes in resonant frequency (Δf), a simultaneous parameter related to the energy loss or dissipation (ΔD) of the system is also measured. Δf essentially measures changes in the mass attached to the sensor surface, while ΔD measures properties related to the viscoelastic properties of the adlayer. Thus, QCM-D measures two totally independent properties of the adlayer. The focus of this review is an overview of the QCM-D technology and highlights of recent applications. Specifically, recent applications dealing with DNA, proteins, lipids, and cells will be detailed. This is not intended as a comprehensive review of all possible applications of the QCM-D technology, but rather a glimpse into a few highlighted application areas in the biomolecular field that were published in 2007. PMID:19137101

  11. Hydrogen-bond-assisted supramolecular assembly of 1,3,5-tris(5-carboxyamyloxy)benzene at the liquid-solid interface: an scanning tunneling microscopy study.

    PubMed

    Yan, Cunji; Han, Li

    2013-02-01

    The well-ordered self-assembled structure of 1,3,5-tris(5-carboxyamyloxy)benzene (TCAB) on Au(111) has been studied by electrochemical scanning tunneling microscopy (ECSTM) in HClO4 solution. Close examination indicates that the complex supramolecular network is formed by the TCAB molecules with flat-lying adsorption geometry and mainly stabilized by the hydrogen bonding interactions between carboxyl groups, except for the molecule-substrate interactions. It is particularly noteworthy that two types of hydrogen bonds, the dimers and tetramers of carboxyl group, coexist at the interface to balance the molecule-molecule and molecule-substrate interactions as well as to minimize the surface energy. Interestingly, the propeller-like motifs in STM image are fabricated by the bent alkoxy chains from four neighboring molecules respectively, bonded together by the cyclic carboxyl group tetramers. Moreover, there are two propellers in one lattice of TCAB adlayer, rotating in the clockwise and counterclockwise directions, respectively. Careful inspection shows that two structure domains of the TCAB adlayer are mirror images of each other since the molecular self-organization breaks the reflection symmetry of the substrate underneath. Our results give a good example of the flexibility adopted by alkyl chains functionalized by carboxyl group for the supramolecular assemblies at the liquid-solid interface. PMID:23646606

  12. Anion effects and the mechanism of Cu UPD on Pt(111): X-ray and electrochemical studies

    NASA Astrophysics Data System (ADS)

    Gómez, R.; Yee, H. S.; Bommarito, G. M.; Feliu, J. M.; Abrun˜a, H. D.

    1995-07-01

    We propose a mechanism for the underpotential deposition of Cu on Pt(111) in 0.1M H 2SO 4 in the presence and absence of halides. The mechanism is based on recent results from electrochemical and in situ surface EXAFS and X-ray standing wave (XSW) studies of Cu UPD on Pt on 0.1M H 2SO 4 and in the presence and absence of halides with emphasis on Cl -, Br - and I -. EXAFS data were obtained in the presence and absence of Cl - at a potential of +0.1 V corresponding to a coverage of approximately 0.75 ML. In the absence of chloride, the data were consistent with the presence of an incompletely discharged copper adlayer. The copper—copper bond distance was found to be 2.85Å. In the presence of chloride the X-ray data suggest the presence of a fully discharged copper layer and the Cu sbnd Cu bond distance, 2.59Å, approached the bulk copper value (2.56Å). In the presence of chloride, no oxygen is present as a backscatterer in the plane of the Cu sbnd Cu adlayer. However, oxygen (from either bisulfate or water) is present as a backscatterer in the absence of chloride giving rise to a copper—oxygen bond distance of 2.16Å. It appears that the chloride acts as a protective overlayer precluding oxygen (from either solvent or electrolyte) adsorption. Qualitatively similar results were obtained for Cu UPD on an iodine treated Pt surface. In addition, XSW data for this last system suggest the presence of electrochemically inactive (solvated) copper ions in the vicinity of but not in contact with the platinum surface which we describe as representing a "pre-adsorbed" state. From electrochemical studies at low (10 μM) copper concentrations, we find that the underpotential deposition of submonolayer amounts of copper induces an enhanced adsorption of chloride and bromide on Pt(111) that is reflected in exceedingly sharp voltammetric peaks that are transient in nature. The adsorbed anions are believed to be in contact with the platinum surface and in the vicinity of the

  13. [Consensuses on lung cancer treatment by Chinese medicine experts from Beijing and Guangzhou and medication features in the North and South China].

    PubMed

    Wang, Shu-mei; Lin, Li-zhu; Nie, Hui

    2011-07-01

    To study the consensuses on lung cancer treatment by Chinese medicine experts from North China and South China, and to analyze their medication features from viewpoints such as the medication frequency, combination laws, medication classification by collecting 800 recipes on the treatment of lung cancer patients prescribed by 8 Chinese oncologists from Guanganmen Hospital of China Academy of Chinese Medical Sciences, the Affiliated Hospital of Guangzhou University of Traditional Chinese Medicine, and Guangdong Provincial Hospital of Traditional Chinese Medicine. Results showed that coix seed, poria, pinelliae tuber were the three herbs most commonly used in treatment of lung cancer by all experts. They generally accepted Pi invigorating and phlegm removing method as the basic treatment method for treating lung cancer. Secondly, they usually used white peony root, heterophylla falsestarwort root, and ophiopogonis tuber, etc. (with higher medication frequency) to nourish yin and moisten Fei. Thirdly, consistency was also shown in clearing heat, detoxication, and anticancer. Smilacis glabra, Rhizoma Smilacis Glabrae, Herba Hedyotis diffusae, Herba Scutellariae Barbatae were herbs used by all experts. However, there were differences between oncologists in North China and South China. Oncologists in South China paid more attention to heat toxin and blood stasis, while those in North China paid more attention to supplementing both qi and yin. PMID:21866673

  14. Integrative Medicine for Relief of Nausea and Vomiting in the Treatment of Colorectal Cancer Using Oxaliplatin-Based Chemotherapy: A Systematic Review and Meta-Analysis.

    PubMed

    Chen, Meng Hua; May, Brian H; Zhou, Iris W; Zhang, Anthony L; Xue, Charlie C

    2016-05-01

    The management of chemotherapy-induced nausea and vomiting (CINV) remains an issue in the treatment of colorectal cancer using oxaliplatin-based regimens. Certain traditional plant-based medicines (TMs) have histories of use for nausea and vomiting and have been integrated with conventional therapies for CINV. To assess the effectiveness of integrative management of CINV, meta-analysis was conducted of 27 randomised controlled studies (1843 participants) published from 2005 to 2013. The oxaliplatin plus TM groups showed significantly reduced CINV (risk ratio 0.65 [0.59, 0.71], I(2)  = 28%) compared with oxaliplatin controls, with or without the addition of conventional anti-emetics. Further sensitivity analyses based on the ingredients of the TMs identified six plants (Atractylodes macrocephala, Poria cocos, Coix lacryma-jobi, Astragalus membranaceus, Glycyrrhiza uralensis and Panax ginseng) that were associated with significant reductions in CINV without important heterogeneity. Experimental studies of these six plants have reported inhibitory effects on nausea and vomiting (or its animal equivalent), regulation of gastrointestinal motility, gastroprotective effects and antioxidant actions, which may at least partially explain the effects identified in the meta-analyses of the clinical trial results. These plants warrant further clinical research as potential additions to chemotherapy regimens in patients whose CINV is not sufficiently well controlled by conventional therapies. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26912094

  15. Oxaliplatin-based chemotherapy combined with traditional medicines for neutropenia in colorectal cancer: A meta-analysis of the contributions of specific plants.

    PubMed

    Chen, Menghua; May, Brian H; Zhou, Iris W; Sze, Daniel Man-Yuen; Xue, Charlie C; Zhang, Anthony L

    2016-09-01

    This review assessed the effects on chemotherapy induced neutropenia (CIN) of combining oxaliplatin regimens with traditional plant-based medicines (TMs) in the management of colorectal cancer (CRC). 32 RCTs (2224 participants) were included. Meta-analysis showed reduced incidence of grade 3/4 CIN (RR 0.45[0.31, 0.65], I(2)=0%). No studies reported serious adverse events or reduction in tumour response rates associated with concurrent use of oxaliplatin and TM. Due to small sample sizes and risk of bias, these results should be interpreted with caution. Analyses of sub-groups of studies that used similar TM interventions assessed the relative contributions of individual plant-based ingredients to the results. Astragalus, Codonopsis, Atractylodes, Poria and Coix, in various combinations were consistently associated with reduced CIN incidence when administered orally. Experimental studies of these plants have reported reduced myelosuppression and/or enhanced immune response. Further studies of these plants may lead to the development of interventions to supplement conventional CIN treatment. PMID:27497028

  16. Antitumor effect of Kanglaite® injection in human pancreatic cancer xenografts

    PubMed Central

    2014-01-01

    Background Kanglaite® injection (KLT), with a main ingredient of Coix seed oil (a traditional Chinese medicine), has been widely used for cancer treatment in China. KLT has an inhibitory effect on many kinds of tumors and PI3K/Akt/mTOR signaling promotes cell survival, proliferation, and progression in cancer cells. Therefore, targeting this pathway may lead to the development of novel therapeutic approaches for human cancers. Methods Here, we examined the effects of KLT on the PI3K/Akt/mTOR pathway in pancreatic cancer xenografts in mice, and assessed its therapeutic potential. Growth and apoptosis of tumor xenografts were examined, and the expression levels of genes and proteins involved in the PI3K/Akt/mTOR pathway were measured by RT-PCR and western blotting, respectively. Results Our results revealed that KLT dramatically inhibited the growth of pancreatic cancer xenografts and induced apoptosis simultaneously. Furthermore, it downregulated the expression of phospho-Akt and phospho-mTOR. Conclusions These results suggest that KLT can suppress growth and induce apoptosis of pancreatic cancer xenografts. Moreover, KLT can downregulate the expression of phospho-Akt and phospho-mTOR to modulate the PI3K/Akt/mTOR signaling pathway. PMID:25005526

  17. The transcriptional activator Opaque2 recognizes two different target sequences in the 22-kD-like alpha-prolamin genes.

    PubMed Central

    Yunes, J A; Cord Neto, G; da Silva, M J; Leite, A; Ottoboni, L M; Arruda, P

    1994-01-01

    The maize Opaque2 (O2) protein is a "leucine zipper" DNA binding factor that interacts with the sequence TCCACGTAGA in the promoters of the 22-kD alpha-zein genes and activates its transcription. A completely different consensus sequence (GATGAPyPuTGPu) identified in b-32, a gene that encodes an abundant albumin that is also under control of the O2 locus, can also be bound by the O2 protein. We showed that the gene encoding the 22-kD-like alpha-coixin, the alpha-prolamin of the maize-related grass Coix, can also be transactivated by the O2 protein. A binding assay in vitro and footprint analysis demonstrated that the GACATGTC sequence of the alpha-coixin promoter can be recognized and protected by the maize O2 protein. Employing transient expression experiments in immature maize endosperm and tobacco mesophyll protoplasts, we demonstrated that the O2 protein can activate expression of the beta-glucuronidase reporter gene placed under the control of the 22-kD-like alpha-coixin promoter. We also demonstrated that a 22-kD-like alpha-coixin pseudogene promoter is transactivated by the maize O2 protein. PMID:8148647

  18. Kanglaite stimulates anticancer immune responses and inhibits HepG2 cell transplantation‑induced tumor growth.

    PubMed

    Huang, Xinli; Qin, Jianjie; Lu, Sen

    2014-10-01

    Previous studies revealed that Kanglaite (KLT) exhibits antitumor and immunomodulatory activities. In the present study, we show that KLT treatment stimulated the immune response by increasing the number of T cells and natural killer (NK) cells in the blood of hepatocellular carcinoma (HCC) patients. Experiments in tumor-bearing mice were further designed in order to explore the effects of KLT on the immune system and the underlying molecular mechanisms. The results showed that KLT improves the tumor cell transplantation-induced reduction in the serum level of the cytokines IFN‑γ and IL‑2, and rescues the levels of CD4+ T cells in host mice. These events enhanced the cytotoxic activities of natural killer and CD8+ T cells against the hepatic HepG2 cancer cells. KLT administration further increased the mRNA level of certain nuclear factor κB (NF‑κB)‑responsive genes in CD4+ cells. The chromatin immunoprecipitation assay showed that KLT increases the association of the NF-κB p65 subunit to the promoter regions of interleukin (IL)-2- and B-cell lymphoma (Bcl)-2-encoding genes in CD4+ T cells. Our study demonstrated that KLT is the main active ingredient of coix seed exhibiting anticancer and immunomodulatory properties. Induction of NF-κB‑mediated gene transcription in CD4+ T cells is involved in the immunomodulatory activity of KLT. PMID:25119060

  19. Chinese herb related molecules of cancer-cell-apoptosis: a minireview of progress between Kanglaite injection and related genes.

    PubMed

    Lu, Yun; Li, Chang-Sheng; Dong, Qian

    2008-01-01

    Many kinds of Chinese herb had been confirmed to have the character of anti-tumor, clinical reports about anti-tumor effects of Chinese herb had also been found in recent years, but most of the reports were focused on the clinical treatment of effectiveness for Chinese herb, on the other hand, review about Chinese herbal related with molecules on cancer-cell-apoptosis was seldom, many scientists could not believe such kinds of clinical describes about anti-tumor effects for Chinese herb, because these describes were lack of molecular biology evidence. Kanglaite(KLT) injection is an anti-tumor new drug which extracts from Chinese medicine-coix seed with modern advanced pharmaceutical technology, it is also a new biphase extended-spectrum anticancer medicine, the food and drug administration(FDA) of United States also approved a phase II trial of KLT to test its efficacy in treating non-small-cell lung cancer. Some studies show it could inhibit some anti-apoptotic gene and activate some pro-apoptotic gene, its injection solution is one of the new anticancer medicine that can significantly inhibit a various kinds of tumor cells, so it has become the core of research that how to further explore KLT injection to promote tumor cell apoptosis by impacting on related genes. In this review, the relationship between KLT and some tumor cell apoptosis molecules had been discussed and reviewed generally. PMID:18718024

  20. Short-term parasite-infection alters already the biomass, activity and functional diversity of soil microbial communities

    NASA Astrophysics Data System (ADS)

    Li, Jun-Min; Jin, Ze-Xin; Hagedorn, Frank; Li, Mai-He

    2014-11-01

    Native parasitic plants may be used to infect and control invasive plants. We established microcosms with invasive Mikania micrantha and native Coix lacryma-jobi growing in mixture on native soils, with M. micrantha being infected by parasitic Cuscuta campestris at four intensity levels for seven weeks to estimate the top-down effects of plant parasitism on the biomass and functional diversity of soil microbial communities. Parasitism significantly decreased root biomass and altered soil microbial communities. Soil microbial biomass decreased, but soil respiration increased at the two higher infection levels, indicating a strong stimulation of soil microbial metabolic activity (+180%). Moreover, a Biolog assay showed that the infection resulted in a significant change in the functional diversity indices of soil microbial communities. Pearson correlation analysis indicated that microbial biomass declined significantly with decreasing root biomass, particularly of the invasive M. micrantha. Also, the functional diversity indices of soil microbial communities were positively correlated with soil microbial biomass. Therefore, the negative effects on the biomass, activity and functional diversity of soil microbial community by the seven week long plant parasitism was very likely caused by decreased root biomass and root exudation of the invasive M. micrantha.

  1. Electron Transfer Reactivity Patterns at Chemically Modified Electrodes: Fundamentals and Application to the Optimization of Redox Recycling Amplification Systems

    SciTech Connect

    Adam Johan Bergren

    2006-05-01

    Electroanalytical chemistry is often utilized in chemical analysis and Fundamental studies. Important advances have been made in these areas since the advent of chemically modified electrodes: the coating of an electrode with a chemical film in order to impart desirable, and ideally, predictable properties. These procedures enable the exploitation of unique reactivity patterns. This dissertation presents studies that investigate novel reaction mechanisms at self-assembled monolayers on gold. In particular, a unique electrochemical current amplification scheme is detailed that relies on a selective electrode to enable a reactivity pattern that results in regeneration of the analyte (redox recycling). This regenerating reaction can occur up to 250 times for each analyte molecule, leading to a notable enhancement in the observed current. The requirements of electrode selectivity and the resulting amplification and detection limit improvements are described with respect to the heterogeneous and homogeneous electron transfer rates that characterize the system. These studies revealed that the heterogeneous electrolysis of the analyte should ideally be electrochemically reversible, while that for the regenerating agent should be held to a low level. Moreover, the homogeneous reaction that recycles the analyte should occur at a rapid rate. The physical selectivity mechanism is also detailed with respect to the properties of the electrode and redox probes utilized. It is shown that partitioning of the analyte into/onto the adlayer leads to the extraordinary selectivity of the alkanethiolate monolayer modified electrode. Collectively, these studies enable a thorough understanding of the complex electrode mechanism required for successful redox recycling amplification systems, Finally, in a separate (but related) study, the effect of the akyl chain length on the heterogeneous electron transfer behavior of solution-based redox probes is reported, where an odd-even oscillation

  2. The role of adsorbed hydroxyl species in the electrocatalytic carbon monoxide oxidation reaction on platinum.

    PubMed

    Kucernak, Anthony R; Offer, Gregory J

    2008-07-01

    The assumption that "OH(ads)" or other oxygen containing species is formed on polycrystalline or nanoparticulate platinum through a fast and reversible process at relatively low potentials is often made. In this paper we discuss the implications of this assumption and the difficulty in reconciling it with experimental phenomena. We show how presenting chrono-amperometric transients as log-log plots for potentials steps in the presence and absence of an adlayer of carbon monoxide on polycrystalline platinum is particularly useful in understanding the time evolution of the CO oxidation reaction. When using log-log plots a clear power law decay can be observed in the transients both in the presence and absence of an adlayer of carbon monoxide. We explain this as an extension of current theory, such that the rate determining step in both cases is the formation of a hydrogen bonded water-OH(ads) network, strongly influenced by anions, and that CO(ads) oxidation occurs, at least in part by the diffusion of OH(ads) through this network. We hypothesize that, at low potentials the formation of OH(ads) at active sites is fast and reversible but that transport of OH(ads) away from those sites may be rate limiting. The assumption that overall OH(ads) formation on platinum is fast and reversible is therefore highly dependent upon the platinum surface and the experimental conditions and it may not be appropriate for polycrystalline surfaces in sulfuric acid. Therefore, although the formation of OH(ads) on platinum in the absence of strongly adsorbing anions on 'ideal' surfaces is almost certainly fast and reversible, on realistic fuel cell relevant surfaces under non-ideal conditions this assumption cannot be made, and instead the formation of an OH(ads) adlayer may be somewhat slow and is associated with the formation of hydrogen bonded water-OH(ads) networks on the surface. We expect this to be a more realistic description for what occurs during CO(ads) oxidation on fuel cell

  3. Statics and dynamics of halide sub-monolayer electrosorption on silver: Computer simulations with comparison to experiments

    NASA Astrophysics Data System (ADS)

    Abou Hamad, Ibrahim

    This dissertation investigates equilibrium and dynamical properties of sub-monolayer chemical adsorption of Br and Cl on single-crystal Ag(100) electrodes. Computational methods, such as Monte Carlo simulations with First-order Reversal Curve analysis, are used along with experimental data in this study. Monte Carlo simulations of a two-dimensional lattice-gas approximation for the adlayer are used to explore equilibrium properties of the system. Lateral interaction energies between adsorbates, as well other system parameters like the electrosorption valency, are determined by fitting simulations to experimental chronocoulometry isotherms. While neither the electrosorption valency nor the lateral interactions show any dependence on the adsorbate coverage for the Br/Ag(100) system, a model in which both are coverage dependent is required to adequately describe the Cl/Ag(100) system. A self-consistent, entirely electrostatic picture of the lateral interactions with coverage dependence is developed, and a relationship between the lateral interactions and the electrosorption valency is investigated for Cl on Ag(100). The adsorbates form a disordered adlayer at low electrochemical potentials. At a more positive elctrochemical potential the adlayer undergoes a disorder-order phase transition at to an ordered c(2 x 2) phase. This phase transition produces a peak in the current density observed in cyclic-voltammetry experiments. Kinetic Monte Carlo of the lattice-gas model are used to simulate cyclic-voltammetry experiments. The scan-rate dependence of the separation between positive- and negative-going peaks in cyclic voltammetry simulations are compared to experimental peak separations. This dynamics study identifies the inverse Monte Carlo attempt frequency with a physical timescale. Although kinetic Monte Carlo simulations can provide long-time simulations of the dynamics of physical and chemical systems, this identification is not yet possible in general. To further

  4. Organic pollutant photodecomposition by Ag/KNbO3 nanocomposites: A combined experimental and theoretical study

    DOE PAGESBeta

    Zhang, Tingting; Liu, Ping; Lei, Wanying; Rodriguez, J. A.; Yu, Jiaguo; Qi, Yang; Liu, Gang; Liu, Minghua

    2016-01-12

    In this study, Ag nanoparticles supported on well-defined perovskite orthorhombic KNbO3 nanowires are synthesized via facile photoreduction and systematically characterized by XRD, Raman, DRUV–vis, XPS, PL, TEM, HRTEM, and HAADF-STEM. The photoreactivity of Ag/KNbO3 nanocomposites as a function of Ag contents (0.4–2.8 wt %) is assessed toward aqueous rhodamine B degradation under UV- and visible-light, respectively. It is found that the UV-induced photoreactivity initially increases and then decreases with increasing Ag contents. At an optimal Ag content (ca. 1.7 wt %), the greatest photoreactivity is achieved under UV light, with the photocatalytic reaction rate of 1.7 wt % Ag/KNbO3 exceedingmore » that of pristine KNbO3 by a factor of ca. 13. In contrast, visible light-induced photoreactivity monotonically increases with increasing Ag contents in the range of 0.4–2.8 wt %. On the basis of the detected active species and intermediate products in the photocatalytic processes, conjugated structure cleavage and N-deethylation are revealed to be the respective predominant pathway under UV and visible-light illumination. To gain an insight into the observed photoreactivity, the electronic properties of Ag/KNbO3 have been investigated using spin-polarized DFT calculations. Herein, Ag extended adlayers (1–4 ML) on the slab models of KNbO3 (101) are employed to mimic large supported Ag nanoparticles. A Bader analysis of the electron density shows a small net charge transfer (ca. 0.1 e) from KNbO3 to Ag. The electron localization function of Ag/KNbO3 (101) illustrates that Ag adlayers with thickness larger than 2 ML are essentially metallic, and weak polarization occurs at the interface. In addition, the metallic Ag adlayers generate a continuum of Ag bandgap states, which play a key role in determining different Ag content-dependent behavior between UV and visible-light illumination.« less

  5. Hreels Studies of Surface Phonons in Ultrathin Epitaxial Films, NICKEL/COPPER(001) and COBALT/COPPER(001)

    NASA Astrophysics Data System (ADS)

    Kim, Jae-Sung

    High Resolution Electron Energy Loss Spectroscopy (HREELS) is applied to observe surface phonons in ultrathin epitaxial overlayers on the Cu(001) substrate surfaces, Ni/Cu(001) and Co/Co(001), along the high symmetry directions (from |Gamma to |{X} and from |Gamma to |{ M}). From analysis of the phonon dispersion curves and scattering cross sections, information about structure and elastic properties of the overlayers is obtained. As preliminary work, the substrate surface, Cu(001), is studied extensively to clarify the still unsettled characterization of its surface by finding salient surface sensitive modes, the gap mode(S_6) and the S _2 mode, and applying a first principles calculation analysis for the first time. Finally, the bonding properties of the overlayer surfaces are studied by observing adsorbate--substrate vibrations in ordered oxygen adlayers, C(2 x 2) O/Co/Cu, P(2 x 2) O/Co/Cu(001) and C(2 x 2) O/Ni/Cu(001).

  6. Self-assembly of mechanically interlocked and threaded rings: a HREELS and XPS study of thiol-functionalised catenane and rotaxane molecules on Au(111)

    NASA Astrophysics Data System (ADS)

    De Nadaı̈, C.; Whelan, C. M.; Perollier, C.; Clarkson, G.; Leigh, D. A.; Caudano, R.; Rudolf, P.

    2000-05-01

    Thiol-functionalised catenane and rotaxane thin films were investigated in order to understand the self-assembly of such complex molecules on Au(111). Adsorption from the liquid phase at 300 K leads to the formation of overlayers without long-range order, as evidenced by high-resolution electron energy-loss spectroscopy (HREELS). As expected for thiol adsorption, the sulfur 2p binding energies determined by X-ray photoelectron spectroscopy (XPS) are consistent with the formation of thiolate surface intermediates. The properties of these films are explored as a function of annealing. Changes in vibrational spectra such as the emergence of a AuO band and variations in core-level binding energies and intensities reveal molecular rearrangement due to partial desorption. In addition, based on coherent domain sizes estimated by the angular width of the elastic beam intensity, annealing promotes long-range order within the adlayers.

  7. A van der Waals density functional investigation of carboranethiol self-assembled monolayers on Au(111).

    PubMed

    Mete, Ersen; Yılmaz, Ayşen; Danışman, Mehmet Fatih

    2016-05-14

    Isolated and full monolayer adsorption of various carboranethiol (C2B10H12S) isomers on the gold(111) surface has been investigated using both the standard and van der Waals density functional theory calculations. The effect of different molecular dipole moment orientations on the low energy adlayer geometries, the binding characteristics and the electronic properties of the self-assembled monolayers of these isomers has been studied. Specifically, the binding energy and work function changes associated with different molecules show a correlation with their dipole moments. The adsorption is favored for the isomers with dipole moments parallel to the surface. Of the two possible unit cell structures, (5 × 5) was found to be more stable than . PMID:27108565

  8. Strong affinity of hydrogen for the GaN(000-1) surface: Implications for molecular beam epitaxy and metalorganic chemical vapor deposition

    SciTech Connect

    Northrup, J.E.; Neugebauer, J.

    2004-10-18

    The stabilities of clean and hydrogen covered GaN(000-1) surfaces are determined using density functional theory together with a finite temperature thermodynamics approach. Hydrogen has an extremely high affinity for the N-face surface: Even under ultrahigh vacuum conditions as realized in molecular beam epitaxial growth, with a residual hydrogen pressure of 10{sup -12} atm, the hydrogen terminated surface is, for very N-rich conditions, more stable than any clean surface. A transition to a surface covered by a Ga adlayer is predicted to occur as the Ga chemical potential increases. In typical metalorganic chemical vapor deposition conditions the (000-1) surface is predicted to be covered by 0.75 monolayers of hydrogen. The slower growth rate on the (000-1) surface in comparison to the (0001) surface is attributed to low adsorption of N on the H-covered (000-1) surface.

  9. Controlled Immobilization Strategies to Probe Short Hyaluronan-Protein Interactions

    PubMed Central

    Minsky, Burcu Baykal; Antoni, Christiane H.; Boehm, Heike

    2016-01-01

    Well-controlled grafting of small hyaluronan oligosaccharides (sHA) enables novel approaches to investigate biological processes such as angiogenesis, immune reactions and cancer metastasis. We develop two strategies for covalent attachment of sHA, a fast high-density adsorption and a two-layer system that allows tuning the density and mode of immobilization. We monitored the sHA adlayer formation and subsequent macromolecular interactions by label-free quartz crystal microbalance with dissipation (QCM-D). The modified surfaces are inert to unspecific protein adsorption, and yet retain the specific binding capacity of sHA. Thus they are an ideal tool to study the interactions of hyaluronan-binding proteins and short hyaluronan molecules as demonstrated by the specific recognition of LYVE-1 and aggrecan. Both hyaladherins recognize sHA and the binding is independent to the presence of the reducing end. PMID:26883791

  10. Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

    SciTech Connect

    Walen, Holly; Liu, Da-Jiang; Oh, Junepyo; Lim, Hyunseob; Kim, Yousoo; Evans, J. W.; Thiel, P. A.

    2015-07-07

    Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed clean surface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, derived using a limited cluster expansion based on density functional theory energetics. Models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.

  11. Experimental studies of hydrogen on boron nitride: I. Adsorption isotherms of HD

    SciTech Connect

    Evans, M.D.; Sullivan, N.S.

    1995-09-01

    The authors report the results of measurements of adsorption isotherms of deuterium hydride (HD) adsorbed onto boron nitride. From this data they derive both the two-dimensional critical point temperatures (using Larher`s method) and the heat of adsorption for the first few layers of this system. These results are compared with similar measurements of HD adsorbed onto graphite and MgO. While substantial substeps within some adlayer steps are evident in the adsorption isotherms of HD on graphite and MgO and have been shown to indicate a two-dimensional liquid-solid transition within the layer, no substep is evident at the level of one percent of a step level for HD adsorbed onto BN.

  12. Characterization of Monolayer Formation on Aluminum-Doped Zinc Oxide Thin Films

    SciTech Connect

    Rhodes,C.; Lappi, S.; Fischer, D.; Sambasivan, S.; Genzer, J.; Franzen, S.

    2008-01-01

    The optical and electronic properties of aluminum-doped zinc oxide (AZO) thin films on a glass substrate are investigated experimentally and theoretically. Optical studies with coupling in the Kretschmann configuration reveal an angle-dependent plasma frequency in the mid-IR for p-polarized radiation, suggestive of the detection of a Drude plasma frequency. These studies are complemented by oxygen depletion density functional theory studies for the calculation of the charge carrier concentration and plasma frequency for bulk AZO. In addition, we report on the optical and physical properties of thin film adlayers of n-hexadecanethiol (HDT) and n-octadecanethiol (ODT) self-assembled monolayers (SAMs) on AZO surfaces using reflectance FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), contact angle, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Our characterization of the SAM deposition onto the AZO thin film reveals a range of possible applications for this conducting metal oxide.

  13. Surface structures and frictional properties of Au(100) in an electrochemical environment

    NASA Astrophysics Data System (ADS)

    Hausen, F.; Zimmet, J. A.; Bennewitz, R.

    2013-01-01

    Friction on Au(100) surfaces has been studied by atomic force microscopy under electrochemical control. Atomic-scale stick-slip pattern in the lateral force signal reveal changes in the surface structure upon changing electrochemical potential, in particular between the hexagonal reconstruction and the Au(100)-(1 × 1) structure. Friction on Au(100) is higher on its (1 × 1) structure than on its hexagonal reconstruction. The frictional response after switching between the two structures is delayed due to the necessary surface reorganization. Atomic periodicity in the stick-slip pattern indicates that the increased friction on Au(100)-(1 × 1) is not caused by an ordered anion adlayer, but by the open structure of the (100) surface. Friction is highest on the oxidized surface, and can be switched reversibly between high and low values on the oxidized and the reduced surface.

  14. Oxidation processes in magneto-optic and related materials

    NASA Technical Reports Server (NTRS)

    Lee, Paul A.; Armstrong, Neal R.; Danzinger, James L.; England, Craig D.

    1992-01-01

    The surface oxidation processes of thin films of magneto-optic materials, such as the rare-earth transition metal alloys have been studied, starting in ultrahigh vacuum environments, using surface analysis techniques, as a way of modeling the oxidation processes which occur at the base of a defect in an overcoated material, at the instant of exposure to ambient environments. Materials examined have included FeTbCo alloys, as well as those same materials with low percentages of added elements, such a Ta, and their reactivities to both O2 and H2O compared with materials such as thin Fe films coated with ultrathin adlayers of Ti. The surface oxidation pathways for these materials is reviewed, and XPS data presented which indicates the type of oxides formed, and a critical region of Ta concentration which provides optimum protection.

  15. Atomistic lattice-gas modeling of CO oxidation on Pd(100): temperature-programmed spectroscopy and steady-state behavior.

    PubMed

    Liu, Da-Jiang; Evans, J W

    2006-04-21

    We have developed an atomistic lattice-gas model for the catalytic oxidation of CO on single-crystal Pd(100) surfaces under ultrahigh vacuum conditions. This model necessarily incorporates an detailed description of adlayer ordering and adsorption-desorption kinetics both for CO on Pd(100), and for oxygen on Pd(100). Relevant energetic parameters are determined by comparing model predictions with experiment, together with some guidance from density functional theory calculations. The latter also facilitates description of the interaction and reaction of adsorbed CO and oxygen. Kinetic Monte Carlo simulations of this reaction model are performed to predict temperature-programmed reaction spectra, as well as steady-state bifurcation behavior. PMID:16674249

  16. In situ chemical probing of the electrode-electrolyte interface by ToF-SIMS

    SciTech Connect

    Liu, Bingwen; Yu, Xiao-Ying; Zhu, Zihua; Hua, Xin; Yang, Li; Wang, Zhaoying

    2014-01-01

    A portable vacuum interface allowing direct probing of the electrode-electrolyte interface was developed. A classical electrochemical system consisting of gold working electrode, platinum counter electrode, platinum reference electrode, and potassium iodide electrolyte was used to demonstrate real-time observation of the gold iodide adlayer on the electrode and chemical species as a result of redox reactions using cyclic voltammetry (CV) and the time-of-flight secondary ion mass spectrometry (ToF-SIMS, a vacuum-based surface analytical technique) simultaneously. This microfluidic electrochemical probe provides a new way to investigate the surface region with adsorbed molecules and region of diffused layer with chemical speciation in liquids in situ by surface sensitive techniques.

  17. Effects of size polydispersity on the extinction spectra of colloidal nanoparticle aggregates

    NASA Astrophysics Data System (ADS)

    Ershov, Alexander E.; Isaev, Ivan L.; Semina, Polina N.; Markel, Vadim A.; Karpov, Sergei V.

    2012-01-01

    We investigate the effect of particle polydispersity on the optical extinction spectra of colloidal aggregates of spherical metallic (silver) nanoparticles, taking into account the realistic interparticle gaps caused by layers of stabilizing polymer adsorbed on the metal surface (adlayers). The spectra of computer-generated aggregates are computed using two different methods. The coupled-multipole method is used in the quasistatic approximation and the coupled-dipole method beyond the quasistatics. The latter approach is applicable if the interparticle gaps are sufficiently wide relative to the particle radii. Simulations are performed for two different particle size distribution functions (bimodal and Gaussian), varying the number of particles per aggregate, and different distribution functions of the interparticle gap width. The strong influence of the latter factor on the spectra is demonstrated and investigated in detail.

  18. The interfacial interactions of Tb-doped silica nanoparticles with surfactants and phospholipids revealed through the fluorescent response.

    PubMed

    Bochkova, Olga D; Mustafina, Asiya R; Mukhametshina, Alsu R; Burilov, Vladimir A; Skripacheva, Viktoriya V; Zakharova, Lucia Ya; Fedorenko, Svetlana V; Konovalov, Alexander I; Soloveva, Svetlana E; Antipin, Igor S

    2012-04-01

    The quenching effect of dyes (phenol red and bromothymol blue) on Tb(III)-centered luminescence enables to sense the aggregation of cationic and anionic surfactants near the silica surface of Tb-doped silica nanoparticles (SN) in aqueous solutions. The Tb-centered luminescence of non-decorated SNs is diminished by the inner filter effect of both dyes. The decoration of the silica surface by cationic surfactants induces the quenching through the energy transfer between silica coated Tb(III) complexes and dye anions inserted into surfactant aggregates. Thus the distribution of surfactants aggregates at the silica/water interface and in the bulk of solution greatly affects dynamic quenching efficiency. The displacement of dye anions from the interfacial surfactant adlayer by anionic surfactants and phospholipids is accompanied by the "off-on" switching of Tb(III)-centered luminescence. PMID:22209651

  19. UV photoreaction cross sections of CO and D2O on NiAl(110)

    NASA Astrophysics Data System (ADS)

    Nagai, Kenta; Watanabe, Kazuo

    2016-01-01

    Adsorption states and photoreactions of CO and D2O adsorbed on NiAl(110) at 90 K were studied by temperature-programmed desorption (TPD). Coverage dependence of TPD spectra showed growth behavior of adlayers of these molecules consistent with the literature, but a new path of thermal dissociation of D2O upon adsorption at 90 K was found. The photoreaction cross sections of CO and D2O at 4.7 eV were estimated in the order of 10- 21 cm2 and 10- 20 cm2, respectively. This result suggests that photoexcitation of the NiAl(110) substrate itself, a typical substrate used in supported model catalyst studies, will induce only negligible photoreactions of molecules adsorbed at surfaces of metal nanoparticles supported on ultrathin alumina films formed on NiAl(110).

  20. Growth and Raman spectra of single-crystal trilayer graphene with different stacking orientations.

    PubMed

    Zhao, Haiming; Lin, Yung-Chang; Yeh, Chao-Hui; Tian, He; Chen, Yu-Chen; Xie, Dan; Yang, Yi; Suenaga, Kazu; Ren, Tian-Ling; Chiu, Po-Wen

    2014-10-28

    Understanding the growth mechanism of graphene layers in chemical vapor deposition (CVD) and their corresponding Raman properties is technologically relevant and of importance for the application of graphene in electronic and optoelectronic devices. Here, we report CVD growth of single-crystal trilayer graphene (TLG) grains on Cu and show that lattice defects at the center of each grain persist throughout the growth, indicating that the adlayers share the same nucleation site with the upper layers and these central defects could also act as a carbon pathway for the growth of a new layer. Statistics shows that ABA, 30-30, 30-AB, and AB-30 make up the major stacking orientations in the CVD-grown TLG, with distinctive Raman 2D characteristics. Surprisingly, a high level of lattice defects results whenever a layer with a twist angle of θ = 30° is found in the multiple stacks of graphene layers. PMID:25295851

  1. Controlled Immobilization Strategies to Probe Short Hyaluronan-Protein Interactions

    NASA Astrophysics Data System (ADS)

    Minsky, Burcu Baykal; Antoni, Christiane H.; Boehm, Heike

    2016-02-01

    Well-controlled grafting of small hyaluronan oligosaccharides (sHA) enables novel approaches to investigate biological processes such as angiogenesis, immune reactions and cancer metastasis. We develop two strategies for covalent attachment of sHA, a fast high-density adsorption and a two-layer system that allows tuning the density and mode of immobilization. We monitored the sHA adlayer formation and subsequent macromolecular interactions by label-free quartz crystal microbalance with dissipation (QCM-D). The modified surfaces are inert to unspecific protein adsorption, and yet retain the specific binding capacity of sHA. Thus they are an ideal tool to study the interactions of hyaluronan-binding proteins and short hyaluronan molecules as demonstrated by the specific recognition of LYVE-1 and aggrecan. Both hyaladherins recognize sHA and the binding is independent to the presence of the reducing end.

  2. Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

    SciTech Connect

    Walen, Holly; Liu, Da -Jiang; Oh, Junepyo; Lim, Hyunseob; Evans, J. W.; Kim, Yousoo; Thiel, P. A.

    2015-07-06

    Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed cleansurface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, we derived using a limited cluster expansion based on density functional theory energetics. Furthermore, models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.

  3. Intermolecular vs molecule–substrate interactions: A combined STM and theoretical study of supramolecular phases on graphene/Ru(0001)

    PubMed Central

    Roos, Michael; Uhl, Benedikt; Künzel, Daniela; Hoster, Harry E; Groß, Axel

    2011-01-01

    Summary The competition between intermolecular interactions and long-range lateral variations in the substrate–adsorbate interaction was studied by scanning tunnelling microscopy (STM) and force field based calculations, by comparing the phase formation of (sub-) monolayers of the organic molecules (i) 2-phenyl-4,6-bis(6-(pyridin-3-yl)-4-(pyridin-3-yl)pyridin-2-yl)pyrimidine (3,3'-BTP) and (ii) 3,4,9,10-perylene tetracarboxylic-dianhydride (PTCDA) on graphene/Ru(0001). For PTCDA adsorption, a 2D adlayer phase was formed, which extended over large areas, while for 3,3'-BTP adsorption linear or ring like structures were formed, which exclusively populated the areas between the maxima of the moiré structure of the buckled graphene layer. The consequences for the competing intermolecular interactions and corrugation in the adsorption potential are discussed and compared with the theoretical results. PMID:22003444

  4. Intermolecular vs molecule-substrate interactions: A combined STM and theoretical study of supramolecular phases on graphene/Ru(0001).

    PubMed

    Roos, Michael; Uhl, Benedikt; Künzel, Daniela; Hoster, Harry E; Groß, Axel; Behm, R Jürgen

    2011-01-01

    The competition between intermolecular interactions and long-range lateral variations in the substrate-adsorbate interaction was studied by scanning tunnelling microscopy (STM) and force field based calculations, by comparing the phase formation of (sub-) monolayers of the organic molecules (i) 2-phenyl-4,6-bis(6-(pyridin-3-yl)-4-(pyridin-3-yl)pyridin-2-yl)pyrimidine (3,3'-BTP) and (ii) 3,4,9,10-perylene tetracarboxylic-dianhydride (PTCDA) on graphene/Ru(0001). For PTCDA adsorption, a 2D adlayer phase was formed, which extended over large areas, while for 3,3'-BTP adsorption linear or ring like structures were formed, which exclusively populated the areas between the maxima of the moiré structure of the buckled graphene layer. The consequences for the competing intermolecular interactions and corrugation in the adsorption potential are discussed and compared with the theoretical results. PMID:22003444

  5. A versatile strategy towards non-covalent functionalization of graphene by surface-confined supramolecular self-assembly of Janus tectons

    PubMed Central

    Du, Ping; Bléger, David; Charra, Fabrice; Bouchiat, Vincent; Kreher, David; Mathevet, Fabrice

    2015-01-01

    Summary Two-dimensional (2D), supramolecular self-assembly at surfaces is now well-mastered with several existing examples. However, one remaining challenge to enable future applications in nanoscience is to provide potential functionalities to the physisorbed adlayer. This work reviews a recently developed strategy that addresses this key issue by taking advantage of a new concept, Janus tecton materials. This is a versatile, molecular platform based on the design of three-dimensional (3D) building blocks consisting of two faces linked by a cyclophane-type pillar. One face is designed to steer 2D self-assembly onto C(sp2)-carbon-based flat surfaces, the other allowing for the desired functionality above the substrate with a well-controlled lateral order. In this way, it is possible to simultaneously obtain a regular, non-covalent paving as well as supramolecular functionalization of graphene, thus opening interesting perspectives for nanoscience applications. PMID:25821703

  6. Controlling single and few-layer graphene crystals growth in a solid carbon source based chemical vapor deposition

    SciTech Connect

    Papon, Remi; Sharma, Subash; Shinde, Sachin M.; Vishwakarma, Riteshkumar; Tanemura, Masaki; Kalita, Golap

    2014-09-29

    Here, we reveal the growth process of single and few-layer graphene crystals in the solid carbon source based chemical vapor deposition (CVD) technique. Nucleation and growth of graphene crystals on a polycrystalline Cu foil are significantly affected by the injection of carbon atoms with pyrolysis rate of the carbon source. We observe micron length ribbons like growth front as well as saturated growth edges of graphene crystals depending on growth conditions. Controlling the pyrolysis rate of carbon source, monolayer and few-layer crystals and corresponding continuous films are obtained. In a controlled process, we observed growth of large monolayer graphene crystals, which interconnect and merge together to form a continuous film. On the other hand, adlayer growth is observed with an increased pyrolysis rate, resulting few-layer graphene crystal structure and merged continuous film. The understanding of monolayer and few-layer crystals growth in the developed CVD process can be significant to grow graphene with controlled layer numbers.

  7. Cu/ZnO(0001) under oxidating and reducing conditions: A first-principles survey of surface structures

    NASA Astrophysics Data System (ADS)

    Warschkow, O.; Chuasiripattana, K.; Lyle, M. J.; Delley, B.; Stampfl, C.

    2011-09-01

    We investigate the stability of Cu-exposed ZnO(0001) surface structures in an oxygen environment using density functional theory and the method of ab initio atomistic thermodynamics. A two-dimensional phase diagram is constructed which identifies stable surface structures as a function of the copper and oxygen chemical potentials. Two structures with a (3×3)R30∘ unit cell are found to be prominently stable at intermediate oxygen and copper chemical potentials. These phases are characterized by a single adlayer of Cu4O3 and Cu12O13 stoichiometry on ZnO(0001). We rationalize recent experimental observations in the literature in terms of our results.

  8. Self-organization of S adatoms on Au(111): √3R30° rows at low coverage

    DOE PAGESBeta

    Walen, Holly; Liu, Da -Jiang; Oh, Junepyo; Lim, Hyunseob; Evans, J. W.; Kim, Yousoo; Thiel, P. A.

    2015-07-06

    Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed cleansurface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30° from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, we derivedmore » using a limited cluster expansion based on density functional theory energetics. Furthermore, models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures.« less

  9. Dual-polarization interferometry: an analytical technique to measure changes in protein structure in real time, to determine the stoichiometry of binding events, and to differentiate between specific and nonspecific interactions.

    PubMed

    Swann, Marcus J; Peel, Louise L; Carrington, Simon; Freeman, Neville J

    2004-06-15

    The study of solution-phase interactions between small molecules and immobilized proteins is of intense interest, especially to the pharmaceutical industry. An optical sensing technique, dual polarization interferometry, has been employed for the detailed study of a model protein system, namely, d-biotin interactions with streptavidin immobilized on a solid surface. Changes in thickness and density of an immobilized streptavidin layer as a result of the binding of d-biotin have been directly measured in solution and in real time. The results obtained from this approach are in excellent agreement with X-ray crystallographic data for the structural changes expected in the streptavidin-D-biotin system. The mass changes measured on binding d-biotin also agree closely with anticipated binding capacity values. Determination of the density changes occurring in the protein adlayer provides a means for differentiation between specific and nonspecific interactions. PMID:15158477

  10. Surface disordering of Pb(110)

    NASA Technical Reports Server (NTRS)

    Tibbits, P.; Karimi, M.; Ila, D.; Dalins, I.; Vidali, G.

    1991-01-01

    A molecular dynamics simulation of Pb(110), using embedded atom method energy functional and two-body potential derived for the purpose, shows that near 400 K the three surface layers begin to disorder well before the bulk (interior) layers. Transfer of atoms from the first subsurface layer to the surface layer occurs. Disordering propagates beyond the top three layers above 550 K, accompanied by formation of an adlayer and vacancies in the top three layers. Behavior of the two-dimensional layer structure factors indicates that disordering is anisotropic. Simulation results are consistent with experimental observations of surface roughening near 400 K and more extensive surface ordering above 525 K. Results are consistent with simulations for Ni and Al.

  11. Concentration-dependent structure and structural transition from chirality to nonchirality at the liquid-solid interface by coassembly

    NASA Astrophysics Data System (ADS)

    Xu, Li; Miao, Xinrui; Cui, Lihua; Liu, Pei; Chen, Xiaofeng; Deng, Wenli

    2015-07-01

    Understanding the formation and structural transition of the two-dimensional chirality of self-assembly is a subject which still gains significant interest in surface or interface chirality studies. Here, we present the solvent-induced chiral structural transition of a 2-hydroxy-7-pentadecyloxy-9-fluorenone (HPF) molecules' self-assembled adlayer through coassembly with achiral aliphatic solvents under different concentrations. Polymorphic chiral patterns are obtained at low concentrations of aliphatic solvents with different chain lengths. The HPF molecules form coassembled structures with these solvents through van der Waals interactions. At the same time, at high concentrations, HPF molecules uniformly form a nonchiral multimer structure without coadsorbed aliphatic solvent molecules. What is interesting is that these structures under different concentrations will finally change into a zigzag structure, which is the thermodynamically most stable configuration. Especially when using n-hexadecane as the solvent, the adlayer shows perfect steric matching due to the close chain length of HPF and n-hexadecane, which can maximize the molecule-solvent interactions. Thus, HPF molecules in n-hexadecane exhibit the most diversiform configuration. The distinct concentration-dependence has proven that the solvent molecules can act as a coadsorbed component through van der Waals interactions rather than simply a dispersant and further result in the probability and stability of chiral self-assembled monolayers by subtle tuning of the solvent-molecule and solvent-substrate interactions. This result provides a simple and alternative strategy to construct the 2D chiral assembled monolayer.Understanding the formation and structural transition of the two-dimensional chirality of self-assembly is a subject which still gains significant interest in surface or interface chirality studies. Here, we present the solvent-induced chiral structural transition of a 2-hydroxy-7-pentadecyloxy

  12. Adsorption and intercalation of Cs atoms on epitaxial graphene on Ir(111)

    NASA Astrophysics Data System (ADS)

    Lazic, Predrag; Petrovic, Marin; Srut, Iva; Pletikosic, Ivo; Milun, Milorad; Pervan, Petar; Runte, Sven; Busse, Carsten; Michely, Thomas; Sokcevic, Damir; Brako, Radovan; Atodiresei, Nicolae; Sadowski, Jurek; Pan, Zhi-Hu; Valla, Tonica; Kralj, Marko

    2013-03-01

    From the experimental studies of surface adsorption of Cs atoms and their intercalation under epitaxial graphene on Ir(111) it is known that both - adsorbed and intercalated phase of Cs atoms coexist. However, adsorbed phase is realized as a diluted superlattice adlayer of Cs atom while intercalated phase is a dense Cs layer. The preference for intercalated phase at large Cs layer densities can not be obtained from the DFT calculations with semilocal (GGA) functionals. Only after the van der Waals interaction is taken into account the agreement with experiment is achieved. From the results of calculations it follows that the main energy contribution responsible for the switching of preference from adsorption to intercalation is the graphene delamination energy from the Ir(111) surface which is dominantly of the van der Waals nature.

  13. Effect of oxygen and ozone on p-type doping of ultra-thin WSe2 and MoSe2 field effect transistors.

    PubMed

    Wang, Shunfeng; Zhao, Weijie; Giustiniano, Francesco; Eda, Goki

    2016-02-14

    We report on the p-type doping effect of oxygen and ozone molecules on mono- and few-layer WSe2 and MoSe2 field effect transistors. We show that adsorption of oxygen and ozone under ambient conditions results in subtantial doping and corresponding enhancement in the hole conductivity of the devices. Ozone-induced doping is found to be rapid and efficient, saturating within minutes of exposure whereas oxygen-induced doping occurs over a period of days to reach the equivalent level of doping. Our observations reveal that the water adlayer on the material surface plays a crucial role in solubilizing oxygen and ozone and in forming a redox couple with a large chemical potential. PMID:26790367

  14. Surface sensitivity of straight long-range surface plasmon waveguides for attenuation-based biosensing

    NASA Astrophysics Data System (ADS)

    Wong, Wei Ru; Mahamd Adikan, Faisal Rafiq; Berini, Pierre

    2014-08-01

    The sensing performance of straight long-range surface plasmon waveguides consisting of a thin gold stripe embedded in Cytop is explored theoretically as a function of the metal stripe cross-sectional dimensions and the length of the sensing channel, and as a function of the sensing medium refractive index. The surface sensitivity and detection limit of such waveguides for attenuation-based biosensing are assessed. We find that changes in coupling efficiency between the sensing waveguide and the access waveguides, and changes in attenuation constant, due to adlayer formation, can contribute additively to the sensing performance. We observed a trade-off between the insertion loss and the change in insertion loss occurring during sensing. Optimum designs leading to compact, sensitive, and cost-effective biosensors are reported.

  15. Predicting the stability of surface phases of molybdenum selenides

    SciTech Connect

    Roma, Guido; Ghorbani, Elaheh; Mirhosseini, Hossein; Kühne, Thomas D.; Kiss, Janos; Felser, Claudia

    2014-02-10

    The selenization of molybdenum might become an important step in the production of nanostructures based on the layered compound MoSe{sub 2}. It is already technologically relevant for the production of thin film chalcopyrite solar cells. However, the control of the process is still very poor, due to the lack of basic knowledge of the surface thermodynamics of the system. Here, we present a theoretical study on the stability of surface adlayers of Se on the Mo(110) surface, predicting surface patterns and their stability range in terms of temperature and selenium partial pressure. Our results, based on density functional theory, show that the attainable Se coverages range from 1/4 to 3/4 of a monolayer for systems in equilibrium with a gas formed of Se molecules. We provide simulated scanning tunneling microscopy images to help the experimental characterization of adsorbed surface patterns.

  16. Nanoscale Bio-Molecular Control Using EC-OWLS

    SciTech Connect

    Bearinger, J P; Voros, J; Hubbell, J A; Textor, M

    2002-11-20

    A recently developed technique termed ''Electrochemical Optical Waveguide Lightmode Spectroscopy'' (EC-OWLS) [1] combines evanescent-field optical sensing with electrochemical control of surface adsorption processes. Initial EC-OWLS investigations efficiently monitored molecular surface adsorption and layer thickness changes of an adsorbed polymer layer examined in situ as a function of potential applied to a waveguide1. A layer of indium tin oxide (ITO) served as both a high refractive index waveguide for optical sensing, and a conductive electrode; an electrochemical flow-through fluid cell incorporated working, reference and counter electrodes. Poly(L-lysine)-grafted-poly(ethylene glycol) (PLL-g-PEG) served as a model, polycation adsorbate. Results indicate that adsorption and desorption of PLL-g-PEG from aqueous buffer are a function of applied potential, and that binding events subsequent to PLL-g-PEG functionalization are dependent on reorganization in the molecular adlayer.

  17. Surface engineering of nanoparticles in suspension for particle based bio-sensing

    NASA Astrophysics Data System (ADS)

    Sen, Tapas; Bruce, Ian J.

    2012-08-01

    Surface activation of nanoparticles in suspension using amino organosilane has been carried out via strict control of a particle surface ad-layer of water using a simple but efficient protocol `Tri-phasic Reverse Emulsion' (TPRE). This approach produced thin and ordered layers of particle surface functional groups which allowed the efficient conjugation of biomolecules. When used in bio-sensing applications, the resultant conjugates were highly efficient in the hybrid capture of complementary oligonucleotides and the detection of food borne microorganism. TPRE overcomes a number of fundamental problems associated with the surface modification of particles in aqueous suspension viz. particle aggregation, density and organization of resultant surface functional groups by controlling surface condensation of the aminosilane. The approach has potential for application in areas as diverse as nanomedicine, to food technology and industrial catalysis.

  18. Size selected cluster deposition on well characterized surfaces: Ag{sub n}/Pd(100)

    SciTech Connect

    Vandoni, G.; Felix, C.; Harbich, W.; Monot, R.; Buttet, J.; Massobrio, C.

    1997-06-20

    We study the deposition of Ag ions, and size selected Ag{sub 7} and Ag{sub 19} cluster ions on Pd(100) at total kinetic energies of 20 eV and 95 eV using Thermal Energy Atom Scattering and Molecular Dynamics simulations. We find that at all energies Ag atoms are implanted into the substrate and Pd atoms are ejected in the adlayer. The experimental results in the case of Ag{sub 7} can be understood in taking into account both implantation of Ag atoms and heavy fragmentation. In the case of Ag{sub 19} the deposition leads at low temperature to non compact structures localized around the impact point. We propose a model in which morphology changes take place between 200 K and 300 K resulting in well separated compact structures formed of Ag and Pd adatoms.

  19. Two-dimensional semiconductor HfSe{sub 2} and MoSe{sub 2}/HfSe{sub 2} van der Waals heterostructures by molecular beam epitaxy

    SciTech Connect

    Aretouli, K. E.; Tsipas, P.; Tsoutsou, D.; Marquez-Velasco, J.; Xenogiannopoulou, E.; Giamini, S. A.; Vassalou, E.; Kelaidis, N.; Dimoulas, A.

    2015-04-06

    Using molecular beam epitaxy, atomically thin 2D semiconductor HfSe{sub 2} and MoSe{sub 2}/HfSe{sub 2} van der Waals heterostructures are grown on AlN(0001)/Si(111) substrates. Details of the electronic band structure of HfSe{sub 2} are imaged by in-situ angle resolved photoelectron spectroscopy indicating a high quality epitaxial layer. High-resolution surface tunneling microscopy supported by first principles calculations provides evidence of an ordered Se adlayer, which may be responsible for a reduction of the measured workfunction of HfSe{sub 2} compared to theoretical predictions. The latter reduction minimizes the workfunction difference between the HfSe{sub 2} and MoSe{sub 2} layers resulting in a small valence band offset of only 0.13 eV at the MoSe{sub 2}/HfSe{sub 2} heterointerface and a weak type II band alignment.

  20. Graphite edge controlled registration of monolayer MoS{sub 2} crystal orientation

    SciTech Connect

    Lu, Chun-I; Butler, Christopher John; Yang, Hung-Hsiang; Chu, Yu-Hsun; Luo, Chi-Hung; Sun, Yung-Che; Hsu, Shih-Hao; Yang, Kui-Hong Ou; Huang, Jing-Kai; Hsing, Cheng-Rong; Wei, Ching-Ming Li, Lain-Jong; Lin, Minn-Tsong

    2015-05-04

    Transition metal dichalcogenides such as the semiconductor MoS{sub 2} are a class of two-dimensional crystals. The surface morphology and quality of MoS{sub 2} grown by chemical vapor deposition are examined using atomic force and scanning tunneling microscopy techniques. By analyzing the moiré patterns from several triangular MoS{sub 2} islands, we find that there exist at least five different superstructures and that the relative rotational angles between the MoS{sub 2} adlayer and graphite substrate lattices are typically less than 3°. We conclude that since MoS{sub 2} grows at graphite step-edges, it is the edge structure which controls the orientation of the islands, with those growing from zig-zag (or armchair) edges tending to orient with one lattice vector parallel (perpendicular) to the step-edge.

  1. Nitric-oxide adsorption and oxidation on Pt( 1 1 1 ) in electrolyte solution under potential control

    NASA Astrophysics Data System (ADS)

    Casero, E.; Alonso, C.; Martín-Gago, J. A.; Borgatti, F.; Felici, R.; Renner, F.; Lee, T.-L.; Zegenhagen, J.

    2002-06-01

    We studied the adsorption and oxidation of NO adlayers on Pt(1 1 1) prepared from different NO precursors in an electrochemical cell in situ by surface X-ray diffraction and ex situ by X-ray photoemission spectroscopy. We found that NO adsorbs molecularly, independent of the preparation method. There is no relaxation of the outermost Pt atomic layer induced by the presence of adsorbed NO. We observe a surface structure of the Pt(1 1 1) very similar to the clean surface prepared under ultra-high vacuum conditions. A surface mediated oxidation process of the NO towards NO 2 is initiated at a potential of around 0.95 V vs. normal hydrogen electrode. The in situ measurements of crystal truncation rods show that this process is accompanied by a significant roughening of the surface.

  2. Active site density and reactivity for the photocatalytic dehydrogenation of 2-propanol on TiO 2 (110)

    NASA Astrophysics Data System (ADS)

    Brinkley, David; Engel, Thomas

    1998-10-01

    By combining molecular beam experiments at 350 K with low temperature experiments on an immobile adlayer, we determine the fraction of surface sites active for the photocatalytic dehydrogenation of 2-propanol to acetone to be 0.08 on a fully oxidized surface. We also find that the reaction probability at these sites is essentially unity. The presence of oxygen vacancies (≈0.1 monolayer) increases the fraction of active sites to 0.15 without changing the reaction probability, reaction kinetics, or product distribution. From this, we conclude that only sites which can bind O 2 strongly are active for the reaction. Candidates for such sites include steps and kinks on fully oxidized surfaces and oxygen lattice vacancies on reduced surfaces.

  3. Molecular structure and chiral separation in {alpha}-sexithiophene ultrathin films on Au(111): Low-energy electron diffraction and scanning tunneling microscopy

    SciTech Connect

    Kiel, Mario; Duncker, Klaus; Hagendorf, Christian; Widdra, Wolf

    2007-05-15

    The adsorption of the {pi}-conjugated organic molecule {alpha}-sexithiophene which is widely used in molecular electronics has been studied on Au(111) by low-energy electron diffraction and scanning tunneling microscopy. For monolayer adsorption at room temperature, large, well-ordered domains of flat-lying molecules which arrange in molecular rows are observed. A detailed structure analysis reveals an incommensurate, line-on-line oriented monolayer with one molecule per unit cell. In contrast to the behavior in the three-dimensional bulk structure, flat-lying adsorption introduces molecular chirality: Right- and left-handed molecules separate into domains of different orientations which are mirror symmetric with respect to the [112] substrate direction. Details of the adlayer structure and the chiral self-recognition can be rationalized based on the van der Waals contour of the adsorbed molecules.

  4. Measurement of film thickness up to several hundreds of nanometers using optical waveguide lightmode spectroscopy.

    PubMed

    Picart, Catherine; Gergely, Csilla; Arntz, Youri; Voegel, Jean-Claude; Schaaf, Pierre; Cuisinier, Frédéric J G; Senger, Bernard

    2004-10-15

    Up to now, most studies based on optical waveguide lightmode spectroscopy (OWLS) were dedicated to thin adlayers, assumed to be isotropic and homogeneous, for which data analysis was based on an approximation of the mode equations valid when the thickness is small with respect to the wavelength of the laser light. The aim of the present paper is to extend the use of OWLS to thicker deposited layers (up to approximately 400 nm). Both the simplified and extended models are compared in terms of optical parameters, i.e. the refractive index nA, the thickness dA, and the optical mass QA, for experimental data obtained with polyelectrolyte multilayer films. The deviation of these parameters can be quite large when derived using the simplified model instead of the extended model. This observation evidences that OWLS is well suited for the study of "thick" films if the appropriate model is applied to the data analysis. PMID:15494239

  5. Adsorption properties of decyl thiocyanate and decanethiol on platinum substrates studied by sum-frequency generation spectroscopy

    NASA Astrophysics Data System (ADS)

    Sartenaer, Yannick; Dreesen, Laurent; Humbert, Christophe; Volcke, Cédric; Tourillon, Gérard; Louette, Pierre; Thiry, Paul A.; Peremans, André

    2007-03-01

    Recently, thiocyanate groups were successfully used as precursors for thiolate assemblies. Indeed, they provide a useful alternative to thiol groups for self-assembly on metallic substrates. In order to check the adsorption properties and the quality of the thiocyanate-based self-assembled monolayers (SAMs), we use sum-frequency generation spectroscopy (SFG) and apply it to characterize the ad-layers of two similar molecules: decanethiol (DT) and decyl thiocyanate (DTCN) adsorbed on platinum surfaces. By comparing the SFG signals of the methyl and methylene vibration modes, we show that DTCN SAMs are less ordered than DT ones. These effects are related to the SAMs quality which depends on the molecular packing as highlighted by scanning tunnelling microscopy and X-ray photoelectron spectroscopy.

  6. Underpotential deposition of Cu on Au(111): Implications of the HB model

    NASA Astrophysics Data System (ADS)

    Blum, L.; Huckaby, Dale A.

    1994-05-01

    In recent papers a model for the underpotential deposition of Cu on Au(111) in the presence of bisulfate ions was proposed. In this model it was assumed that the bisulfate ions formed a square root of 3 times square root of 3 template. This template leaves a honeycomb lattice of free sites for the adsorption of copper. The clear implication is that the first peak has 2/3 of a monolayer of Cu. The second peak corresponds to the replacement of the bisulfate by copper in the adlayer. We showed also that the broad foot of the first peak is due to a second order hard hexagon like transition, which is seen experimentally by Itaya and Kolb. The interpretation, based on the STM and LEED observations, that the first peak corresponds to only 1/3 of a monolayer, is consistent with our model if it is the bisulfate ion that is actually seen in those experiments.

  7. Scanning Tunneling Microscopy and Spectroscopy of Air Exposure Effects on Molecular Beam Epitaxy Grown WSe2 Monolayers and Bilayers.

    PubMed

    Park, Jun Hong; Vishwanath, Suresh; Liu, Xinyu; Zhou, Huawei; Eichfeld, Sarah M; Fullerton-Shirey, Susan K; Robinson, Joshua A; Feenstra, Randall M; Furdyna, Jacek; Jena, Debdeep; Xing, Huili Grace; Kummel, Andrew C

    2016-04-26

    The effect of air exposure on 2H-WSe2/HOPG is determined via scanning tunneling microscopy (STM). WSe2 was grown by molecular beam epitaxy on highly oriented pyrolytic graphite (HOPG), and afterward, a Se adlayer was deposited in situ on WSe2/HOPG to prevent unintentional oxidation during transferring from the growth chamber to the STM chamber. After annealing at 773 K to remove the Se adlayer, STM images show that WSe2 layers nucleate at both step edges and terraces of the HOPG. Exposure to air for 1 week and 9 weeks caused air-induced adsorbates to be deposited on the WSe2 surface; however, the band gap of the terraces remained unaffected and nearly identical to those on decapped WSe2. The air-induced adsorbates can be removed by annealing at 523 K. In contrast to WSe2 terraces, air exposure caused the edges of the WSe2 to oxidize and form protrusions, resulting in a larger band gap in the scanning tunneling spectra compared to the terraces of air-exposed WSe2 monolayers. The preferential oxidation at the WSe2 edges compared to the terraces is likely the result of dangling edge bonds. In the absence of air exposure, the dangling edge bonds had a smaller band gap compared to the terraces and a shift of about 0.73 eV in the Fermi level toward the valence band. However, after air exposure, the band gap of the oxidized WSe2 edges became about 1.08 eV larger than that of the WSe2 terraces, resulting in the electronic passivation of the WSe2. PMID:26991824

  8. Succinimidyl Ester Surface Chemistry: Implications of the Competition between Aminolysis and Hydrolysis on Covalent Protein Immobilization

    PubMed Central

    2015-01-01

    N-Hydroxysuccinimide (NHS) ester terminal groups are commonly used to covalently couple amine-containing biomolecules (e.g., proteins and peptides) to surfaces via amide linkages. This one-step aminolysis is often performed in buffered aqueous solutions near physiological pH (pH 6 to pH 9). Under these conditions, the hydrolysis of the ester group competes with the amidization process, potentially degrading the efficiency of the coupling chemistry. The work herein examines the efficiency of covalent protein immobilization in borate buffer (50 mM, pH 8.50) using the thiolate monolayer formed by the chemisorption of dithiobis (succinimidyl propionate) (DSP) on gold films. The structure and reactivity of these adlayers are assessed via infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), electrochemical reductive desorption, and contact angle measurements. The hydrolysis of the DSP-based monolayer is proposed to follow a reaction mechanism with an initial nucleation step, in contrast to a simple pseudo first-order reaction rate law for the entire reaction, indicating a strong dependence of the interfacial reaction on the packing and presence of defects in the adlayer. This interpretation is used in the subsequent analysis of IR-ERS kinetic plots which give a heterogeneous aminolysis rate constant, ka, that is over 3 orders of magnitude lower than that of the heterogeneous hydrolysis rate constant, kh. More importantly, a projection of these heterogeneous kinetic rates to protein immobilization suggests that under coupling conditions in which low protein concentrations and buffers of near physiological pH are used, proteins are more likely physically adsorbed rather than covalently linked. This result is paramount for biosensors that use NHS chemistry for protein immobilization due to effects that may arise from noncovalently linked proteins. PMID:25317495

  9. Enhanced spectroscopic gas sensors using in-situ grown carbon nanotubes

    NASA Astrophysics Data System (ADS)

    De Luca, A.; Cole, M. T.; Hopper, R. H.; Boual, S.; Warner, J. H.; Robertson, A. R.; Ali, S. Z.; Udrea, F.; Gardner, J. W.; Milne, W. I.

    2015-05-01

    In this letter, we present a fully complementary-metal-oxide-semiconductor (CMOS) compatible microelectromechanical system thermopile infrared (IR) detector employing vertically aligned multi-walled carbon nanotubes (CNT) as an advanced nano-engineered radiation absorbing material. The detector was fabricated using a commercial silicon-on-insulator (SOI) process with tungsten metallization, comprising a silicon thermopile and a tungsten resistive micro-heater, both embedded within a dielectric membrane formed by a deep-reactive ion etch following CMOS processing. In-situ CNT growth on the device was achieved by direct thermal chemical vapour deposition using the integrated micro-heater as a micro-reactor. The growth of the CNT absorption layer was verified through scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The functional effects of the nanostructured ad-layer were assessed by comparing CNT-coated thermopiles to uncoated thermopiles. Fourier transform IR spectroscopy showed that the radiation absorbing properties of the CNT adlayer significantly enhanced the absorptivity, compared with the uncoated thermopile, across the IR spectrum (3 μm-15.5 μm). This led to a four-fold amplification of the detected infrared signal (4.26 μm) in a CO2 non-dispersive-IR gas sensor system. The presence of the CNT layer was shown not to degrade the robustness of the uncoated devices, whilst the 50% modulation depth of the detector was only marginally reduced by 1.5 Hz. Moreover, we find that the 50% normalized absorption angular profile is subsequently more collimated by 8°. Our results demonstrate the viability of a CNT-based SOI CMOS IR sensor for low cost air quality monitoring.

  10. Optical reflectivity and Raman scattering in few-layer-thick graphene highly doped by K and Rb.

    PubMed

    Jung, Naeyoung; Kim, Bumjung; Crowther, Andrew C; Kim, Namdong; Nuckolls, Colin; Brus, Louis

    2011-07-26

    We report the optical reflectivity and Raman scattering of few layer (L) graphene exposed to K and Rb vapors. Samples many tens of layers thick show the reflectivity and Raman spectra of the stage 1 bulk alkali intercalation compounds (GICs) KC(8) and RbC(8). However, these bulk optical and Raman properties only begin to appear in samples more than about 15 graphene layers thick. The 1 L to 4 L alkali exposed graphene Raman spectra are profoundly different than the Breit-Wigner-Fano (BWF) spectra of the bulk stage 1 compounds. Samples less than 10 layers thick show Drude-like plasma edge reflectivity dip in the visible; alkali exposed few layer graphenes are significantly more transparent than intrinsic graphene. Simulations show the in-plane free electron density is lower than in the bulk stage 1 GICs. In few layer graphenes, alkalis both intercalate between layers and adsorb on the graphene surfaces. Charge transfer electrically dopes the graphene sheets to densities near and above 10(+14) electrons/cm(2). New intrinsic Raman modes at 1128 and 1264 cm(-1) are activated by in-plane graphene zone folding caused by strongly interacting, locally crystalline alkali adlayers. The K Raman spectra are independent of thickness for L = 1-4, indicating that charge transfer from adsorbed and intercalated K layers are similar. The Raman G mode is downshifted and significantly broadened from intrinsic graphene. In contrast, the Rb spectra vary strongly with L and show increased doping by intercalated alkali as L increases. Rb adlayers appear to be disordered liquids, while intercalated layers are locally crystalline solids. A significant intramolecular G mode electronic resonance Raman enhancement is observed in K exposed graphene, as compared with intrinsic graphene. PMID:21682332

  11. Direct evidence of arsenic(III)-carbonate complexes obtained using electrochemical scanning tunneling microscopy.

    PubMed

    Han, Mei-Juan; Hao, Jumin; Christodoulatos, Christos; Korfiatis, George P; Wan, Li-Jun; Meng, Xiaoguang

    2007-05-15

    Electrochemical scanning tunneling microscopy (ECSTM), ion chromatography (IC), and electrospray ionization-mass spectrometry/mass spectrometry were applied to investigate the interactions between arsenite [As(III)] and carbonate and arsenate [As(V)] and carbonate. The chemical species in the single and binary component solutions of As(III), As(V), and carbonate were attached to a Au(111) surface and then imaged in a 0.1 M NaClO4 solution at the molecular level by ECSTM. The molecules formed highly ordered adlayers on the Au(111) surface. High-resolution STM images revealed the orientation and packing arrangement of the molecular adlayers. Matching the STM images with the molecular models constructed using the Hyperchem software package indicated that As(III) formed two types of complexes with carbonate, including As(OH)2CO3- and As(OH)3(HCO3-)2. No complexes were formed between As(V) and carbonate. IC chromatograms of the solutions revealed the emergence of the new peak only in the aged As(III)-carbonate solution. MS spectra showed the presence of a new peak at m/z 187 in the aged As(III)-carbonate solution. The results obtained with the three independent methods confirmed the formation of As(OH)2CO3-. The results also indicated that As(OH)3 could be associated with HCO3- through a hydrogen bond. The knowledge of the formation of the As(III) and carbonate complexes will improve the understanding of As(III) mobility in the environment and removal of As(III) in water treatment systems. PMID:17441685

  12. Efficient Ceria-Platinum Inverse Catalyst for Partial Oxidation of Methanol.

    PubMed

    Ostroverkh, Anna; Johánek, Viktor; Kúš, Peter; Šedivá, Romana; Matolín, Vladimír

    2016-06-28

    Ceria-platinum-based bilayered thin films deposited by magnetron sputtering were developed and tested in regard to their catalytic activity for methanol oxidation by employing a temperature-programmed reaction (TPR) technique. The composition and structure of the samples were characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Both conventional (oxide-supported metal nanoparticles [NPs]) and inverse configurations (metal with oxide overlayer) were analyzed to uncover the structural dependence of activity and selectivity of these catalysts with respect to different pathways of methanol oxidation. We clearly demonstrate that the amount of cerium oxide (ceria) loading has a profound influence on methanol oxidation reaction characteristics. Adding a noncontinuous adlayer of ceria greatly enhances the catalytic performance of platinum (Pt) in favor of partial oxidation of methanol (POM), gaining an order of magnitude in the absolute yield of hydrogen. Moreover, the undesired by-production of carbon monoxide (CO) is strongly suppressed, making the ceria-platinum inverse catalyst a great candidate for clean hydrogen production. It is suggested that the methanol oxidation process is facilitated by the synergistic effect between both components of the inverse catalyst (involving oxygen from ceria and providing a reaction site on the adjacent Pt surface) as well as by the fact that the ability of ceria to exchange oxygen (i.e., to alter the oxidation state of Ce between 3+ and 4+) during the reaction is inversely proportional to its thickness. The increased redox capability of the discontinuous ceria adlayer shifts the preferred reaction pathway from dehydrogenation of hydroxymethyl intermediate to CO in favor of its oxidation to formate. PMID:27254727

  13. Spectral evidence for hydrogen-induced reversible segregation of CO adsorbed on titania-supported rhodium.

    PubMed

    Panayotov, D; Mihaylov, M; Nihtianova, D; Spassov, T; Hadjiivanov, K

    2014-07-14

    The reduction of a 1.3% Rh/TiO2 sample with carbon monoxide leads to the formation of uniform Rh nanoparticles with a mean diameter of dp ≈ 2.2 nm. Adsorption of CO on the reduced Rh/TiO2 produces linear and bridged carbonyls bound to metallic Rh(0) sites and only a few geminal dicarbonyls of Rh(I). The ν(CO) of linear Rh(0)-CO complexes is strongly coverage dependent: it is observed at 2078 cm(-1) at full coverage and at ca. 2025 cm(-1) at approximated zero coverage. At low coverage, this shift is mainly caused by a dipole-dipole interaction between the adsorbed CO molecules while at high coverage, the chemical shift also becomes important. Hydrogen hardly affects the CO adlayer at high CO coverages. However, on a partially CO-covered surface (θCO ≈ 0.5), the adsorption of H2 at increasing pressure leads to a gradual shift in the band of linear Rh(0)-CO from 2041 to 2062 cm(-1). Subsequent evacuation almost restores the original spectrum, demonstrating the reversibility of the hydrogen effect. Through the use of (12)CO + (13)CO isotopic mixtures, it is established that the addition of hydrogen to the CO-Rh/TiO2 system leads to an increase in the dynamic interaction between the adsorbed CO molecules. This evidences an increase in the density of the adsorbed CO molecules and indicates segregation of the CO and hydrogen adlayers. When CO is adsorbed on a hydrogen-precovered surface, the carbonyl band maximum is practically coverage independent and is observed at 2175-2173 cm(-1). These results are explained by a model according to which CO successively occupies different rhodium nanoparticles. PMID:24866330

  14. Nonspecific detection of lead ions in water using a simple integrated optical polarimetric interferometer

    NASA Astrophysics Data System (ADS)

    Lu, Dan-feng; Li, Jinyang; Qi, Zhi-mei

    2013-06-01

    Real-time detection of heavy metal ions in water was implemented by using a composite optical waveguide (COWG) based polarimetric interferometer. The COWG was made by local deposition of a tapered nanometric layer of high-index materials onto a single-mode slab glass waveguide, and it is a low-cost robust waveguide with a locally large modal birefringence. The COWG-based polarimetric interferometer operates with a single incident laser beam and uses the transverse electric and transverse magnetic modes as the sensing and reference beams, respectively, and it can easily detect 0.1 ppm lead(II) ions in water via nonspecific adsorption on the tapered layer of TiO2. The excellent linearity was obtained between the lead(II) concentration and the ratio of concentration to the phase-difference change (Δϕ), suggesting that adsorption of lead(II) ions on the TiO2 film follows the Langmuir isotherm model. The saturation adsorption leads to Δϕmax = 7.485π. By use of the eigenvalue equations for a homogeneous waveguide to fit the measured refractive-index (RI) sensitivity of the interferometer, the equivalent thickness of Teq = 26.05 nm for the tapered TiO2 layer used was achieved. With Teq = 26.05 nm and Δϕmax = 7.485π and the thickness of 0.264 nm for the lead(II) adlayer, the adlayer RI was derived to be nad ≈ 1.945 at the maximum coverage.

  15. Enhanced spectroscopic gas sensors using in-situ grown carbon nanotubes

    SciTech Connect

    De Luca, A.; Cole, M. T.; Milne, W. I.; Hopper, R. H.; Boual, S.; Ali, S. Z.; Warner, J. H.; Robertson, A. R.; Udrea, F.; Gardner, J. W.

    2015-05-11

    In this letter, we present a fully complementary-metal-oxide-semiconductor (CMOS) compatible microelectromechanical system thermopile infrared (IR) detector employing vertically aligned multi-walled carbon nanotubes (CNT) as an advanced nano-engineered radiation absorbing material. The detector was fabricated using a commercial silicon-on-insulator (SOI) process with tungsten metallization, comprising a silicon thermopile and a tungsten resistive micro-heater, both embedded within a dielectric membrane formed by a deep-reactive ion etch following CMOS processing. In-situ CNT growth on the device was achieved by direct thermal chemical vapour deposition using the integrated micro-heater as a micro-reactor. The growth of the CNT absorption layer was verified through scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The functional effects of the nanostructured ad-layer were assessed by comparing CNT-coated thermopiles to uncoated thermopiles. Fourier transform IR spectroscopy showed that the radiation absorbing properties of the CNT adlayer significantly enhanced the absorptivity, compared with the uncoated thermopile, across the IR spectrum (3 μm–15.5 μm). This led to a four-fold amplification of the detected infrared signal (4.26 μm) in a CO{sub 2} non-dispersive-IR gas sensor system. The presence of the CNT layer was shown not to degrade the robustness of the uncoated devices, whilst the 50% modulation depth of the detector was only marginally reduced by 1.5 Hz. Moreover, we find that the 50% normalized absorption angular profile is subsequently more collimated by 8°. Our results demonstrate the viability of a CNT-based SOI CMOS IR sensor for low cost air quality monitoring.

  16. Selectively Labeling the Heterologous Protein in Escherichia coli for NMR Studies: A Strategy to Speed Up NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Almeida, F. C. L.; Amorim, G. C.; Moreau, V. H.; Sousa, V. O.; Creazola, A. T.; Américo, T. A.; Pais, A. P. N.; Leite, A.; Netto, L. E. S.; Giordano, R. J.; Valente, A. P.

    2001-01-01

    Nuclear magnetic resonance is an important tool for high-resolution structural studies of proteins. It demands high protein concentration and high purity; however, the expression of proteins at high levels often leads to protein aggregation and the protein purification step can correspond to a high percentage of the overall time in the structural determination process. In the present article we show that the step of sample optimization can be simplified by selective labeling the heterologous protein expressed in Escherichia coli by the use of rifampicin. Yeast thioredoxin and a coix transcription factor Opaque 2 leucine zipper (LZ) were used to show the effectiveness of the protocol. The 1H/15N heteronuclear correlation two-dimensional NMR spectrum (HMQC) of the selective 15N-labeled thioredoxin without any purification is remarkably similar to the spectrum of the purified protein. The method has high yields and a good 1H/15N HMQC spectrum can be obtained with 50 ml of M9 growth medium. Opaque 2 LZ, a difficult protein due to the lower expression level and high hydrophobicity, was also probed. The 15N-edited spectrum of Opaque 2 LZ showed only the resonances of the protein of heterologous expression (Opaque 2 LZ) while the 1H spectrum shows several other resonances from other proteins of the cell lysate. The demand for a fast methodology for structural determination is increasing with the advent of genome/proteome projects. Selective labeling the heterologous protein can speed up NMR structural studies as well as NMR-based drug screening. This methodology is especially effective for difficult proteins such as hydrophobic transcription factors, membrane proteins, and others.

  17. Wet-chemical passivation of InAs: toward surfaces with high stability and low toxicity.

    PubMed

    Jewett, Scott A; Ivanisevic, Albena

    2012-09-18

    In a variety of applications where the electronic and optical characteristics of traditional, siliconbased materials are inadequate, recently researchers have employed semiconductors made from combinations of group III and V elements such as InAs. InAs has a narrow band gap and very high electron mobility in the near-surface region, which makes it an attractive material for high performance transistors, optical applications, and chemical sensing. However, silicon-based materials remain the top semiconductors of choice for biological applications, in part because of their relatively low toxicity. In contrast to silicon, InAs forms an unstable oxide layer under ambient conditions, which can corrode over time and leach toxic indium and arsenic components. To make InAs more attractive for biological applications, researchers have investigated passivation, chemical and electronic stabilization, of the surface by adlayer adsorption. Because of the simplicity, low cost, and flexibility in the type of passivating molecule used, many researchers are currently exploring wet-chemical methods of passivation. This Account summarizes much of the recent work on the chemical passivation of InAs with a particular focus on the chemical stability of the surface and prevention of oxide regrowth. We review the various methods of surface preparation and discuss how crystal orientation affects the chemical properties of the surface. The correct etching of InAs is critical as researchers prepare the surface for subsequent adlayer adsorption. HCl etchants combined with a postetch annealing step allow the tuning of the chemical properties in the near-surface region to either arsenic- or indium-rich environments. Bromine etchants create indium-rich surfaces and do not require annealing after etching; however, bromine etchants are harsh and potentially destructive to the surface. The simultaneous use of NH(4)OH etchants with passivating molecules prevents contact with ambient air that can

  18. Guiding neuron development with planar surface gradients of substrate cues deposited using microfluidic devices

    PubMed Central

    Millet, Larry J.; Stewart, Matthew E.; Nuzzo, Ralph G.

    2010-01-01

    Wiring the nervous system relies on the interplay of intrinsic and extrinsic signaling molecules that control neurite extension, neuronal polarity, process maturation and experience-dependent refinement. Extrinsic signals establish and enrich neuron-neuron interactions during development. Understanding how such extrinsic cues direct neurons to establish neural connections in vitro will facilitate the development of organised neural networks for investigating the development and function of nervous system networks. Producing ordered networks of neurons with defined connectivity in vitro presents special technical challenges because the results must be compliant with the biological requirements of rewiring neural networks. Here we demonstrate the ability to form stable, instructive surface-bound gradients of laminin that guide postnatal hippocampal neuron development in vitro. Our work uses a three-channel, interconnected microfluidic device that permits the production of adlayers of planar substrates through the combination of laminar flow, diffusion and physisorption. Through simple flow modifications, a variety of patterns and gradients of laminin (LN) and flourescein-conjugated poly-lysine (FITC-PLL) were deposited to present neurons with an instructive substratum to guide neuronal development. We present three variations in substrate design that produce distinct growth regimens for postnatal neurons in dispersed cell cultures. In the first approach, diffusion-mediated gradients of LN were formed on coverslips to guide neurons toward increasing LN concentrations. In the second approach, a combined gradient of LN and FITC-PLL was produced using aspiration-driven laminar flow to restrict neuronal growth to a 15 μm-wide growth zone at the center of the two superimposed gradients. The last approach demonstrates the capacity to combine binary lines of FITC-PLL in conjunction with surface gradients of LN and bovine serum albumin (BSA) to produce substrate adlayers

  19. Understanding and optimising the packing density of perylene bisimide layers on CVD-grown graphene

    NASA Astrophysics Data System (ADS)

    Berner, Nina C.; Winters, Sinéad; Backes, Claudia; Yim, Chanyoung; Dümbgen, Kim C.; Kaminska, Izabela; Mackowski, Sebastian; Cafolla, Attilio A.; Hirsch, Andreas; Duesberg, Georg S.

    2015-10-01

    The non-covalent functionalisation of graphene is an attractive strategy to alter the surface chemistry of graphene without damaging its superior electrical and mechanical properties. Using the facile method of aqueous-phase functionalisation on large-scale CVD-grown graphene, we investigated the formation of different packing densities in self-assembled monolayers (SAMs) of perylene bisimide derivatives and related this to the amount of substrate contamination. We were able to directly observe wet-chemically deposited SAMs in scanning tunnelling microscopy (STM) on transferred CVD graphene and revealed that the densely packed perylene ad-layers adsorb with the conjugated π-system of the core perpendicular to the graphene substrate. This elucidation of the non-covalent functionalisation of graphene has major implications on controlling its surface chemistry and opens new pathways for adaptable functionalisation in ambient conditions and on the large scale.The non-covalent functionalisation of graphene is an attractive strategy to alter the surface chemistry of graphene without damaging its superior electrical and mechanical properties. Using the facile method of aqueous-phase functionalisation on large-scale CVD-grown graphene, we investigated the formation of different packing densities in self-assembled monolayers (SAMs) of perylene bisimide derivatives and related this to the amount of substrate contamination. We were able to directly observe wet-chemically deposited SAMs in scanning tunnelling microscopy (STM) on transferred CVD graphene and revealed that the densely packed perylene ad-layers adsorb with the conjugated π-system of the core perpendicular to the graphene substrate. This elucidation of the non-covalent functionalisation of graphene has major implications on controlling its surface chemistry and opens new pathways for adaptable functionalisation in ambient conditions and on the large scale. Electronic supplementary information (ESI) available

  20. Adsorption of Potassium on the MoS2(100) Surface: A First-Principles Investigation

    SciTech Connect

    Andersen, Amity; Kathmann, Shawn M.; Lilga, Michael A.; Albrecht, Karl O.; Hallen, Richard T.; Mei, Donghai

    2011-04-15

    Periodic density functional theory calculations were performed to investigate the interaction that potassium with the Mo and S edges of the MoS2(100) surface. Both neutral and cationic (+1) charged potassium-promoted systems at different sulfur coverages were considered. Our calculations indicate that the potassium atom readily donates its single 4s valence electron to the MoS2 structure for the neutral potassium-promoted system, and the neutral and cationic potassium-promoted systems demonstrate a similar adsorption behavior. Moreover, potassium changes the magnetic properties known to occur at the metallic edge surface, which have implications for electron spin dependent surface characterization methods (i.e., electron spin/paramagnetic spectroscopy). Potassium in both the neutral and cationic systems tends to maximize its interactions with the available sulfur atoms at the edge surface, preferring sites over four-fold S hollows on fully sulfided Mo and S edges and over the interstitial gap where two to four edge surface S atoms are available for coordination. As the potassium coverage increases, the adsorption energy per potassium atom, surface work function, and transfer of the K 4s electron to the MoS2(100) surface decreases, which is in line with an increased metallization of the potassium adlayer. The potassium adlayer tends to form chains along the interstitial with K-K distances ~1 Å, which is notably less than those of bulk bcc K metal (4.61 Å). Density of states for the potassium-saturated surface suggests enhanced involvement of broad K 3d states beginning just above the Fermi level. Potassium-promotion of MoS2(100) has implications for alcohol catalysis: increasing the surface basicity by increasing the electron charge of the surface, providing hydrogenation-promoting CO site, blocking edge surface that dissociate CO and lead to methanation, and limiting H2 dissociative adsorption to the edge surface and possibly inhibiting the H2 dissociative

  1. Adsorption of oxygen on Au(111) by exposure to ozone

    NASA Astrophysics Data System (ADS)

    Saliba, N.; Parker, D. H.; Koel, B. E.

    1998-08-01

    Atomic oxygen coverages of up to 1.2 ML may be cleanly adsorbed on the Au(111) surface by exposure to O 3 at 300 K. We have studied the adsorbed oxygen layer by AES, XPS, HREELS, LEED, work function measurements and TPD. A plot of the O(519 eV)/Au(239 eV) AES ratio versus coverage is nearly linear, but a small change in slope occurs at ΘO=0.9 ML. LEED observations show no ordered superlattice for the oxygen overlayer for any coverage studied. One-dimensional ordering of the adlayer occurs at low coverages, and disordering of the substrate occurs at higher coverages. Adsorption of 1.0 ML of oxygen on Au(111) increases the work function by +0.80 eV, indicating electron transfer from the Au substrate into an oxygen adlayer. The O(1s) peak in XPS has a binding energy of 530.1 eV, showing only a small (0.3 eV) shift to a higher binding energy with increasing oxygen coverage. No shift was detected for the Au 4f 7/2 peak due to adsorption. All oxygen is removed by thermal desorption of O 2 to leave a clean Au(111) surface after heating to 600 K. TPD spectra initially show an O 2 desorption peak at 520 K at low ΘO, and the peak shifts to higher temperatures for increasing oxygen coverages up to ΘO=0.22 ML. Above this coverage, the peak shifts very slightly to higher temperatures, resulting in a peak at 550 K at ΘO=1.2 ML. Analysis of the TPD data indicates that the desorption of O 2 from Au(111) can be described by first-order kinetics with an activation energy for O 2 desorption of 30 kcal mol -1 near saturation coverage. We estimate a value for the Au-O bond dissociation energy D(Au-O) to be ˜56 kcal mol -1.

  2. Controllable poly-crystalline bilayered and multilayered graphene film growth by reciprocal chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Wu, Qinke; Jung, Seong Jun; Jang, Sung Kyu; Lee, Joohyun; Jeon, Insu; Suh, Hwansoo; Kim, Yong Ho; Lee, Young Hee; Lee, Sungjoo; Song, Young Jae

    2015-06-01

    We report the selective growth of large-area bilayered graphene film and multilayered graphene film on copper. This growth was achieved by introducing a reciprocal chemical vapor deposition (CVD) process that took advantage of an intermediate h-BN layer as a sacrificial template for graphene growth. A thin h-BN film, initially grown on the copper substrate using CVD methods, was locally etched away during the subsequent graphene growth under residual H2 and CH4 gas flows. Etching of the h-BN layer formed a channel that permitted the growth of additional graphene adlayers below the existing graphene layer. Bilayered graphene typically covers an entire Cu foil with domain sizes of 10-50 μm, whereas multilayered graphene can be epitaxially grown to form islands a few hundreds of microns in size. This new mechanism, in which graphene growth proceeded simultaneously with h-BN etching, suggests a potential approach to control graphene layers for engineering the band structures of large-area graphene for electronic device applications.We report the selective growth of large-area bilayered graphene film and multilayered graphene film on copper. This growth was achieved by introducing a reciprocal chemical vapor deposition (CVD) process that took advantage of an intermediate h-BN layer as a sacrificial template for graphene growth. A thin h-BN film, initially grown on the copper substrate using CVD methods, was locally etched away during the subsequent graphene growth under residual H2 and CH4 gas flows. Etching of the h-BN layer formed a channel that permitted the growth of additional graphene adlayers below the existing graphene layer. Bilayered graphene typically covers an entire Cu foil with domain sizes of 10-50 μm, whereas multilayered graphene can be epitaxially grown to form islands a few hundreds of microns in size. This new mechanism, in which graphene growth proceeded simultaneously with h-BN etching, suggests a potential approach to control graphene layers for

  3. Exploring the complexity of supramolecular interactions for patterning at the liquid-solid interface.

    PubMed

    Mali, Kunal S; Adisoejoso, Jinne; Ghijsens, Elke; De Cat, Inge; De Feyter, Steven

    2012-08-21

    The use of self-assembly to fabricate surface-confined adsorbed layers (adlayers) from molecular components provides a simple means of producing complex functional surfaces. The molecular self-assembly process relies on supramolecular interactions sustained by noncovalent forces such as van der Waals, electrostatic, dipole-dipole, and hydrogen bonding interactions. Researchers have exploited these noncovalent bonding motifs to construct well-defined two-dimensional (2D) architectures at the liquid-solid interface. Despite myriad examples of 2D molecular assembly, most of these early findings were serendipitous because the intermolecular interactions involved in the process are often numerous, subtle, cooperative, and multifaceted. As a consequence, the ability to tailor supramolecular patterns has evolved slowly. Insight gained from various studies over the years has contributed significantly to the knowledge of supramolecular interactions, and the stage is now set to systematically engineer the 2D supramolecular networks in a "preprogrammed" fashion. The control over 2D self-assembly of molecules has many important implications. Through appropriate manipulation of supramolecular interactions, one can "encode" the information at the molecular level via structural features such as functional groups, substitution patterns, and chiral centers which could then be retrieved, transferred, or amplified at the supramolecular level through well-defined molecular recognition processes. This ability allows for precise control over the nanoscale structure and function of patterned surfaces. A clearer understanding and effective use of these interactions could lead to the development of functional surfaces with potential applications in molecular electronics, chiral separations, sensors based on host-guest systems, and thin film materials for lubrication. In this Account, we portray our various attempts to achieve rational design of self-assembled adlayers by exploiting the

  4. Mesoscale imperfections in MoS2 atomic layers grown by a vapor transport technique.

    PubMed

    Liu, Yingnan; Ghosh, Rudresh; Wu, Di; Ismach, Ariel; Ruoff, Rodney; Lai, Keji

    2014-08-13

    The success of isolating small flakes of atomically thin layers through mechanical exfoliation has triggered enormous research interest in graphene and other two-dimensional materials. For device applications, however, controlled large-area synthesis of highly crystalline monolayers with a low density of electronically active defects is imperative. Here, we demonstrate the electrical imaging of dendritic ad-layers and grain boundaries in monolayer molybdenum disulfide (MoS2) grown by a vapor transport technique using microwave impedance microscopy. The micrometer-sized precipitates in our films, which appear as a second layer of MoS2 in conventional height and optical measurements, show ∼ 2 orders of magnitude higher conductivity than that of the single layer. The zigzag grain boundaries, on the other hand, are shown to be more resistive than the crystalline grains, consistent with previous studies. Our ability to map the local electrical properties in a rapid and nondestructive manner is highly desirable for optimizing the growth process of large-scale MoS2 atomic layers. PMID:25019334

  5. An ab initio-based approach to the stability of GaN(0 0 0 1) surfaces under Ga-rich conditions

    NASA Astrophysics Data System (ADS)

    Ito, Tomonori; Akiyama, Toru; Nakamura, Kohji

    2009-05-01

    Structural stability of GaN(0 0 0 1) under Ga-rich conditions is systematically investigated by using our ab initio-based approach. The surface phase diagram for GaN(0 0 0 1) including (2×2) and pseudo-(1×1) is obtained as functions of temperature and Ga beam equivalent pressure by comparing chemical potentials of Ga atom in the gas phase with that on the surface. The calculated results reveal that the pseudo-(1×1) appearing below 684-973 K changes its structure to the (2×2) with Ga adatom at higher temperatures beyond 767-1078 K via the newly found (1×1) with two adlayers of Ga. These results are consistent with the stable temperature range of both the pseudo-(1×1) and (2×2) with Ga adatom obtained experimentally. Furthermore, it should be noted that the structure with another coverage of Ga adatoms between the (1×1) and (2×2)-Ga does not appear as a stable structure of GaN(0 0 0 1). Furthermore, ghost island formation observed by scanning tunneling microscopy is discussed on the basis of the phase diagram.

  6. Controllable poly-crystalline bilayered and multilayered graphene film growth by reciprocal chemical vapor deposition.

    PubMed

    Wu, Qinke; Jung, Seong Jun; Jang, Sung Kyu; Lee, Joohyun; Jeon, Insu; Suh, Hwansoo; Kim, Yong Ho; Lee, Young Hee; Lee, Sungjoo; Song, Young Jae

    2015-06-21

    We report the selective growth of large-area bilayered graphene film and multilayered graphene film on copper. This growth was achieved by introducing a reciprocal chemical vapor deposition (CVD) process that took advantage of an intermediate h-BN layer as a sacrificial template for graphene growth. A thin h-BN film, initially grown on the copper substrate using CVD methods, was locally etched away during the subsequent graphene growth under residual H2 and CH4 gas flows. Etching of the h-BN layer formed a channel that permitted the growth of additional graphene adlayers below the existing graphene layer. Bilayered graphene typically covers an entire Cu foil with domain sizes of 10-50 μm, whereas multilayered graphene can be epitaxially grown to form islands a few hundreds of microns in size. This new mechanism, in which graphene growth proceeded simultaneously with h-BN etching, suggests a potential approach to control graphene layers for engineering the band structures of large-area graphene for electronic device applications. PMID:26006180

  7. Enhanced gypsum scaling by organic fouling layer on nanofiltration membrane: Characteristics and mechanisms.

    PubMed

    Wang, Jiaxuan; Wang, Lei; Miao, Rui; Lv, Yongtao; Wang, Xudong; Meng, Xiaorong; Yang, Ruosong; Zhang, Xiaoting

    2016-03-15

    To investigate how the characteristics of pregenerated organic fouling layers on nanofiltration (NF) membranes influence the subsequent gypsum scaling behavior, filtration experiments with gypsum were carried out with organic-fouled poly(piperazineamide) NF membranes. Organic fouling layer on membrane was induced by bovine serum albumin (BSA), humic acid (HA), and sodium alginate (SA), respectively. The morphology and components of the scalants, the role of Ca(2+) adsorption on the organic fouling layer during gypsum crystallization, and the interaction forces of gypsum on the membrane surface were investigated. The results indicated that SA- and HA-fouled membranes had higher surface crystallization tendency along with more severe flux decline during gypsum scaling than BSA-fouled and virgin membranes because HA and SA macromolecules acted as nuclei for crystallization. Based on the analyses of Ca(2+) adsorption onto organic adlayers and adhesion forces, it was found that the flux decline rate and extent in the gypsum scaling experiment was positively related to the Ca(2+)-binding capacity of the organic matter. Although the dominant gypsum scaling mechanism was affected by coupling physicochemical effects, the controlling factors varied among foulants. Nevertheless, the carboxyl density of organic matter played an important role in determining surface crystallization on organic-fouled membrane. PMID:26799710

  8. Antioxidant properties of fruiting bodies, mycelia, and fermented products of the culinary-medicinal king oyster mushroom, Pleurotus eryngii (higher Basidiomycetes), with high ergothioneine content.

    PubMed

    Liang, Chih-Hung; Ho, Kung-Jui; Huang, Ling-Yi; Tsai, Ching-Hsuan; Lin, Shin-Yi; Mau, Jeng-Leun

    2013-01-01

    The culinary-medicinal king oyster mushroom Pleurotus eryngii is known to contain ergothioneine, and its products, including fruiting bodies, mycelia, and solid-state fermented products (adlay and buckwheat), were prepared to study their antioxidant properties. Fruiting bodies, regular and Hi-Ergo mycelia, and fermented products contained 2.05, 1.68, 5.76, 0.79-0.80 mg/g of ergothioneine, respectively. On the basis of the results obtained, P. eryngii products had effective antioxidant activity, reducing power, and scavenging ability on 1,1-diphenyl-2-picrylhydrazyl radicals and chelating ability on ferrous ions. Hi-Ergo mycelia was the most effective in the first 3 antioxidant properties in addition to its ergothioneine content. In addition, fruiting bodies were more effective in all antioxidant properties than regular mycelia. For ethanolic and hot water extracts from mycelia and fruiting bodies, the correlation coefficients between total phenol contents and each antioxidant attribute were 0.483-0.921. Overall, P. eryngii products with high amounts of ergothioneine could be used beneficially as a functional food. PMID:23662614

  9. Self-assembly of bis(phthalocyaninato)terbium on metal surfaces

    NASA Astrophysics Data System (ADS)

    Deng, Zhitao; Rauschenbach, Stephan; Stepanow, Sebastian; Klyatskaya, Svetlana; Ruben, Mario; Kern, Klaus

    2015-09-01

    Single-molecule magnets represent the smallest stable magnetic entities available to technology, with promising applications in data storage and quantum computation in sight. Therefore, an interface between devices and single-molecule magnets must be developed, for which the self-assembly behavior at surfaces is highly relevant. The molecular magnet bis(phthalocyaninato)terbium (TbPc2) represents a molecular system with interesting magnetic properties. In order to fabricate low dimensional nanostructures based on TbPc2, the self-assembly behavior on Cu(100), Cu(111) and Au(111) substrates is studied in ultra-high vacuum (UHV). On Cu(100), TbPc2 does not aggregate even at high coverage, which yields a good zero-dimensional system. On Cu(111), the TbPc2 molecules self-assemble into ribbon-like islands with a high aspect ratio, or an isotropically growing phase, depending on the coverage. On Au(111), TbPc2 molecules form two-dimensional domains from the initial growth stage and extend to highly ordered films, which cover entire terraces at high coverage. The molecular ordering of TbPc2 can be understood based on the behavior of single Pc adlayers, taking into account the molecular double-decker structure. The freedom in the dihedral angle between top and bottom Pc ligands allows one to optimize the molecular ordering through a flexible conformation.

  10. Formation of GaPd2 and GaPd intermetallic compounds on GaN(0001)

    NASA Astrophysics Data System (ADS)

    Grodzicki, M.; Mazur, P.; Pers, J.; Brona, J.; Zuber, S.; Ciszewski, A.

    2015-09-01

    Palladium was deposited gradually under ultrahigh vacuum onto a well-defined surface of (0001)-oriented n-type GaN, at room temperature. Each deposition step was followed by annealing. Physicochemical properties of the Pd adlayers were in situ investigated prior to and after annealing by the X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, low-energy electron diffraction, scanning tunneling microscopy and atomic force microscopy techniques. Annealing resulted in the formation of GaPd2 and GaPd intermetallic compounds at 550 °C and at 800 °C. Even for thicker layers, the compounds were strongly dispersed, forming 3D nanostructures. The substrate uncovered by the compounds revealed Ga-rich GaN(0001)-(1 × 1) surface. Formation of Ga-Pd-N bonds or Pd nitrides was not detected at the surface. The Ga-Pd intermetallic compound surface engineered on the GaN(0001) substrate can be used as the strongly dispersed catalyst or a model catalyst.

  11. Self-assembled monolayer of o-aminothiophenol on Fe(1 1 0) surface: a combined study by electrochemistry, in situ STM, and molecular simulations

    NASA Astrophysics Data System (ADS)

    Kong, De-Sheng; Yuan, Shi-Ling; Sun, Yu-Xi; Yu, Zhang-Yu

    2004-12-01

    Electrochemical measurements, in situ scanning tunneling microscopy (STM) observation, and molecular mechanics (MM) simulations were performed to study the physiochemical properties such as the corrosion-inhibition effect and the optimal packing structure of o-aminothiophenol (OATP) self-assembled monolayer (SAM) formed on Fe(1 1 0) surface in 0.1 M NaClO 4 solution. The formation of OATP SAMs drastically depressed the Faradaic processes at the Fe(1 1 0) surface and reduced the electrical double-layer capacitance at the electrode/electrolyte interface, revealing the anticorrosion property and the blocking behavior of OATP adlayers. Two-dimensional ordered molecular arrays of OATP on Fe(1 1 0) surface with a p(2 × 2) commensurate structure were observed by STM measurements. MM calculations showed that the p(2 × 2) packing pattern is indeed the preferable structure for OATP molecules adsorbed on Fe(1 1 0), in accordance with STM experiments. The OATP SAM on Fe(1 1 0) is ≈0.50 nm in thickness and with a dielectric constant of ˜7.0.

  12. CO Adsorption on Pd(111) at 0.5ML: a First Principles Study

    NASA Astrophysics Data System (ADS)

    Hooshmand Gharehbagh, Zahra; Le, Duy; Rahman, Talat S.

    2015-03-01

    While the adlayer structures formed by CO molecules on Pd(111) are well-understood both experimentally and theoretically, for low and high coverages, it is still a matter of discussion for medium coverage (0.5ML). At this medium coverage, it is well-known that the c(4 × 2) phase is formed but the adsorption sites of CO molecules have been reported differently by various studies: at the bridge sites, at the hollow sites, or at both bridge and hollow sites. Using density functional theory calculations we studied the overlayer structure of CO at 0.5ML on Pd(111) with all possible highly symmetric adsorption sites leading to c(4 × 2) structures. We will show that, on the same surface, CO molecules adsorb either only on bridge or hollow sites and that there is no overlayer structure in which CO binds at both bridge and hollow sites. By means of ab initio thermodynamics simulation, we will also report the conditions (temperature, pressure) in which each overlayer structure exists. Work support in part by NSF Grant CHE-1310327.

  13. The onset of sub-surface oxidation induced by defects in a chemisorbed oxygen layer

    SciTech Connect

    Li, Jonathan; Li, Liang; Zhou, Guangwen

    2015-02-28

    We investigate the onset of internal oxidation of a Cu(110) surface induced by oxygen subsurface adsorption via defects in the Cu(110)–(2 × 1)–O chemisorbed layer. The presence of a boundary formed by merged add-row structure domains due to a mismatch of half unit-cell leads to preferred oxygen adsorption at the subsurface tetrahedral sites. The resulting distorted Cu–O tetrahedra along the domain boundary have comparable bond length and angles to those of the bulk oxide phase of Cu{sub 2}O. Our results indicate that the presence of defects in the oxygen-chemisorbed adlayer can lead to the internal oxidation via the formation of Cu{sub 2}O-like tetrahedra in between the topmost and second outermost atomic layers at the oxygen coverage θ = 0.53 and the second and third outermost atomic layers at θ = 0.56. These results show that the internal oxidation of a metal surface can occur in the very beginning of the oxygen chemisorption process enabled by the presence of defects in the oxygen chemisorbed layer.

  14. Identification of parameters through which surface chemistry determines the lifetimes of hot electrons in small Au nanoparticles.

    PubMed

    Aruda, Kenneth O; Tagliazucchi, Mario; Sweeney, Christina M; Hannah, Daniel C; Schatz, George C; Weiss, Emily A

    2013-03-12

    This paper describes measurements of the dynamics of hot electron cooling in photoexcited gold nanoparticles (Au NPs) with diameters of ∼3.5 nm, and passivated with either a hexadecylamine or hexadecanethiolate adlayer, using ultrafast transient absorption spectroscopy. Fits of these dynamics with temperature-dependent Mie theory reveal that both the electronic heat capacity and the electron-phonon coupling constant are larger for the thiolated NPs than for the aminated NPs, by 40% and 30%, respectively. Density functional theory calculations on ligand-functionalized Au slabs show that the increase in these quantities is due to an increased electronic density of states near the Fermi level upon ligand exchange from amines to thiolates. The lifetime of hot electrons, which have thermalized from the initial plasmon excitation, increases with increasing electronic heat capacity, but decreases with increasing electron-phonon coupling, so the effects of changing surface chemistry on these two quantities partially cancel to yield a hot electron lifetime of thiolated NPs that is only 20% longer than that of aminated NPs. This analysis also reveals that incorporation of a temperature-dependent electron-phonon coupling constant is necessary to adequately fit the dynamics of electron cooling. PMID:23440215

  15. Robust and tunable itinerant ferromagnetism at the silicon surface of the antiferromagnet GdRh2Si2

    NASA Astrophysics Data System (ADS)

    Güttler, M.; Generalov, A.; Otrokov, M. M.; Kummer, K.; Kliemt, K.; Fedorov, A.; Chikina, A.; Danzenbächer, S.; Schulz, S.; Chulkov, E. V.; Koroteev, Yu. M.; Caroca-Canales, N.; Shi, M.; Radovic, M.; Geibel, C.; Laubschat, C.; Dudin, P.; Kim, T. K.; Hoesch, M.; Krellner, C.; Vyalikh, D. V.

    2016-04-01

    Spin-polarized two-dimensional electron states (2DESs) at surfaces and interfaces of magnetically active materials attract immense interest because of the idea of exploiting fermion spins rather than charge in next generation electronics. Applying angle-resolved photoelectron spectroscopy, we show that the silicon surface of GdRh2Si2 bears two distinct 2DESs, one being a Shockley surface state, and the other a Dirac surface resonance. Both are subject to strong exchange interaction with the ordered 4f-moments lying underneath the Si-Rh-Si trilayer. The spin degeneracy of the Shockley state breaks down below ~90 K, and the splitting of the resulting subbands saturates upon cooling at values as high as ~185 meV. The spin splitting of the Dirac state becomes clearly visible around ~60 K, reaching a maximum of ~70 meV. An abrupt increase of surface magnetization at around the same temperature suggests that the Dirac state contributes significantly to the magnetic properties at the Si surface. We also show the possibility to tune the properties of 2DESs by depositing alkali metal atoms. The unique temperature-dependent ferromagnetic properties of the Si-terminated surface in GdRh2Si2 could be exploited when combined with functional adlayers deposited on top for which novel phenomena related to magnetism can be anticipated.

  16. Tuning friction with an external magnetic field: A Quartz Crystal Microbalance study of physisorbed oxygen monolayers and multilayers sliding on nickel substrates

    NASA Astrophysics Data System (ADS)

    Fredricks, Z. B.; Stevens, K. M.; Acharya, B.; Krim, J.

    The sliding friction levels of oxygen monolayer and multilayer films adsorbed on nickel close to the oxygen monolayer solid-liquid melting transition temperature have been monitored by means of a Quartz Crystal Microbalance (QCM) technique in the presence and absence of a weak external magnetic field. Friction levels for the monolayers in the presence of the field were observed to be half of those observed in the absence of a field. For thick films, the reduction was proportionately less, indicating an interfacial effect as the source of the magnetic sensitivity. While the presence of the field is expected to increase the normal force between the paramagnetic oxygen overlayer and the ferromagnetic substrate, the impact of this mechanism on friction appears to be minimal, or possibly masked by more dominant mechanisms. These include magnetically induced structural reorientation (magnetostriction), and/or realignment of adlayer spins in response to the applied field, both of which would reduce the physical or magnetic interfacial commensurability, thus lowering friction levels. Work supported by NSF DMR1310456.

  17. Growth kinetics and island evolution during double-pulsed molecular beam epitaxy of InN

    NASA Astrophysics Data System (ADS)

    Kraus, A.; Hein, C.; Bremers, H.; Rossow, U.; Hangleiter, A.

    2016-06-01

    The kinetic processes of InN growth using alternating source fluxes with sub-monolayer In pulses in plasma-assisted molecular beam epitaxy have been investigated. Growth at various temperatures reveals the existence of two growth regimes. While growth at low temperatures is solely governed by surface diffusion, a combination of decomposition, desorption, and diffusion becomes decisive at growth temperatures of 470 °C and above. At this critical temperature, the surface morphology changes from a grainy structure to a structure made of huge islands. The formation of those islands is attributed to the development of an indium adlayer, which can be observed via reflection high energy electron diffraction monitoring. Based on the growth experiments conducted at temperatures below TGrowth = 470 °C, an activation energy for diffusion of 0.54 ± 0.02 eV has been determined from the decreasing InN island density. A comparison between growth on metalorganic vapor phase epitaxy GaN templates and pseudo bulk GaN indicates that step edges and dislocations are favorable nucleation sites. Based on the results, we developed a growth model, which describes the main mechanisms of the growth.

  18. Chiral Selective Chemistry Induced by Natural Selection of Spin-Polarized Electrons.

    PubMed

    Rosenberg, Richard A; Mishra, Debabrata; Naaman, Ron

    2015-06-15

    The search to understand the origin of homochirality in nature has been ongoing since the time of Pasteur. Previous work has shown that DNA can act as a spin filter for low-energy electrons and that spin-polarized secondary electrons produced by X-ray irradiation of a magnetic substrate can induce chiral selective chemistry. In the present work it is demonstrated that secondary electrons from a substrate that are transmitted through a chiral overlayer cause enantiomeric selective chemistry in an adsorbed adlayer. We determine the quantum yields (QYs) for dissociation of (R)- or (S)-epichlorohydrin adsorbed on a chiral self-assembled layer of DNA on gold and on bare gold (for control). The results show that there is a significant difference in the QYs between the two enantiomers when adsorbed on DNA, but none when they are adsorbed on bare Au. We propose that the effect results from natural spin filtering effects cause by the chiral monolayer. PMID:25950284

  19. CVD formation of graphene on SiC surface in argon atmosphere.

    PubMed

    Wierzbowska, Małgorzata; Dominiak, Adam; Tokar, Kamil

    2013-06-14

    We investigate the microscopic processes leading to graphene growth by the chemical vapor deposition of propane in an argon atmosphere at the SiC surface. Experimentally, it is known that the presence of argon fastens the dehydrogenation processes at the surface, at high temperatures of about 2000 K. We perform ab initio calculations, at zero temperature, to check whether chemical reactions can explain this phenomenon. Density functional theory and supporting quantum chemistry methods qualitatively describe formation of the graphene wafers. We find that the 4H-SiC(0001) surface exhibits a large catalytic effect in the adsorption process of hydrocarbon molecules, this is also supported by preliminary molecular dynamics results. The existence of the ArH(+) molecule, and an observation from the Raman spectra that the negative charge transfers into the SiC surface, would suggest that presence of argon atoms leads to a deprotonization on the surface, which is necessary to obtain a pure carbon adlayer. But the zero-temperature description shows that the cold environment is insufficient to promote argon-assisted surface cleaning. PMID:23640518

  20. Multilayer thin film growth on crystalline and quasicrystalline surfaces: A phase-field crystal study

    NASA Astrophysics Data System (ADS)

    Muralidharan, Srevatsan; Khodadad, Raika; Sullivan, Ethan; Haataja, Mikko

    2012-06-01

    In this paper, we explore the effects of misfit strain fields on both heterogeneous nucleation behavior and anisotropic growth of islands at submonolayer coverages and compositional patterning at complete monolayer coverage via simulations of a phase-field crystal model. In particular, deposition on top of a herringbone structure and quasicrystalline (QC) substrate are considered, the former representing a system with spatially periodic misfit strain fields arising from the presence of surface dislocations, and the latter representing a system which inherently possesses a wide range of local, aperiodic misfit patterns. In the case of single-component systems, we demonstrate that misfit strain fields lead to heterogeneous nucleation behavior and anisotropic island growth. In the case of QC substrate, a wide range of morphologies, such as coexistence of locally hexagonally ordered atomic clusters within a larger scale arrangement with overall QC symmetry and so-called “starfish” aggregates, is observed in a pure system at submonolayer coverages when the adlayer-substrate interaction strength and lattice mismatch are tuned. In the case of bulk-immiscible binary systems at complete monolayer coverage, strain-stabilized compositional domains emerge at low line tension values for both substrates. Interestingly, the compositional domains on the QC substrate inherit their symmetries at sufficiently low line tension values, while at larger line tension values, the domain structure begins to resemble the classical spinodal microstructure. Such domain structures should be readily observable in colloidal systems in which attractive interparticle and particle-substrate interactions can be tuned.

  1. Surface-Confined Supramolecular Self-Assembly of Molecular Nanocranes for Chemically Lifting and Positioning C60 above a Conducting Substrate.

    PubMed

    Du, Ping; Kreher, David; Mathevet, Fabrice; Maldivi, Pascale; Charra, Fabrice; Attias, André-Jean

    2015-12-21

    2D supramolecular self-assembly is a good way to form well-defined nanostructures on various substrates. One of the current challenges is to extend this approach to 3D functional building blocks. Here, we address this issue by providing a strategy for the controlled lifting and positioning of functional units above a graphitic substrate. This is the first time that multistory cyclophane-based 3D tectons incorporating C60 units have been designed and synthesized. Molecular modelling provides a description of the 3D geometries and evidences the flexible character of the building blocks. Despite this later feature, the supramolecular self-assembly of Janus tectons on HOPG yields well-ordered adlayers incorporating C60 arrays at well-defined mean distances from the surface. As our approach is not limited to C60 , the results reported here open-up possibilities for applications where the topological and electronic interactions between the substrate and the functional unit are of prime importance. PMID:26488211

  2. Growth mechanism of pulsed laser fabricated few-layer MoS₂ on metal substrates.

    PubMed

    Loh, Tamie A J; Chua, Daniel H C

    2014-09-24

    Pulsed laser deposition (PLD) on metal substrates has recently been discovered to present an alternative method for producing highly crystalline few-layer MoS2. However, not every metal behaves in the same manner during film growth, and hence, it is crucial that the ability of various metals to produce crystalline MoS2 be thoroughly investigated. In this work, MoS2 was deposited on metal substrates, Al, Ag, Ni, and Cu, using a pulsed laser. Highly crystalline few-layer MoS2 was successfully grown on Ag, but is absent in Al, Ni, and Cu under specific growth conditions. This discrepancy was attributed to either excessively strong or insufficient adlayer-substrate interactions. In the case of Al, the effects of the strong interface interactions can be offset by increasing the amount of source atoms supplied, thereby producing semicrystalline few-layer MoS2. The results show that despite PLD being a physical vapor deposition technique, both physical and chemical processes play an important role in MoS2 growth on metal substrates. PMID:25203278

  3. Periodic Modulation of the Doping Level in Striped MoS2 Superstructures.

    PubMed

    Zhou, Xiebo; Shi, Jianping; Qi, Yue; Liu, Mengxi; Ma, Donglin; Zhang, Yu; Ji, Qingqing; Zhang, Zhepeng; Li, Cong; Liu, Zhongfan; Zhang, Yanfeng

    2016-03-22

    Although the recently discovered monolayer transition metal dichalcogenides exhibit novel electronic and optical properties, fundamental physical issues such as the quasiparticle bandgap tunability and the substrate effects remain undefined. Herein, we present the report of a quasi-one-dimensional periodically striped superstructure for monolayer MoS2 on Au(100). The formation of the unique striped superstructure is found to be mainly modulated by the symmetry difference between MoS2 and Au(100) and their lattice mismatch. More intriguingly, we find that the monolayer MoS2 is heavily n-doped on the Au(100) facet with a bandgap of 1.3 eV, and the Fermi level is upshifted by ∼0.10 eV on the ridge (∼0.2 eV below the conduction band) in contrast to the valley regions (∼0.3 eV below the conduction band) of the striped patterns after high-temperature sample annealing process. This tunable doping effect is considered to be caused by the different defect densities over the ridge/valley regions of the superstructure. Additionally, an obvious bandgap reduction is observed in the vicinity of the domain boundary for monolayer MoS2 on Au(100). This work should therefore inspire intensive explorations of adlayer-substrate interactions, the defects, and their effects on band-structure engineering of monolayer MoS2. PMID:26913990

  4. Pt on graphene monolayers supported on a Ni(111) substrate: Relativistic density-functional calculations

    NASA Astrophysics Data System (ADS)

    Błoński, Piotr; Hafner, Jürgen

    2012-02-01

    The structural, energetic, and magnetic properties of Pt atoms and dimers adsorbed on a Ni-supported graphene layer have been investigated using density-functional calculations, including the influence of dispersion forces and of spin-orbit coupling. Dispersion forces are found to be essential to stabilize a chemisorbed graphene layer on the Ni(111) surface. The presence of the Ni-substrate leads not only to a stronger interaction of Pt atoms and dimers with graphene but also to a locally increased binding between graphene and the substrate and a complex reconstruction of the adlayer. The stronger binding of the dimer also stabilizes a flat adsorption geometry in contrast to the upright geometry on a free-standing graphene layer. These effects are further enhanced by dispersion corrections. Isolated Pt adatoms and flat dimers are found to be non-magnetic, while an upright Pt dimer has strongly anisotropic spin and orbital moments. For the clean C/Ni(111) system, we calculate an in-plane magnetic anisotropy, which is also conserved in the presence of isolated Pt adatoms. Surprisingly, upright Pt-dimers induce a re-orientation of the easy magnetic axis to a direction perpendicular to the surface, in analogy to Pt2 on a free-standing graphene layer and to the axial anisotropy of a gas-phase Pt2 dimer.

  5. Study of the Au Schottky contact formation on oxygen plasma treated n-type SnO{sub 2} (101) thin films

    SciTech Connect

    Nagata, Takahiro; Bierwagen, Oliver; White, Mark E.; Speck, James S.; Tsai, Min-Ying

    2010-02-15

    As-grown and oxygen plasma treated n-type tin dioxide (SnO{sub 2}) (101) thin films were investigated regarding the properties of Au contacts, surface structure, and band bending. The plasma treatment was performed in a conventional oxygen plasma cleaning system with maximum oxygen ion energies of 400 eV. Whereas the as-deposited SnO{sub 2} film formed non-Schottky contacts with Au, the oxygen plasma treated films formed Schottky contacts with Au. Capacitance-voltage and differential Hall measurements indicated the introduction of bulk electron traps up to several 100 nm below the surface due to the oxygen plasma treatment. Angle resolved x-ray photoelectron spectroscopy (AR-XPS) revealed a surface accumulation layer on the as-grown film that was absent after the plasma treatment. These measurements further revealed chemical differences between the as-deposited and the plasma treated SnO{sub 2} surfaces. All SnO{sub 2} films had Sn{sup 2+}-O bonds. The AR-XPS Sn{sup 2+}-O signal intensity increased after plasma treatment, indicating that the oxygen plasma damaged the SnO{sub 2} surface. Additionally, an O{sub 2} adlayer was formed due to the oxygen plasma treatment. The damaged layer due to oxygen ion bombardment, oxygen adsorption layer, and possibly bulk traps depleted the surface carriers which enabled the formation of a Schottky contact with Au.

  6. The Structure of Dithiol Monolayers on Au(111).

    NASA Astrophysics Data System (ADS)

    Gallagher, M. C.; Macdairmid, A. R.; Banks, J. T.

    2003-03-01

    Using scanning tunneling microscopy (STM), Auger electron spectroscopy (AES), and contact angle measurements, we have studied the properties of Dithiothreitol (DTT) and Dithioerythritol (DTE) monolayers adsorbed on Au(111). DTT and DTE are both O-H functionalized α - ω dithiols. DTT is a chiral form whereas DTE is achiral. For comparison we have also studied the structure of octanethiol (n-alkanethiol, n = 8) SAMs. Octanethiol forms the characteristic close packed 3x3 monolayer with c(4x2) superstructure. In contrast, STM measurements of DTT films indicate much of the layer is disordered, however regions with local c(23x3) symmetry are observed. AES indicates the sulphur coverage for both DTT and octanethiol films are similar. AES studies involving Ellman's reagent, a marker species, also suggest a significant fraction of the DTT molecules in the adlayer bind to the gold via two Au-S bonds. Based on these results, we propose a structural model in which the majority of DTT molecules bind to the gold surface via two Au-S bonds and the distance between these two bonds is 3 times the underlying Au lattice spacing. Any differences between DTT and DTE layers due to differences in molecular structure will also be discussed.

  7. Persistence of explosives under real world conditions

    NASA Astrophysics Data System (ADS)

    Papantonakis, Michael R.; Furstenberg, Robert; Nguyen, Viet; Fischer, Thomas; Howard, Andrew; Adams, Katy; Kendziora, Christopher A.; McGill, R. Andrew

    2016-05-01

    Those that handle explosives materials invariably become contaminated with particulates of materials, which become entrapped in the grooves of the fingers and are then transferred by contact to other surfaces. These particles provide an evidentiary trail which is useful for security applications, a fact which is enhanced by the fact that many explosives materials of interest have low vapor pressures, augmenting their longevity. The persistence or stability of explosives particles on a substrate is a function of several environmental parameters or particle properties, including vapor pressure, particle size and geometry, airflow, particle field size, substrate topography, humidity, reactivity, adlayers, admixtures, particle areal density, and temperature. In this work we deposited particles of 2,4-dinitrotoluene on standard microscope glass slides by particle sieving and studied their sublimation as a function of temperature and relative humidity. A custom airflow cell allowed us to monitor the particles with in situ photomicroscopy while keeping the airflow over the particles, substrate type, and areal field size constant for each experiment. We define the size-independent radial sublimation velocity for the equivalent sphere of a particle as the parameter to characterize the sublimation rate. The dependence of the sublimation rate for an ensemble of particles on temperature was quantified according the radial sublimation velocity, while the sublimation of 2,4-dinintrotoluene was found to independent of relative humidity between 25-90%.

  8. Robust and tunable itinerant ferromagnetism at the silicon surface of the antiferromagnet GdRh2Si2

    PubMed Central

    Güttler, M.; Generalov, A.; Otrokov, M. M.; Kummer, K.; Kliemt, K.; Fedorov, A.; Chikina, A.; Danzenbächer, S.; Schulz, S.; Chulkov, E. V.; Koroteev, Yu. M.; Caroca-Canales, N.; Shi, M.; Radovic, M.; Geibel, C.; Laubschat, C.; Dudin, P.; Kim, T. K.; Hoesch, M.; Krellner, C.; Vyalikh, D. V.

    2016-01-01

    Spin-polarized two-dimensional electron states (2DESs) at surfaces and interfaces of magnetically active materials attract immense interest because of the idea of exploiting fermion spins rather than charge in next generation electronics. Applying angle-resolved photoelectron spectroscopy, we show that the silicon surface of GdRh2Si2 bears two distinct 2DESs, one being a Shockley surface state, and the other a Dirac surface resonance. Both are subject to strong exchange interaction with the ordered 4f-moments lying underneath the Si-Rh-Si trilayer. The spin degeneracy of the Shockley state breaks down below ~90 K, and the splitting of the resulting subbands saturates upon cooling at values as high as ~185 meV. The spin splitting of the Dirac state becomes clearly visible around ~60 K, reaching a maximum of ~70 meV. An abrupt increase of surface magnetization at around the same temperature suggests that the Dirac state contributes significantly to the magnetic properties at the Si surface. We also show the possibility to tune the properties of 2DESs by depositing alkali metal atoms. The unique temperature-dependent ferromagnetic properties of the Si-terminated surface in GdRh2Si2 could be exploited when combined with functional adlayers deposited on top for which novel phenomena related to magnetism can be anticipated. PMID:27052006

  9. Layer-by-layer deposition of vesicles mediated by supramolecular interactions.

    PubMed

    Roling, Oliver; Wendeln, Christian; Kauscher, Ulrike; Seelheim, Patrick; Galla, Hans-Joachim; Ravoo, Bart Jan

    2013-08-13

    Vesicles are dynamic supramolecular structures with a bilayer membrane consisting of lipids or synthetic amphiphiles enclosing an aqueous compartment. Lipid vesicles have often been considered as mimics for biological cells. In this paper, we present a novel strategy for the preparation of three-dimensional multilayered structures in which vesicles containing amphiphilic β-cyclodextrin are interconnected by proteins using cyclodextrin guests as bifunctional linker molecules. We compared two pairs of adhesion molecules for the immobilization of vesicles: mannose-concanavalin A and biotin-streptavidin. Microcontact printing and thiol-ene click chemistry were used to prepare suitable substrates for the vesicles. Successful immobilization of intact vesicles through the mannose-concanavalin A and biotin-streptavidin motifs was verified by fluorescence microscopy imaging and dynamic light scattering, while the vesicle adlayer was characterized by quartz crystal microbalance with dissipation monitoring. In the case of the biotin-streptavidin motif, up to six layers of intact vesicles could be immobilized in a layer-by-layer fashion using supramolecular interactions. The construction of vesicle multilayers guided by noncovalent vesicle-vesicle junctions can be taken as a minimal model for artificial biological tissue. PMID:23898918

  10. Adsorption of halide anions at the Pt(111)-solution interfacestudied by in situ surface x-ray scattering

    NASA Astrophysics Data System (ADS)

    Lucas, C. A.; Marković, N. M.; Ross, P. N.

    1997-03-01

    In this paper we present x-ray scattering results of iodide, bromide, and chloride adsorption onto the Pt(111) surface in solution. Iodide forms two commensurate adlayer structures, a (7×7)R19.1° phase and a hexagonal (3×3) phase, which coexist on the Pt surface. Formation of the (3×3) phase appears to be kinetically limited, whereas the 7 phase shows a hysteretic effect as a function of the electrode potential, associated with an order-disorder transition. Bromide forms a series of high-order commensurate structures on Pt(111) that are poorly ordered unless the size of the unit cell is small. No ordered structures for chloride adsorption are observed and specular x-ray reflectivity results suggest that the chloride coverage at low potential is too small to form a close-packed monolayer on the surface. The differences between the structures formed by the adsorbed anions, and the differences between results for Pt(111) and Au(111), are discussed in terms of the strength of the metal-halide interaction.

  11. Restructuring of an Ir(210) electrode surface by potential cycling

    PubMed Central

    Soliman, Khaled A; Kolb, Dieter M; Jacob, Timo

    2014-01-01

    Summary This study addresses the electrochemical surface faceting and restructuring of Ir(210) single crystal electrodes. Cyclic voltammetry measurements and in situ scanning tunnelling microscopy are used to probe structural changes and variations in the electrochemical behaviour after potential cycling of Ir(210) in 0.1 M H2SO4. Faceted structures are obtained electrochemically as a function of time by cycling at a scanrate of 1 V·s−1 between −0.28 and 0.70 V vs SCE, i.e., between the onset of hydrogen evolution and the surface oxidation regime. The electrochemical behaviour in sulfuric acid solution is compared with that of thermally faceted Ir(210), which shows a sharp characteristic voltammetric peak for (311) facets. Structures similar to thermally-induced faceted Ir(210) are obtained electrochemically, which typically correspond to polyoriented facets at nano-pyramids. These structures grow anisotropically in a preferred direction and reach a height of about 5 nm after 4 h of cycling. The structural changes are reflected in variations of the electrocatalytic activity towards carbon monoxide adlayer oxidation. PMID:25247118

  12. A high efficiency label-free photonic biosensor based on vertically stacked ring resonators

    NASA Astrophysics Data System (ADS)

    Campanella, C. E.; Campanella, C. M.; De Leonardis, F.; Passaro, V. M. N.

    2014-09-01

    In this paper we propose an optical biosensor based on two vertically stacked Silicon on Insulator (SOI) micro-ring resonators interacting with a microfluidic ring channel. This device behaves as a resonant optical coupler and it is very sensitive to the variation of the coupling coefficient between the two vertically stacked ring resonators. A ring microfluidic channel is proposed in the coupling region between the two vertically stacked ring resonators. The inner walls of the channel are funzionalized in order to the trap a specific biological species. Assuming a biotin-streptavidin system, the straptividin trapping gives rise to a change of the biological thickness of about 3 nm. This thickness increase of the deposited layer leads to a consequent change in the coupling strength between the two rings. These theoretical predictions have been validated by using both 3D Finite-Difference Time-Domain (FDTD) and 3D full-vectorial Finite Element Method (FEM) approaches. Moreover, by appropriately choosing the design parameters of the micro-resonant structure, we evaluate a sensitivity of the spectral response to the streptavidin adlayer variation of about 20% nm-1 for TE polarization and 34% nm-1 for TM polarization, which represents an important achievement to obtain selective SOI bio-sensors with ultra-high resolution.

  13. Residual thermal desorption studies of Ga adatoms on trenched Si(5 5 12) surface

    NASA Astrophysics Data System (ADS)

    Kumar, Praveen; Kumar, Mahesh; Shivaprasad, S. M.

    2013-10-01

    We present here the thermal stability studies of the room temperature adsorbed Ga/Si(5 5 12) interfaces in the monolayer coverage regime, using AES and LEED as in-situ UHV characterization probes. Ga grows in Stranski-Krastanov growth mode at RT on the 2 × 1 reconstructed Si(5 5 12) surface where islands form on top of 2 ML of flat pseudomorphic Ga, yielding a (1 × 1) LEED pattern for coverages of 1.2 ML and above. When this RT adsorbed Ga/Si(5 5 12) interface is annealed at different temperatures, initially the strained Ga adlayers relax by agglomerating into 3D islands on top of a single Ga monolayer with an activation energy of 0.19 eV in the temperature range of 200-300 °C. The remnant Ga monolayer with a sharp (1 × 1) LEED pattern desorbs at temperature >400 °C, yielding the (1 1 2)-6 × 1 and 2 × (3 3 7) sub-monolayer superstructural. Finally at 720 °C Ga completely desorbs from the surface and leaves the clean 2 × 1 reconstructed Si(5 5 12) surface. The studies demonstrate the richness of the atomically trenched high index Si(5 5 12) surface, in obtaining several anisotropic features that can be used as templates to grow self-assembled nanostructures.

  14. A photoemission study of Pd ultrathin films on Pt(111)

    SciTech Connect

    Mun, Bongjin Simon; Lee, Choongman; Stamenkovic, Vojislav; Markovic, Nenad M.; Ross Jr., Philip N.

    2005-05-11

    The origin of surface core-level shift (SCLS) of Pd thin films on Pt(111) substrate is investigated. At sub-monolayer coverage of Pd thin films, the splitting of Pd 3d core level peaks indicate the contribution of both initial and final-state of photo-ionization processes while there is almost no change on valence band (VB) spectra. When the coverage of Pd reaches to single monolayer, the final-state relaxation effect on the Pd 3d vanishes and only the initial-state effect, a negative SCLS, is present. Also, the VB spectrum at Pd monolayer films shows a clear band narrowing, that is the origin of the negative SCLS at monolayer coverage. As the Pd coverage is increased to more than monolayer thickness, the Pd 3d peaks start to show the surface layer contribution from second and third layers, positive SCLS, and the VB spectrum shows even narrower band width, possibly due to the formation of surface states and strained effect of Pd adlayers on top of the first pseudomorphic layer.

  15. Structure of ultrathin Ag films on the Al(100) surface

    SciTech Connect

    Choi, D. S.; Kopczyk, M.; Kayani, A.; Smith, R. J.; Bozzolo, Guillermo

    2006-09-15

    The structure for submonolayer amounts of Ag deposited on the Al(100) surface at room temperature has been studied using low-energy electron diffraction (LEED) and low-energy ion-scattering spectroscopy (LEIS/ISS). The Ag coverage was determined using Rutherford backscattering spectroscopy. We conclude that the Ag atoms form two domains of a buckled, quasihexagonal coincident lattice structure on the Al(100) surface, having a repeat distance of 5 Al interatomic spacings in the [110] direction. The LEED pattern shows a double-domain (5x1) structure with additional intensity in those spots corresponding to a (111) close-packed hexagonal layer. The analysis of the ISS results suggests that the heights of the adsorbed Ag atoms above the Al surface are not all the same, leading to the proposed buckling model that is in agreement with recent scanning tunneling microscopy measurements. In addition, some Al atoms move from the substrate up into the Ag adlayer to form a surface alloy. Model calculations using the quantum approximate Bozzolo-Ferrante-Smith (BFS) method indicate that the hexagonal layer is energetically preferred as a result of increased nearest-neighbor coordination within the Ag layer.

  16. Anisotropic mechanical amorphization drives wear in diamond

    NASA Astrophysics Data System (ADS)

    Pastewka, Lars; Moser, Stefan; Gumbsch, Peter; Moseler, Michael

    2011-01-01

    Diamond is the hardest material on Earth. Nevertheless, polishing diamond is possible with a process that has remained unaltered for centuries and is still used for jewellery and coatings: the diamond is pressed against a rotating disc with embedded diamond grit. When polishing polycrystalline diamond, surface topographies become non-uniform because wear rates depend on crystal orientations. This anisotropy is not fully understood and impedes diamond’s widespread use in applications that require planar polycrystalline films, ranging from cutting tools to confinement fusion. Here, we use molecular dynamics to show that polished diamond undergoes an sp3-sp2 order-disorder transition resulting in an amorphous adlayer with a growth rate that strongly depends on surface orientation and sliding direction, in excellent correlation with experimental wear rates. This anisotropy originates in mechanically steered dissociation of individual crystal bonds. Similarly to other planarization processes, the diamond surface is chemically activated by mechanical means. Final removal of the amorphous interlayer proceeds either mechanically or through etching by ambient oxygen.

  17. Electrochemical infrared characterization of CO comains on ruthenium-decorated platinum nanoparticles.

    PubMed

    Park, Sungho; Wieckowski, Andrzej; Weaver, Michael J

    2003-02-26

    Spectra obtained by electrochemical infrared reflection absorption spectroscopy (EC-IRAS) for carbon monoxide (CO) adlayers formed by partial CO dosing on various ruthenium-decorated platinum nanoparticle films are reported. The need to achieve a well distributed rather than aggregated metal nanoparticle array is demonstrated, given that such nanoparticle aggregates induce complex dielectric behavior. The strategy here is to use an "organic glue matrix" (short chain SAMs) between the nanoparticles and the gold substrates. The observed promotion in CO electrooxidation by the existence of a Ru island on Pt nanoparticles, of interest to fuel-cell catalysis, showed a strong relationship with Ru surface concentrations, consistent with previous studies on single crystal or polycrystalline bimetallic surfaces. Two distinctive CO infrared bands, one for the Pt-CO and one for Ru-CO domain were found after the dipole coupling of CO within the two CO domains was minimized. Interestingly, those two CO bands showed independent electrooxidation behavior with electrode potential changes. Also, it is shown that the electrooxidation of CO on large Ru islands is less facile than on small Ru islands. In addition, the activity of commercial Pt/Ru alloy nanoparticles to CO stripping was tested and IRAS spectra were reported as a comparison to our Ru-decorated Pt nanoparticles. PMID:12590558

  18. All-semiconductor plasmonic gratings for biosensing applications in the mid-infrared spectral range.

    PubMed

    Barho, Franziska B; Gonzalez-Posada, Fernando; Milla-Rodrigo, Maria-José; Bomers, Mario; Cerutti, Laurent; Taliercio, Thierry

    2016-07-11

    We propose 1D periodic, highly doped InAsSb gratings on GaSb substrates as biosensing platforms applicable for surface plasmon resonance and surface enhanced infrared absorption spectroscopies. Based on finite-difference time-domain simulations, the electric field enhancement and the sensitivity on refractive index variations are investigated for different grating geometries. The proposed, optimized system achieves sensitivities of 900 nm RIU-1. A clear red shift of the plasmon resonance as well as the enhancement of an absorption line are presented for 2 nm thin adlayers in simulations. We experimentally confirm the high sensitivity of the InAsSb grating by measurements of the wavelength shift induced by a 200 nm thin polymethylmethacrylate layer and demonstrate an enhancement of vibrational signals. A comparison to a gold grating with equivalent optical properties in the mid-infrared is performed. Our simulations and experimental results underline the interest in the alternative plasmonic material InAsSb for highly sensitive biosensors for the mid-infrared spectral range. PMID:27410884

  19. Importance of the Anchor Group Position (Para versus Meta) in Tetraphenylmethane Tripods: Synthesis and Self-Assembly Features.

    PubMed

    Lindner, Marcin; Valášek, Michal; Homberg, Jan; Edelmann, Kevin; Gerhard, Lukas; Wulfhekel, Wulf; Fuhr, Olaf; Wächter, Tobias; Zharnikov, Michael; Kolivoška, Viliam; Pospíšil, Lubomír; Mészáros, Gábor; Hromadová, Magdaléna; Mayor, Marcel

    2016-09-01

    The efficient synthesis of tripodal platforms based on tetraphenylmethane with three acetyl-protected thiol groups in either meta or para positions relative to the central sp(3) carbon for deposition on Au (111) surfaces is reported. These platforms are intended to provide a vertical arrangement of the substituent in position 4 of the perpendicular phenyl ring and an electronic coupling to the gold substrate. The self-assembly features of both derivatives are analyzed on Au (111) surfaces by low-temperature ultra-high-vacuum STM, high-resolution X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and reductive voltammetric desorption studies. These experiments indicated that the meta derivative forms a well-ordered monolayer, with most of the anchoring groups bound to the surface, whereas the para derivative forms a multilayer film with physically adsorbed adlayers on the chemisorbed para monolayer. Single-molecule conductance values for both tripodal platforms are obtained through an STM break junction experiment. PMID:27505302

  20. Electrochemical and scanning probe microscopic characterization of spontaneously adsorbed organothiolate monolayers at gold

    SciTech Connect

    Wong, Sze-Shun Season

    1999-12-10

    This dissertation presented several results which add to the general knowledge base regarding organothiolates monolayer spontaneously adsorbed at gold films. Common to the body of this work is the use of voltammetric reductive resorption and variants of scanning probe microscopy to gain insight into the nature of the monolayer formation process as well as the resulting interface. The most significant result from this work is the success of using friction force microscopy to discriminate the end group orientation of monolayer chemisorbed at smooth gold surfaces with micrometer resolution (Chapter 4). The ability to detect the differences in the orientational disposition is demonstrated by the use PDMS polymer stamp to microcontact print an adlayer of n-alkanethiolate of length n in a predefine pattern onto a gold surface, followed by the solution deposition of a n-alkanethiol of n {+-} 1 to fill in the areas on the gold surface intentionally not coated by the stamping process. These two-component monolayers can be discriminated by using friction force microscopy which detects differences in friction contributed by the differences in the orientation of the terminal groups at surfaces. This success has recently led to the detection of the orientation differences at nanometer scale. Although the substrates examined in this work consisted entirely of smooth gold films, the same test can be performed on other smooth substrates and monolayer materials.

  1. Antifouling Polymer Brushes Displaying Antithrombogenic Surface Properties.

    PubMed

    de Los Santos Pereira, Andres; Sheikh, Sonia; Blaszykowski, Christophe; Pop-Georgievski, Ognen; Fedorov, Kiril; Thompson, Michael; Rodriguez-Emmenegger, Cesar

    2016-03-14

    The contact of blood with artificial materials generally leads to immediate protein adsorption (fouling), which mediates subsequent biological processes such as platelet adhesion and activation leading to thrombosis. Recent progress in the preparation of surfaces able to prevent protein fouling offers a potential avenue to mitigate this undesirable effect. In the present contribution, we have prepared several types of state-of-the-art antifouling polymer brushes on polycarbonate plastic substrate, and investigated their ability to prevent platelet adhesion and thrombus formation under dynamic flow conditions using human blood. Moreover, we compared the ability of such brushes-grafted on quartz via an adlayer analogous to that used on polycarbonate-to prevent protein adsorption from human blood plasma, assessed for the first time by means of an ultrahigh frequency acoustic wave sensor. Results show that the prevention of such a phenomenon constitutes one promising route toward enhanced resistance to thrombus formation, and suggest that antifouling polymer brushes could be of service in biomedical applications requiring extensive blood-material surface contact. PMID:26882214

  2. Theory, modeling and instrumentation for materials by design: Proceedings of workshop

    SciTech Connect

    Allen, R.E.; Cocke, D.L.; Eberhardt, J.J.; Wilson, A.

    1984-01-01

    The following topics are contained in this volume: how can materials theory benefit from supercomputers and vice-versa; the materials of xerography; relationship between ab initio and semiempirical theories of electronic structure and renormalization group and the statistical mechanics of polymer systems; ab initio calculations of materials properties; metals in intimate contact; lateral interaction in adsorption: revelations from phase transitions; quantum model of thermal desorption and laser stimulated desorption; extended fine structure in appearance potential spectroscopy as a probe of solid surfaces; structural aspects of band offsets at heterojunction interfaces; multiconfigurational Green's function approach to quantum chemistry; wavefunctions and charge densities for defects in solids: a success for semiempirical theory; empirical methods for predicting the phase diagrams of intermetallic alloys; theoretical considerations regarding impurities in silicon and the chemisorption of simple molecules on Ni; improved Kohn-Sham exchange potential; structural stability calculations for films and crystals; semiempirical molecular orbital modeling of catalytic reactions including promoter effects; theoretical studies of chemical reactions: hydrolysis of formaldehyde; electronic structure calculations for low coverage adlayers; present status of the many-body problem; atomic scattering as a probe of physical adsorption; and, discussion of theoretical techniques in quantum chemistry and solid state physics.

  3. Robust and tunable itinerant ferromagnetism at the silicon surface of the antiferromagnet GdRh2Si2.

    PubMed

    Güttler, M; Generalov, A; Otrokov, M M; Kummer, K; Kliemt, K; Fedorov, A; Chikina, A; Danzenbächer, S; Schulz, S; Chulkov, E V; Koroteev, Yu M; Caroca-Canales, N; Shi, M; Radovic, M; Geibel, C; Laubschat, C; Dudin, P; Kim, T K; Hoesch, M; Krellner, C; Vyalikh, D V

    2016-01-01

    Spin-polarized two-dimensional electron states (2DESs) at surfaces and interfaces of magnetically active materials attract immense interest because of the idea of exploiting fermion spins rather than charge in next generation electronics. Applying angle-resolved photoelectron spectroscopy, we show that the silicon surface of GdRh2Si2 bears two distinct 2DESs, one being a Shockley surface state, and the other a Dirac surface resonance. Both are subject to strong exchange interaction with the ordered 4f-moments lying underneath the Si-Rh-Si trilayer. The spin degeneracy of the Shockley state breaks down below ~90 K, and the splitting of the resulting subbands saturates upon cooling at values as high as ~185 meV. The spin splitting of the Dirac state becomes clearly visible around ~60 K, reaching a maximum of ~70 meV. An abrupt increase of surface magnetization at around the same temperature suggests that the Dirac state contributes significantly to the magnetic properties at the Si surface. We also show the possibility to tune the properties of 2DESs by depositing alkali metal atoms. The unique temperature-dependent ferromagnetic properties of the Si-terminated surface in GdRh2Si2 could be exploited when combined with functional adlayers deposited on top for which novel phenomena related to magnetism can be anticipated. PMID:27052006

  4. Investigation of thin polymer layers for biosensor applications

    NASA Astrophysics Data System (ADS)

    Saftics, András; Agócs, Emil; Fodor, Bálint; Patkó, Dániel; Petrik, Péter; Kolari, Kai; Aalto, Timo; Fürjes, Péter; Horvath, Robert; Kurunczi, Sándor

    2013-09-01

    Novel biosensors made of polymers may offer advantages over conventional technology such as possibility of mass production and tunability of the material properties. With the ongoing work on the polymer photonic chip fabrication in our project, simple model samples were tested parallel for future immobilization and accessing conditions for applications in typical aqueous buffers. The model samples consist of a thin, high refractive index polyimide film on top of TEOS on Si wafer. These model samples were measured by in situ spectroscopic ellipsometry using different aqueous buffers. The experiments revealed a high drift in aqueous solutions; the drift in the ellipsometric parameters (delta, psi) can be evaluated and presented as changes in thickness and refractive index of the polyimide layer. The first molecular layer of immobilization is based on polyethyleneimine (PEI). The signal for the PEI adsorption was detected on a stable baseline, only after a long conditioning. The stability of polyimide films in aqueous buffer solutions should be improved toward the real biosensor application. Preliminary results are shown on the possibilities to protect the polyimide. Optical Waveguide Lightmode Spectroscopy (OWLS) has been used to demonstrate the shielding effect of the thin TiO2 adlayer in biosensor applications.

  5. Charge transport in C60-based dumbbell-type molecules: mechanically induced switching between two distinct conductance states.

    PubMed

    Moreno-García, Pavel; La Rosa, Andrea; Kolivoška, Viliam; Bermejo, Daniel; Hong, Wenjing; Yoshida, Koji; Baghernejad, Masoud; Filippone, Salvatore; Broekmann, Peter; Wandlowski, Thomas; Martín, Nazario

    2015-02-18

    Single molecule charge transport characteristics of buckminsterfullerene-capped symmetric fluorene-based dumbbell-type compound 1 were investigated by scanning tunneling microscopy break junction (STM-BJ), current sensing atomic force microscopy break junction (CS-AFM-BJ), and mechanically controlled break junction (MCBJ) techniques, under ambient conditions. We also show that compound 1 is able to form highly organized defect-free surface adlayers, allowing the molecules on the surface to be addressed specifically. Two distinct single molecule conductance states (called high G(H)(1) and low G(L)(1)) were observed, depending on the pressure exerted by the probe on the junction, thus allowing molecule 1 to function as a mechanically driven molecular switch. These two distinct conductance states were attributed to the electron tunneling through the buckminsterfullerene anchoring group and fully extended molecule 1, respectively. The assignment of conductance features to these configurations was further confirmed by control experiments with asymmetrically designed buckminsterfullerene derivative 2 as well as pristine buckminsterfullerene 3, both lacking the G(L) feature. PMID:25651069

  6. Shape-selected nanocrystals for in situ spectro-electrochemistry studies on structurally well defined surfaces under controlled electrolyte transport: A combined in situ ATR-FTIR/online DEMS investigation of CO electrooxidation on Pt

    PubMed Central

    Jusys, Zenonas; Behm, R Jürgen

    2014-01-01

    Summary The suitability and potential of shape selected nanocrystals for in situ spectro-electrochemical and in particular spectro-electrocatalytic studies on structurally well defined electrodes under enforced and controlled electrolyte mass transport will be demonstrated, using Pt nanocrystals prepared by colloidal synthesis procedures and a flow cell set-up allowing simultaneous measurements of the Faradaic current, FTIR spectroscopy of adsorbed reaction intermediates and side products in an attenuated total reflection configuration (ATR-FTIRS) and differential electrochemical mass spectrometry (DEMS) measurements of volatile reaction products. Batches of shape-selected Pt nanocrystals with different shapes and hence different surface structures were prepared and structurally characterized by transmission electron microscopy (TEM) and electrochemical methods. The potential for in situ spectro-electrocatalytic studies is illustrated for COad oxidation on Pt nanocrystal surfaces, where we could separate contributions from two processes occurring simultaneously, oxidative COad removal and re-adsorption of (bi)sulfate anions, and reveal a distinct structure sensitivity in these processes and also in the structural implications of (bi)sulfate re-adsorption on the CO adlayer. PMID:24991511

  7. Effect of humic acid (HA) on sulfonamide sorption by biochars.

    PubMed

    Lian, Fei; Sun, Binbin; Chen, Xi; Zhu, Lingyan; Liu, Zhongqi; Xing, Baoshan

    2015-09-01

    Effect of quantity and fractionation of loaded humic acid (HA) on biochar sorption for sulfonamides was investigated. The HA was applied in two different modes, i.e. pre-coating and co-introduction with sorbate. In pre-coating mode, the polar fractions of HA tended to interact with low-temperature biochars via H-bonding, while the hydrophobic fractions were likely to be adsorbed by high-temperature biochars through hydrophobic and π-π interactions, leading to different composition and structure of the HA adlayers. The influences of HA fractionation on biochar sorption for sulfonamides varied significantly, depending on the nature of interaction between HA fraction and sorbate. Meanwhile, co-introduction of HA with sulfonamides revealed that the effect of HA on sulfonamide sorption was also dependent on HA concentration. These findings suggest that the amount and fractionation of adsorbed HA are tailored by the surface properties of underlying biochars, which differently affect the sorption for organic contaminants. PMID:26057361

  8. Potential-step chronocoulometric investigation of the surface coverages of coadsorbed Bi and hydroxide on Au(111) electrodes

    SciTech Connect

    Niece, B.K.; Gewirth, A.A.

    1996-10-02

    Bi underpotentially deposited on Au(111) has been studied using potential-step chronocoulometry to determine the actual surface coverage of Bi. In the potential region where this system exhibits catalytic activity for the electroreduction of peroxide to water, the observed coverage is 0.25 monolayer (ML), which agrees well with the coverage of the reported (2 x 2) Bi overlayer observed by scanning probe microscopy in this region. At more cathodic potentials, the coverage increases to 0.67 ML. This coverage agrees with the expected based on the (p x {radical}3) structure proposed from scanning tunneling microscopy, atomic force microscopy, and SXS measurements in this region. The electrosorption valency calculated based on these coverages is 3, indicating that the Bi is fully discharged on the surface. Potential-step chronocoulometry has been used at various pH values to determine the surface coverage of hydroxide anion in the presence of underpotentially deposited (upd) Bi. The coverage is negligible in the absence of upd Bi and at potentials where the Bi adlayer condenses. It rises to a peak of 0.17 ML in the region where the coverage is 0.25 ML, indicating that OH{sup -} is coadsorbed with the Bi. 30 refs., 10 figs.

  9. Ultra-high frequency piezoelectric aptasensor for the label-free detection of cocaine.

    PubMed

    Neves, Miguel A D; Blaszykowski, Christophe; Bokhari, Sumra; Thompson, Michael

    2015-10-15

    This paper describes a label-free and real-time piezoelectric aptasensor for the detection of cocaine. The acoustic wave sensing platform is a quartz substrate functionalized with an adlayer of S-(11-trichlorosilyl-undecanyl)-benzenethiosulfonate (BTS) cross-linker onto which the anti-cocaine MN4 DNA aptamer is next immobilized. Preparation of the sensor surface was monitored using X-ray photoelectron spectroscopy (XPS), while the binding of cocaine to surface-attached MN4 was evaluated using the electromagnetic piezoelectric acoustic sensor (EMPAS). The MN4 aptamer, unlike other cocaine aptamer variants, has its secondary structure preformed in the unbound state with only tertiary structure changes occurring during target binding. It is postulated that the highly sensitive EMPAS detected the binding of cocaine through target mass loading coupled to aptamer tertiary structure folding. The sensor achieved an apparent Kd of 45 ± 12 µM, and a limit of detection of 0.9 µM. Repeated regenerability of the sensor platform was also demonstrated. This work constitutes the first application of EMPAS technology in the field of aptasensors. Furthermore, it is so far one of the very few examples of a bulk acoustic wave aptasensor that is able to directly detect the binding interaction between an aptamer and a small molecule in a facile one-step protocol without the use of a complex assay or signal amplification step. PMID:26022784

  10. The effect of Ru and Sn additions to Pt on the electrocatalysis of methanol oxidation: An in situ XAS investigation

    SciTech Connect

    Mukerjee, S.; McBreen, J.

    1997-07-01

    Elements such as Ru and Sn used as ad-atoms or as alloying elements are known to enhance methanol oxidation reaction (MOR). Ru, both as alloying element as well as upd deposited on Pt/C is widely acknowledged for enhancing MOR. Sn on the other hand is more controversial, with evidence indicating enhancements for MOR when present as upd layer and marginally effective when present as an alloying element. In situ XAS is used to investigate some of these inconsistencies in the electrocatalysis of MOR. Results indicate that alloying Sn with Pt (Pt{sub 3}Sn primary phase) causes partial filling of the Pt 5 d-band vacancies and increase in the Pt-Pt bond distances which is directly opposite to a similar situation with Ru. Upd Sn however does not perturb Pt structurally or electronically. Ru and Sn (both as alloying element and as upd ad-layer) are associated with oxygenated species, the nature and strength of the Ru. and Sn - oxygen interactions are potential dependent. Hence alloying with Sn renders Pt surface unfavorable for methanol adsorption in contrast to alloying with Ru. Both Ru and Sn however promote MOR via their ability to nucleate oxygenated species on their surface at lower potentials as compared to pure Pt.

  11. Viruses at Solid-Water Interfaces: A Systematic Assessment of Interactions Driving Adsorption.

    PubMed

    Armanious, Antonius; Aeppli, Meret; Jacak, Ronald; Refardt, Dominik; Sigstam, Thérèse; Kohn, Tamar; Sander, Michael

    2016-01-19

    Adsorption to solid-water interfaces is a major process governing the fate of waterborne viruses in natural and engineered systems. The relative contributions of different interaction forces to adsorption and their dependence on the physicochemical properties of the viruses remain, however, only poorly understood. Herein, we systematically studied the adsorption of four bacteriophages (MS2, fr, GA, and Qβ) to five model surfaces with varying surface chemistries and to three dissolved organic matter adlayers, as a function of solution pH and ionic strength, using quartz crystal microbalance with dissipation monitoring. The viruses were selected to have similar sizes and shapes but different surface charges, polarities, and topographies, as identified by modeling the distributions of amino acids in the virus capsids. Virus-sorbent interactions were governed by long-ranged electrostatics and favorable contributions from the hydrophobic effect, and shorter-ranged van der Waals interactions were of secondary importance. Steric effects depended on the topographic irregularities on both the virus and sorbent surfaces. Differences in the adsorption characteristics of the tested viruses were successfully linked to differences in their capsid surface properties. Besides identifying the major interaction forces, this work highlights the potential of computable virus surface charge and polarity descriptors to predict virus adsorption to solid-water interfaces. PMID:26636722

  12. Temperature dependent optical properties of pentacene films on zinc oxide

    SciTech Connect

    Helzel, J.; Jankowski, S.; El Helou, M.; Witte, G.; Heimbrodt, W.

    2011-11-21

    The optical transitions of pentacene films deposited on ZnO have been studied by absorption spectroscopy as a function of temperature in the range of room temperature down to 10 K. The pentacene films were prepared with thicknesses of 10 nm, 20 nm, and 100 nm on the ZnO-O(000-1) surface by molecular beam deposition. A unique temperature dependence has been observed for the two Davydov components of the excitons for different film thicknesses. At room temperature, the energetic positions of the respective absorption bands are the same for all films, whereas the positions differ more than 20 meV at 10 K caused by the very different expansion coefficients of pentacene and ZnO. Although the pentacene is just bonded via van der Waals interaction to the ZnO substrate, the very first pentacene monolayer (adlayer) is forced to keep the initial position on the ZnO surface and suffering, therefore, a substantial tensile strain. For all the subsequent pentacene monolayers, the strain is reduced step by step resulting electronically in a strong potential gradient at the interface.

  13. Characterization of Surface Chemical States of a Thick Insulator: Chemical State Imaging on MgO Surface

    NASA Astrophysics Data System (ADS)

    Yi, Yeonjin; Cho, Sangwan; Noh, Myungkeun; Whang, Chung-Nam; Jeong, Kwangho; Shin, Hyun-Joon

    2005-02-01

    We report a surface characterization tool that can be effectively used to investigate the chemical state and subtle radiation damage on a thick insulator surface. It has been used to examine the MgO surface of a plasma display panel (PDP) consisting of a stack of insulator layers of approximately 51 μm thickness on a 2-mm-thick glass plate. The scanning photoelectron microscopy (SPEM) image of the insulating MgO surface was obtained by using the difference in Au 4f peak shift due to the surface charging at each pixel, where a Au adlayer of approximately 15 {\\AA} thickness was formed on the surface to overcome the serious charging shift of the peak position and the spectral deterioration in the photoelectron spectra. The observed contrast in the SPEM image reveals the chemical modification of the underlying MgO surface induced by the plasma discharge damage. The chemical state analysis of the MgO surface was carried out by comparing the Mg 2p, C 1s and O 1s photoemission spectra collected at each pixel of the SPEM image. We assigned four suboxide phases, MgO, MgCO3, Mg(OH)2 and Mg1+, on the initial MgO surface, where the Mg(OH)2 and Mg1+ phases vanished rapidly as the discharge-induced surface damage began.

  14. Interaction of a Self-Assembled Ionic Liquid Layer with Graphite(0001): A Combined Experimental and Theoretical Study.

    PubMed

    Buchner, Florian; Forster-Tonigold, Katrin; Bozorgchenani, Maral; Gross, Axel; Behm, R Jürgen

    2016-01-21

    The interaction between (sub)monolayers of the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide [BMP](+)[TFSA](-) and graphite(0001), which serves as a model for the anode|electolyte interface in Li-ion batteries, was investigated under ultrahigh vacuum conditions in a combined experimental and theoretical approach. High-resolution scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and dispersion-corrected density functional theory (DFT-D) calculations were employed. After vapor deposition at 300 K, XPS indicates molecular adsorbates with a 1:1 ratio of cations/anions. Cool down to ∼100 K leads to the formation of an ordered (2D) crystalline phase, which coexists with a mobile (2D) liquid. DFT-D calculations reveal that adsorbed [BMP](+) and [TFSA](-) species are arranged alternately in a row-like adsorption structure (cation-anion-cation-anion) and that adsorption is dominated by dispersion interactions between adlayer and substrate, on the one hand, and electrostatic interactions between the ions in a row, on the other hand. Simulated STM images of that structure closely resemble the experimental molecular resolved STM images and show that the resolved features mostly stem from the cations. PMID:26713562

  15. Tailored stimuli-responsive interaction between particles adjusted by straightforward adsorption of mixed layers of Poly(lysine)-g-PEG and Poly(lysine)-g-PNIPAM on anionic beads.

    PubMed

    Malinge, Jeremy; Mousseau, Fanny; Zanchi, Drazen; Brun, Geoffrey; Tribet, Christophe; Marie, Emmanuelle

    2016-01-01

    We report a simple and versatile method to functionalize anionic colloid particles and control particle solubility. Poly(lysine)-based copolymers (PLL) grafted with polyethylene oxide (PLL-g-PEG) or poly(N-isopropylacrylamide) (PLL-g-PNIPAM) spontaneously adsorb on bare beads dispersed in aqueous solutions of the copolymers. The final composition of the mixed ad-layers formed (i.e. PEG/PNIPAM ratio) was adjusted by the polymer concentrations in solutions. While the (PLL-g-PEG)-coated particles were stable in a wide range of temperature, the presence of PLL-g-PNIPAM in the outer layer provided a reversible temperature-triggered aggregation at 32±1 °C. In the range of PNIPAM fraction going from 100% (beads fully covered by PLL-g-PNIPAM) down to a threshold 20% weight ratio (with 80% PLL-g-PEG), the particles aggregated rapidly to form micrometer size clusters. Below 20% weight fraction of PLL-g-PNIPAM, the kinetic was drastically lowered. Using PLL derivatives provides a straightforward route allowing to control the fraction of a functional chain (here PNIPAM) deposited on PEGylated particles, and in turn to adjust surface interaction and here the rate of particle-particle aggregation as a function of the density of functional chains. This approach can be generalized to many anionic surfaces onto which PLL is known to adhere tightly, such as glass or silica. PMID:26397909

  16. Role of water in the chlorine evolution reaction at RuO(2)-based electrodes--understanding electrocatalysis as a resonance phenomenon.

    PubMed

    Zeradjanin, Aleksandar R; Menzel, Nadine; Strasser, Peter; Schuhmann, Wolfgang

    2012-10-01

    The reaction path of the Cl(2) evolution reaction (CER) was investigated by combining electrochemical and spectroscopic methods. It is shown that oxidation and reconstruction of the catalyst surface during CER is a consequence of the interaction between RuO(2) and water. The state of the RuO(2) surface during the electrochemical reaction was analyzed in situ by using Raman spectroscopy to monitor vibrations of the crystal lattice of RuO(2) and changes in the surface concentration of the adsorbed species as a function of the electrode potential. The role of the solvent was recognized as being crucial in the formation of an oxygen-containing hydrophilic layer, which is a key prerequisite for electrocatalytic Cl(2) formation. Water (more precisely the OH adlayer) is understood not just as a medium that allows adsorption of intermediates, but also as an integral part of the intermediate formed during the electrochemical reaction. New insights into the general understanding of electrocatalysis were obtained by utilizing the vibration frequencies of the crystal lattice as a dynamic catalytic descriptor instead of thermodynamic descriptors, such as the adsorption energy of intermediates. Interpretation of the derived "volcano" curve suggests that electrocatalysis is governed by a resonance phenomenon. PMID:22893626

  17. Fully relativistic surface green function and its application to surface spectroscopies

    SciTech Connect

    Tamura, E.

    1993-06-30

    A fully relativistic layer-KKR formalism was developed and implemented for calculating the single-particle Green function in atomic layers parallel to crystalline surfaces magnetic and non magnetic materials: The method was applied to the calculation surface spectroscopies, such as low energy electron diffraction (LEED), angle-resolve ultraviolet photo emission spectroscopy (UPS), and photoelectron scattering. Numeric tests were performed for non magnetic actinide surfaces and magnetic Fe surface Theoretical angle-resolved UPS spectra are presented for uranium monolayers on Pt(111) and for f.c.c. u(lll) surfaces. We find that u island formation can take place if a peak in the UPS spectra appears just before the Fermi energy immediately as u is deposited on P and we suggest an experimental procedure for testing this prediction. An intensity map photo excited electrons from the 2p{sub 3/2} core states of Fe(110) surface is also show Sizable magnetic anisotropy is found due to the interference between exchange and spin-orbit interaction, which is suitable for studying a possible surface-induced magnetism actinide adlayers.

  18. Local structural models of complex oxygen- and hydroxyl-rich GaP/InP(001) surfaces.

    PubMed

    Wood, Brandon C; Ogitsu, Tadashi; Schwegler, Eric

    2012-02-14

    We perform density-functional theory calculations on model surfaces to investigate the interplay between the morphology, electronic structure, and chemistry of oxygen- and hydroxyl-rich surfaces of InP(001) and GaP(001). Four dominant local oxygen topologies are identified based on the coordination environment: M-O-M and M-O-P bridges for the oxygen-decorated surface; and M-[OH]-M bridges and atop M-OH structures for the hydroxyl-decorated surface (M = In, Ga). Unique signatures in the electronic structure are linked to each of the bond topologies, defining a map to structural models that can be used to aid the interpretation of experimental probes of native oxide morphology. The M-O-M bridge can create a trap for hole carriers upon imposition of strain or chemical modification of the bonding environment of the M atoms, which may contribute to the observed photocorrosion of GaP/InP-based electrodes in photoelectrochemical cells. Our results suggest that a simplified model incorporating the dominant local bond topologies within an oxygen adlayer should reproduce the essential chemistry of complex oxygen-rich InP(001) or GaP(001) surfaces, representing a significant advantage from a modeling standpoint. PMID:22360213

  19. Supramolecular structures of halogenated oligothiophenes on the Si(111)-√3 ×√3-Ag surface

    NASA Astrophysics Data System (ADS)

    Liu, R.; Fu, C.; Perepichka, D. F.; Gallagher, M. C.

    2016-05-01

    We have studied the adsorption of brominated tetrathienoanthracene (TBTTA) molecules onto the Si(111)-√3 × √ 3-Ag surface at room temperature. The two-dimensional √ 3 silver adlayer acts to passivate the silicon surface and provides a high-mobility template for TBTTA adsorption. Scanning tunneling microscopy (STM) images reveal that at low coverage, the molecules readily migrate to step edges and defects in the √ 3 overlayer. With increasing coverage, the molecules eventually form compact supramolecular structures. In terms of the hexagonal √ 3 lattice vectors (a√ 3 and b√ 3), the oblique unit cell of these structures can be defined by lattice vectors am = 3a√ 3 + 2b√ 3, and bm = - a√ 3 + b√ 3. The structures are quite fragile and can decompose under repeated STM imaging. This is particularly true at higher bias and suggests an electric field-induced dissociation in these instances. With increasing molecular dose, the size and stability of the structures increases. At higher coverage, the spatial extent of the supramolecular structures is often limited by defects in the underlying √ 3 layer. Our results suggest that the √ 3-Ag surface provides a relatively inert substrate for the adsorption of TBTTA molecules, and that the supramolecular structures are held together by relatively weak intermolecular forces.

  20. Controlled n-Type Doping of Carbon Nanotube Transistors by an Organorhodium Dimer.

    PubMed

    Geier, Michael L; Moudgil, Karttikay; Barlow, Stephen; Marder, Seth R; Hersam, Mark C

    2016-07-13

    Single-walled carbon nanotube (SWCNT) transistors are among the most developed nanoelectronic devices for high-performance computing applications. While p-type SWCNT transistors are easily achieved through adventitious adsorption of atmospheric oxygen, n-type SWCNT transistors require extrinsic doping schemes. Existing n-type doping strategies for SWCNT transistors suffer from one or more issues including environmental instability, limited carrier concentration modulation, undesirable threshold voltage control, and/or poor morphology. In particular, commonly employed benzyl viologen n-type doping layers possess large thicknesses, which preclude top-gate transistor designs that underlie high-density integrated circuit layouts. To overcome these limitations, we report here the controlled n-type doping of SWCNT thin-film transistors with a solution-processed pentamethylrhodocene dimer. The charge transport properties of organorhodium-treated SWCNT thin films show consistent n-type behavior when characterized in both Hall effect and thin-film transistor geometries. Due to the molecular-scale thickness of the organorhodium adlayer, large-area arrays of top-gated, n-type SWCNT transistors are fabricated with high yield. This work will thus facilitate ongoing efforts to realize high-density SWCNT integrated circuits. PMID:27253896

  1. Adhesion properties of hydrogen on Sb(111) probed by helium atom scattering

    NASA Astrophysics Data System (ADS)

    Kraus, P.; Gösweiner, Ch.; Tamtögl, A.; Apolloner, F.; Ernst, W. E.

    2016-06-01

    We have carried out a series of helium atom scattering measurements in order to characterise the adsorption properties of hydrogen on antimony(111). Molecular hydrogen does not adsorb at temperatures above 110 K in contrast to pre-dissociated atomic hydrogen. Depending on the substrate temperature, two different adlayer phases of atomic hydrogen on Sb(111) occur. At low substrate temperatures (110 K), the deposited hydrogen layer does not show any ordering while we observe a perfectly ordered (1× 1) H/Sb(111) structure for deposition at room temperature. Furthermore, the amorphous hydrogen layer deposited at low temperature forms an ordered overlayer upon heating the crystal to room temperature. Hydrogen starts to desorb at Tm = 430 \\text{K} which corresponds to a desorption energy of Edes=(1.33+/-0.06) \\text{eV} . Using measurements of the helium reflectivity during hydrogen exposure at different surface temperatures, we conclude that the initial sticking coefficient of atomic hydrogen on Sb(111) decreases with increasing surface temperature. Furthermore, the scattering cross-section for the diffuse scattering of helium from hydrogen on Sb(111) is determined as Σ = (12 +/- 1) \\unicode{8491}2 .

  2. Adsorption of linear alkanes on Cu(111): Temperature and chain-length dependence of the softened vibrational mode

    NASA Astrophysics Data System (ADS)

    Fosser, Kari A.; Kang, Joo H.; Nuzzo, Ralph G.; Wöll, Christof

    2007-05-01

    The vibrational spectra of linear alkanes, with lengths ranging from n-propane to n-octane, were examined on a copper surface by reflection-absorption infrared spectroscopy. The appearance and frequency of the "soft mode," a feature routinely seen in studies of saturated hydrocarbons adsorbed on metals, were examined and compared between the different adsorbates. The frequency of the mode was found to be dependent on both the number of methylene units of each alkane as well as specific aspects of the order of the monolayer phase. Studies of monolayer coverages at different temperatures provide insights into the nature of the two-dimensional (2D) melting transitions of these adlayer structures, ones that can be inferred from observed shifts in the soft vibrational modes appearing in the C-H stretching region of the infrared spectrum. These studies support recently reported hypotheses as to the origins of such soft modes: the metal-hydrogen interactions that mediate them and the dynamics that underlay their pronounced temperature dependencies. The present data strongly support a model for the 2D to one-dimensional order-order phase transition arising via a continuous rather than discrete first-order process.

  3. Substrate responsive colloidal system based on luminescent Tb(III) doped silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Mustafina, Asiya R.; Bochkova, Olga D.; Fedorenko, Svetlana V.; Skripacheva, Viktoriya V.; Zakharova, Lucia Ya.; Kadirov, Marcil K.; Nizameyev, Irek R.; Konovalov, Alexander I.; Soloveva, Svetlana E.

    2010-09-01

    Positively charged luminescent silica nanoparticles loaded with Tb(III) complex were prepaired by reverse microemulsion procedure with further modification by gemini surfactant. The ξ-potential values and dynamic light scattering data indicate high positive charge and colloidal stability of the as prepaired nanoparticles. The high affinity of these nanoparticles to anions is verified by spectrophotometric measurements with dye molecules, namely phenol red. The insertion of phenol red anions into surfactant bilayer at silica/water interface results in the quenching effect on Tb(III)-centered luminescence of the nanoparticles. Thus "on-off" switching of Tb-centered luminescence indicates the formation of the positively charged bilayer at the silica/water interface. The binding of dodecylsulfate anions with cationic adlayer at the silica/water interface results in the recharging of silica nanoparticles. This recharging can be manifested through the "off-on" luminescent switching, resulted from the displacement of dye anions and reestablishment of Tb(III)-centered luminescence.

  4. Substrate responsive colloidal system based on luminescent Tb(III) doped silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Mustafina, Asiya R.; Bochkova, Olga D.; Fedorenko, Svetlana V.; Skripacheva, Viktoriya V.; Zakharova, Lucia Ya.; Kadirov, Marcil K.; Nizameyev, Irek R.; Konovalov, Alexander I.; Soloveva, Svetlana E.

    2011-02-01

    Positively charged luminescent silica nanoparticles loaded with Tb(III) complex were prepaired by reverse microemulsion procedure with further modification by gemini surfactant. The ξ-potential values and dynamic light scattering data indicate high positive charge and colloidal stability of the as prepaired nanoparticles. The high affinity of these nanoparticles to anions is verified by spectrophotometric measurements with dye molecules, namely phenol red. The insertion of phenol red anions into surfactant bilayer at silica/water interface results in the quenching effect on Tb(III)-centered luminescence of the nanoparticles. Thus "on-off" switching of Tb-centered luminescence indicates the formation of the positively charged bilayer at the silica/water interface. The binding of dodecylsulfate anions with cationic adlayer at the silica/water interface results in the recharging of silica nanoparticles. This recharging can be manifested through the "off-on" luminescent switching, resulted from the displacement of dye anions and reestablishment of Tb(III)-centered luminescence.

  5. Use of zirconium-phosphate-carbonate chemistry to immobilize polycyclic aromatic hydrocarbons on boron-doped diamond.

    PubMed

    Mazur, Maciej; Krysiński, Paweł; Blanchard, G J

    2005-09-13

    We report on the formation of monomolecular layers of perylene- and pyrene-alkanoic acids on boron-doped diamond (BDD) substrates. The carboxylic acid layers are bound by coordination to zirconium phosphate (ZP) functionalities on the BDD substrate surface. The resulting Zr-phosphate-carbonate (ZPC) linkages between the substrate and the adlayer are asymmetric, of the form -(OPO3(2-) Zr4+-O2C-R)+ X-. Pyrene and perylene are well-established optical probes of polarity and viscosity at interfaces. We have used electrochemical and steady-state fluorescence techniques to study the loading density and behavior of these monomolecular films, allowing comparison of BDD and indium-doped tin oxide (ITO) substrates. Electrochemical data suggest that the pyrene chromophores are positioned roughly at the same distance from the surface, regardless of the length of the anchoring alkanoic acid chain, a finding that can be explained by the pyrene lying on the substrate surface. Such a conformation is plausible given the surface coverage (5 x 10(-11) mol/cm2, ca. 0.1 monolayer) we measure for these systems. PMID:16142963

  6. Preparation and characterization of dense films of poly(amidoamine) dendrimers on indium tin oxide.

    PubMed

    Schlapak, Robert; Armitage, David; Saucedo-Zeni, Nadia; Latini, Gianluca; Gruber, Hermann J; Mesquida, Patrick; Samotskaya, Yulia; Hohage, Michael; Cacialli, Franco; Howorka, Stefan

    2007-08-14

    Indium tin oxide (ITO) substrates were modified with a layer of poly(amidoamine) (PAMAM) dendrimers to change their surface properties and, in particular, the substrates' work function. The functionalization procedure involved the electrostatic adsorption of positively charged PAMAM dendrimers of generation five onto negatively polarized ITO surfaces. Three different PAMAM dendrimers were used: PAMAM-NH2 and PAMAM-OH with terminal amine and hydroxyl groups, respectively, as well as Q-PAMAM-NH2, which had been prepared from PAMAM-NH2 by quaternization of the dendrimer's terminal and internal amine groups with methyl iodide. The resulting organic films were analyzed by contact angle goniometry, X-ray photoelectron spectroscopy, ellipsometry, and Kelvin probe force microscopy to confirm the presence of a dense layer. A Langmuir isotherm was derived from surface densities of fluorescence-labeled PAMAM-NH2 dendrimers from which we deduced an equilibrium binding constant, K(eq), of (1.3 +/- 0.3) x 10(5) M(-1). Kelvin probe measurements of the contact potential difference revealed a high reduction of the work function from 4.9 eV for bare ITO to 4.3 eV for ITO with a dense film of PAMAM-NH2 of generation five. PAMAM-OH and Q-PAMAM-NH2 resulted in slightly smaller work function changes. This study illustrates that the work function of ITO can be tuned by adlayers composed of PAMAM dendrimers. PMID:17636991

  7. Organic surfaces exposed by self-assembled organothiol monolayers: Preparation, characterization, and application

    NASA Astrophysics Data System (ADS)

    Kind, Martin; Wöll, Christof

    2009-07-01

    Organic surfaces play a major role in materials science. Most surfaces that we touch in our daily lives are made from organic materials, e.g., vegetables, fruit, skin, wood, and textiles made from natural fibers. In the context of biology, organic surfaces play a prominent role too, proteins docking onto cell surfaces are a good example. To better understand the characteristics of organic surfaces, including physico-chemical properties like wettability or chemical reactivities and physical properties like friction and lubrication, a structurally well-defined model system that can be investigated with numerous analytical techniques is desirable. In the last two decades, one particular system, self-assembled monolayers or SAMs, have demonstrated their suitability for this purpose. In particular, organothiols consisting of an organic molecule with an attached SH-group are well suited to fabricating structurally well-defined adlayers of monolayer thickness on gold substrates using a simple preparation procedure. These ultrathin monolayers expose an organic surface with properties that can be tailored by varying the type of organothiol employed. After a short introduction into the preparation of SAMs, this article provides an overview of the possibilities and limitations of organic surfaces exposed by Au-thiolate SAMs. Applications are as diverse as the metallization of organic surfaces, a fundamental problem in materials science, and the fabrication of surfaces that resist the adsorption of proteins. In addition to a number of different case studies, we will also discuss the most powerful analytical techniques needed to characterize these important model systems.

  8. High resolution electrochemical STM : new structural results for underpotentially deposited Cu on Au(111) in acid sulfate solution.

    SciTech Connect

    Sieradzki, Karl; Vasiljevic, Natasa; Viyannalage, L.K.T.; Dimitrov, Nikolay

    2007-09-01

    Adsorption of sulfate assists Cu monolayer underpotential deposition (upd) on Au(111) in a unique way, rendering two distinct structural stages: (i) formation of a low-density Cu phase at coverage of 2/3 ML known as the ({radical}3 x {radical}3) R30{sup o} or honeycomb phase; (ii) formation of a complete monolayer, i.e., Cu-(1 x 1) phase pseudomorphic with respect to underlying Au(111) substrate. In this paper we present new structural in situ scanning tunneling microscopy (STM) results for this system. We show and discuss the STM imaging of the copper honeycomb superstructure probed underneath the co-adsorbed ({radical}3 x {radical}3)R30{sup o} sulfate adlayer in the low-density phase. High resolution imaging during the phase transition from the low to high density copper phase unambiguously shows the existence of an ordered sulfate structure p(2 x 2) on the pseudomorphic Cu-(1 x 1) layer. The new structure is seen during the co-existence of two copper phases as well as upon completion of the Cu-(1 x 1) monolayer. While supported by earlier chronocoulometric measurements in the same system, the new structural results raise questions that need to be addressed in a future work.

  9. Surface chemistry at the nanometer scale

    NASA Astrophysics Data System (ADS)

    Cao, Peigen

    -templated scanning probe microscopy, has been developed and applied for the study on the condensation process of water and small organic molecules on mica. We found that these molecular adlayers grow epitaxially on the mica substrate in a layer-by-layer fashion. In particular, submonolayers of water form atomically flat, faceted islands of height 0.37 plus or minus 0.02 nm, in agreement with the height of a monolayer of ice. The second adlayers also appear ice-like, and thicker layers appear liquid-like. This general mechanism, however, is not universal. Exclusively three-dimensional droplets of water are observed on chemically modified (hydrophobic) mica surfaces, suggesting a 3D growth mechanism. This thesis also includes my work on the design of a quartz-tuning-fork-based force sensor and related electronics for applications on low-temperature atomic force microscopy. Results show that the force-sensor-global-feedback circuit detector system induced lowest noise floor. The high detection sensitivity of this system demonstrates its ability to be used in frequency-modulated AFM at cryogenic temperatures. Surface topographic imaging of H-terminated Si(111) has been achieved at low temperatures.

  10. Os layers spontaneously deposited on the Pt(111) electrode : XPS, STM and GIF-XAS study.

    SciTech Connect

    Rhee, C. K.; Wakisaka, M.; Tolmachev, Y.; Johnston, C.; Haasch, R.; Attenkofer, K.; Lu, G. Q.; You, H.; Wieckowski, A.; Univ. of Illinois Champaigh-Urbana

    2003-01-01

    Scanning tunneling microscopy (STM) characterized adlayers of spontaneously deposited osmium on a Pt(111) electrode were investigated using ex-situ X-ray photoemission spectroscopy (XPS) and in-situ grazing incidence fluorescence X-ray absorption spectroscopy (GIF-XAS). After a single spontaneous deposition, monoatomic (or nearly monoatomic) nanoislands of osmium are formed. The island diameter varies from 2 to 5 nm depending on the Os coverage, which in turn is adjusted by varying the concentration of the Os precursor salt (OsCl3) in the deposition bath and/or by the deposition time. XPS reveals three oxidation states: a metallic Os (the 4f7/2 core level binding energy of 50.8 eV), Os(IV) (51.5 eV) and Os(VIII) (52.4 eV). The metallic osmium exists at potentials below 500 mV (vs. RHE) while above 500 mV osmium is oxidized to Os(IV). Electrodissolution of osmium begins above 900 mV and occurs simultaneously with platinum oxidation. At ca. 1200 mV V versus the RHE reference, the oxidation state of some small amounts of osmium that survive dissolution is the Os(VIII). We demonstrate, for the first time, that mixed or odd valencies of osmium exist on the platinum surface at potentials higher that 800 mV. In-situ GIF-XAS measurements of an Os LIII edge also reveal the presence of three Os oxidation states. Namely, below the electrode potential of 400 mV, the X-ray fluorescent energy at maximum absorption is 10.8765 keV, and is characteristic of the metallic Os. In the potential range between 500 and 1000 mV this energy is gradually shifted to higher values, assignable to higher valencies of osmium, like Os(IV). This tendency continues to higher potentials consistent with the third, highly oxidized osmium form present, most likely Os(VIII). The variation of the 'raw edge jump height' of Os with the electrode potential, which is equivalent to a drop in osmium surface concentration, demonstrates that the electrochemical stripping of Os begins below 1.0 V versus RHE, as

  11. Surface-Mediated Hydrogen Bonding of Proteinogenic α-Amino Acids on Silicon.

    PubMed

    Rahsepar, Fatemeh R; Moghimi, Nafiseh; Leung, K T

    2016-05-17

    a covalent-bond driven interfacial layer (first adlayer), followed by that of a transitional layer driven by interlayer and intralayer hydrogen bonding (second adlayer), and then finally the zwitterionic multilayers (with intralayer hydrogen bonding). The important role of surface-mediated hydrogen bonding as the key for this universal three-stage growth process is demonstrated. This finding provides new insight into biomolecule-semiconductor surface interactions often found in biosensors and biomolecular electronic devices. We also establish the trends in the H-bond length among different types of the hydrogen bonding for dimolecular structures in the gas phase and on the Si(111)7×7 surface, the latter of which could be validated by their STM images. Finally, five simple rules of thumb are developed to summarize the adsorption properties of these proteinogenic biomolecules as mediated by hydrogen bonding, and they are expected to provide a helpful guide to future studies of larger biomolecules and their potential applications. PMID:27014956

  12. In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

    NASA Astrophysics Data System (ADS)

    Pasquale, M. A.; Nieto, F. J. Rodríguez; Arvia, A. J.

    The electrochemical formation and reduction of O-layers on gold (111) films in 1 m sulfuric acid under different potentiodynamic routines are investigated utilizing in situ scanning tunneling microscopy. The surface dynamics is interpreted considering the anodic and cathodic reaction pathways recently proposed complemented with concurrent relaxation phenomena occurring after gold (111) lattice mild disruption (one gold atom deep) and moderate disruption (several atoms deep). The dynamics of both oxidized and reduced gold topographies depends on the potentiodynamic routine utilized to form OH/O surface species. The topography resulting from a mild oxidative disruption is dominated by quasi-2D holes and hillocks of the order of 5 nm, involving about 500-600 gold atoms each, and their coalescence. A cooperative turnover process at the O-layer, in which the anion ad-layer and interfacial water play a key role, determines the oxidized surface topography. The reduction of these O-layers results in gold clusters, their features depending on the applied potential routine. A moderate oxidative disruption produces a surface topography of hillocks and holes several gold atoms high and deep, respectively. The subsequent reduction leads to a spinodal gold pattern. Concurrent coalescence appears to be the result of an Ostwald ripening that involves the surface diffusion of both gold atoms and clusters. These processes produce an increase in surface roughness and an incipient gold faceting. The dynamics of different topographies can be qualitatively explained employing the arguments from colloidal science theory. For 1.1 V ≤ E ≅ Epzc weak electrostatic repulsions favor gold atom/cluster coalescence, whereas for E < Epzc the attenuated electrostatic repulsions among gold surfaces stabilize small clusters over the substrate producing string-like patterns.

  13. Oxygen-free conversion of methane to higher hydrocarbons through a dual-temperature two-step reaction sequence on platinum and ruthenium. 2: Removal of products at a fixed temperature

    SciTech Connect

    Amariglio, H.; Belgued, M.; Pareja, P.; Amariglio, A.

    1998-07-01

    In order to study the effect of the temperature (T{sub CH{sub 4}}) at which the catalysts were exposed to CH{sub 4} upon the C{sub 2+} products of the further hydrogenation, the latter process was conducted at a fixed temperature (T{sub H{sub 2}}) while different values were ascribed to T{sub CH{sub 4}} in a set of successive experiments. T{sub CH{sub 4}} did not exceed 320 C. Different sets were effected, corresponding to different values of T{sub H{sub 2}} (from room temperature to 200 C). If T{sub H{sub 2}} {le} 120 C hydrogenolysis was negligible, so that the variations of the production were only due to the changes affecting the adlayer. On both catalysts and at every value of T{sub H{sub 2}}, the production displayed a maximum versus T{sub CH{sub 4}}. On Pt, the selectivity to ethane and propane at a given T{sub H{sub 2}} monotonically decreased when T{sub CH{sub 4}} increased while that corresponding to the heavier products (C{sub 6}-C{sub 8}) increased. In contrast, on Ru, the selectivities to ethane and propane exhibited a minimum versus T{sub CH{sub 4}} while those to heptanes and octanes exhibited a maximum. The results are interpreted by assuming that, during the chemisorption of CH{sub 4}, several families of hydrocarbon precursors of different weights and shapes are formed on the metal surfaces. It must be assumed that, on Pt, the average weight of the precursors was an increasing function of T{sub CH{sub 4}}, whereas on Ru it displayed an optimum in the upper part of the explored range of T{sub CH{sub 4}}. No appreciable amount of unreactive carbon was formed under the conditions of the described experiments.

  14. Direct observation of electron propagation and dielectric screening on the atomic length scale.

    PubMed

    Neppl, S; Ernstorfer, R; Cavalieri, A L; Lemell, C; Wachter, G; Magerl, E; Bothschafter, E M; Jobst, M; Hofstetter, M; Kleineberg, U; Barth, J V; Menzel, D; Burgdörfer, J; Feulner, P; Krausz, F; Kienberger, R

    2015-01-15

    The propagation and transport of electrons in crystals is a fundamental process pertaining to the functioning of most electronic devices. Microscopic theories describe this phenomenon as being based on the motion of Bloch wave packets. These wave packets are superpositions of individual Bloch states with the group velocity determined by the dispersion of the electronic band structure near the central wavevector in momentum space. This concept has been verified experimentally in artificial superlattices by the observation of Bloch oscillations--periodic oscillations of electrons in real and momentum space. Here we present a direct observation of electron wave packet motion in a real-space and real-time experiment, on length and time scales shorter than the Bloch oscillation amplitude and period. We show that attosecond metrology (1 as = 10(-18) seconds) now enables quantitative insight into weakly disturbed electron wave packet propagation on the atomic length scale without being hampered by scattering effects, which inevitably occur over macroscopic propagation length scales. We use sub-femtosecond (less than 10(-15) seconds) extreme-ultraviolet light pulses to launch photoelectron wave packets inside a tungsten crystal that is covered by magnesium films of varied, well-defined thicknesses of a few ångströms. Probing the moment of arrival of the wave packets at the surface with attosecond precision reveals free-electron-like, ballistic propagation behaviour inside the magnesium adlayer--constituting the semi-classical limit of Bloch wave packet motion. Real-time access to electron transport through atomic layers and interfaces promises unprecedented insight into phenomena that may enable the scaling of electronic and photonic circuits to atomic dimensions. In addition, this experiment allows us to determine the penetration depth of electrical fields at optical frequencies at solid interfaces on the atomic scale. PMID:25592539

  15. Parallel kinetic Monte Carlo simulation framework incorporating accurate models of adsorbate lateral interactions

    SciTech Connect

    Nielsen, Jens; D’Avezac, Mayeul; Hetherington, James; Stamatakis, Michail

    2013-12-14

    Ab initio kinetic Monte Carlo (KMC) simulations have been successfully applied for over two decades to elucidate the underlying physico-chemical phenomena on the surfaces of heterogeneous catalysts. These simulations necessitate detailed knowledge of the kinetics of elementary reactions constituting the reaction mechanism, and the energetics of the species participating in the chemistry. The information about the energetics is encoded in the formation energies of gas and surface-bound species, and the lateral interactions between adsorbates on the catalytic surface, which can be modeled at different levels of detail. The majority of previous works accounted for only pairwise-additive first nearest-neighbor interactions. More recently, cluster-expansion Hamiltonians incorporating long-range interactions and many-body terms have been used for detailed estimations of catalytic rate [C. Wu, D. J. Schmidt, C. Wolverton, and W. F. Schneider, J. Catal. 286, 88 (2012)]. In view of the increasing interest in accurate predictions of catalytic performance, there is a need for general-purpose KMC approaches incorporating detailed cluster expansion models for the adlayer energetics. We have addressed this need by building on the previously introduced graph-theoretical KMC framework, and we have developed Zacros, a FORTRAN2003 KMC package for simulating catalytic chemistries. To tackle the high computational cost in the presence of long-range interactions we introduce parallelization with OpenMP. We further benchmark our framework by simulating a KMC analogue of the NO oxidation system established by Schneider and co-workers [J. Catal. 286, 88 (2012)]. We show that taking into account only first nearest-neighbor interactions may lead to large errors in the prediction of the catalytic rate, whereas for accurate estimates thereof, one needs to include long-range terms in the cluster expansion.

  16. Interaction of Co with an Fe(111) surface

    NASA Astrophysics Data System (ADS)

    Seip, U.; Tsai, M.-C.; Christmann, K.; Küppers, J.; Ertl, G.

    1984-04-01

    Adsorption of CO on Fe(111) below 300 K causes the appearance of three different non-dissociated species as distinguished by their CO stretch frequencies of about 1530 cm -1 (a), 1800 cm -1 (b), and 2000 cm -1 (c). At T ≳ 220 K the b-state is first filled up and saturates after 1.5 L exposure; upon increasing the temperature it partly desorbs around 400 K and partly dissociates. Recombination of the C and O atoms followed by CO desorption takes place at about 800 K. Above 1.5 L exposure the a- and c-states are occupied simultaneously; in the thermal desorption spectrum in turn they show up as a relatively broad shoulder at ˜ 340 K, which indicates similar adsorption energies for these two species. Saturation of the surface is reached after about 6 L exposure, which is paralleled by a continuous work function increase of up to Δφ = 1.6 eV. A high background intensity in the LEED pattern suggests substantial disorder in the adlayer. Evaluation of the TDS data yields about 2:1 population of the b- and (c + a)-states. The unusual low CO frequency of the a-state finds its analogues in reports on CO adsorption at stepped surfaces, as well as with complex compounds where the π-orbitals of the ligand directly interact with a neighboring metal atom. This species is therefore identified with adsorption in the "deep hollow" sites on the rather open Fe(111) surface. The b-state is tentatively attributed to the "shallow hollow" sites, and the c-state to adsorption on the "on top" sites.

  17. DNA bases assembled on the Au(110)/electrolyte interface: a combined experimental and theoretical study.

    PubMed

    Salvatore, Princia; Nazmutdinov, Renat R; Ulstrup, Jens; Zhang, Jingdong

    2015-02-19

    Among the low-index single-crystal gold surfaces, the Au(110) surface is the most active toward molecular adsorption and the one with fewest electrochemical adsorption data reported. Cyclic voltammetry (CV), electrochemically controlled scanning tunneling microscopy (EC-STM), and density functional theory (DFT) calculations have been employed in the present study to address the adsorption of the four nucleobases adenine (A), cytosine (C), guanine (G), and thymine (T), on the Au(110)-electrode surface. Au(110) undergoes reconstruction to the (1 × 3) surface in electrochemical environment, accompanied by a pair of strong voltammetry peaks in the double-layer region in acid solutions. Adsorption of the DNA bases gives featureless voltammograms with lower double-layer capacitance, suggesting that all the bases are chemisorbed on the Au(110) surface. Further investigation of the surface structures of the adlayers of the four DNA bases by EC-STM disclosed lifting of the Au(110) reconstruction, specific molecular packing in dense monolayers, and pH dependence of the A and G adsorption. DFT computations based on a cluster model for the Au(110) surface were performed to investigate the adsorption energy and geometry of the DNA bases in different adsorbate orientations. The optimized geometry is further used to compute models for STM images which are compared with the recorded STM images. This has provided insight into the physical nature of the adsorption. The specific orientations of A, C, G, and T on Au(110) and the nature of the physical adsorbate/surface interaction based on the combination of the experimental and theoretical studies are proposed, and differences from nucleobase adsorption on Au(111)- and Au(100)-electrode surfaces are discussed. PMID:25611676

  18. Visualization of compression and spillover in a coadsorbed system: syngas on cobalt nanoparticles.

    PubMed

    Lewis, Emily A; Le, Duy; Jewell, April D; Murphy, Colin J; Rahman, Talat S; Sykes, E Charles H

    2013-05-28

    Competitive adsorption and lateral pressure between surface-bound intermediates are important effects that dictate chemical reactivity. Lateral, or two-dimensional, pressure is known to promote reactivity by lowering energetic barriers and increasing conversion to products. We examined the coadsorption of CO and H2, the two reactants in the industrially important Fischer-Tropsch synthesis, on Co nanoparticles to investigate the effect of two-dimensional pressure. Using scanning tunneling microscopy, we directly visualized the coadsorption of H and CO on Co, and we found that the two adsorbates remain in segregated phases. CO adsorbs on the Co nanoparticles via spillover from the Cu(111) support, and when deposited onto preadsorbed adlayers of H, CO exerts two-dimensional pressure on H, compressing it into a higher-density, energetically less-preferred structure. By depositing excess CO, we found that H on the Co surface is forced to spill over onto the Cu(111) support. Thus, spillover of H from Co onto Cu, where it would not normally reside due to the high activation barrier, is preferred over desorption. We corroborated the mechanism of this spillover-induced displacement by calculating the relevant energetics using density functional theory, which show that the displacement of H from Co is compensated for by the formation of strong CO-Co bonds. These results may have significant ramifications for Fischer-Tropsch synthesis kinetics on Co, as the segregation of CO and H, as well as the displacement of H by CO, limits the interface between the two molecules. PMID:23565854

  19. CO chemisorption and dissociation at high coverages during CO hydrogenation on Ru catalysts.

    PubMed

    Loveless, Brett T; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2013-04-24

    Density functional theory (DFT) and infrared spectroscopy results are combined with mechanism-based rate equations to assess the structure and thermodynamics of chemisorbed CO (CO*) and its activation during Fischer-Tropsch synthesis (FTS). CO* binding becomes weaker with increasing coverage on Ru(0001) and Ru201 clusters, but such decreases in binding energy occur at higher coverages on Ru201 clusters than on Ru(0001) surfaces (CO*/Ru = 1.55 to 0.75); such differences appear to reflect weaker repulsive interactions on the curved surfaces prevalent on small Ru201 clusters. Ru201 clusters achieve stable supramonolayer coverages (CO*/Ru > 1) by forming geminal dicarbonyls at low-coordination corner/edge atoms. CO* infrared spectra on Ru/SiO2 (~7 nm diameter) detect mobile adlayers that anneal into denser structures at saturation. Mechanism-based FTS rate equations give activation energies that reflect the CO*-saturated surfaces prevalent during catalysis. DFT-derived barriers show that CO* predominantly reacts at (111) terraces via H-assisted reactions, consistent with measured effects of H2 and CO pressures and cluster size effects on rates and O-rejection selectivities. Barriers are much higher for unassisted CO* dissociation on (111) terraces and low-coordination atoms, including step-edge sites previously proposed as active sites for CO* dissociation during FTS. DFT-derived barriers indicate that unassisted CO* dissociation is irreversible, making such steps inconsistent with measured rates. The modest activation barriers of H-assisted CO* dissociation paths remove a requirement for special low-coordination sites for unassisted CO* activation, which is inconsistent with higher rates on larger clusters. These conclusions seem generally applicable to Co, Fe, and Ru catalysts, which show similar FTS rate equations and cluster size effects. This study also demonstrates the feasibility and relevance of DFT treatments on the curved and crowded cluster surfaces where

  20. The role of co-adsorbed O 2 on the catalytic reduction of NO with 13C 2H 5OH on the surface of Pt(3 3 2)

    NASA Astrophysics Data System (ADS)

    Hu, Yuhai; Griffiths, Keith

    2007-11-01

    The influence of pre-dosed O 2 on the catalytic reduction of NO with 13C 2H 5OH on the surface of stepped Pt(3 3 2) was investigated using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). We show that the oxidation of 13C 2H 5OH with O 2 is a very effective reaction, occurring at 150 K and giving rise to acetate. The presence of NO does not lead to any evident oxidation of 13C 2H 5OH irrespective of the annealing temperature. For the case of O 2 + 13C 2H 5OH + NO co-adlayers, oxidation of 13C 2H 5OH also takes place at 150 K. However, no new surface species that are supposed to be an intermediate for the production of N 2 are detected. The influence of O 2 on the production and desorption of N 2 is intimately related to both O 2 and 13C 2H 5OH coverage. The presence of pre-dosed O 2 does not greatly promote N 2 desorption. In fact, N 2 desorption is suppressed quantitatively with increasing O 2 coverage, after which unreacted, or left-over O atoms appear and remain on steps. It is concluded that the presence of pre-dosed O 2 does not play a role of activating reactants in the catalytic reduction of NO with 13C 2H 5OH on the surface of Pt(3 3 2).

  1. A colorimetric method for the molecular weight determination of polyethylene glycol using gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Ling, Kai; Jiang, Hongyan; Zhang, Qiqing

    2013-12-01

    A gold nanoparticle (AuNP)-based colorimetric method was developed for the molecular weight (MW) determination of polyethylene glycol (PEG), a commonly used hydrophilic polymer. Addition of a salt solution to PEG-coated AuNP solutions helps in screening the electrostatic repulsion between nanoparticles and generating a color change of the solutions from wine red to blue in 10 min in accordance with the MW of PEG, which illustrates the different stability degrees (SDs) of the AuNPs. The SDs are calculated by the absorbance ratios of the stable to the aggregated AuNPs in the solution. The root mean square end-to-end length (< h 2>1/2) of PEG molecules shows a linear fit to the SDs of the PEG-coated AuNPs in a range of 1.938 ± 0.156 to 10.151 ± 0.176 nm. According to the Derjaguin-Landau-Verwey-Overbeek theory, the reason for this linear relationship is that the thickness of the PEG adlayer is roughly equivalent to the < h 2>1/2 of the PEG molecules in solution, which determines the SDs of the AuNPs. Subsequently, the MW of the PEG can be obtained from its < h 2>1/2 using a mathematical relationship between < h 2>1/2 and MW of PEG molecule. Applying this approach, we determined the < h 2>1/2 and the MW of four PEG samples according to their absorbance values from the ordinary ultraviolet-visible spectrophotometric measurements. Therefore, the MW of PEG can be distinguished straightforwardly by visual inspection and determined by spectrophotometry. This novel approach is simple, rapid, and sensitive.

  2. Interactions between glycine and amorphous solid water nanoscale films

    NASA Astrophysics Data System (ADS)

    Tzvetkov, George; Koller, Georg; Netzer, Falko P.

    2012-12-01

    The interactions of glycine (Gly) with amorphous solid water (ASW) nanolayers (≤ 100 ML), vapor-deposited on single crystalline AlOx surfaces at 100 K, have been investigated by near-edge X-ray absorption fine structure spectroscopy (NEXAFS) at the oxygen K-edge, temperature-programmed thermal desorption (TPD), X-ray photoelectron spectroscopy (XPS), and temperature-dependent work function measurements. Gly-on-ASW, ASW-on-Gly, and Gly on top of ASW-on-Gly ultrathin films have been fabricated. In contrast to the uniform ASW films grown directly on the hydrophilic AlOx, water molecules adsorb on the hydrophobic Gly films in the form of 3D ASW clusters. This leads to significant differences in the NEXAFS and work function data obtained from ASW-on-AlOx and ASW-on-Gly films, respectively. Furthermore, these structural differences influence the chemical state of Gly molecules (neutral vs. zwitterionic) adsorbed on top of ASW films. N1s XPS measurements revealed an increased amount of neutral Gly molecules in the film top-deposited on the ASW-on-Gly structure in comparison to the neutral Gly in the films directly condensed on AlOx or grown on the ASW substrate. H2O TPD spectra demonstrate that the crystallization and desorption processes of ASW are affected in a different way by the Gly layers, top-deposited on to ASW-on-AlOx and ASW-on-Gly films. At the same time, Gly adlayers sink into the ASW film during crystallization/desorption of the latter and land softly on the alumina surface in the form of zwitterionic clusters.

  3. Substitutional geometry and strain effects in overlayers of phosphorus on Si(111)

    NASA Astrophysics Data System (ADS)

    Vitali, L.; Ramsey, M. G.; Netzer, F. P.

    1998-06-01

    The structure and bonding topology of phosphorus adatoms on Si(111) surfaces have been investigated by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy, in conjunction with low-energy electron diffraction and Auger electron spectroscopy. At room temperature P adatoms substitute for the Si adatoms of the Si(111)7×7 surface at low coverages as revealed by the chemical contrast between P and Si adatoms in the filled-state STM images. A statistical evaluation of the STM images within the framework of a simple reaction model suggests that the corner adatoms of the faulted half of the (7×7) unit cell act as primary reaction centers for the P2 molecules from the gas phase, in agreement with theoretical expectation. At elevated temperature (500-650 °C) a (63×63)R30° structure is the prevailing P-induced surface reconstruction. Atomically resolved STM images show that this structure is a domain-wall structure containing hexagonal domains that tesselate the entire surface. The 6% contracted (1×1) phosphorus domains are separated by straight, 4% expanded light domain walls of irregular lengths. The structure displays a complex in-phase-antiphase-stacking fault relationship between adjacent domains, which has been modeled successfully with a P adlayer in a substitutional bonding geometry on an unreconstructed Si(111) surface. The large tensile surface stress introduced by the P-Si bonding is responsible for the domain-wall formation and precludes the formation of a global (1×1)-P structure on Si(111) surfaces.

  4. Origin of Asymmetry of Paired Nanogap Voltammograms Based on Scanning Electrochemical Microscopy: Contamination Not Adsorption.

    PubMed

    Chen, Ran; Balla, Ryan J; Li, Zhiting; Liu, Haitao; Amemiya, Shigeru

    2016-08-16

    Formation of a nanometer-wide gap between tip and substrate electrodes by scanning electrochemical microscopy (SECM) enables voltammetric measurement of ultrafast electron-transfer kinetics. Herein, we demonstrate the advantage of SECM-based nanogap voltammetry to assess the cleanness of the substrate surface in solution by confirming that airborne contamination of highly oriented pyrolytic graphite (HOPG) causes the nonideal asymmetry of paired nanogap voltammograms of (ferrocenylmethyl)trimethylammonium (Fc(+)). We hypothesize that the amperometric response of a 1 μm-diameter Pt tip is less enhanced in the feedback mode, where more hydrophilic Fc(2+) is generated from Fc(+) at the tip and reduced voltammetrically at the HOPG surface covered with airborne hydrophobic contaminants. The tip current is more enhanced in the substrate generation/tip collection mode, where less charged Fc(+) is oxidized at the contaminated HOPG surface. In fact, symmetric pairs of nanogap voltammograms are obtained with the cleaner HOPG surface that is exfoliated in humidified air and covered with a nanometer-thick water adlayer to suppress airborne contamination. This result disproves a misconception that the asymmetry of paired nanogap voltammograms is due to electron exchange mediated by Fc(2+) adsorbed on the glass sheath of the tip. Moreover, weak Fc(+) adsorption on the HOPG surface causes only the small hysteresis of each voltammogram upon forward and reverse sweeps of the HOPG potential. Significantly, no Fc(2+) adsorption on the HOPG surface ensures that the simple outer-sphere pathway mediates ultrafast electron transfer of the Fc(2+/+) couple with standard rate constants of ≥12 cm/s as estimated from symmetric pairs of reversible nanogap voltammograms. PMID:27426255

  5. Structural and surface coverage effects on CO oxidation reaction over carbon-supported Pt nanoparticles studied by quadrupole mass spectrometry and diffuse reflectance FTIR spectroscopy.

    PubMed

    Cheah, Seng Kian; Bernardet, Véronique P; Franco, Alejandro A; Lemaire, Olivier; Gelin, Patrick

    2016-06-01

    The CO oxidation reaction on carbon-supported Pt nanoparticles (average size of 2.8 to 7.7 nm) was studied under flowing conditions at atmospheric pressure and temperatures between 300 and 353 K by coupling quadrupole mass spectrometry (QMS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The Pt loading was varied between 20 and 60 wt%. Gases diluted in He (0.5 mol%) were used together with Ar as a tracer. Reactions with CO and O2 introduced separately onto the samples were studied by QMS, applying successive step changes of the reaction mixtures. Variations in the rate of the reactions were observed and correlated with changes of the calculated coverage of the Pt surface by CO and/or O adspecies at varying steps of the experiment. The transient reaction of CO(g) with adsorbed O (Oad) was fast and mass transport-limited while that of O2(g) with adsorbed CO (COad) was sluggish. Following the same experimental procedures, FTIR spectra of adsorbed CO after varying steps were recorded, confirming the variations of COad and Oad as determined by QMS and indicating changes in the CO distribution over varying types of Pt surface sites. The influence of the adlayer composition (co-adsorption of COad and Oad), the particle size/structure and some possible surface reconstruction effects on the CO oxidation rate were evidenced and discussed. The structure of the Pt nanoparticles supported on carbon appears as an important factor for the efficiency of the so-called O2 bleeding as a CO mitigation strategy in polymer electrolyte membrane fuel cells. PMID:27212705

  6. Adsorption of Water on JSC-1A Lunar Simulant Samples

    NASA Technical Reports Server (NTRS)

    Goering, John; Sah, Shweta; Burghaus, Uwe; Street, Kenneth W.

    2008-01-01

    Remote sensing probes sent to the moon in the 1990s indicated that water may exist in areas such as the bottoms of deep, permanently shadowed craters at the lunar poles, buried under regolith. Water is of paramount importance for any lunar exploration and colonization project which would require self-sustainable systems. Therefore, investigating the interaction of water with lunar regolith is pertinent to future exploration. The lunar environment can be approximated in ultra-high vacuum systems such as those used in thermal desorption spectroscopy (TDS). Questions about water dissociation, surface wetting, degree of crystallization, details of water-ice transitions, and cluster formation kinetics can be addressed by TDS. Lunar regolith specimens collected during the Apollo missions are still available though precious, so testing with simulant is required before applying to use lunar regolith samples. Hence, we used for these studies JSC-1a, mostly an aluminosilicate glass and basaltic material containing substantial amounts of plagioclase, some olivine and traces of other minerals. Objectives of this project include: 1) Manufacturing samples using as little raw material as possible, allowing the use of surface chemistry and kinetics tools to determine the feasibility of parallel studies on regolith, and 2) Characterizing the adsorption kinetics of water on the regolith simulant. This has implications for the probability of finding water on the moon and, if present, for recovery techniques. For condensed water films, complex TDS data were obtained containing multiple features, which are related to subtle rearrangements of the water adlayer. Results from JSC-1a TDS studies indicate: 1) Water dissociation on JSC-1a at low exposures, with features detected at temperatures as high as 450 K and 2) The formation of 3D water clusters and a rather porous condensed water film. It appears plausible that the sub- m sized particles act as nucleation centers.

  7. The effect of the particle size on the kinetics of CO electrooxidation on high surface area Pt catalysts.

    PubMed

    Arenz, Matthias; Mayrhofer, Karl J J; Stamenkovic, Vojislav; Blizanac, Berislav B; Tomoyuki, Tada; Ross, Phil N; Markovic, Nenad M

    2005-05-11

    Using high-resolution transmission electron microscopy (TEM), infrared reflection-absorption spectroscopy (IRAS), and electrochemical (EC) measurements, platinum nanoparticles ranging in size from 1 to 30 nm are characterized and their catalytic activity for CO electrooxidation is evaluated. TEM analysis reveals that Pt crystallites are not perfect cubooctahedrons, and that large particles have "rougher" surfaces than small particles, which have some fairly smooth (111) facets. The importance of "defect" sites for the catalytic properties of nanoparticles is probed in IRAS experiments by monitoring how the vibrational frequencies of atop CO (nu(CO)) as well as the concomitant development of dissolved CO(2) are affected by the number of defects on the Pt nanoparticles. It is found that defects play a significant role in CO "clustering"on nanoparticles, causing CO to decrease/increase in local coverage, which yields to anomalous redshift/blueshift nu(CO) frequency deviations from the normal Stark-tuning behavior. The observed deviations are accompanied by CO(2) production, which increases by increasing the number of defects on the nanoparticles, that is, 1 < or = 2 < 5 < 30 nm. We suggest that the catalytic activity for CO adlayer oxidation is predominantly influenced by the ability of the surface to dissociate water and to form OH(ad) on defect sites rather than by CO energetics. These results are complemented by chronoamperometric and rotating disk electrode (RDE) data. In contrast to CO stripping experiments, we found that in the backsweep of CO bulk oxidation, the activity increases with decreasing particle size, that is, with increasing oxophilicity of the particles. PMID:15869305

  8. Advances in sublimation studies for particles of explosives

    NASA Astrophysics Data System (ADS)

    Furstenberg, Robert; Nguyen, Viet; Fischer, Thomas; Abrishami, Tara; Papantonakis, Michael; Kendziora, Chris; Mott, David R.; McGill, R. Andrew

    2015-05-01

    When handling explosives, or related surfaces, the hands routinely become contaminated with particles of explosives and related materials. Subsequent contact with a solid surface results in particle crushing and deposition. These particles provide an evidentiary trail which is useful for security applications. As such, the opto-physico-chemical characteristics of these particles are critical to trace explosives detection applications in DOD or DHS arenas. As the persistence of these particles is vital to their forensic exploitation, it is important to understand which factors influence their persistence. The longevity or stability of explosives particles on a substrate is a function of several environmental parameters or particle properties including: Vapor pressure, particle geometry, airflow, particle field size, substrate topography, humidity, reactivity, adlayers, admixtures, particle areal density, and temperature. In this work we deposited particles of 2,4-dinitrotoluene on standard microscopy glass slides by particle sieving and studied their sublimation as a function of airflow velocity, areal particle density and particle field size. Analysis of 2D microscopic images was used to compute and track particle size and geometrical characteristics. The humidity, temperature and substrate type were kept constant for each experiment. A custom airflow cell, using standard microscopy glass slide, allowed in-situ photomicroscopy. Areal particle densities and airflow velocities were selected to provide relevant loadings and flow velocities for a range of potential applications. For a chemical of interest, we define the radial sublimation velocity (RSV) for the equivalent sphere of a particle as the parameter to characterize the sublimation rate. The RSV is a useful parameter because it is independent of particle size. The sublimation rate for an ensemble of particles was found to significantly depend on airflow velocity, the areal density of the particles, and the

  9. A survey of state-of-the-art surface chemistries to minimize fouling from human and animal biofluids.

    PubMed

    Blaszykowski, Christophe; Sheikh, Sonia; Thompson, Michael

    2015-10-15

    Upon contact with bodily fluids, synthetic materials spontaneously acquire a layer of various species (most notably proteins) on their surface. The concern with respect to biomedical equipment, implants or devices resides in the possibility for biological processes with potentially harmful effects to ensue. In biosensor technology, the issue with this natural fouling phenomenon is that of non-specific adsorption to sensing platforms, which generates an often overwhelming interference signal that prevents the detection, not to mention the quantification, of target analytes present at considerably lower concentration. To alleviate this ubiquitous, recurrent problem - this genuine biotechnological plague - considerable research efforts have been devoted over the last few decades to engineer antifouling coatings. Extensive literature now exists that describes stealth organic adlayers capable of reducing fouling surface coverage Γ down to a few ng cm(-2)- however from biotechnologically irrelevant buffered solutions free or nearly depleted of any potentially interfering species. Regrettably indeed, few coatings are known to display/retain such level of performance when exposed to otherwise more complex, real-life biosamples (even diluted). Herein, we comprehensively review the state-of-the-art surface chemistries developed to date (January 2015) to minimize fouling from 8 such uncomparatively more challenging biological media (blood plasma, blood serum, cell lysate, cerebrospinal fluid, egg, milk, saliva, and urine) - whether of human or animal origin. Literature search for another 25 biological milieux generated no (exploitable) hit. Also discussed in this Review are the identification of the species responsible for fouling, and the dependence of antifouling properties on biosample source variability. PMID:26215763

  10. Effect of growth temperature on composition control for vapor deposition of YBa{sub 2}Cu{sub 3}O{sub 7−δ} precursor films

    SciTech Connect

    Liu, Chong; Wang, Lianhong; Shu, Yonghua; Fan, Jing

    2014-12-09

    This work aims at exploiting the role of growth temperature on the dynamic behavior of deposition atoms as well as its resultant impact on the composition control during the synthesis of YBa{sub 2}Cu{sub 3}O{sub 7−δ} precursor films by vapor codeposition. The codeposition of Yt, BaF{sub 2} and Cu is performed in vacuum chamber under a wide range of growth temperature from 25°C to 600°C, the mass of each element deposited on LaAlO{sub 3} substrate and thus the film composition is examined by the inductively coupled plasma atomic emission spectroscopy. It is shown that the deposition amount of Cu decreases obviously with the increase of growth temperature; however, the mass of Yt and BaF{sub 2} deposited on the substrate appears to be insensitive to growth temperature. Moreover, high temperature may also trigger the influence of adsorbates composition on Cu desorption, and therefore the deposition amount of Cu decreases almost linearly as the mol fraction of BaF{sub 2} in the adlayers increases. Nevertheless, when the deposition is conducted at room temperature, the influence of mol fraction of BaF{sub 2} on Cu desorption vanishes. The detailed mechanisms associated with above phenomena are unveiled by molecular dynamics analysis, additionally the physical picture about adsorption behaviors on the growing interface under different deposition conditions is summarized, which is valuable for handling the composition control during the vapor codeposition of different functional films.

  11. H 2 splitting on Pt, Ru and Rh nanoparticles supported on sputtered HOPG

    NASA Astrophysics Data System (ADS)

    Fiordaliso, E. M.; Murphy, S.; Nielsen, R. M.; Dahl, S.; Chorkendorff, I.

    2012-02-01

    The equilibrium hydrogen exchange rate between adsorbed and gas phase hydrogen at 1 bar is measured for Pt, Ru and Rh nanoparticles supported on a sputtered HOPG substrate. The particles are prepared by Electron Beam Physical Vapor Deposition and the diameter of the particles varies between 2 and 5 nm. The rate of hydrogen exchange is measured in the temperature range 40-200 °C at 1 bar, by utilization of the H-D exchange reaction. We find that the rate of hydrogen exchange increases with the particle diameter for all the metals, and that the rate for Ru and Rh is higher than for Pt. In the case of Pt, the equilibrium dissociative sticking probability, S, is found to be nearly independent of particle diameter. For Ru and Rh, S is found to depend strongly on particle diameter, with the larger particles being more active. The apparent energy of desorption at equilibrium, Eapp, shows a dramatic increase with decreasing particle diameter for diameters below 5 nm for Ru and Rh, whereas Eapp is only weakly dependent on particle diameter for Pt. We suggest that the strong variation in the apparent desorption energy with particle diameter for Ru and Rh is due to the formation of compressed hydrogen adlayers on the terraces of the larger particles. Experiments are also carried out in the presence of 10 ppm CO. Pt is found to be very sensitive to CO poisoning and the H-D exchange rate drops below the detection limit when CO is added to the gas mixture. In the case of Ru and Rh nanoparticles, CO decreases the splitting rate significantly, also at 200 °C. The variation of the sensitivity to CO poisoning with particle diameter for Ru and Rh is found to be weak.

  12. Deep-Probe Optical Waveguides for Chemical and Biosensors

    NASA Astrophysics Data System (ADS)

    Zourob, Mohammed; Skivesen, Nina; Horvath, Robert; Mohr, Stephan; Goddard, Nicholas J.

    Typical evanescent wave biosensors generate an electromagnetic wave at the sensor surface that penetrates 100-200 nm into the analysed medium. This has proven to be a highly sensitive tool to monitor refractive index changes in the close vicinity of the sensor surface. The sensitivity of such sensors can be enhanced significantly to monitor interactions caused by large micron scale objects such as bacterial and mammalian cells by increasing the penetration depth of the evanescent field. Recently, different formats of deep-probe optical waveguides including reverse waveguides (RW) based on low refractive index substrates (below 1.33) and metal-clad leaky waveguides (MCLW) have been developed for various sensing applications. These sensors are designed to maximize the overlap between the optical mode and the adlayer (superstrate layer) to be sensed. Increasing the penetration depth of the evanescent field opens up new perspectives for the detection of larger biological objects as it accommodates the majority of their body within the evanescent field. RWs use substrate materials with lower refractive index than that of the monitored superstrate layer (aqueous solution). In MCLWs, a thin metal layer is inserted between the substrate and the thicker waveguide layer. These sensor designs facilitate both increasing and tuning the penetration depth of the modes into the monitored aqueous solution and thereby significantly extend the range of possible application areas of optical waveguide sensors. The developed devices have been used for a range of biosensing applications, including the detection of bacteria, mammalian cells, organophosphorous pesticides and glucose using refractive index changes, absorbance and fluorescence monitoring. Integrating deep-probe sensors with an external electrical field or ultrasonic standing waves shortens analysis time significantly and reduces non-specific binding due to enhanced diffusion of analytes to the immobilized recognition

  13. Interaction of the ionic liquid [BMP][TFSA] with rutile TiO2(110) and coadsorbed lithium.

    PubMed

    Uhl, Benedikt; Hekmatfar, Maral; Buchner, Florian; Behm, R Jürgen

    2016-03-01

    Aiming at a fundamental understanding of the processes at the electrode|ionic liquid interface in Li ion batteries, we investigated the interaction of the ionic liquid n-butyl-n-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [BMP][TFSA] and of Li with a reduced rutile TiO2(110) (1 × 1) surface as well as the interaction between [BMP][TFSA] and Li on the TiO2(110) surface under ultrahigh vacuum (UHV) conditions by X-ray photoelectron spectroscopy and scanning tunnelling microscopy. Between 80 K and 340 K [BMP][TFSA] adsorbs molecularly on the surface and at higher temperatures decomposition is observed, resulting in products such as Sad, Fad and TiNx. The decomposition pattern is compared to proposals based on theory. Small amounts of Li intercalate even at 80 K into TiO2(110), forming Li(+) and Ti(3+) species. The stoichiometry in the near surface region corresponds to Li7Ti5O12. For higher coverages in the range of several monolayers part of the Li remains on the surface, forming a Li2O cover layer. At 300 K, Ti(3+) species become sufficiently mobile to diffuse into the bulk. Li post-deposition on a [BMP][TFSA] covered TiO2(110) surface at 80 K results in two competing reactions, Li intercalation and reaction with the IL, resulting in the decomposition of the IL. Upon warming up, the Ti(3+) formed at low T is consumed by reaction with the IL adlayer and intermediate decomposition products. Post-deposition of [BMP][TFSA] (300 K) on a surface pre-covered with a Li2O/Li7Ti5O12 layer results in the partial reaction of [BMP][TFSA] with the Li(+) and Ti(3+) species, which gets completed at higher temperatures. PMID:26869155

  14. Strong electric fields at a prototypical oxide/water interface probed by ab initio molecular dynamics: MgO(001).

    PubMed

    Laporte, Sara; Finocchi, Fabio; Paulatto, Lorenzo; Blanchard, Marc; Balan, Etienne; Guyot, François; Saitta, Antonino Marco

    2015-08-21

    We report a density-functional theory (DFT)-based study of the interface of bulk water with a prototypical oxide surface, MgO(001), and focus our study on the often-overlooked surface electric field. In particular, we observe that the bare MgO(001) surface, although charge-neutral and defectless, has an intense electric field on the Å scale. The MgO(001) surface covered with 1 water monolayer (1 ML) is investigated via a supercell accounting for the experimentally-observed (2 × 3) reconstruction, stable at ambient temperature, and in which two out of six water molecules are dissociated. This 1 ML-hydrated surface is also found to have a high, albeit short-ranged, normal component of the field. Finally, the oxide/water interface is studied via room-temperature ab initio molecular dynamics (AIMD) using 34 H2O molecules between two MgO(001) surfaces. To our best knowledge this is the first AIMD study of the MgO(001)/liquid water interface in which all atoms are treated using DFT and including several layers above the first adsorbed layer. We observe that the surface electric field, averaged over the AIMD trajectories, is still very strong on the fully-wet surface, peaking at about 3 V Å(-1). Even in the presence of bulk-like water, the structure of the first layer in contact with the surface remains similar to the (2 × 3)-reconstructed ice ad-layer on MgO(001). Moreover, we observe proton exchange within the first layer, and between the first and second layers - indeed, the O-O distances close to the surface are found to be distributed towards shorter distances, a property which has been shown to directly promote proton transfer. PMID:26193818

  15. Cetyltrimethylammonium Bromide-Modified Spherical and Cube-Like Gold Nanoparticles as Extrinsic Raman Lables in Surface-Enhanced Raman Spectroscopy Based Heterogeneous Immunoassays

    SciTech Connect

    Narayanan, R.; Lipert, R.; Porter, M.

    2008-02-22

    This paper reports on the characterization and preliminary comparison of gold nanoparticles of differing surface modification and shape when used as extrinsic Raman labels (ERLs) in high-sensitivity heterogeneous immunoassays based on surface enhanced Raman scattering (SERS). ERLs are gold nanoparticles coated with an adlayer of an intrinsically strong Raman scatterer, followed by a coating of a molecular recognition element (e.g., antibody). Three types of ERLs, all with a nominal size of {approx}30 nm, were fabricated by using spherical citrate-capped gold nanoparticles (sp-cit-Au NPs), spherical CTAB-capped gold nanoparticles (sp-CTAB-Au NPs), or cube-like CTAB-capped gold nanoparticles (cu-CTAB-Au NPs) as cores. The performance of these particles was assessed via a sandwich immunoassay for human IgG in phosphate buffered saline. The ERLs fabricated with sp-CTAB-Au NPs as cores proved to be more than 50 times more sensitive than those with sp-cit-Au NPs as cores; the same comparison showed that the ERLs with cu-CTAB-Au NPs as cores were close to 200 times more sensitive. Coupled with small differences in levels of nonspecific adsorption, these sensitivities translated to a limit of detection (LOD) of 94, 2.3, and 0.28 ng/mL, respectively, for the detection of human IgG in the case of sp-cit-Au NPs, sp-CTAB-Au NPs, and cu-CTAB-Au NPs. The LOD of the cu-CTAB-Au NPs is therefore {approx}340 times below that for the sp-cit-Au NPs. Potential applications of these labels to bioassays are briefly discussed.

  16. Image potential states at metal-dielectric interfaces

    SciTech Connect

    Merry, W.R. Jr.

    1992-04-01

    Angle-resolved two-photon laser photoemission was used to observe the image potential electronic states on the (111) face of a silver single crystal. The transient image potential states were excited from the occupied bulk bands with photons whose energy was tunable around 4 eV. Photoemission of the image potential states was accomplished with photons of energy tunable around 2 eV. Image potential states were found to persist in the presence of physisorbed adlayers of xenon and cyclohexane. On clean Ag(111), the effective mass of the n=1 image potential state was found to be 1.4{plus minus}0.1 times the mass of a free electron (m{sub e}). A binding energy of 0.77 eV, measured by earlier workers, was assumed in analysis of the data for the clean surface. On Ag(111), at 75 K covered by one monolayer of xenon, the binding energy of the n=1 image potential state was unchanged relative to its value on the clean surface. An effective mass of (1.00{plus minus}0.05) {center dot} m{sub e} was obtained. On Ag(111) at 167 K, covered by one monolayer of cyclohexane, the binding energy of the n=2 member of the image potential series was 0.30{plus minus}0.05 eV. The energy of the n=1 state was again unchanged by deposition of the adsorbate. The effective masses of both states were (0.90{plus minus}0.1) {center dot} m{sub e}.

  17. Image potential states at metal-dielectric interfaces

    SciTech Connect

    Merry, W.R. Jr.

    1992-04-01

    Angle-resolved two-photon laser photoemission was used to observe the image potential electronic states on the (111) face of a silver single crystal. The transient image potential states were excited from the occupied bulk bands with photons whose energy was tunable around 4 eV. Photoemission of the image potential states was accomplished with photons of energy tunable around 2 eV. Image potential states were found to persist in the presence of physisorbed adlayers of xenon and cyclohexane. On clean Ag(111), the effective mass of the n=1 image potential state was found to be 1.4{plus_minus}0.1 times the mass of a free electron (m{sub e}). A binding energy of 0.77 eV, measured by earlier workers, was assumed in analysis of the data for the clean surface. On Ag(111), at 75 K covered by one monolayer of xenon, the binding energy of the n=1 image potential state was unchanged relative to its value on the clean surface. An effective mass of (1.00{plus_minus}0.05) {center_dot} m{sub e} was obtained. On Ag(111) at 167 K, covered by one monolayer of cyclohexane, the binding energy of the n=2 member of the image potential series was 0.30{plus_minus}0.05 eV. The energy of the n=1 state was again unchanged by deposition of the adsorbate. The effective masses of both states were (0.90{plus_minus}0.1) {center_dot} m{sub e}.

  18. Electronic structure and electron dynamics at an organic molecule/metal interface: interface states of tetra-tert-butyl-imine/Au(111)

    NASA Astrophysics Data System (ADS)

    Hagen, Sebastian; Luo, Ying; Haag, Rainer; Wolf, Martin; Tegeder, Petra

    2010-12-01

    Time- and angle-resolved two-photon photoemission (2PPE) spectroscopies have been used to investigated the electronic structure, electron dynamics and localization at the interface between tetra-tert-butyl imine (TBI) and Au(111). At a TBI coverage of one monolayer (ML), the two highest occupied molecular orbitals, HOMO and HOMO-1, are observed at an energy of -1.9 and -2.6 eV below the Fermi level (EF), respectively, and coincide with the d-band features of the Au substrate. In the unoccupied electronic structure, the lowest unoccupied molecular orbital (LUMO) has been observed at 1.6 eV with respect to EF. In addition, two delocalized states that arise from the modified image potential at the TBI/metal interface have been identified. Their binding energies depend strongly on the adsorption structure of the TBI adlayer, which is coverage dependent in the submonolayer (<=1 ML) regime. Thus the binding energy of the lower interface state (IS) shifts from 3.5 eV at 1.0 ML to 4.0 eV at 0.5 ML, which is accompanied by a pronounced decrease in its lifetime from 100 fs to below 10 fs. This is a result of differences in the wave function overlap with electronic states of the Au(111) substrate at different binding energies. This study shows that in order to fully understand the electronic structure of organic adsorbates at metal surfaces, not only adsorbate- and substrate-induced electronic states have to be considered but also ISs, which are the result of a potential formed by the interaction between the adsorbate and the substrate.

  19. Growth of gold on a pinwheel TiO(∼1.2) encapsulation film prepared on rhodium nanocrystallites.

    PubMed

    Gubó, R; Óvári, L; Kónya, Z; Berkó, A

    2014-12-01

    Rh nanoparticles of 50-100 nm diameter and 20-40 atomic layer thickness with a (111) flat top facet parallel to the support surface were grown on a TiO2(110) surface via physical vapor deposition (PVD) at room temperature (RT) followed by annealing at 1050 K. These nanoparticles were completely encapsulated by an ordered hexagonal pinwheel TiO∼1.2 ultrathin oxide (w-TiO-UTO) film. STM, XPS, and low energy ion scattering (LEIS) methods were used to characterize the postdeposition of gold and the effects of annealing on the Au/w-TiO-UTO/Rh-particle system. The adlayer exhibits 3D growth and Rh-Au bond formation at 500 K. The 3D Au nanoparticles of 2-3 nm diameter and ∼1 nm height are partially covered by TiOx species at RT and sinter via an Ostwald-ripening in the range of 500-800 K. The adparticles are gradually getting free of TiOx decoration, and at around 900 K they exhibit a double layer height with 2D character. Two different arrangements were found for these Au particles: (i) a compressed Au(111)-(1 × 1) and (ii) a reconstructed Au(111)-(2 × 1), both of them pseudomorphic with the Rh lattice underneath. Above 900 K, the thickness of these 2D particles tends to become a single layer, while they spread out and form a continuous gold layer on the Rh nanoparticles. This behavior indicates a thermally activated replacement of the w-TiO-UTO film by an Au ultrathin layer. The gold layer is stable up to 1000 K, where extended 1D interfaces are formed between gold and w-TiO-UTO layers. PMID:25417893

  20. Atmospheric corrosion effects of HNO 3—Influence of temperature and relative humidity on laboratory-exposed copper

    NASA Astrophysics Data System (ADS)

    Samie, Farid; Tidblad, Johan; Kucera, Vladimir; Leygraf, Christofer

    The effect of HNO 3 on the atmospheric corrosion of copper has been investigated at varied temperature (15-35 °C) and relative humidity (0-85% RH). Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD) confirmed the existence of cuprite and gerhardtite as the two main corrosion products on the exposed copper surface. For determination of the corrosion rate and for estimation of the deposition velocity ( Vd) of HNO 3 on copper, gravimetry and ion chromatography has been employed. Temperature had a low effect on the corrosion of copper. A minor decrease in the mass gain was observed as the temperature was increased to 35 °C, possibly as an effect of lower amount of cuprite due to a thinner adlayer on the metal surface at 35 °C. The Vd of HNO 3 on copper, however, was unaffected by temperature. The corrosion rate and Vd of HNO 3 on copper was the lowest at 0% RH, i. e. dry condition, and increased considerably when changing to 40% RH. A maximum was reached at 65% RH and the mass gain remained constant when the RH was increased to 85% RH. The Vd of HNO 3 on copper at ⩾65% RH, 25 °C and 0.03 cm s -1 air velocity was as high as 0.15±0.03 cm s -1 to be compared with the value obtained for an ideal absorbent, 0.19±0.02 cm s -1. At sub-ppm levels of HNO 3, the corrosion rate of copper decreased after 14 d and the growth of the oxide levelled off after 7 d of exposure.

  1. Utilizing a Key Aptamer Structure-Switching Mechanism for the Ultrahigh Frequency Detection of Cocaine.

    PubMed

    Neves, Miguel A D; Blaszykowski, Christophe; Thompson, Michael

    2016-03-15

    Aptasensing of small molecules remains a challenge as detection often requires the use of labels or signal amplification methodologies, resulting in both difficult-to-prepare sensor platforms and multistep, complex assays. Furthermore, many aptasensors rely on the binding mechanism or structural changes associated with target capture by the aptameric probe, resulting in a detection scheme customized to each aptamer. It is in this context that we report herein a sensitive cocaine aptasensor that offers both real-time and label-free measurement capabilities. Detection relies on the electromagnetic piezoelectric acoustic sensor (EMPAS) platform. The sensing interface consists of a S-(11-trichlorosilyl-undecanyl)benzenethiosulfonate (BTS) adlayer-coated quartz disc onto which a structure-switching cocaine aptamer (MN6) is immobilized, completing the preparation of the MN6 cocaine aptasensor (M6CA). The EMPAS system has recently been employed as the foundation of a cocaine aptasensor based on a structurally rigid cocaine aptamer variant (MN4), an aptasensor referred to by analogy as M4CA. M6CA represents a significant increase in terms of analytical performance, compared to not only M4CA but also other cocaine aptamer-based sensors that do not rely on signal amplification, producing an apparent K(d) of 27 ± 6 μM and a 0.3 μM detection limit. Remarkably, the latter is in the range of that achieved by cocaine aptasensors relying on signal amplification. Furthermore, M6CA proved to be capable not only of regaining its cocaine-binding ability via simple buffer flow over the sensing interface (i.e., without the necessity to implement an additional regeneration step, such as in the case of M4CA), but also of detecting cocaine in a multicomponent matrix possessing potentially assay-interfering species. Finally, through observation of the distinct shape of its response profiles to cocaine injection, demonstration was made that the EMPAS system in practice offers the

  2. Oxidation of CO on a Pt-Fe alloy electrode studied by surface enhanced infrared reflection--absorption spectroscopy

    SciTech Connect

    Watanabe, Masahiro; Zhu, Yimin; Uchida, Hiroyuki

    2000-03-02

    To clarify the CO-tolerant mechanism at Pt-based alloy anode catalysts, surface-enhanced infrared reflection-absorption spectroscopy with the attenuated total reflection technique (ATR-SEIRAS), coupled with CV measurement, was used to observe the oxidation process of adsorbed CO on a typical Pt-Fe (Pt-Fe = 0.27/0.73) alloy. The alloy electrode exhibits a lower saturated coverage of CO ({theta}{sub co} = 0.55) than that of pure Pt ({theta}{sub co} = 1.0). The dominating linear CO is observed around 2,000 cm{sup {minus}1} when the equilibrium adlayer of CO covers the alloy electrode; however, linear and bridged CO and also COOH were found at the pure Pt electrode at the same CO coverage in the non-steady-state. On the basis of previous results that a Pt skin is formed during the repetitive potential cycling due to the dissolution of Fe on the alloy surface and the skin exhibits less electronic density in the d band, it can be explained that the lowered linear CO coverage and almost no bridged CO are obtained as the result of the lowered back-donation of d electrons from the Pt skin to adsorbates on the alloy surface. The wavenumber shift of the linear CO stretching to a lower value at the alloy, which is not simple predicted by the lowering of the back-donation of the electron, is ascribed to the weakening of the C -Pt bond. As a presumable effect of the electronic structure change at the Pt skin, the dissociation-oxidation of adsorbed water as well as a formation of adsorbed HOOH species are clearly observed beyond 0.6 V in the electrolyte solution without CO, which is different from that at the pure Pt electrode. Carbonate species can also be detected around 1,300--1,450 cm{sup {minus}1}, which are possibly produced by the surface reaction of CO{sub 2} with water.

  3. Thermal and Nonthermal Processes on Single Crystal Transition Metal Surfaces

    NASA Astrophysics Data System (ADS)

    Guo, Xingcai

    This dissertation contains three parts. Part I, "Fundamentals", provides concise description of concepts, detailed accounts of historic studies, and extensive reviews of current activities. Chapter 1 deals with thermal processes (adsorption and desorption), and Chapter 2 with nonthermal processes induced by electrons and by photons. Part II, "Experimental" (Chapter 3), describes the ultrahigh vacuum apparatus, surface science techniques, and procedures for single crystal preparation and gas exposure. Part III, "Results", is a collection of ten selected publications in refereed journals. Each chapter is self-contained. Thermal desorption of CO from Pd(111) (Chapter 4) has been studied by temperature programmed desorption. It is demonstrated that the effective desorption kinetic parameters extracted from desorption spectra are correlated with the adlayer structures and dependent on the sizes of ordered domains--a nonequilibrium effect. Site exchange of CO (Chapter 5) and site retention of O_2 (Chapter 6) on Pt(112) during thermal desorption are observed with isotope labeled adsorption on specific sites--steps or terraces. The adsorption and desorption kinetics of O _2 are compared on Pt(111) and Pt(112) surfaces (Chapter 7). The mechanisms of adsorption and the effect of well-defined defects are elucidated. O_2 adsorbed on Pd(111) is studied with thermal activation (Chapter 8), electron impact (Chapter 9), and photon irradiation (Chapter 10 -12). Various thermal processes are delineated with isotopic mixing experiments. Electron-induced conversion, dissociation, and desorption processes are observed. Cross sections (10^{-17} cm^2 ) and their electron energy dependences (0-500 eV) are measured. A resonance-enhanced desorption of atomic oxygen from Pd(111) is found at ~10 eV. Photon-induced conversion, dissociation, and desorption processes are observed. Cross sections (10^ {-19} cm^2) and photon energy dependence (1.4-5.4 eV) are extracted. Possible mechanisms are

  4. Continuum studies of microstructure formation in metallic and organic thin films

    NASA Astrophysics Data System (ADS)

    Muralidharan, Srevatsan

    In this dissertation, microstructure formation processes in binary metallic ultra-thin films and organic polycrystalline thin films are studied through a combination of theoretical model development, analysis, and numerical simulations. In binary metallic films, to investigate compositional patterning and misfit dislocation formation, a quantitative approach based on the so called phase-field crystal method is developed. Both through analysis and simulations of the model, a number of generic and limiting cases of surface alloy epitaxial systems are investigated to examine the effects of lattice mismatch, adlayer-substrate interaction potential, and line tension on equilibrium compositional domain size. A procedure is developed to quantitatively relate the parameters of the model to a specific system [CoAg/Ru(0001)], and it is demonstrated that simulations capture experimentally observed morphologies. Then, the model is employed to investigate the effects of misfit strain fields in the substrate on both heterogeneous nucleation behavior and anisotropic growth of islands at submonolayer coverages and compositional patterning at complete monolayer coverage via simulations. In particular, in the case of binary systems at complete monolayer coverage, strain-stabilized compositional domains emerge at low line tension values for both substrates. Interestingly, the compositional domains on the QC substrate inherit their symmetries at sufficiently low line tension values, while at larger line tension values, the domain structure begins to resemble the classical spinodal microstructure. These studies will enable physically-based design of nanoscale features for a broad range of applications, such as catalysis. In organic polycrystalline films, our focus is on determining the effects of additives and substrate templating on nucleation and grain growth behavior of solution processed triethylsilylethynyl anthradithiophene films. Through a mean-field approach, it is demonstrated

  5. The Impact of Back-Sputtered Carbon on the Accelerator Grid Wear Rates of the NEXT and NSTAR Ion Thrusters

    NASA Technical Reports Server (NTRS)

    Soulas, George C.

    2013-01-01

    A study was conducted to quantify the impact of back-sputtered carbon on the downstream accelerator grid erosion rates of the NASA's Evolutionary Xenon Thruster (NEXT) Long Duration Test (LDT1). A similar analysis that was conducted for the NASA's Solar Electric Propulsion Technology Applications Readiness Program (NSTAR) Life Demonstration Test (LDT2) was used as a foundation for the analysis developed herein. A new carbon surface coverage model was developed that accounted for multiple carbon adlayers before complete surface coverage is achieved. The resulting model requires knowledge of more model inputs, so they were conservatively estimated using the results of past thin film sputtering studies and particle reflection predictions. In addition, accelerator current densities across the grid were rigorously determined using an ion optics code to determine accelerator current distributions and an algorithm to determine beam current densities along a grid using downstream measurements. The improved analysis was applied to the NSTAR test results for evaluation. The improved analysis demonstrated that the impact of back-sputtered carbon on pit and groove wear rate for the NSTAR LDT2 was negligible throughout most of eroded grid radius. The improved analysis also predicted the accelerator current density for transition from net erosion to net deposition considerably more accurately than the original analysis. The improved analysis was used to estimate the impact of back-sputtered carbon on the accelerator grid pit and groove wear rate of the NEXT Long Duration Test (LDT1). Unlike the NSTAR analysis, the NEXT analysis was more challenging because the thruster was operated for extended durations at various operating conditions and was unavailable for measurements because the test is ongoing. As a result, the NEXT LDT1 estimates presented herein are considered preliminary until the results of future post-test analyses are incorporated. The worst-case impact of carbon

  6. The Impact of Back-Sputtered Carbon on the Accelerator Grid Wear Rates of the NEXT and NSTAR Ion Thrusters

    NASA Technical Reports Server (NTRS)

    Soulas, George C.

    2013-01-01

    A study was conducted to quantify the impact of back-sputtered carbon on the downstream accelerator grid erosion rates of the NEXT (NASA's Evolutionary Xenon Thruster) Long Duration Test (LDT1). A similar analysis that was conducted for the NSTAR (NASA's Solar Electric Propulsion Technology Applications Readiness Program) Life Demonstration Test (LDT2) was used as a foundation for the analysis developed herein. A new carbon surface coverage model was developed that accounted for multiple carbon adlayers before complete surface coverage is achieved. The resulting model requires knowledge of more model inputs, so they were conservatively estimated using the results of past thin film sputtering studies and particle reflection predictions. In addition, accelerator current densities across the grid were rigorously determined using an ion optics code to determine accelerator current distributions and an algorithm to determine beam current densities along a grid using downstream measurements. The improved analysis was applied to the NSTAR test results for evaluation. The improved analysis demonstrated that the impact of back-sputtered carbon on pit and groove wear rate for the NSTAR LDT2 was negligible throughout most of eroded grid radius. The improved analysis also predicted the accelerator current density for transition from net erosion to net deposition considerably more accurately than the original analysis. The improved analysis was used to estimate the impact of back-sputtered carbon on the accelerator grid pit and groove wear rate of the NEXT Long Duration Test (LDT1). Unlike the NSTAR analysis, the NEXT analysis was more challenging because the thruster was operated for extended durations at various operating conditions and was unavailable for measurements because the test is ongoing. As a result, the NEXT LDT1 estimates presented herein are considered preliminary until the results of future posttest analyses are incorporated. The worst-case impact of carbon back

  7. Surface chemical deposition of advanced electronic materials

    NASA Astrophysics Data System (ADS)

    Bjelkevig, Cameron

    The focus of this work was to examine the direct plating of Cu on Ru diffusion barriers for use in interconnect technology and the substrate mediated growth of graphene on boron nitride for use in advanced electronic applications. The electrodeposition of Cu on Ru(0001) and polycrystalline substrates (with and without pretreatment in an iodine containing solution) has been studied by cyclic voltammetry (CV), current--time transient measurements (CTT), in situ electrochemical atomic force microscopy (EC-AFM), and X-ray photoelectron spectroscopy (XPS). The EC-AFM data show that at potentials near the OPD/UPD threshold, Cu crystallites exhibit pronounced growth anisotropy, with lateral dimensions greatly exceeding vertical dimensions. XPS measurements confirmed the presence and stability of adsorbed I on the Ru surface following pre-treatment in a KI/H2SO4 solution and following polarization to at least -200 mV vs. Ag/AgCl. CV data of samples pre-reduced in I-containing electrolyte exhibited a narrow Cu deposition peak in the overpotential region and a UPD peak. The kinetics of the electrodeposited Cu films was investigated by CTT measurements and applied to theoretical models of nucleation. The data indicated that a protective I adlayer may be deposited on an airexposed Ru electrode as the oxide surface is electrochemically reduced, and that this layer will inhibit reformation of an oxide during the Cu electroplating process. A novel method for epitaxial graphene growth directly on a dielectric substrate of systematically variable thickness was studied. Mono/multilayers of BN(111) were grown on Ru(0001) by atomic layer deposition (ALD), exhibiting a flat (non-nanomesh) R30(✓3x✓3) structure. BN(111) was used as a template for growth of graphene by chemical vapor deposition (CVD) of C2H4 at 1000 K. Characterization by LEED, Auger, STM/STS and Raman indicate the graphene is in registry with the BN substrate, and exhibits a HOPG-like 0 eV bandgap density

  8. Ultrafast studies of electron dynamics at metal-dielectric interfaces

    SciTech Connect

    Ge, Nien-Hui

    1998-10-01

    Femtosecond time- and angle-resolved two-photon photoemission spectroscopy has been used to study fundamental aspects of excited electron dynamics at metal-dielectric interfaces, including layer-by-layer evolution of electronic structure and two-dimensional electron localization. On bare Ag(111), the lifetimes of image states are dominated by their position with respect to the projected bulk band structure. The n = 2 state has a shorter lifetime than the n = 1 state due to degeneracy with the bulk conduction band. As the parallel momentum of the n = 1 image electron increases, the lifetime decreases. With decreasing temperatures, the n = 1 image electrons, with zero or nonzero parallel momentum, all become longer lived. Adsorption of one to three layers of n-heptane results in an approximately exponential increase in lifetime as a function of layer thickness. This results from the formation of a tunneling barrier through which the interfacial electrons must decay, consistent with the repulsive bulk electron affinity of n-alkanes. The lifetimes of the higher quantum states indicate that the presence of the monolayer significantly reduces coupling of the image states to the bulk band structure. These results are compared with predictions of a dielectric continuum model. The study of electron lateral motion shows that optical excitation creates interfacial electrons in quasifree states for motion parallel to the n-heptane/Ag(111) interface. These initially delocalized electrons decay into a localized state within a few hundred femtoseconds. The localized electrons then decay back to the metal by tunneling through the adlayer potential barrier. The localization time depends strongly on the electron's initial parallel momentum and exhibits a non-Arrhenius temperature dependence. The experimental findings are consistent with a 2-D self-trapping process in which electrons become localized by interacting with the topmost plane of the alkane layer. The energy dependence of

  9. The Effect of Hydrogen on the Bonding and Dissociation of Carbon Monoxide on AN IRON(100) Surface

    NASA Astrophysics Data System (ADS)

    Nassir, Mohamed Husain

    1993-01-01

    results in isolating the alpha^'_2 state. Another effect of preadsorbed hydrogen appears in the alpha_3 state. The ratio of dissociation to desorption changes and suggests that hydrogen may induce island formation in the CO adlayer. Both factors, weakening CO-Fe bonds and influencing the dissociation/desorption ratio, might play an important role in the Fischer-Tropsch synthesis.

  10. Surface relaxation phenomena at electrified interfaces: Revealing adsorbate, potential, and solvent effects by combined x-ray diffraction, STM and DFT studies

    NASA Astrophysics Data System (ADS)

    Saracino, Martino; Broekmann, Peter; Gentz, Knud; Becker, Moritz; Keller, Hubert; Janetzko, Florian; Bredow, Thomas; Wandelt, Klaus; Dosch, Helmut

    2009-03-01

    Surface relaxation phenomena have been studied in an electrochemical environment using halide modified Cu(100) electrodes as model systems to unravel the impact of the chemical nature of the adsorbed halide, the applied potential, and the presence of solvent species on the surface interlayer spacings. Both, in situ STM and in situ x-ray scattering data point to lateral structures of the adsorbed halides on Cu(100) which are identical for both chloride and bromide. Under saturation conditions both halides form a p(1×1) adlayer on Cu(100) with reference to a conventional choice of the substrate fcc unit cell. The in situ x-ray scattering data clearly indicate that the copper-halide and the copper-copper interlayer spacings are much more affected by potential changes when bromide is adsorbed on the copper surface and are less affected when chloride is present. This difference in the potential dependence of both halides can be attributed to the larger polarizability of the bromide anion that is almost discharged on the copper surface at the highest applied potentials, while chloride remains largely ionic in the adsorbed state even at the highest applied potential. At the lowest applied potential of Ework=-150mV [vs reversible hydrogen electrode (RHE)] the Br-Cu and the topmost Cu-Cu layer distances are expanded by 0.150 and 0.058Å , respectively, with reference to their bulk analogs CuBr and Cu. These spacings continuously contract by up to 0.075 and 0.038Å when the electrode potential is increased to Ework=+50mV (RHE). Intriguingly, the second Cu layer experiences a potential-dependent buckling due to a different second-shell coordination of Cu by bromide while deeper Cu layers retain the bulk spacing at all potentials. Changes in the halide-copper and the copper-copper interlayer spacings are strongly correlated. An understanding of the in situ x-ray results is achieved by periodic quantum-chemical calculations at density-functional level that allow a modeling of

  11. Water Accommodation on Bare and Coated Ice

    NASA Astrophysics Data System (ADS)

    Kong, Xiangrui

    2015-04-01

    A good understanding of water accommodation on ice surfaces is essential for quantitatively predicting the evolution of clouds, and therefore influences the effectiveness of climate models. However, the accommodation coefficient is poorly constrained within the literature where reported values vary by up to three orders of magnitude. In addition, the complexity of the chemical composition of the atmosphere plays an important role in ice phase behavior and dynamics. We employ an environmental molecular beam (EMB) technique to investigate molecular water interactions with bare and impurity coated ice at temperatures from 170 K to 200 K. In this work, we summarize results of water accommodation experiments on bare ice (Kong et al., 2014) and on ice coated by methanol (Thomson et al., 2013), butanol (Thomson et al., 2013) and acetic acid (Papagiannakopoulos et al., 2014), and compare those results with analogous experiments using hexanol and nitric acid coatings. Hexanol is chosen as a complementary chain alcohol to methanol and butanol, while nitric acid is a common inorganic compound in the atmosphere. The results show a strong negative temperature dependence of water accommodation on bare ice, which can be quantitatively described by a precursor model. Acidic adlayers tend to enhance water uptake indicating that the system kinetics are thoroughly changed compared to bare ice. Adsorbed alcohols influence the temperature dependence of the accommodation coefficient and water molecules generally spend less time on the surfaces before desorbing, although the measured accommodation coefficients remain high and comparable to bare ice for the investigated systems. We conclude that impurities can either enhance or restrict water uptake in ways that are influenced by several factors including temperature and type of adsorbant, with potential implications for the description of ice particle growth in the atmosphere. This work was supported by the Swedish Research Council and

  12. Photooxidation and Photodesorption in the Photochemistry of Isobutene on TiO2(110)

    SciTech Connect

    Henderson, Michael A.

    2013-07-11

    The photochemistry of isobutene was examined on the rutile TiO2(110) surface as a function of the surface pretreatment condition and irradiation temperature using temperature programmed desorption (TPD) and photon stimulated desorption (PSD). Isobutene adsorbs molecularly on the clean TiO2(110) surface without detectable thermal decomposition. Preadsorption of oxygen, either as atoms or chemisorbed molecules, did not promote thermal reactions with isobutene, but instead blocked isobutene adsorption sites. Ultraviolet (UV) light irradiation of isobutene adsorbed on the clean surface led to depletion through photodesorption without significant photodecomposition. Isobutene PSD yields increased with increasing surface temperature suggesting that activated molecules sample their physisorbed potential energy surface during photodesorption. Preadsorption of oxygen promoted partial photooxidation of adsorbed isobutene to acetone, methacrolein and isobutanal. Acetone was only detected when molecular oxygen was present, indicating that O2 addition occurred across the C=C bond. In contrast, results from use of D6-isobutene indicated that coadsorption with either O adatoms or O2 molecules led to photochemical production of methacrolein (and likely isobutanal) through C-H bond cleavage on a methyl group. Irradiation an adlayer comprised of isobutene isolated from the surface by 1 ML of preadsorbed O2 showed the most photoconversion of isobutene, which suggests that photoactivation of adsorbed O2 is a key step in partial photooxidation of isobutene. Comparison of the isobutene PSD and oxidation product yields as a function of surface temperature between 20 and 120 K indicates a competition between photooxidation and photodesorption that varies with temperature. ‘Direct’ charge transfer events between isobutene and the surface, favored at higher temperature, compete with partial oxidation pathways initiated by ‘indirect’ activation of isobutene by O2, which is favored at

  13. Trimethylaluminum and Oxygen Atomic Layer Deposition on Hydroxyl-Free Cu(111)

    PubMed Central

    2015-01-01

    Atomic layer deposition (ALD) of alumina using trimethylaluminum (TMA) has technological importance in microelectronics. This process has demonstrated a high potential in applications of protective coatings on Cu surfaces for control of diffusion of Cu in Cu2S films in photovoltaic devices and sintering of Cu-based nanoparticles in liquid phase hydrogenation reactions. With this motivation in mind, the reaction between TMA and oxygen was investigated on Cu(111) and Cu2O/Cu(111) surfaces. TMA did not adsorb on the Cu(111) surface, a result consistent with density functional theory (DFT) calculations predicting that TMA adsorption and decomposition are thermodynamically unfavorable on pure Cu(111). On the other hand, TMA readily adsorbed on the Cu2O/Cu(111) surface at 473 K resulting in the reduction of some surface Cu1+ to metallic copper (Cu0) and the formation of a copper aluminate, most likely CuAlO2. The reaction is limited by the amount of surface oxygen. After the first TMA half-cycle on Cu2O/Cu(111), two-dimensional (2D) islands of the aluminate were observed on the surface by scanning tunneling microscopy (STM). According to DFT calculations, TMA decomposed completely on Cu2O/Cu(111). High-resolution electron energy loss spectroscopy (HREELS) was used to distinguish between tetrahedrally (Altet) and octahedrally (Aloct) coordinated Al3+ in surface adlayers. TMA dosing produced an aluminum oxide film, which contained more octahedrally coordinated Al3+ (Altet/Aloct HREELS peak area ratio ≈ 0.3) than did dosing O2 (Altet/Aloct HREELS peak area ratio ≈ 0.5). After the first ALD cycle, TMA reacted with both Cu2O and aluminum oxide surfaces in the absence of hydroxyl groups until film closure by the fourth ALD cycle. Then, TMA continued to react with surface Al–O, forming stoichiometric Al2O3. O2 half-cycles at 623 K were more effective for carbon removal than O2 half-cycles at 473 K or water half-cycles at 623 K. The growth rate was approximately 3–4

  14. Amphiphilic Macromolecule Self-Assembled Monolayers Suppress Smooth Muscle Cell Proliferation.

    PubMed

    Chan, Jennifer W; Zhang, Yingyue; Uhrich, Kathryn E

    2015-07-15

    A significant limitation of cardiovascular stents is restenosis, where excessive smooth muscle cell (SMC) proliferation following stent implantation causes blood vessel reocclusion. While drug-eluting stents minimize SMC proliferation through releasing cytotoxic or immunosuppressive drugs from polymer carriers, significant issues remain with delayed healing, inflammation, and hypersensitivity reactions associated with drug and polymer coatings. Amphiphilic macromolecules (AMs) comprising a sugar-based hydrophobic domain and a hydrophilic poly(ethylene glycol) tail are noncytotoxic and recently demonstrated a concentration-dependent ability to suppress SMC proliferation. In this study, we designed a series of AMs and studied their coating properties (chemical composition, thickness, grafting density, and coating uniformity) to determine the effect of headgroup chemistry on bioactive AM grafting and release properties from stainless steel substrates. One carboxyl-terminated AM (1cM) and two phosphonate- (Me-1pM and Pr-1pM) terminated AMs, with varying linker lengths preceding the hydrophobic domain, were grafted to stainless steel substrates using the tethering by aggregation and growth (T-BAG) approach. The AMs formed headgroup-dependent, yet uniform, biocompatible adlayers. Pr-1pM and 1cM demonstrated higher grafting density and an extended release from the substrate over 21 days compared to Me-1pM, which exhibited lower grafting density and complete release within 7 days. Coinciding with their release profiles, Me-1pM and 1cM coatings initially suppressed SMC proliferation in vitro, but their efficacy decreased within 7 and 14 days, respectively, while Pr-1pM coatings suppressed SMC proliferation over 21 days. Thus, AMs with phosphonate headgroups and propyl linkers are capable of sustained release from the substrate and have the ability to suppress SMC proliferation during the restenosis that occurs in the 3-4 weeks after stent implantation, demonstrating the

  15. Surface modeling of thin film growth: A study of silicon oxide deposition from tetraethoxysilane and silicon deposition from disilane on the Si(100) surface

    SciTech Connect

    Cho, Hee-Chuen.

    1993-01-01

    In this thesis, surface reactions brought about by the pyrolysis of adsorbed TEOS, the modeling of this reaction with ethanol, and the photolysis of adsorbed disilane have been investigated under ultrahigh vacuum conditions, using mainly temperature programmed desorption (TPD). TEOS molecularly desorbs at about 195K when adsorbed on clean Si(100) at low temperatures. When adsorbed at 300K, the primary surface species produced is a mixture of ethoxysiloxanes. Upon heating the surface in vacuum, the adsorbed ethoxysiloxanes decompose the evolve ethylene and hydrogen, with trace production of acetylene and acetaldehyde. In a parallel study, the adsorption and subsequent deposition of ethanol (C[sub 2]H[sub 5]OH, C[sub 2]D[sub 5]OD, and CH[sub 3]CD[sub 2]OH) on Si(100) has been shown to model the TEOS system. The molecular desorption temperature is ca. 150K. When adsorbed at 200K, ethanol dissociatively chemisorbs as an ethoxide and the monohydride species. The adlayer decomposes at higher temperature to evolve ethylene, hydrogen, acetaldehyde, and acetylene. The adsorption and decomposition of ethanol on Si(100)-2x1:H has also been studied in gathering additional information about the competition between distinct decomposition mechanisms, and the nature of the reaction site. In the Si[sub 2]H[sub 6]/Si(100) system, with no UV irradiation, disilane adsorption at 120K produces a chemisorbed SiH[sub x] (x = 1 - 3) layer and, for high exposures, a disilane multilayer. Upon heating the surface in vacuum, molecular desorption is observed at ca. 150K, while hydrogen and silane are evolved at much higher temperatures. For Si[sub 2]H[sub 6] exposure during photo-irradiation, the desorption yields of hydrogen and silane are enhanced. Model studies using the partially and fully deuterated Si(100)-2x1:D surface reveals that the photo-induced surface reaction is dominated by an insertion reaction by the photo-generated silylene species.

  16. The effects of the specific adsorption of anion on the reactivity of the Ru(0001) surface towards CO adsorption and oxidation: in situ FTIRS studies.

    PubMed

    Jin, J M; Lin, W F; Christensen, P A

    2008-07-01

    The dynamics of adsorption and oxidation of CO on Ru(0001) electrode in sulfuric acid solution have been studied using in situ FTIR spectroscopy under potential control and at open circuit, the latter at 20 and 55 degrees C. The in situ IR data show clearly that the bisulfate anion adsorbs on the Ru(0001) surface over the potential range from -200 mV to 350 mV (vs. Ag/AgCl) at 20 degrees C in the absence and presence of adsorbed CO; however, increasing the temperature to 55 degrees C and/or increasing the concentration of dissolved O(2) reduces the bisulfate adsorption. The formation of surface (hydro-) oxide at higher potentials replaces the bisulfate adsorbates. Both linear (CO(L)) and three-fold hollow bonded CO (CO(H)) adsorbates were produced following CO adsorption at Ru(0001) in H(2)SO(4), as was observed in our previous studies in HClO(4). However, the amount of adsorbed CO observed in H(2)SO(4) was ca. 10% less than that in HClO(4); in addition, the CO(L) and CO(H) frequencies were higher in H(2)SO(4), and the onset potential for CO(ads) oxidation 25 mV lower. These new results are interpreted in terms of a model in which the adsorbed bisulfate weakens the CO adlayer, allowing the active Ru oxide layer to form at lower potentials. Significantly different results were observed at open circuit in H(2)SO(4) compared both to the data under potential control and to our earlier data in HClO(4), and these observations were rationalized in terms of the adsorbed HSO(4)(-) anions (pre-adsorbed at -200 mV) inhibiting the oxidation of the surface at open circuit (after stepping from the initial potential of -200 mV), as the latter was no longer driven by the imposed electrochemical potential but via chemical oxidation by trace dissolved O(2). Results from experiments at open circuit at 55 degrees C and using oxygen-saturated H(2)SO(4) supported this model. The difference in Ru surface chemistry between imposed electrochemical control and chemical control has potential

  17. Structure and dynamics of ultrathin organic films

    NASA Astrophysics Data System (ADS)

    Kiktyeva, Tatyana A.

    Existing and newly developed nonlinear optical methods have been used to characterize molecular structure, orientation and dynamics at interfaces. Optical second harmonic generation (SHG) studies have been conducted on molecular films of the organic dyes, rhodamine 6G and malachite green, adsorbed at the fused silica/air interface. The second harmonic response from the organic dye films was found to be a non-monotonic function of the surface concentration with discontinuities corresponding to completion of successive monolayers. This behavior reflects ordering of molecular adlayers, which extends for several layers. Polarized SHG studies in conjunction with optical absorbance and fluorescence measurements were used to determine the type of interactions responsible for the adsorption in the ordered layers. The results indicate that the well-defined order within the first layer is due to the specific adsorbate-substrate interactions. Orientation in subsequent layers is teed by adsorbate-adsorbate interactions, dependent on the nature of the adsorbate and consequently on its orientation within the first layer. These results provide a direct measure of the extent of the interfacial ordering and molecular interactions at the solid/air interface and can be used to determine an adsorbate's filling factor. Time and frequency resolved vibrational spectra of a monolayer of amphiphilic molecules at the CaF2/air interface were investigated using infrared-visible sum frequency generation. Vibrational wave packet dynamics following coherent excitation of CH3 vibrational modes with broad bandwidth infrared pulses is reported. The induced macroscopic polarization displays quantum interference effects (quantum beats) and decays on a time scale dependent on the nature of the interfacial environment. These observations provide a link between the degree of structural order of the monolayer and the vibrational coherence lifetime. Monitoring interfacial wave packet dynamics represents a

  18. Surface structure and composition determination by low-energy electron scattering and Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Sun, Jiebing

    -IV technique. The reconstructed Si(001)-2x1 surface has been intriguing due to its great scientific and technical significance. Unfortunately, no satisfactory agreement between the LEED experimental and theoretical data have been achieved. Some controversies over this surface, such as the flip-flop dimer dynamics and the ground-state structure, still require further study. Utilizing LEEM to get electron scattering spectra from a single domain, we get a refined asymmetric tilted dimer structure. We investigate the 6H-SiC(0001) surface phase transition in order to ultimately understand the formation of graphene on it. LEEM diffraction data from a large single domain are analyzed for 3x3, 1x1 and 3x3 phases. All the surface structures turn out to have an "A" bi-layer bulk termination. It is found that the amount of Si at the surface decreases with increased temperature. Adatom-trimer-adlayer model for the 3x3 surface does not give a satisfactory result and more work needs to be done to resolve this structure. A mixed Si-vacancy top-site overlayer on the 1x1 surface is found. A 3x3 overlayer at the T4 registry on the substrate surface generates a best fit between experimental and calculated data.

  19. CO oxidation on Pt-modified Rh(111) electrodes.

    PubMed

    Housmans, T H M; Feliu, J M; Gómez, R; Koper, M T M

    2005-08-12

    the Pt4-Rh(111) current-time transients recorded at 0.635, 0.675, and 0.750 V versus RHE (reversible hydrogen electrode) with those of pure Rh(111) and Pt(111) shows greatly reduced reaction times. A Cottrellian decay at long times indicates surface-diffusion-limited CO oxidation on the bare Rh(111) surface, while the peak visible at short times is indicative of CO reacting at the monolayer platinum islands. The results presented here show that, as indicated by density functional theory (DFT) calculations, the CO-adlayer oxidation for this system is enhanced compared to both pure Rh and Pt. PMID:16035023

  20. Roles of Fe2+, Fe3+, and Cr3+ Surface Sites in the Oxidation of NO on the (Fe,Cr)3O4(1 1 1) Surface Termination of an α-(Fe,Cr)2O3(0 0 0 1) Mixed Oxide

    SciTech Connect

    Henderson, Michael A.

    2014-10-01

    +O2 adlayer to 250 K prior to 460 nm light irradiation restored the level of thermal NO oxidation, revealing both that thermal activation is required for NO oxidation on the (Fe,Cr)3O4(111) surface and that the nitrate product was insensitive to 460 nm light. The author thanks Drs. Sara Chamberlin and Scott Chambers for supplying the film used in this work. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. The research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.