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Sample records for adlay coix lachryma-jobi

  1. Characterization of oil bodies in adlay (Coix lachryma-jobi L).

    PubMed

    Lu, Hsi-Chi; Jiang, Pei-Luen; Hsu, Light R C; Chyan, Chia-Lin; Tzen, Jason T C

    2010-01-01

    Oil bodies were observed in cells of both embryo and aleurone layers of mature adlay grains (Coix lachryma-jobi L. var. ma-yuen Stapf). Stable oil bodies were successfully isolated from the adlay grains. Thin-layer chromatography revealed that the contents stored in the adlay oil bodies were mainly neutral lipids (>90% triacylglycerols and about 5% diacylglycerols). The integrity of the isolated oil bodies was presumably maintained via electronegative repulsion and steric hindrance provided by their surface proteins. Immunological cross-recognition using antibodies against sesame oil-body proteins indicated that two oleosin isoforms (termed oleosin-H and oleosin-L) and one caleosin were present in the adlay oil bodies. Full-length cDNA fragments encoding these three unique oil-body proteins were obtained by PCR cloning. MALDI-MS analyses confirmed that the three full-length cDNA fragments encoded the two oleosin isoforms and one caleosin observed in the oil bodies isolated from the adlay grains.

  2. Osteoporosis Prevention by Adlay ( Yì Yǐ: The Seeds of Coix Lachryma-Jobi L. var. ma-yuen Stapf) in a Mouse Model.

    PubMed

    Yang, Rong-Sen; Lu, Yi-Hsiang; Chiang, Wenchang; Liu, Shing-Hwa

    2013-04-01

    Osteoporosis is characterized by reduced bone mass and quality due to an imbalanced bone remodeling. A grass crop, adlay (Coix lachryma-jobi), is a kind of nourishing food, which has also been used in traditional Chinese medicine. In this study, we investigated the effect of adlay (C. lachryma-jobi L. var. ma-yuen Stapf) on osteoporosis using an ovariectomized mouse model. The adlay diet (10% and 30% adlay in mouse diet) or water extract of adlay (0.3 g/kg/day) was given to ovariectomized mice for 4 weeks. In some experiments, the primary rat osteoblast cells were used to test the possible mechanism of adlay on osteoporosis. The body weight was slightly increased and uterus weight was markedly decreased in ovariectomized mice, which were not affected by adlay treatment. Adlay diet (30%) and adlay extract feedings significantly reversed the decreased bone alkaline phosphatase activity and calcium contents and bone mineral density in ovariectomized mice. Moreover, adlay extracts increased the osteoblast cell proliferation in a dose-dependent manner. Adlay extracts also increased the protein expressions of proliferating cell nuclear antigen and phosphorylated extracellular signal-regulated kinase (ERK) 1/2 in osteoblast cells. ERK inhibitor PD98059 significantly reversed the increased osteoblast cell proliferation by adlay extracts. Taken together, these findings indicate that adlay effectively alleviates the osteoporotic status in ovariectomized mice. Adlay is capable of increasing the proliferation of osteoblast cells via an ERK-regulated signaling pathway. Adlay may be a helpful healthy food for osteoporosis prevention.

  3. Molecular cloning, mass spectrometric identification, and nutritional evaluation of 10 coixins in adlay ( Coix lachryma-jobi L.).

    PubMed

    Lin, Li-Jen; Hsiao, Eric S L; Tseng, Hsen-Shong; Chung, Mei-Chu; Chua, Anna C N; Kuo, Ming-En; Tzen, Jason T C

    2009-11-25

    Adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) is regarded as a nutritive food source as well as herbal medicine. The food nutrition is a consequence of its high protein content and superior amino acid composition. From ca. 200 expressed sequence tag (EST) sequences in maturing adlay grains, clones encoding precursor polypeptides of 10 seed storage proteins in the prolamin family, including 8 alpha-coixin isoforms, 1 delta-coixin, and 1 gamma-coixin, were identified. Full-length cDNA fragments encoding these 10 coixins were obtained by PCR cloning. Mass spectrometric analyses confirmed the presence of these 10 coixins in the extract of adlay grain. Calculated amino acid compositions indicate that all 10 coixins are rich in glutamine (>20% in alpha-coixin isoforms, 13.3% in delta-coixin, and 31.2% in gamma-coixin). The 8 alpha-coixin isoforms are low in methionine, cysteine, and lysine (on average, 0.8, 0.6, and 0.1%, respectively). However, the delta-coixin is a sulfur-rich protein (18.2% methionine and 9.1% cysteine), and the gamma-coixin is a nutritive protein composed of 2.0% methionine, 6.6% cysteine, 2.6% lysine, and 8.9% histidine. The company of delta-coixin and gamma-coixin with alpha-coixin isoforms enhances the nutritional value of alday grain for human consumption.

  4. Osteoporosis Prevention by Adlay (薏苡 Yì Yǐ: The Seeds of Coix Lachryma-Jobi L. var. ma-yuen Stapf) in a Mouse Model

    PubMed Central

    Yang, Rong-Sen; Lu, Yi-Hsiang; Chiang, Wenchang; Liu, Shing-Hwa

    2013-01-01

    Osteoporosis is characterized by reduced bone mass and quality due to an imbalanced bone remodeling. A grass crop, adlay (Coix lachryma-jobi), is a kind of nourishing food, which has also been used in traditional Chinese medicine. In this study, we investigated the effect of adlay (C. lachryma-jobi L. var. ma-yuen Stapf) on osteoporosis using an ovariectomized mouse model. The adlay diet (10% and 30% adlay in mouse diet) or water extract of adlay (0.3 g/kg/day) was given to ovariectomized mice for 4 weeks. In some experiments, the primary rat osteoblast cells were used to test the possible mechanism of adlay on osteoporosis. The body weight was slightly increased and uterus weight was markedly decreased in ovariectomized mice, which were not affected by adlay treatment. Adlay diet (30%) and adlay extract feedings significantly reversed the decreased bone alkaline phosphatase activity and calcium contents and bone mineral density in ovariectomized mice. Moreover, adlay extracts increased the osteoblast cell proliferation in a dose-dependent manner. Adlay extracts also increased the protein expressions of proliferating cell nuclear antigen and phosphorylated extracellular signal-regulated kinase (ERK) 1/2 in osteoblast cells. ERK inhibitor PD98059 significantly reversed the increased osteoblast cell proliferation by adlay extracts. Taken together, these findings indicate that adlay effectively alleviates the osteoporotic status in ovariectomized mice. Adlay is capable of increasing the proliferation of osteoblast cells via an ERK-regulated signaling pathway. Adlay may be a helpful healthy food for osteoporosis prevention. PMID:24716168

  5. 2,2'-Diphenyl-1-picrylhydrazyl radical-scavenging active components from adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) hulls.

    PubMed

    Kuo, Ching-Chuan; Chiang, Wenchang; Liu, Guey-Ping; Chien, Ya-Lin; Chang, Jang-Yang; Lee, Ching-Kuo; Lo, Jir-Mehng; Huang, Shou-Ling; Shih, Ming-Chih; Kuo, Yueh-Hsiung

    2002-10-09

    An activity-directed fractionation and purification process was used to identify the antioxidative components of adlay hulls. Hulls of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) were extracted with methanol and then separated into water, 1-butanol, ethyl acetate, and hexane fractions. The 1-butanol-soluble fraction exhibited greater capacity to scavenge 2,2'-diphenyl-1-picrylhydrazyl (DPPH) radicals when compared with fractions soluble in water, ethyl acetate, and hexane phases. The 1-butanol fraction was then subjected to separation and purification using Diaion HP-20 chromatography, silica gel chromatography, and HPLC. Six compounds showing strong antioxidant activity were identified by spectroscopic methods ((1)H NMR, (13)C NMR, IR, and MS) and by comparison with authentic samples to be coniferyl alcohol (1), syringic acid (2), ferulic acid (3), syringaresinol (4), 4-ketopinoresinol (5), and a new lignan, mayuenolide (6).

  6. 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.

  7. Mast cell-dependent allergic responses are inhibited by ethanolic extract of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) testa.

    PubMed

    Chen, Hong-Jhang; Shih, Chun-Kuang; Hsu, Hsin-Yi; Chiang, Wenchang

    2010-02-24

    Allergy is an immune dysfunction caused by degranulation from mast cells in the early phase and cytokine secretion in the late phase of the cell. The purpose of this study was to investigate the effects of adlay (Job's tears, Coix lachryma-jobi L. var. ma-yuen Stapf) testa against beta-hexosaminidase release as a marker of degranulation in rat basophilic leukemia (RBL)-2H3 cells. The ethyl acetate fraction from ethanolic extracts of adlay testa (ATE-EtOAc) exhibited potent inhibitory activity that suppressed degranulation from RBL-2H3 cells stimulated by 1 microM A23187. The 20%-80% EtOAc/Hex subfractions of ATE-EtOAc significantly inhibited histamine release with a IC(50) of 75-100 microg/mL. In addition, the ATE-EtOAc subfractions suppressed interleukin (IL)-4, IL-6, and tumor necrosis factor-alpha secretion in RBL-2H3 cells, indicating that adlay testa were able to inhibit cytokine secretion. In order to explore the inhibitory mechanism of adlay testa in mast cell degranulation, we examined the activation of intracellular signaling molecules. Adlay testa inhibited the phosphorylation ERK expression. Furthermore, the two major active compounds, 4-hydroxyacetophenone and p-coumaric acid, were isolated from the ATE-EtOAc subfractions. These results suggest that ATE had an inhibitory effect on allergic response via the ERK signaling transduction in RBL-2H3 cells.

  8. Isolation and characterization of new lactam compounds that inhibit lung and colon cancer cells from adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) bran.

    PubMed

    Lee, Ming-Yi; Lin, Huan-You; Cheng, Faiwen; Chiang, Wenchang; Kuo, Yueh-Hsiung

    2008-06-01

    Five active compounds that inhibit cancer cells were isolated from adlay bran (Coix lachryma-jobi L. var. ma-yuen Stapf), and their structures and activities in vitro were characterized. The ethyl acetate-soluble fraction of methanol extracts of adlay bran (ABM-EtOAc) exhibited a stronger anti-proliferative effect on human lung cancer cell A549, human colorectal carcinoma cell HT-29, and COLO 205 than other fractions by MTT (3-4,5-dimethylthiazol-2-yl-2,5-diphenyl-tetrazolium bromide) assay. Assay-guided isolation gave five lactams including three that were previously undocumented; coixspirolactam A (1), coixspirolactam B (2), and coixspirolactam C (3); one isolated from the natural plant for the first time, coixlactam (4); and one known compound, methyl dioxindole-3-acetate (5). Pure active compounds were identified by spectral analysis including IR, 1H and 13C NMR, UV-vis, MS and 2D NMR techniques. All the compounds were tested for their anti-proliferative effect on A549, HT-29 and COLO 205 cells. These compounds showed anti-cancer activities with IC50 values between 28.6 and 72.6microg/mL.

  9. Protective effect of polyphenols extract of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) on hypercholesterolemia-induced oxidative stress in rats.

    PubMed

    Wang, Lifeng; Sun, Jing; Yi, Qida; Wang, Xuefeng; Ju, Xingrong

    2012-07-26

    The present study examines the effect of polyphenols extract of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) (APE) on high cholesterol diet fed rats (HCD). APE was orally administrated by gavage at doses of 10, 40 and 200 mg total phenolics/kg body weight of rats once a day for 28 days. At the end of four weeks, serum triglyceride (TG), total cholesterol (TC), low density lipoprotein cholesterol (LDL-C) and high density lipoprotein cholesterol (HDL-C), and markers of oxidative stress viz., malondialdehyde (MDA), superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GSH-Px) in the serum and liver of HCD and normal rats were assessed and compared. The results showed that administration of APE was significantly effective in decreasing the serum levels of TC, LDL-C and MDA, increasing the serum level of HDL-C and antioxidant capacity. In addition, oral gavage of APE could also increase the antioxidant capacity, CAT and GSH-Px activities in liver. These results suggested that APE exerted a high hypocholesterolemic and antioxidant activities, which might be characterized by a protective effect on cardiovascular health in vivo.

  10. Effects of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf.) hull extracts on the secretion of progesterone and estradiol in vivo and in vitro.

    PubMed

    Hsia, Shih-Min; Yeh, Chih-Lan; Kuo, Yueh-Hsiung; Wang, Paulus S; Chiang, Wenchang

    2007-10-01

    Adlay (Coix lachryma-jobi L. var. ma-yuen Stapf.) has been used as a traditional Chinese medicine for dysfunction of the endocrine system. However, there have been few studies on the effects of adlay seed on the endocrine system. In the present study, both the in vivo and in vitro effects of methanolic extracts of adlay hull (AHM) on progesterone synthesis were studied. AHM was partitioned with four different solvents: water, 1-butanol, ethyl acetate, and n-hexane. Four fractions, namely, AHM-Wa (water fraction), AHM-Bu (1-butanol fraction), AHM-EA (ethyl acetate fraction), and AHM-Hex (n-hexane fraction), were respectively obtained. Granulosa cells (GCs) were prepared from pregnant mare serum gonadotropin-primed immature female rats and were challenged with different reagents, including human chorionic gonadotropin (hCG; 0.5 IU/ml), 8-bromo-adenosine-3',5'-cyclic monophosphate (8-Br-cAMP; 0.1 mM), forskolin (10 microM), 25-OH-cholesterol (10 microM), and pregnenolone (10 microM), in the presence or absence of AHM (100 microg/ml). The functions of steroidogenic enzymes, including protein expression of the steroidogenic acute regulatory protein (StAR), cytochrome P450 side chain cleavage enzyme (P450scc), protein kinase A (PKA), and aromatase activity, were investigated. The expression of StAR mRNA was also explored by using real-time reverse transcription-polymerase chain reaction. In the in vivo study, AHM decreased plasma progesterone and estradiol levels after an intravenous injection of AHM (2 mg/ ml/kg). In the in vitro studies, AHM decreased progesterone and estradiol via inhibition of (i) the cAMP-PKA signal transduction pathway, (ii) cAMP accumulation, (iii) P450scc and 3beta-HSD enzyme activities, (iv) PKA, P450scc and StAR protein expressions and StAR mRNA expression, and (v) aromatase activity in rat GCs. These results suggest that AHM decreased the production of progesterone via mechanisms involving the inhibition of the cAMP pathway, enzyme activities

  11. Downregulation of progesterone biosynthesis in rat granulosa cells by adlay (Coix lachryma-jobi L. var. ma-yuen Stapf.) bran extracts.

    PubMed

    Hsia, S-M; Chiang, W; Kuo, Y-H; Wang, P S

    2006-01-01

    Adlay (Coix lachryma-jobi L. var. ma-yuen Stapf.) has long been used as a traditional Chinese medicine for dysfunctions of the endocrine system and inflammation conditions. However, the effect of adlay seed on the endocrine system has not yet been reported. In the present study, the effects and the mechanisms of methanolic extract of adlay bran (ABM) on progesterone synthesis in rat granulosa cell were studied. ABM was further partitioned with different solvents including water, 1-butanol, ethyl acetate and n-hexane. Four subfractions named ABM-Wa (water fraction), ABM-Bu (1-butanol fraction), ABM-EA (ethyl acetate fraction) and ABM-Hex (n-hexane fraction) were obtained. ABM-Bu was further fractionated using Diaion HP-20 resin column chromatography with gradient elution. Granulosa cells were prepared from pregnant mare serum gonadotropin-primed immature female rats and challenged with different reagents including human chorionic gonadotropin (hCG 0.5 IU/ml), forskolin (10 microM), 8-bromo-adenosine-3',5'-cyclic monophosphate (8-Br-cAMP, 1 mM), A23187 (10 microM), phorbol 12-myristate 13-acetate (PMA, 0.01 microM), 25-OH-cholesterol (0.1-10 microM) and pregnenolone (0.1-10 microM) in the presence or absence of ABM-Bu (100 microg/ml). The functions of steroidogenic enzyme including protein expression of the steroidogenic acute regulatory protein (StAR) and cytochrome P450 side-chain cleavage enzyme (P450scc) protein were investigated. Expressions of both P450scc and StAR mRNA have also been explored. We found that ABM decreased progesterone production via an inhibition on (1) the cAMP-PKA and PKC signal transduction pathway, (2) P450scc and 3beta-hydroxysteroid dehydrogenase (3beta-HSD) enzyme activity, (3) P450scc and StAR protein and mRNA expressions and (4) the phosphorylation of ERK1/2 in rat granulosa cells.

  12. Antimutagenic constituents of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) with potential cancer chemopreventive activity.

    PubMed

    Chen, Huang-Hui; Chiang, Wenchang; Chang, Jang-Yang; Chien, Ya-Lin; Lee, Ching-Kuo; Liu, Ko-Jiunn; Cheng, Yen-Ting; Chen, Ting-Fang; Kuo, Yueh-Hsiung; Kuo, Ching-Chuan

    2011-06-22

    Adlay has long been used in traditional Chinese medicine and as a nourishing food. The acetone extract of adlay hull had previously been demonstrated to possess potent antimutagenic activity. The aims of this study were to identify the antimutagenic constituents from adlay hull by using Ames antimutagenic activity-guide isolation procedures and to investigate their chemopreventive efficacies in cultured cells. The results demonstrated that six compounds showing great antimutagenic activity were identified by spectroscopic methods and by comparison with authentic samples to be p-hydroxybenzaldehyde, vanillin, syringaldehyde, trans-coniferylaldehyde, sinapaldehyde, and coixol. Two of them, trans-coniferylaldehyde and sinapaldehyde, exhibit relatively potent scavenging of DPPH radicals, inhibit TPA stimulated superoxide anion generation in neutrophil-like leukocytes, and induce Nrf2/ARE-driven luciferase activity in HSC-3 cells. Moreover, trans-coniferylaldehyde possesses cytoprotective efficacy against tert-butyl hydroperoxide-induced DNA double-strand breaks in cultured cells, and the chemopreventive potency induced by trans-coniferylaldehyde may be through the activation of kinase signals, including p38, ERK1/2, JNK, MEK1/2, and MSK1/2. In summary, we first identified six antimutagenic constituents from adlay hull. Among them, trans-coniferylaldehyde would be a highly promising agent for cancer chemoprevention and merits further investigation.

  13. Adlay seed extract (Coix lachryma-jobi L.) decreased adipocyte differentiation and increased glucose uptake in 3T3-L1 cells.

    PubMed

    Ha, Do Thi; Nam Trung, Trinh; Bich Thu, Nguyen; Van On, Tran; Hai Nam, Nguyen; Van Men, Chu; Thi Phuong, Tran; Bae, KiHwan

    2010-12-01

    The aim of the present study was to investigate effects of the ethyl acetate fraction of an ethanol extract of Coix lachryma-jobi (ECLJ) on glucose uptake and adipocyte differentiation in 3T3-L1 cells. ECLJ phosphorylated AMP-activated protein kinase (AMPK) and its downstream substrate acetyl-coenzymeA carboxylase in 3T3-L1 cells in a time- and dose-dependent manner. Moreover, we discovered that compound C inhibits ECLJ-stimulated ACC phosphorylation. In addition, ECLJ exhibited a dose-dependent stimulation of glucose uptake in 3T3-L1 cells, and this increase was obviously attenuated by compound C. ECLJ also caused a decrease in the expression levels of adipogenesis factors such as fatty acid synthase, sterol-regulatory-element-binding protein-1c, peroxisome proliferator-activated receptor γ, and CAATT/enhancer binding protein α in a dose-dependent manner. Differentiation was examined by Oil red O staining activity after ECLJ treatment for 6 days. ECLJ decreased mean droplet size. These results suggest a possible role for AMPK in the process of adipose differentiation and that ECLJ targeted for adipocyte functions could be effective in improving the symptoms of metabolic syndrome.

  14. Gastroprotective activities of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) on the growth of the stomach cancer AGS cell line and indomethacin-induced gastric ulcers.

    PubMed

    Chung, Cheng-Pei; Hsia, Shih-Min; Lee, Ming-Yi; Chen, Hong-Jhang; Cheng, Faiwen; Chan, Lu-Chi; Kuo, Yueh-Hsiung; Lin, Yun-Lian; Chiang, Wenchang

    2011-06-08

    Adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) seeds have long been used to treat warts, chapped skin, rheumatism, and neuralgia in traditional Chinese medicine (TCM). Recently, studies demonstrated its anti-inflammatory, antiproliferative, antitumor, and antiallergic activities. In the present study, we first report the gastroprotective effects of dehulled adlay (DA) seeds, which consist of bran (AB) and endosperm (AE). The DA ethanolic extract (DAE) was prepared, along with the AB and AE ethanolic extracts (ABE and AEE), and the inhibitory effects of these extracts were tested on the AGS gastric cancer cell line. Results indicated that the ABE showed better antiproliferative activity, and 19 compounds were purified from AB in a further phenolic-compound-guided separation. Among the isolated compounds, caffeic and chlorogenic acids significantly suppressed the growth of AGS cells. In addition, the antiulcer activity of DA was examined in an indomethacin-induced gastric lesion model. The ulcer index (UI) and oxidative biomarkers in animals decreased, while the non-protein sulfhydryl (NPSH) groups were elevated when given DA. This is the first investigation of antiulcer activity of adlay, and we demonstrated that the antioxidative-active phenolic acids in DA contribute to some portion of the gastroprotective effects.

  15. Adlay (薏苡 yì yĭ; “soft-shelled job's tears”; the seeds of Coix lachryma-jobi L. var. ma-yuen Stapf) is a Potential Cancer Chemopreventive Agent toward Multistage Carcinogenesis Processes

    PubMed Central

    Kuo, Ching-Chuan; Chen, Huang-Hui; Chiang, Wenchang

    2012-01-01

    Adlay (薏苡 yì yĭ “soft-shelled job's tears”, the seeds of Coix lachryma-jobi L. var. ma-yuen Stapf) is a grass crop that has long been used in traditional Chinese medicine (TCM) and as a nourishing food in China for the treatment of warts, chapped skin, rheumatism, neuralgia, inflammatory, and neoplastic diseases. In addition, adlay also has been said to have stomachic, diuretic, antipholgistic, anodynic, and antispasmodic effects. Carcinogenesis is a multistage process that begins with exposure of viruses or chemicals that are found in the environment. Chemoprevention refers to the use of natural or synthetic, non-toxic chemical substances to reverse, repress, or prevent carcinogenesis. In this review, we summarize recent research attempting to study the chemopreventive blocking and suppressing potential of adlay and its active components in scavenging electrophiles and reactive oxygen species, antimutagenicity, enhancing Nrf2-mediated detoxification and antioxidant effect, altering carcinogen metabolism, suppressing proliferation, decreasing inflammation, and enhancing antitumor immunity. In addition, several active components with diverse chemopreventive properties have been also mentioned in this review article. PMID:24716141

  16. Adlay ( yì yĭ; "soft-shelled job's tears"; the seeds of Coix lachryma-jobi L. var. ma-yuen Stapf) is a Potential Cancer Chemopreventive Agent toward Multistage Carcinogenesis Processes.

    PubMed

    Kuo, Ching-Chuan; Chen, Huang-Hui; Chiang, Wenchang

    2012-10-01

    Adlay ( yì yĭ "soft-shelled job's tears", the seeds of Coix lachryma-jobi L. var. ma-yuen Stapf) is a grass crop that has long been used in traditional Chinese medicine (TCM) and as a nourishing food in China for the treatment of warts, chapped skin, rheumatism, neuralgia, inflammatory, and neoplastic diseases. In addition, adlay also has been said to have stomachic, diuretic, antipholgistic, anodynic, and antispasmodic effects. Carcinogenesis is a multistage process that begins with exposure of viruses or chemicals that are found in the environment. Chemoprevention refers to the use of natural or synthetic, non-toxic chemical substances to reverse, repress, or prevent carcinogenesis. In this review, we summarize recent research attempting to study the chemopreventive blocking and suppressing potential of adlay and its active components in scavenging electrophiles and reactive oxygen species, antimutagenicity, enhancing Nrf2-mediated detoxification and antioxidant effect, altering carcinogen metabolism, suppressing proliferation, decreasing inflammation, and enhancing antitumor immunity. In addition, several active components with diverse chemopreventive properties have been also mentioned in this review article.

  17. The abortifacient effects from the seeds of Coix lachryma-jobi L. var. ma-yuen Stapf.

    PubMed

    Tzeng, Hui-Ping; Chiang, Wenchang; Ueng, Tzuu-Huei; Liu, Shing-Hwa

    2005-09-01

    This study evaluated the abortifacient effects of the extracts of seeds of Coix lachryma-jobi L. var. ma-yuen Stapf (adlay) in pregnant rats. Pregnant rats were treated with oral administration of adlay seed extracts on d 6 of pregnancy and their fetuses were examined for growth and malformations on d 20 of pregnancy. Following oral administration of 1 g/kg body weight of water extracts but not methanolic extracts, fetal resorptions were significantly increased and mortality of postimplantation was increased. There were no significant differences in the uterine and fetal weight compared to control. Fetal malformations were not observed in the adlay seed extracts-treated pregnant rats. The contractile activity of uteri isolated from rats on d 20 of pregnancy was assessed. The spontaneous uterine contractions were significantly enhanced in rats treated with water extracts of adlay seeds (1 g/kg body weight). Immunoblotting of uteri from rats treated with water extracts of adlay seeds demonstrated an induction of cyclooxygenase-2 (COX-2) protein expression. The water extracts of adlay seeds also enhanced extracellular signal-regulated protein kinase (ERK) 1/2 phosphorylation and protein kinase C (PKC)-alpha translocation from cytosolic to particulate fractions in uteri. These results indicate that the water extracts of adlay seeds are capable of inducing embryotoxicity and enhancing uterine contractility during pregnancy. The enhanced activities of PKC-alpha, ERK1/2, and COX-2 may contribute to these responses.

  18. Effect of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf.) hull extracts on testosterone release from rat Leydig cells.

    PubMed

    Hsia, Shih-Min; Tseng, Yi-Wen; Wang, Shyi-Wu; Kuo, Yueh-Hsiung; Huang, Din-Wen; Wang, Paulus S; Chiang, Wenchang

    2009-05-01

    Adlay has been used as a traditional Chinese medicine for the treatment of many diseases. However, few studies have reported the effects of adlay seeds on the endocrine system. In the present study, the effects of methanol extracts of adlay hull (AHM) on testosterone synthesis were studied. Rat Leydig cells were incubated with different reagents including human chorionic gonadotropin, 8-bromo-adenosine-3',5'-cyclic monophosphate, forskolin, A23187, progesterone and androstenedione in the presence or absence of AHM. The rat anterior pituitary (AP) gland was treated with gonadotropin-releasing hormone (GnRH) in vitro in the presence or absence of AHM, and the concentrations of luteinizing hormone (LH) in the media were measured. AHM decreased testosterone release via the inhibition of (1) the PKA and PKC signal transduction pathways, (2) 17beta-HSD enzyme activity in rat Leydig cells, and (3) in vitro GnRH-induced LH secretion.

  19. 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.

  20. Identification of compounds in adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) seed hull extracts that inhibit lipopolysaccharide-induced inflammation in RAW 264.7 macrophages.

    PubMed

    Huang, Din-Wen; Chung, Cheng-Pei; Kuo, Yueh-Hsiung; Lin, Yun-Lian; Chiang, Wenchang

    2009-11-25

    We investigated the effects of adlay seed hull (AH) extracts on the lipopolysaccharide-induced inflammatory response in RAW 264.7 macrophages. An AH ethanol extract (AHE) was partitioned into ethyl acetate, n-butanol, and water fractions. Silica gel chromatography of the ethyl acetate fraction yielded 15 subfractions: AHE-Ea-A to AHE-Ea-O. Subfractions AHE-Ea-J, AHE-Ea-K, and AHE-Ea-M had anti-inflammatory activities, as they counteracted the increased cellular production of nitric oxide and prostaglandin E2 induced by lipopolysaccharide by down-regulating inducible nitric oxide synthase and cyclooxygenase 2 expression. Eriodictyol (1), the ceramide (2S,3S,4R)-2-[(2'R)-2'-hydroxytetracosanoyl-amino]-1,3,4-octadecanetriol (2), and p-coumaric acid (3) were found in the subfractions, and the first two compounds appeared to be primarily responsible for the anti-inflammatory activity. This is the first time that eriodictyol (1) and this ceramide (2) have been found in AH, and the anti-inflammatory properties of the AHE-Ea fraction can be attributed, at least in part, to the presence of these two compounds.

  1. Effect of Adlay ( Coix lachryma-jobi L. var. ma-yuen Stapf) Testa and its phenolic components on Cu2+-treated low-density lipoprotein (LDL) oxidation and lipopolysaccharide (LPS)-induced inflammation in RAW 264.7 macrophages.

    PubMed

    Huang, Din-Wen; Kuo, Yueh-Hsiung; Lin, Fang-Yi; Lin, Yun-Lian; Chiang, Wenchang

    2009-03-25

    The aims of this study were to investigate the effects of adlay testa (AT) on Cu(2+)-treated low-density lipoprotein (LDL) oxidation, 2,2'-diphenyl-1-picrylhydrazyl (DPPH)-scavenging capacity, and lipopolysaccharide (LPS)-induced inflammation in RAW 264.7 macrophages and determine its active components. The AT ethanolic extract (ATE) was partitioned into four fractions by various solvents as follows: n-hexane (ATE-Hex), ethyl acetate (ATE-Ea), n-butanol (ATE-Bu), and water (ATE-H(2)O). ATE-Ea and ATE-Bu were further fractionated into ATE-Ea-a-ATE-Ea-h and ATE-Bu-A-ATE-Bu-F, respectively, by column chromatography. Results showed that ATE-Ea, ATE-Bu, ATE-Ea-e, and ATE-Bu-C expressed antiradical, antioxidative, and anti-inflammatory activities with respect to the DPPH-scavenging capacity, LDL protection effect, and nitric oxide (NO) inhibitory activity. Inflammation was further modulated by ATE-Ea, ATE-Bu, ATE-Ea-e, and ATE-Bu-C through downregulating the expression of inducible nitric oxide synthase (iNOS) and cyclooxygenase 2 (COX-2) proteins. The following components were found in ATE-Ea-e and ATE-Bu-C after purification and high-performance liquid chromatographic analysis: chlorogenic acid (CGA), vanillic acid (VA), caffeic acid (CA), p-coumaric acid (PCA), ferulic acid (FA), and 2-O-beta-glucopyranosyl-7-methoxy-4((2)H)-benzoxazin-3-one (GMBO). Results showed that CGA, CA, and FA were the major components responsible for the antioxidative and anti-inflammatory activities of ATE-Ea-e and ATE-Bu-C. Subsequently, each gram of ATE-Bu-C had 30.3 mg of CGA, 9.02 mg of CA, and 189 mg of GMBO, while each gram of ATE-Ea-e had 1.31 mg of VA, 3.89 mg of PCA, and 47.6 microg of FA. In conclusion, ATE has antioxidative and anti-inflammatory activities, and its effects are partially related to its phenolic components. Thus, ATE has the potential to be developed as a functional food targeting chronic diseases.

  2. In vitro anti-cancer activities of Job’s tears (Coix lachryma-jobi Linn.) extracts on human colon adenocarcinoma

    PubMed Central

    Manosroi, Aranya; Sainakham, Mathukorn; Chankhampan, Charinya; Manosroi, Worapaka; Manosroi, Jiradej

    2015-01-01

    The whole seed (W), endosperm (E) and hull (H) of five cultivars of Job’s tears (Coix lachryma-jobi Linn. var. ma-yuen Stapf) including Thai Black Phayao, Thai Black Loei, Laos Black Loei, Laos White Loei and Laos Black Luang Phra Bang were processed before solvent extraction by non-cooking, roasting, boiling and steaming Each part of the Job’s tears was extracted by the cold and hot process by refluxing with methanol and hexane. The total of 330 extracts included 150 methanol extracts and 180 hexane extracts were investigated for anti-proliferative activity on human colon adenocarcinoma cell line (HT-29) by the sulforhodamine B (SRB) assay. The extracts which gave high anti-proliferative activity were tested for apoptotic activity by acridine orange and ethidium bromide double staining and anti-oxidative activities including free radical scavenging and lipid peroxidation inhibition activities. The extract from the hull of Thai Black Loei roasted before extracting by hot methanol (M-HTBL-R2) showed the highest anti-proliferative activity on HT-29 with the IC50 values of 11.61 ± 0.95 μg/ml, while the extract from the non-cooked hull of Thai Black Loei by cold methanol extraction (M-HTBL-N1) gave the highest apoptosis (8.17 ± 1.18%) with no necrosis. In addition, M-HTBL-R2 and M-HTBL-N1 indicated free radical scavenging activity at the SC50 values of 0.48 ± 0.12 and 2.47 ± 1.15 mg/ml, respectively. This study has demonstrated the anti-colorectal cancer potential of the M-HTBL-R2 and M-HTBL-N1 extracts. PMID:26981007

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

    PubMed

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

    2013-01-11

    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.

  4. Evaluation of osteoporosis prevention by adlay using a tissue culture model.

    PubMed

    Yang, Rong Sen; Chiang, Wenchang; Lu, Yi Hsiang; Liu, Shing Hwa

    2008-01-01

    Adlay (Coix lachryma-jobi L. var. ma-yuen Stapf ) is a grass crop, which has been used in traditional Chinese medicine and also as a nourishing food. Recently, some studies have indicated that adlay possesses some pharmacological effects including anti-allergic, anti-mutagenic, hypolipemic, and anti-diabetic effects. However, the effect of adlay on osteoporosis is still unknown. In this study, we investigated and evaluated the effect of adlay seed on the osteoporosis prevention. The methods of in vitro cultures of neonatal rat calvaria tissues or adult rat femoral metaphyseal tissues of bones isolated from normal or ovariectomized female rats were used for further investigation. Treatment with water extract of adlay seed could reverse the decreased alkaline phosphatase activities and calcium levels and increased tartrate-resistant acidic phosphatase activities induced by parathyroid hormone in cultured metaphyseal tissues. In ovariectomized rats, the alkaline phosphatase activities and calcium levels were significantly decreased and tartrate-resistant acidic phosphatase activities were increased in femoral metaphyseal tissues as compared with sham-control. Treatment with water extract of adlay seed could counteract these effects in ovariectomized rats. Taken together, these findings imply that adlay is capable of reversing the osteoporotic status in rats, and may be a helpful healthy food for osteoporosis prevention.

  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. Effects of dehulled adlay on the culture count of some microbiota and their metabolism in the gastrointestinal tract of rats.

    PubMed

    Chiang, W; Cheng, C y; Chiang, M t; Chung, K T

    2000-03-01

    Experiments were conducted to study the effect of a dietary supplement of dehulled adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) on the culture counts of some important groups of intestinal bacteria and their metabolism in the gastrointestinal (GI) tract of Sprague-Dawley rats. Rats were divided into four groups, and each group was fed a diet containing different levels of dehulled adlay for 30 days as follows: 0% (control), 5%, 20%, and 40%. All animals fed with adlay had normal healthy intestinal walls and no pathogenic signs whatsoever. There were no significant differences in body weight gain or the cecal pH between different groups of rats. Both the 20% and 40% groups had lower culture counts of enterics in their feces than the 5% and control groups, whereas the culture counts of fecal lactic acid bacteria were higher in feces of rats fed with adlay than in the control group. Cecal total short-chain fatty acid (SCFA) content and fecal SCFA were significantly higher in the 20% and 40% groups than in the control and 5% groups. All the adlay-fed rats had a higher fecal butyric acid concentration than the control rats. It is concluded that adlay has a significant influence on the growth of intestinal bacteria, which may ultimately affect the physiology and other functions of GI tracts of rats.

  7. Anti-inflammatory effects and chemical study of a flavonoid-enriched fraction from adlay bran.

    PubMed

    Chen, Hong-Jhang; Chung, Cheng-Pei; Chiang, Wenchang; Lin, Yun-Lian

    2011-06-15

    Anti-inflammation-guided fractionation and purification were used to evaluate the bioactivity and components of adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) bran. Results showed that the fraction with high phenolic and flavonoid contents from the ethanol extracts of adlay bran suppressed LPS-stimulated IL-6 and TNF-α secretions in a concentration-dependent manner in RAW 264.7 cells and murine peritoneal macrophages. Fifteen compounds, including a novel aurone derivative, two chromones, one dihydrochalcone, one chalcone, four flavanones, five flavones and one isoflavone, were isolated from the active fraction. The structure of the new compound was elucidated by spectroscopic methods, including 1D and 2D NMR and MS. All of the isolates are reported for the first time from adlay except naringenin. LC/MS was also provided as an analytical platform. Our results suggest that flavonoids in adlay bran, partially at least, contribute to its anti-inflammatory effect. Thus, adlay bran may be beneficial to the health of consumers.

  8. Effects of adlay on azoxymethane-induced colon carcinogenesis in rats.

    PubMed

    Shih, Chun-Kuang; Chiang, Wenchang; Kuo, Min-Liang

    2004-08-01

    Adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) is a grass crop used in traditional Chinese medicine and as a nutritious food. It has been reported that adlay has anti-inflammatory and anti-tumor activity. Cyclooxygenase-2 (COX-2) is an inducible enzyme functionally related to both inflammation and colon carcinogenesis and is the target of many chemopreventive agents. This study investigated the effect of adlay on colon carcinogenesis and COX-2 expression. In a short-term experiment, male F344 rats were fed diets containing different doses of dehulled adlay and received the colon-specific carcinogen, azoxymethane (AOM), by intraperitoneal injection. All rats were killed after 5 weeks of feeding, and the colons were examined for the preneoplastic lesion, aberrant crypt foci (ACF). Dietary dehulled adlay at levels of 10%, 20%, or 40% significantly reduced the numbers of ACF and aberrant crypts. Dehulled adlay reduced the number of ACF of different sizes but did not affect the crypt multiplicity. Most ACF were found in the middle and distal colons; dehulled adlay significantly suppressed the formation of ACF in the middle colon. In a long-term experiment, male F344 rats were fed diets containing different doses of dehulled adlay and injected with AOM. All rats were killed after 52 weeks of feeding, and colons were examined for tumors and COX-2 protein expression. The results indicated that dehulled adlay did not inhibit colon tumors in spite of a slight suppressing effect in the proximal colon. Rats fed diets containing 20% dehulled adlay had less COX-2 protein expression in both proximal and distal colon tumors. The inconsistent effects between COX-2 protein expression and tumor outcome may be due to regional differences in the colon and the malignancy of the tumors. These findings suggest that dehulled adlay suppresses early events in colon carcinogenesis but not the formation of tumors.

  9. Effects of adlay hull extracts on uterine contraction and Ca2+ mobilization in the rat.

    PubMed

    Hsia, Shih-Min; Kuo, Yueh-Hsiung; Chiang, Wenchang; Wang, Paulus S

    2008-09-01

    Dysmenorrhea is directly related to elevated PGF(2alpha) levels. It is treated with nonsteroid antiinflammatory drugs (NSAIDs) in Western medicine. Since NSAIDs produce many side effects, Chinese medicinal therapy is considered as a feasible alternative medicine. Adlay (Coix lachryma-jobi L. var. ma-yuen Stapf.) has been used as a traditional Chinese medicine for treating dysmenorrhea. However, the relationship between smooth muscle contraction and adlay extracts remains veiled. Therefore, we investigated this relationship in the rat uterus by measuring uterine contraction activity and recording the intrauterine pressure. We studied the in vivo and in vitro effects of the methanolic extracts of adlay hull (AHM) on uterine smooth muscle contraction. The extracts were fractionated using four different solvents: water, 1-butanol, ethyl acetate, and n-hexane; the four respective fractions were AHM-Wa, AHM-Bu, AHM-EA, and AHM-Hex. AHM-EA and its subfractions (175 microg/ml) inhibited uterine contractions induced by PGF(2alpha), the Ca(2+) channel activator Bay K 8644, and high K(+) in a concentration-dependent manner in vitro. AHM-EA also inhibited PGF(2alpha)-induced uterine contractions in vivo; furthermore, 375 microg/ml of AHM-EA inhibited the Ca(2+)-dependent uterine contractions. Thus 375 microg/ml of AHM-EA consistently suppressed the increases in intracellular Ca(2+) concentrations induced by PGF(2alpha) and high K(+). We also demonstrated that naringenin and quercetin are the major pure chemical components of AHM-EA that inhibit PGF(2alpha)-induced uterine contractions. Thus AHM-EA probably inhibited uterine contraction by blocking external Ca(2+) influx, leading to a decrease in intracellular Ca(2+) concentration. Thus adlay hull may be considered as a feasible alternative therapeutic agent for dysmenorrhea.

  10. Ethyl acetate fraction of adlay bran ethanolic extract inhibits oncogene expression and suppresses DMH-induced preneoplastic lesions of the colon in F344 rats through an anti-inflammatory pathway.

    PubMed

    Chung, Cheng-Pei; Hsu, Hsin-Yi; Huang, Din-Wen; Hsu, Hsing-Hua; Lin, Ju-Tsui; Shih, Chun-Kuang; Chiang, Wenchang

    2010-07-14

    Adlay ( Coix lachryma-jobi L. var. ma-yuen Stapf) is a grass crop and was reported to possess anti-inflammatory activity and an antiproliferative effect in cancer cell lines. The purpose of this study was to evaluate the effects of the ethyl acetate fraction of an adlay bran ethanolic extract (ABE-Ea) on colon carcinogenesis in an animal model and investigate its mechanism. Male F344 rats received 1,2-dimethylhydrazine (DMH) and consumed different doses of ABE-Ea. The medium-dose group (17.28 mg of ABE-Ea/day) exhibited the best suppressive effect on colon carcinogenesis and prevented preneoplastic mucin-depleted foci (MDF) formation. Moreover, RAS and Ets2 oncogenes were significantly down-regulated in this group compared to the negative control group, whereas Wee1, a gene involved in the cell cycle, was up-regulated. Cyclooxygenase-2 (COX-2) protein expression was significantly suppressed in all colons receiving the ABE-Ea, indicating that ABE-Ea delayed carcinogenesis by suppressing chronic inflammation. ABE-Ea included considerable a proportion of phenolic compounds, and ferulic acid was the major phenolic acid (5206 microg/g ABE-Ea) on the basis of HPLC analysis. Results from this study suggest that ABE-Ea suppressed DMH-indued preneoplastic lesions of the colon in F344 rats and that ferulic acid may be one of the active compounds.

  11. Effects of dehulled adlay on plasma glucose and lipid concentrations in streptozotocin-induced diabetic rats fed a diet enriched in cholesterol.

    PubMed

    Yeh, Pao-Hua; Chiang, Wenchang; Chiang, Meng-Tsan

    2006-09-01

    Adlay (Coix lachryma-jobi L. var. ma-yuen Stapf) is a cereal food for humans and has been also used as a superior medical herb substance and functional food for traditional treatment of diabetes in China. However, its scientific basis as a functional food is still unclear. The purpose of this study was to investigate the effect of dietary dehulled adlay on plasma lipid and glucose concentrations in diabetic rats. The diabetic male Sprague-Dawley (SD) rats, induced by injection of streptozotocin (60 mg/kg subcutaneously), were fed a cholesterol-rich diet (0.5% cholesterol) containing corn starch or dehulled adlay for four weeks. After completion of the experimental period, the abdominal adipose tissue and liver of rats were excised and weighed, and the plasma glucose, triglyceride, and lipoprotein cholesterol concentrations were assayed. The results showed that diabetic rats fed a dehulled adlay diet exhibited a greater adipose tissue weight (9.36 +/- 3.43 vs. 5.39 +/- 3.04 g, p < 0.05) and a reduced food intake (39.3 +/- 5.9 vs. 61.0 +/- 11.7 g/day, p < 0.05) when compared with animals fed a cornstarch diet. Significantly decreased plasma glucose (261.6 +/- 96.6 vs. 422.1 +/- 125.4 mg/dL, p < 0.05), total cholesterol (289.4 +/- 140.6 vs. 627.3 +/- 230.5 mg/dL, p < 0.05), and triglyceride (52.3 +/- 14.4 vs. 96.5 +/- 36.6 mg/dL, p < 0.05) levels were observed in rats fed the dehulled adlay diet. In addition, the ingestion of dehulled adlay appears to significantly decrease plasma low-density lipoprotein (LDL) plus very low-density lipoprotein (VLDL) cholesterol concentrations. Rats fed a dehulled adlay diet showed an increase in fecal weight and cholesterol contents of stools. Although a significantly decreased plasma thiobarbituric reactive substances (TBARS) value was observed in diabetic rats fed the dehulled adlay diet (6.2 +/- 3.4 vs. 11.0 +/- 3.8 nmol malondialdehyde (MDA)/mL, p < 0.05), no significant difference in the hepatic TBARS value was observed between

  12. Suppressive effect of the ethanolic extract of adlay bran on cytochrome P-450 enzymes in rat liver and lungs.

    PubMed

    Yao, Hsien-Tsung; Lin, Jia-Hsuan; Chiang, Meng-Tsan; Chiang, Wenchang; Luo, Mei-Nin; Lii, Chong-Kuei

    2011-04-27

    Adlay ( Coix lachryma-jobi L. var. ma-yuen Stapf) is a grass crop and is reported to protect against various diseases such as cancer. To investigate the effect of the ethanolic extract of adlay bran (ABE) on drug-metabolizing enzymes and glutathione-related antioxidant enzymes in rats, three groups of eight male Sprague-Dawley rats each were fed a control diet or a diet containing 5 or 10% ABE for 4 weeks. Significant decreases in microsomal cytochrome P-450 (CYP) 1A1-catalyzed ethoxyresorufin O-deethylation, CYP2C-catalyzed diclofenac 4-hydroxylation, CYP2D-catalyzed dextromethorphan O-demethylation, and CYP3A-catalyzed testosterone 6β-hydroxylation in the liver and CYP1A1-catalyzed ethoxyresorufin O-deethylation in the lungs of rats fed ABE were observed. Immunoblot analyses also showed decreases of CYP1A1, 1A2, 2C6, 2C11, 2D1, 2E1, 3A1, and 3A2 in the liver and CYP1A1 in the lungs. Furthermore, rats fed the 10% ABE diet had a higher glutathione content and glutathione peroxidase, glutathione reductase, and glutathione S-transferase activities in the lungs, but such an increase was not noted in the liver. Inhibition of various CYP-catalyzed enzyme reactions by ABE in rat and human liver microsomes had also been shown. The results of this study indicate that ABE feeding may suppress CYP enzyme activities and CYP protein expression in the liver and lungs of rats. Moreover, the increase of the antioxidant potential by ABE is tissue-specific.

  13. 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.

  14. The water extract of adlay seed (Coix lachrymajobi var. mayuen) exhibits anti-obesity effects through neuroendocrine modulation.

    PubMed

    Kim, Sung Ok; Yun, Su-Jin; Lee, Eunjoo H

    2007-01-01

    To find out whether the immunohistochemical expression of neuropeptid Y (NPY) and leptin receptor (LR) in the rat hypothalamus is influenced by adlay seed water extract (adlay), obesity in rats was induced by high fat diet (HFD) for 8 weeks; these rats were injected with 50 mg/100 g body weight adlay daily for 4 weeks. The results showed that the optical density of NPY immunoreactivity in paraventricular nucleus of rats increased approximately by 3.4 fold in HFD group compared to the normal diet group. Conversely, that of HFD + adlay group was about 2.6 fold lower than HFD group. The pattern of LR expression was similar to that of NPY. Both of NPY and LR mRNA levels, determined by real time PCR, in HFD + adlay group were decreased compared to those of HFD group, but there were no significant changes in the level of LR. These results suggest that adlay may regulate neuroendocrine activity in the brain. Accordingly, administration of adlay may be considered for therapies targeting obesity.

  15. A Novel Antihypertensive Derived from Adlay (Coix larchryma-jobi L. var. ma-yuen Stapf) Glutelin.

    PubMed

    Li, Bin; Qiao, Liansheng; Li, Lingling; Zhang, Yanling; Li, Kai; Wang, Lingzhi; Qiao, Yanjiang

    2017-01-13

    Our previous studies have shown that Coix glutelin pepsin hydrolysate can effectively inhibit angiotensin converting enzyme (ACE) activity in vitro. The main purpose of this study was to obtain potent anti-hypertensive peptides from Coix glutelin. The Coix glutelin hydrolysates (CGH) were prepared by pepsin catalysis and further separated by an ultrafitration (UF) system, gel filtration chromatography (GFC) and reversed-phase high performance liquid chromatography (RP-HPLC). As a result, the sub-fraction F5-3 had the highest ACE-inhibitory activity. Six ACE inhibitory peptides were identifiedusing nano-liquid chromatography coupled to tandem mass spectrometry. The most potent peptide GAAGGAF (IC50 = 14.19 μmol·L(-1)) was finally obtained by further molecular simulation screening and a series of division and optimization. Single oral administration of synthesized GAAGGAF at 15 mg/kg body weight (BW) in spontaneously hypertensively rats (SHR) could reduce the systolic blood pressure (SBP) around 27.50 mmHg and blood pressure-lowering effect lasted for at least 8 h. The study demonstrated for the first time that the ACE inhibitory peptide GAAGGAF from Coix glutelin has a significant antihypertensive effect, and it could be a good natural ingredient for pharmaceuticals against hypertension and the related diseases.

  16. Modulation of gut microbiota by polyphenols from adlay (Coix lacryma-jobi L. var. ma-yuen Stapf.) in rats fed a high-cholesterol diet.

    PubMed

    Wang, Qingyu; Du, Zhongyao; Zhang, Hao; Zhao, Liang; Sun, Jing; Zheng, Xiaonan; Ren, Fazheng

    2015-01-01

    This study aimed to evaluate the beneficial effects of polyphenol extract of adlay (Coix lacryma-jobi L. var. ma-yuen Stapf.) (PEA) on gut microbiota in rats fed a high-cholesterol diet (HCD). Rats were fed HCD containing 1% cholesterol (w/w), with or without a daily intragastric supplement of 200 mg/kg body weight PEA. Results showed that PEA significantly ameliorated increases in serum cholesterol and low-density lipoprotein cholesterol values and significantly restored high-density lipoprotein cholesterol values. The HCD-induced imbalance of gut microflora was modulated by the consumption of PEA. Most bacterial strains influenced by PEA are related to host lipid metabolism. The abundances of one Erysipelotrichales strains and two Clostridia strains were lower in the PEA group than in the control. Phenolic compounds in PEA were identified by HPLC. The findings indicate that PEA may be a useful dietary supplement in the treatment of elevated cholesterol levels and the imbalanced gut microbial ecology.

  17. Peroxisome proliferator-activated receptor gamma ligands isolated from adlay seed (Coix lacryma-jobi L. var. ma-yuen STAPF.).

    PubMed

    Yokoi, Hiroshi; Mizukami, Hajime; Nagatsu, Akito; Ohno, Takamasa; Tanabe, Hiroki; Inoue, Makoto

    2009-04-01

    Through screening for natural ligands against peroxisome proliferator-activated receptor gamma (PPARgamma) using the PPARgamma luciferase reporter assay, 6 hydroxy unsaturated fatty acids were isolated from adlay seed (Coix lacryma-jobi L. var. ma-yuen STAPF.) extracts with acetone and 70% ethanol. The structures of these compounds were determined via spectral analysis as 13-hydroxy-(9E,11E)-octadecadienoic acid (13-E,E-HODE) (1), 9-hydroxy-(10E,12E)-octadecadienoic acid (9-E,E-HODE) (2), 9-hydroxy-(10E)-octadecenoic acid (3), 10-hydroxy-(8E)-octadecenoic acid (4), 8-hydroxy-(9E)-octadecenoic acid (5), 11-hydroxy-(9Z)-octadecenoic acid (6). 9-E,E-HODE (2) exhibited the most potent PPARgamma agonist activity of the isolated hydroxy unsaturated fatty acids. 9-E,E-HODE (2) and 13-E,E-HODE (1) are the respective geometrical isomers of 9-hydroxy-(10E,12Z)-octadecadienoic acid and 13-hydroxy-(9Z,11E)-octadecadienoic acid, both of which are likely to be natural PPARgamma agonists produced in various mammalian cells, suggesting that 9-E,E-HODE may also act as PPARgamma agonist.

  18. Prevalence, Characterization, and Mycotoxin Production Ability of Fusarium Species on Korean Adlay (Coix lacrymal-jobi L.) Seeds

    PubMed Central

    An, Tae Jin; Shin, Kyu Seop; Paul, Narayan Chandra; Kim, Young Guk; Cha, Seon Woo; Moon, Yuseok; Yu, Seung Hun; Oh, Sang-Keun

    2016-01-01

    Adlay seed samples were collected from three adlay growing regions (Yeoncheon, Hwasun, and Eumseong region) in Korea during 2012. Among all the samples collected, 400 seeds were tested for fungal occurrence by standard blotter and test tube agar methods and different taxonomic groups of fungal genera were detected. The most predominant fungal genera encountered were Fusarium, Phoma, Alternaria, Cladosporium, Curvularia, Cochliobolus and Leptosphaerulina. Fusarium species accounted for 45.6% of all species found; and, with phylogenetic analysis based on the combined sequences of two protein coding genes (EF-1α and β-tubulin), 10 Fusarium species were characterized namely, F. incarnatum (11.67%), F. kyushuense (10.33%), F. fujikuroi (8.67%), F. concentricum (6.00%), F. asiaticum (5.67%), F. graminearum (1.67%), F. miscanthi (0.67%), F. polyphialidicum (0.33%), F. armeniacum (0.33%), and F. thapsinum (0.33%). The Fusarium species were then examined for their morphological characteristics to confirm their identity. Morphological observations of the species correlated well with and confirmed their molecular identification. The ability of these isolates to produce the mycotoxins fumonisin (FUM) and zearalenone (ZEN) was tested by the ELISA quantitative analysis method. The result revealed that FUM was produced only by F. fujikuroi and that ZEN was produced by F. asiaticum and F. graminearum. PMID:27801779

  19. Prevalence, Characterization, and Mycotoxin Production Ability of Fusarium Species on Korean Adlay (Coix lacrymal-jobi L.) Seeds.

    PubMed

    An, Tae Jin; Shin, Kyu Seop; Paul, Narayan Chandra; Kim, Young Guk; Cha, Seon Woo; Moon, Yuseok; Yu, Seung Hun; Oh, Sang-Keun

    2016-10-27

    Adlay seed samples were collected from three adlay growing regions (Yeoncheon, Hwasun, and Eumseong region) in Korea during 2012. Among all the samples collected, 400 seeds were tested for fungal occurrence by standard blotter and test tube agar methods and different taxonomic groups of fungal genera were detected. The most predominant fungal genera encountered were Fusarium, Phoma, Alternaria, Cladosporium, Curvularia, Cochliobolus and Leptosphaerulina. Fusarium species accounted for 45.6% of all species found; and, with phylogenetic analysis based on the combined sequences of two protein coding genes (EF-1α and β-tubulin), 10 Fusarium species were characterized namely, F. incarnatum (11.67%), F. kyushuense (10.33%), F. fujikuroi (8.67%), F. concentricum (6.00%), F. asiaticum (5.67%), F. graminearum (1.67%), F. miscanthi (0.67%), F. polyphialidicum (0.33%), F. armeniacum (0.33%), and F. thapsinum (0.33%). The Fusarium species were then examined for their morphological characteristics to confirm their identity. Morphological observations of the species correlated well with and confirmed their molecular identification. The ability of these isolates to produce the mycotoxins fumonisin (FUM) and zearalenone (ZEN) was tested by the ELISA quantitative analysis method. The result revealed that FUM was produced only by F. fujikuroi and that ZEN was produced by F. asiaticum and F. graminearum.

  20. 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

  1. Hypolipidemic effects of crude extract of adlay seed (Coix lachrymajobi var. mayuen) in obesity rat fed high fat diet: relations of TNF-alpha and leptin mRNA expressions and serum lipid levels.

    PubMed

    Kim, Sung Ok; Yun, Su-Jin; Jung, Bomi; Lee, Eunjoo H; Hahm, Dae-Hyun; Shim, Insop; Lee, Hye-Jung

    2004-07-30

    To find out whether the expressions of these adipocyte markers are influenced by oriental medicine, obesity rats induced by high fat diet (HFD) for 8 weeks were injected with 50 mg/100 g body weight adlay seed crude extract (ACE), daily for 4 weeks. The results are summarized as follows: HFD + ACE group significantly reduced food intakes and body weights. Weights of epididymal and peritoneal fat were dramatically increased in HFD groups compared with those of normal diet (ND) group but significantly decreased more in HFD + ACE group than those of HFD + saline group (sham). Those of brown adipocytes were increased in HFD + ACE group compared to ND and sham groups but there was no significant difference. The sizes in white adipose tissue (WAT) by microscope were markedly larger in HFD groups than ND group but considerably reduced in HFD + ACE group compared with sham group. The levels of triglyceride, total-cholesterol and leptin in blood serum were significantly decreased in HFD + ACE group compared to those of sham group. Leptin and TNF-alpha mRNA expressions in WAT of rats were remarkably increased more in sham group than in those of ND group. Those of HFD + ACE group were significantly decreased compared with those of sham group, especially. TNF-alpha mRNA expression in HFD + ACE group was declined more than that of ND group. In conclusion, treatments of ACE modulated expressions of leptin and TNF-alpha and reduced body weights, food intake, fat size, adipose tissue mass and serum hyperlipidemia in obesity rat fed HFD. Accordingly, the oriental medicine extract, adlay seed crude extract, can be considered for obesity therapies controlling.

  2. A comparative study on hulled adlay and unhulled adlay through evaluation of their LPS-induced anti-inflammatory effects, and isolation of pure compounds.

    PubMed

    Choi, Goeun; Han, Ah-Reum; Lee, Joo Hee; Park, Ji-Youn; Kang, Unwoo; Hong, Jongki; Kim, Yeong Shik; Seo, Eun-Kyoung

    2015-03-01

    Coicis semen (=the hulled seed of Coix lacryma-jobi L. var. ma-yuen (Rom.Caill.) Stapf; Gramineae), commonly known as adlay and Job's tears, is widely used in traditional medicine and as a nutritious food. Bioassay-guided fractionation of the AcOEt fraction of unhulled adlays, using measurement of nitric oxide (NO) production on lipopolysaccharide (LPS)-stimulated RAW 264.7 macrophage cells, led to the isolation and identification of two new stereoisomers, (+)-(7'S,8'R,7″S,8″R)-guaiacylglycerol β-O-4'-dihydrodisinapyl ether (1) and (+)-(7'S,8'R,7″R,8″R)-guaiacylglycerol β-O-4'-dihydrodisinapyl ether (2), together with six known compounds, 3-8. Compounds 3 and 4 exhibited inhibitory activities on LPS-induced NO production with IC50 values of 1.4 and 3.7 μM, respectively, and suppressed inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2) protein expressions in RAW 264.7 macrophage cells. Simple high-performance liquid chromatography with ultraviolet detection (HPLC/UV) was used to compare the AcOEt fraction of unhulled adlays responsible for the anti-inflammatory activity in RAW 264.7 cells and the inactive AcOEt fraction of hulled adlays.

  3. Discovery of Anti-Hypertensive Oligopeptides from Adlay Based on In Silico Proteolysis and Virtual Screening

    PubMed Central

    Qiao, Liansheng; Li, Bin; Chen, Yankun; Li, Lingling; Chen, Xi; Wang, Lingzhi; Lu, Fang; Luo, Ganggang; Li, Gongyu; Zhang, Yanling

    2016-01-01

    Adlay (Coix larchryma-jobi L.) was the commonly used Traditional Chinese Medicine (TCM) with high content of seed storage protein. The hydrolyzed bioactive oligopeptides of adlay have been proven to be anti-hypertensive effective components. However, the structures and anti-hypertensive mechanism of bioactive oligopeptides from adlay were not clear. To discover the definite anti-hypertensive oligopeptides from adlay, in silico proteolysis and virtual screening were implemented to obtain potential oligopeptides, which were further identified by biochemistry assay and molecular dynamics simulation. In this paper, ten sequences of adlay prolamins were collected and in silico hydrolyzed to construct the oligopeptide library with 134 oligopeptides. This library was reverse screened by anti-hypertensive pharmacophore database, which was constructed by our research team and contained ten anti-hypertensive targets. Angiotensin-I converting enzyme (ACE) was identified as the main potential target for the anti-hypertensive activity of adlay oligopeptides. Three crystal structures of ACE were utilized for docking studies and 19 oligopeptides were finally identified with potential ACE inhibitory activity. According to mapping features and evaluation indexes of pharmacophore and docking, three oligopeptides were selected for biochemistry assay. An oligopeptide sequence, NPATY (IC50 = 61.88 ± 2.77 µM), was identified as the ACE inhibitor by reverse-phase high performance liquid chromatography (RP-HPLC) assay. Molecular dynamics simulation of NPATY was further utilized to analyze interactive bonds and key residues. ALA354 was identified as a key residue of ACE inhibitors. Hydrophobic effect of VAL518 and electrostatic effects of HIS383, HIS387, HIS513 and Zn2+ were also regarded as playing a key role in inhibiting ACE activities. This study provides a research strategy to explore the pharmacological mechanism of Traditional Chinese Medicine (TCM) proteins based on in silico

  4. Discovery of Anti-Hypertensive Oligopeptides from Adlay Based on In Silico Proteolysis and Virtual Screening.

    PubMed

    Qiao, Liansheng; Li, Bin; Chen, Yankun; Li, Lingling; Chen, Xi; Wang, Lingzhi; Lu, Fang; Luo, Ganggang; Li, Gongyu; Zhang, Yanling

    2016-12-14

    Adlay (Coix larchryma-jobi L.) was the commonly used Traditional Chinese Medicine (TCM) with high content of seed storage protein. The hydrolyzed bioactive oligopeptides of adlay have been proven to be anti-hypertensive effective components. However, the structures and anti-hypertensive mechanism of bioactive oligopeptides from adlay were not clear. To discover the definite anti-hypertensive oligopeptides from adlay, in silico proteolysis and virtual screening were implemented to obtain potential oligopeptides, which were further identified by biochemistry assay and molecular dynamics simulation. In this paper, ten sequences of adlay prolamins were collected and in silico hydrolyzed to construct the oligopeptide library with 134 oligopeptides. This library was reverse screened by anti-hypertensive pharmacophore database, which was constructed by our research team and contained ten anti-hypertensive targets. Angiotensin-I converting enzyme (ACE) was identified as the main potential target for the anti-hypertensive activity of adlay oligopeptides. Three crystal structures of ACE were utilized for docking studies and 19 oligopeptides were finally identified with potential ACE inhibitory activity. According to mapping features and evaluation indexes of pharmacophore and docking, three oligopeptides were selected for biochemistry assay. An oligopeptide sequence, NPATY (IC50 = 61.88 ± 2.77 µM), was identified as the ACE inhibitor by reverse-phase high performance liquid chromatography (RP-HPLC) assay. Molecular dynamics simulation of NPATY was further utilized to analyze interactive bonds and key residues. ALA354 was identified as a key residue of ACE inhibitors. Hydrophobic effect of VAL518 and electrostatic effects of HIS383, HIS387, HIS513 and Zn(2+) were also regarded as playing a key role in inhibiting ACE activities. This study provides a research strategy to explore the pharmacological mechanism of Traditional Chinese Medicine (TCM) proteins based on in silico

  5. Taste quality of monascal adlay.

    PubMed

    Tseng, Yu-Hsiu; Yang, Joan-Hwa; Chang, Hui-Ling; Mau, Jeng-Leun

    2004-04-21

    Monascus purpureus was inoculated into cooked adlay, and a new product was produced after fungal fermentation. Contents of crude ash, fat, fiber, and protein in the inoculated products [monascal polished adlay (MPA) and monascal dehulled adlay (MDA)] were much higher than those in the uninoculated controls [polished adlay (PA) and dehulled adlay (DA)]. Only carbohydrate content was notably higher in DA and PA. The three soluble sugars and polyol found were arabitol, galactose, and glucose. The contents of total soluble sugars and polyol were in the descending order of DA approximately PA (79.6 and 79.1 mg/g, respectively) > MDA (59.8 mg/g) > MPA (53.5 mg/g). The total free amino acid contents ranged from 8.60 to 14.11 mg/g and occurred in the descending order of MDA approximately MPA > DA > PA. Contents of bitter components (4.07-7.61 mg/g) were high as compared to monosodium glutamate-like and sweet components, in the descending order of MDA approximately MPA > DA > PA. No flavor 5'-nucleotides were found. On the basis of the results obtained, monascal adlay products might give a bitter perception.

  6. Ultrasound assisted supercritical fluid extraction of oil and coixenolide from adlay seed.

    PubMed

    Hu, Ai-jun; Zhao, Shuna; Liang, Hanhua; Qiu, Tai-qiu; Chen, Guohua

    2007-02-01

    Oil and coixenolide are important components of adlay seed (Coix lachrymal-jobi L. var. Adlay) with many beneficial functions to human health. In this work, a novel extraction technique--ultrasound assisted supercritical fluid extraction (USFE)--was studied. Effects of operating conditions on the extraction, including extraction temperature (T), pressure (P), time (t), CO(2) flow rate (F) and ultrasonic power (I) were investigated. There are optimum temperatures which gives the maximum extraction yields (EYs) for the supercritical fluid extractions with and without ultrasound. The effect of pressure on EYs for is similar to that of pressure on CO(2) density. Based on the yield of extraction, the favorable conditions for supercritical fluid extraction (SFE) were: T at 45 degrees C, P at 25 MPa, t at 4.0 h and F at 3.5L/h. While ultrasound was applied as in USFE, the following parameters were preferred: T at 40 degrees C, P at 20 MPa, t at 3.5h and F at 3.0 L/h, respectively. The results show that supercritical fluid extraction with the assistance of ultrasound could reduce the temperature, pressure, CO(2) flow rate, as well as time used in the process. Compared with SFE, USFE could give a 14% increase in the yield for extracting oil and coixenolide from adlay seed with less severe operating conditions.

  7. 4-Ketopinoresinol, a novel naturally occurring ARE activator, induces the Nrf2/HO-1 axis and protects against oxidative stress-induced cell injury via activation of PI3K/AKT signaling.

    PubMed

    Chen, Huang-Hui; Chen, Yu-Tsen; Huang, Yen-Wen; Tsai, Hui-Ju; Kuo, Ching-Chuan

    2012-03-15

    The Nrf2/ARE pathway plays an important role in inducing phase II detoxifying enzymes and antioxidant proteins and has been considered a potential target for cancer chemoprevention because it eliminates harmful reactive oxygen species or reactive intermediates generated from carcinogens. The objectives of this study were to identify novel Nrf2/ARE activators and to investigate the mechanistic signaling pathway involved in the activation of Nrf2-mediated cytoprotective effects against oxidative-induced cell injury. A stable ARE-driven luciferase reporter cell line was established to screen a potentially cytoprotective compound. 4-Ketopinoresinol (4-KPR), the (α-γ) double-cyclized type of lignan obtained from adlay (Coix lachryma-jobi L. var. ma-yuen Stapf), activates ARE-driven luciferase activity more effectively than the classical ARE activator tert-butylhydroquinone. 4-KPR treatment resulted in a transient increase in AKT phosphorylation and subsequent phosphorylation and nuclear translocation of Nrf2, along with increased expression of ARE-dependent cytoprotective genes, such as heme oxygenase-1 (HO-1), aldo-keto reductases, and glutathione synthetic enzyme. 4-KPR suppresses oxidative stress-induced DNA damage and cell death via upregulation of HO-1. Inhibition of PI3K/AKT signaling by chemical inhibitors or RNA interference not only suppressed 4-KPR-induced Nrf2/HO-1 activation, but also eliminated the cytoprotective effect against oxidative damage. These observations in an ARE-regulated gene system suggest that 4-KPR is a novel Nrf2/ARE-mediated transcription activator, activates the Nrf2/HO-1 axis, and protects against oxidative stress-induced cell injury via activation of PI3K/AKT signaling.

  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.

  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. Electrochemical polypyrrole formation from pyrrole 'adlayer'.

    PubMed

    Plausinaitis, Deivis; Sinkevicius, Linas; Mikoliunaite, Lina; Plausinaitiene, Valentina; Ramanaviciene, Almira; Ramanavicius, Arunas

    2017-01-04

    In this research study, we investigated the morphology of polypyrrole nanostructures, which were formed during the electrochemical deposition of conducting polymer. An electrochemical quartz crystal microbalance (EQCM) cell equipped with a flow-through system was employed to exchange solutions of different compositions within the EQCM cell. When bare PBS buffer in the EQCM cell was exchanged with PBS buffer with pyrrole we observed a distinct increase in the resonance frequency Δf. This change in the resonance frequency and electrical capacitance, which was calculated from electrochemical impedance spectroscopy (EIS) data, illustrate that pyrrole on the surface of the gold electrode formed an adsorbed layer (adlayer). The formation of a pyrrole adlayer before the potential pulse that induced polymerization was investigated by QCM-based measurements. The electrochemical polymerization of this adlayer was induced by a single potential pulse and a nanostructured layer, which consisted of adsorbed polypyrrole (Ppy) nanoparticles with a diameter of 50 nm, was formed. QCM and EIS data revealed that by the next cycle of the electrochemical formation of Ppy, which was investigated after flow-through-based exchange of solutions, the initially formed Ppy surface was covered by the adlayer of pyrrole. This adlayer was desorbed when pyrrole was removed from the solution. When electrochemical polymerization was performed using 50 potential pulses, a Ppy layer, which had more complex morphology, was formed on the EQCM crystal. Scanning electron microscopy showed that the conductivity of this layer was unequally distributed. We observed that the polypyrrole layer formed by electrochemical deposition, which was performed using potential pulses, was formed out of aggregated spherical Ppy particles with a diameter of 50 nm.

  11. Phytochemical profiles and antioxidant activity of adlay varieties.

    PubMed

    Wang, Lifeng; Chen, Jingyi; Xie, Huihui; Ju, Xingrong; Liu, Rui Hai

    2013-05-29

    Consumption of whole grains has been associated with reduced risk of developing major chronic diseases. These health benefits have been attributed in part to their unique phytochemicals. Little is known about the complete profiles of phytochemicals and antioxidant activities of different adlay varieties. The objectives of this study were to determine the phytochemicals profiles of the three adlay varieties, including both free and bound of total phenolics and total flavonoids, and to determine the total antioxidant activity of adlay. The free, bound, and total phenolic contents of adlay samples ranged from 31.23 to 45.19 mg of gallic acid equiv/100 g of sample, from 28.07 to 30.86 mg of gallic acid equiv/100 g of sample, and from 59.30 to 76.04 mg of gallic acid equiv/100 g of sample, respectively. On average, the bound phenolics contributed 45.3% of total phenolic content of the adlay varieties analyzed. The free, bound, and total flavonoid contents of adlay samples ranged from 6.21 to 18.24 mg of catechin equiv/100 g, from 18.68 to 35.27 mg of catechin equiv/100 g, and from 24.88 to 52.86 mg of catechin equiv/100 g, respectively. The average values of bound flavonoids contributed 71.1% of total flavonoids of the adlay varieties analyzed. The percentage contribution of flavonoid content to phenolic content of free, bound, and total ranged from 11.6 to 35.2%, from 50.5 to 66.8%, and from 24.6 to 50.5%. The free, bound, and total oxygen radical absorbance capacity (ORAC) values of adlay samples ranged from 231.9 to 316.6 mg of Trolox equiv/100 g, from 209.0 to 351.4 mg of Trolox equiv/100 g, and from 440.9 to 668.0 mg of Trolox equiv/100 g, respectively. The average ORAC values of bound phytochemicals contributed 48.1% of total antioxidant activity of the adlay varieties analyzed. The content of total polyphenol and the antioxidant capacity are obviously different among different species. Liaoning 5 adlay and Longyi 1 adlay are significantly better than Guizhou

  12. [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.

  13. Properties of heavy rare-gases adlayers on graphene substrates

    NASA Astrophysics Data System (ADS)

    Madeira, Lucas; Vitiello, Silvio A.

    2017-01-01

    We investigated several properties of heavy rare-gases, Ne, Ar, Kr, Xe and Rn, adsorbed on graphene substrates in a range of temperature near their melting transition and at some of the representative densities. We have determined radial distribution functions and spacial distributions of the rare-gases adlayers using molecular dynamics simulations. We gathered evidences that Ne and Kr adlayers form commensurate solids. The specific heat and the melting temperature of the adlayers were calculated. At the conditions that our simulations were performed, we find indications supporting a continuous melting of the adlayers. We estimated the nearest neighbor distance of the adatoms, and we determined their average distance to the substrate. We briefly comment on the wetting behavior of the system.

  14. Electrochemically active, anti-biofouling polymer adlayers on indium-tin-oxide electrodes.

    PubMed

    Kim, Eun Jeong; Shin, Hee-Young; Park, Sangjin; Sung, Daekyung; Jon, Sangyong; Sampathkumar, Srinivasa-Gopalan; Yarema, Kevin J; Choi, Sung-Yool; Kim, Kyuwon

    2008-08-14

    Here we report the synthesis of a novel electrochemically active polymer, preparation of adlayers of the polymer on optically transparent electrodes, and an application of the adlayers to immobilization of engineered cells through a direct covalent coupling reaction.

  15. Esophageal thermal injury by hot adlay tea.

    PubMed

    Go, Hoon; Yang, Hyeon Woong; Jung, Sung Hee; Park, Young A; Lee, Jung Yun; Kim, Sae Hee; Lim, Sin Hyung

    2007-03-01

    Reversible thermal injury to the esophagus as the result of drinking hot liquids has been reported to generate alternating white and red linear mucosal bands, somewhat reminiscent of a candy cane. This phenomenon is associated with chest pain, dysphagia, odynophagia, and epigastric pain. Here, we report a case of thermal injury to the esophageal and oral cavity due to the drinking of hot tea, including odynophagia and dysphagia. A 69-year-old man was referred due to a difficulty in swallowing which had begun a week prior to referral. The patient, at the time of admission, was unable to swallow even liquids. He had recently suffered from hiccups, and had consumed five cups of hot adlay tea one week prior to admission, as a folk remedy for the hiccups. Upon physical examination, the patient's oral cavity evidenced mucosal erosion, hyperemia, and mucosa covered by a whitish pseudomembrane. Nonspecific findings were detected on the laboratory and radiological exams. Upper endoscopy revealed diffuse hyperemia, and erosions with thick and whitish pseudomembraneous mucosa on the entire esophagus. The stomach and duodenum appeared normal. We diagnosed the patient with thermal esophageal injury inflicted by the hot tea. He was treated with pantoprazole, 40 mg/day, for 14 days, and evidenced significant clinical and endoscopic improvement.

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

    PubMed

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

    2015-11-07

    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.

  17. 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.

  18. The effect of adlay oil on plasma lipids, insulin and leptin in rat.

    PubMed

    Huang, B W; Chiang, M T; Yao, H T; Chiang, W

    2005-06-01

    This study was designed to investigate the effect of dietary adlay oil on plasma lipids, insulin and lipid peroxidation levels in rats. Twenty-four male Wistar rats fed diet containing adlay oil and cholesterol were studied for 4 weeks. The animals were divided into three groups: (1) 10% lard (control) group; (2) 5% lard + 5% adlay oil (5% adlay oil) group; and (3) 10% adlay oil group. Although there was no significant difference in body weight at the end of the feeding study, rats fed a diet containing adlay oil showed a significant decrease in adipose tissue weight and relative adipose weight. In addition, the rats fed the adlay oil showed significantly decreased low-density lipoprotein cholesterol (LDL-C), insulin, leptin and thiobarbituric acid reactive substance (TBARS) concentrations after 4 weeks of the feeding study. Although a significant decrease in total plasma cholesterol was observed in rats fed the 5% adlay oil diet, no significant difference was observed between the 10% adlay oil and control groups, and neither was a significant difference in liver TBARS concentration found between the dietary groups. Results from this study suggest that dietary adlay oil can reduce leptin, adipose tissue and LDL-C levels in rats.

  19. Impact of germination on nutritional and physicochemical properties of adlay seed (Coixlachryma-jobi L.).

    PubMed

    Xu, Lei; Chen, Long; Ali, Barkat; Yang, Na; Chen, Yisheng; Wu, Fengfeng; Jin, Zhengyu; Xu, Xueming

    2017-08-15

    Adlay has garnered a great deal of research attentions in recent years as a highly nutritious food material and herbal medicine. This study characterized the changes of nutritional and physicochemical properties of adlay seeds during a 60-h germination. The results showed that the 60-h germination brought about a 3.4-fold increase in γ-aminobutyric acid (GABA) and 3.6-fold increase in coixol compared to ungerminated adlay seeds, while the triolein content slightly decreased. Some high molecular proteins were hydrolyzed into smaller proteins, peptides and amino acids after germination. Scanning electron micrographs (SEM) showed that the germination process destroyed the continuous matrix structure of adlay flour and created pits and holes on the surface of some starch granules. Germination resulted to changes in the pasting and gelatinization properties of adlay flour. The results of present study suggest that germination efficiently enhances the nutritional compounds while altering the physicochemical characteristics of adlay seeds.

  20. 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.

  1. Melanogenesis inhibitors from Coix lacryma-jobi seeds in B16-F10 melanoma cells.

    PubMed

    Amen, Yhiya; Arung, Enos Tangke; Afifi, Mohamed S; Halim, Ahmed F; Ashour, Ahmed; Fujimoto, Ryoji; Goto, Takahiro; Shimizu, Kuniyoshi

    2017-02-16

    An adenine derivative, 9-β-D-glucopyranosyl adenine, reported for the first time from a natural source, in addition to nine known compounds were isolated from the seeds of Coix lacryma-jobi. Their structures were elucidated based on extensive spectroscopic and chemical studies. The isolated compounds and the ethanol extract have been assayed for melanin inhibition using B16-F10 melanoma cell line. The results of our study suggested the potential use of Coix lacryma-jobi seeds as a skin whitening agent and reveal the seeds to be a rich source of important phytochemicals with melanogenesis inhibitory activity. Among the isolated compounds, coixol (2) and 2-O-β-glucopyranosyl-7-methoxy-2H-1,4-benzoxazin-3(4H)-one (8) exhibited potent melanogenesis inhibitory activity with no obvious melanocytotoxicity. The rest of the compounds showed weak to moderate activity.

  2. 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

  3. Antiproliferative and chemopreventive effects of adlay seed on lung cancer in vitro and in vivo.

    PubMed

    Chang, Hui-Chiu; Huang, Yu-Chun; Hung, Wen-Chun

    2003-06-04

    This study examined the effects of different extracts of adlay seed on the growth of human lung cancer cells in vitro and in vivo. The data showed that a methanolic extract, but not a water extract, of adlay seed exerted an antiproliferative effect on A549 lung cancer cells by inducing cell cycle arrest and apoptosis. It was also found that tumor growth in vivo was inhibited by the methanolic extract in a dose-dependent manner. The chemopreventive effect of adlay seed on the tobacco-specific carcinogen 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK)-induced lung tumorigenesis in A/J mice was also investigated. Groups of mice were pre-fed with different diets, followed by feeding with NNK-containing drinking water for 8 months. The results indicated that feeding with diet containing 30% of powdered adlay seed reduced the number of surface lung tumors by approximately 50%. Taken together, these results indicate that the components of adlay seed exert an anticancer effect in vitro and in vivo and may be useful for the prevention of lung tumorigenesis.

  4. Suppression of allergic reactions by dehulled adlay in association with the balance of TH1/TH2 cell responses.

    PubMed

    Hsu, Hsin-Yi; Lin, Bi-Fong; Lin, Jin-Yuarn; Kuo, Ching-Chuan; Chiang, Wenchang

    2003-06-18

    Dehulled adlay is known as a natural Chinese medicine having antiallergic activity, although its mechanism remains unclear. This study examined the effects of dehulled adlay on antigen-specific antibody and cytokine production. Mice were immunized three times with ovalbumin (OVA) in alum adjuvant. It was found that oral administration of dehulled adlay in mice suppressed the production of IgE against OVA antigen. Serum anti-OVA IgG(2a) antibody levels were significantly increased in mice after oral administration of dehulled adlay. Furthermore, the production of IL-2 by OVA-stimulated splenocytes was augmented in dehulled adlay-fed mice. Although dehulled adlay had no effect on the serum anti-OVA IgG(1) antibody levels, it had a great capacity to reduce IL-5 secretion by means of OVA-stimulated splenocytes. Hydrothermal processes, including steaming and extrusion cooking, did not change the capacity of dehulled adlay to suppress IgE production. Three fractions of dehulled alday, including methanolic extract, warm water extract, and residue, were obtained. The methanolic extract exhibited the greatest capacity to reduce anti-OVA IgE production. These results suggest that dehulled adlay has a modulating ability to shift the balance from Th2 to Th1 dominance in the T cell mediated immune system and may be beneficial for the treatment of allergic disorders.

  5. Indium incorporation into InGaN: The role of the adlayer

    NASA Astrophysics Data System (ADS)

    Rossow, U.; Horenburg, P.; Ketzer, F.; Bremers, H.; Hangleiter, A.

    2017-04-01

    We study the incorporation processes of indium into group-III nitride layers under pulsed and continuous growth conditions by in-situ reflection measurements. We want to clarify which processes limit the incorporation of indium and lead to a degrading layer structure. The data are discussed in the context of the adlayer model proposed by theory [1], which is a liquid-like layer of group-III atoms on the surface. The adlayer is built-up by the incoming flux but the high vapor pressure of indium leads to a high desorption rate and therefore it is apparent in the data only for low growth temperatures. The data suggests that segregated indium on the surface and the environment also contribute to the indium incorporation process likely also via the adlayer.

  6. Metal monolayer deposition by replacement of metal adlayers on electrode surfaces

    NASA Astrophysics Data System (ADS)

    Brankovic, S. R.; Wang, J. X.; Adžić, R. R.

    2001-03-01

    A new metal deposition method is demonstrated by deposition of a submonolayer of Pt, a monolayer of Pd and a bilayer of Ag on Au(1 1 1) surfaces by using a Cu adlayer as a template. The deposition of these metals occurs as a spontaneous irreversible redox process in which a Cu adlayer, obtained by underpotential deposition, is oxidized by more noble metal cations, which are reduced and simultaneously deposited. The Pt deposit is a two-dimensional submonolayer consisting of partially interconnected nano-clusters of monoatomic height. Pd forms a uniform, but textured monolayer, while Ag forms a bilayer. The deposit of each metal uniformly covers the entire gold surface without preferential deposition along the step edges. This method provides surface adlayer-controlled growth, as compared to the current distribution controlled growth in conventional electrodeposition.

  7. 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

  8. Cloning and structural analysis of an Indian little millet (Panicum sumatrense) zein-like storage protein: implications for molecular assembly.

    PubMed

    Sivakumar, S; Franco, O L; Thayumanavan, B; Murad, A M; Manickam, A; Mohan, M; Mridula, M

    2006-11-01

    Zeins are prolamin storage proteins that accumulate in kernel endosperm of several cereals. For cloning of genes coding for zein-like proteins that accumulate in enhanced quantities in the filling stages of little millet (Panicum sumatrense Roth.) developing grains, RT-PCR was performed using specific primers. A 750-bp cDNA was directly sequenced and in silico analysis showed high identity degree to alpha-prolamins. This family is composed of zeins from Zea mays, coixins from Coix lachryma-jobi, and alpha-kafirins from Sorghum bicolor. The putative conserved domain of zein-like proteins was identified by primary structure comparisons. Furthermore, threading analyses indicated that the millet zein-like protein forms an anti-parallel alpha-helical hairpin with two opposite surfaces: one hydrophobic and the other hydrophilic that probably could be involved in protein storage assembly. Knowledge about zein-like alpha-prolamins in little millet will lead to cloning and transfer of this gene to other major food crops, such as cereals and legumes, with inferior nutritional quality for monogastric animals.

  9. 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

    2014-08-06

    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.

  10. Mevinolin, citrinin and pigments of adlay angkak fermented by Monascus sp.

    PubMed

    Pattanagul, Patcharee; Pinthong, Renu; Phianmongkhol, Aphirak; Tharatha, Somsak

    2008-08-15

    Adlay angkak a new developed product from an adlay substrate fermented by Monascus fungi can be used both as a natural coloring and a dietary supplement. However, not only useful secondary metabolites such as mevinolin and pigments are produced; the fungi also produce toxin substance called citrinin. This study conducted the cultivation of M. purpureus (ATCC 16365, BCC 6131, DMKU and FTCMU) and M. ruber TISTR 3006 on the adlay substrate for mevinolin, citrinin, pigments and glucosamine synthesis at room temperature (32-35 degrees C) for 28 days. The results elucidated that glucosamine levels expressed as the mold growth in solid-state fermentation corresponded as a relatively reliable indicator to the mevinolin, citrinin and pigments production. M. purpureus DMKU produced the lowest citrinin content of 0.26 ppm and the highest mevinolin content of 25.03 ppm with pigment concentrations expressed by absorbance at wavelengths of 400, 470 and 500 nm for yellow, orange and red pigments of 9.76, 3.03 and 3.43 units respectively and moisture content and pH of 83.51% and 6.54 respectively. This study suggested that M. purpureus DMKU has a potential for the production of adlay angkak within an authorized citrinin level.

  11. Standing and sitting adlayers in atomic layer deposition of ZnO

    SciTech Connect

    Gao, Zhengning; Banerjee, Parag; Wu, Fei; Myung, Yoon; Fei, Ruixiang; Kanjolia, Ravindra; Yang, Li

    2016-01-15

    The extent of reactivity of diethyl zinc (DEZ) with a hydroxylated surface during atomic layer deposition (ALD) of ZnO using DEZ and water is measured. Two adlayer configurations of DEZ are possible. The “standing” adlayer releases one ethyl group from DEZ. The “sitting” adlayer releases both ethyl groups, thus forming a Zn bridge between two O anions. Density functional theory calculations suggest the sitting configuration is more stable than the standing configuration by 790 meV. In situ quadrupole mass spectroscopy of by-product ethane generated in ALD half cycles indicate that ∼1.56 OH sites react with a DEZ molecule resulting in 71.6% of sitting sites. A simple simulation of a “ball-and-stick” DEZ molecule randomly collapsing on a neighboring site remarkably captures this adlayer behavior. It is concluded that DEZ fraction sitting is a competitive process of a standing DEZ molecule collapsing onto an available neighboring hydroxyl site, as sites vie for occupancy via adsorption and surface diffusion.

  12. 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.

  13. Effect of young barley leaf extract and adlay on plasma lipids and LDL oxidation in hyperlipidemic smokers.

    PubMed

    Yu, Ya-Mei; Chang, Weng-Cheng; Liu, Chu-Sun; Tsai, Ching-Min

    2004-06-01

    Forty hyperlipidemic patients, smokers and non-smokers, were studied. Subjects received 15 g young barley leaf extract (BL) or 60 g adlay daily for four weeks. Overnight fasting blood samples were drawn immediately prior to and after four weeks of supplementation. Blood samples were analyzed for plasma lipid profiles and their susceptibility to low-density lipoprotein (LDL) oxidation. The plasma total and LDL-cholesterol (LDL-C) levels were reduced following treatment with either BL or adlay; furthermore, the lag phase of LDL oxidation increased after either supplementation. However, it seemed that BL had stronger antioxidative effect on the prevention of LDL oxidation than adlay. Our results also indicated that the antioxidative effect was less pronounced in smokers than in non-smokers. Therefore, supplementation with BL or adlay can decrease plasma lipids and inhibit LDL oxidation in hyperlipidemic smokers and/or non-smokers.

  14. Inhibitory effects of adlay extract on melanin production and cellular oxygen stress in B16F10 melanoma cells.

    PubMed

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

    2014-09-19

    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.

  15. 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

  16. 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.

  17. Allergic immune-regulatory effects of adlay bran on an OVA-immunized mice allergic model.

    PubMed

    Chen, Hong-Jhang; Hsu, Hsin-Yi; Chiang, Wenchang

    2012-10-01

    Allergy is an inflammation associated with an elevated T helper (Th) 2 lymphocyte responses to allergens and elevated serum IgE levels and cytokines. In one of our previous studies using a cell model, various flavonoids were found to be involved the anti-inflammatory effects of adlay bran. The present study investigated the effect of the ethyl-acetate fraction of ethanolic extract of adlay bran (ABE-EtOAc) in an ovalbumin (OVA)-immunized murine model. Six-week-old female BALB/c mice underwent OVA sensitization and were used as an allergy model. An orogastric gavage was used to force feed these mice with 240 mg/kg ABE-EtOAc from their sixth week through their twelfth week. Immune reactions were determined by measuring changes in Th2-type cytokine (IL-4 and IL-5) levels and production of antibodies. ABE-EtOAc was found capable of regulating the Th1/Th2 immune reaction through its regulation of IL-2 and IL-4. It also significantly reduced the production of anti-OVA IgE antibodies (10%), increased the secretion of IFN-γ and decreased the secretion of IL-6 (38%). These results suggest that adlay bran extract can reduce an allergic reaction by balancing Th1/Th2 immune responses and that it might be used in the treatment of this condition.

  18. On the hydration of subnanometric antifouling organosilane adlayers: a molecular dynamics simulation.

    PubMed

    Sheikh, Sonia; Blaszykowski, Christophe; Nolan, Robert; Thompson, Damien; Thompson, Michael

    2015-01-01

    The connection between antifouling and surface hydration is a fascinating but daunting question to answer. Herein, we use molecular dynamics (MD) computer simulations to gain further insight into the role of surface functionalities in the molecular-level structuration of water (surface kosmotropicity)--within and atop subnanometric organosilane adlayers that were shown in previous experimental work to display varied antifouling behavior. Our simulations support the hypothesized intimate link between surface hydration and antifouling, in particular the importance of both internal and interfacial hydrophilicity and kosmotropicity. The antifouling mechanism is also discussed in terms of surface dehydration energy and water dynamicity (lability and mobility), notably the crucial requirement for clustered water molecules to remain tightly bound for extensive periods of time--i.e. exhibit slow exchange dynamics. A substrate effect on surface hydration, which would also participate in endowing antifouling adlayers with hydrogel-like characteristics, is also proposed. In contrast, the role of adlayer flexibility, if any, is assigned a secondary role in these ultrathin structures made of short building blocks. The conclusions from this work are well in line with those previously drawn in the literature.

  19. Off lattice Monte Carlo simulation study for different metal adlayers onto (1 1 1) substrates

    NASA Astrophysics Data System (ADS)

    Rojas, M. I.

    2004-10-01

    The structure, energetics, and elastic properties of metallic adlayers adsorbed onto monocrystalline substrate surfaces are analyzed for a set of systems of electrochemical interest. The systems considered involve Ag, Au, Pt, Pd, and Cu. The different adsorbate/substrate (1 1 1) systems were simulated employing off lattice Monte Carlo simulations with embedded atom method potentials in the canonical ensemble at 300 K. The underpotential and overpotential deposition trends observed for this set of transition metal systems are analyzed taking into account the structure of the monolayer, the energy of the systems, and the surface stress change.

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

    SciTech Connect

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

    2011-12-09

    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(10) 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.

  1. Methanolic extract of adlay seed suppresses COX-2 expression of human lung cancer cells via inhibition of gene transcription.

    PubMed

    Hung, Wen-Chun; Chang, Hui-Chiu

    2003-12-03

    Previous results demonstrated that the methanolic extract of adlay seed exerted an antiproliferative effect on human lung cancer cells in vitro and in vivo and might prevent tobacco carcinogen-induced lung tumorigenesis. In this study, the methanolic extract of adlay seed was tested for its regulation of COX-2 expression of human lung cancer cells. Western blot analysis showed that the methanolic extract of adlay seed inhibited basal and TPA-induced COX-2 expression in a dose-dependent fashion, whereas COX-1 expression was not affected. By using a promoter activity assay, it was found that the methanolic extract inhibited basal and TPA-stimulated COX-2 expression at the transcription level. The effect of the methanolic extract on COX-2 expression in vivo was then investigated. The data demonstrated that treatment of the methanolic extract reduced the PGE(2) level in serum and inhibited COX-2 expression of tumor tissues in nude mice. Taken together, these results suggest that inhibition of COX-2 is one of the mechanisms by which the methanolic extract of adlay seed inhibits cancer growth and prevents lung tumorigenesis.

  2. Adlayer-mediated antibody immobilization to stainless steel for potential application to endothelial progenitor cell capture.

    PubMed

    Benvenuto, Pasquale; Neves, Miguel A D; Blaszykowski, Christophe; Romaschin, Alexander; Chung, Timothy; Kim, Sa Rang; Thompson, Michael

    2015-05-19

    This work describes the straightforward surface modification of 316L stainless steel with BTS, S-(11-trichlorosilylundecanyl)-benzenethiosulfonate, a thiol-reactive trichlorosilane cross-linker molecule designed to form intermediary coatings with subsequent biofunctionalization capability. The strategy is more specifically exemplified with the immobilization of intact antibodies and their Fab' fragments. Both surface derivatization steps are thoroughly characterized by means of X-ray photoelectron spectroscopy. The antigen binding capability of both types of biofunctionalized surfaces is subsequently assessed by fluorescence microscopy. It was determined that BTS adlayers achieve robust immobilization of both intact and fragmented antibodies, while preserving antigen binding activity. Another key finding was the observation that the Fab' fragment immobilization strategy would constitute a preferential option over that involving intact antibodies in the context of in vivo capture of endothelial progenitor cells in stent applications.

  3. Optical monitoring of surface adlayers by laser-induced thermal desorption during the plasma etching of semiconductors

    NASA Astrophysics Data System (ADS)

    Choe, Jae Young

    1999-11-01

    Laser induced thermal desorption with optical detection by laser induced fluorescence and transient plasma induced emission is used to analyze the surface adlayer during plasma etching of semiconductors, including Si, Ge, and InP. In the investigation of Si etching in a Cl2 inductively coupled plasma (ICP), 308 nm radiation from a XeCl excimer laser heats the surface to desorb the surface species (LD) and excites laser induced fluorescence (LIF) in the desorbing SiCl. This measured LD-LIF optical signal indicates the adlayer chlorine content during steady-state plasma etching. The LD-LIF of SiCl increases with dc substrate bias voltage indicating that the adlayer chlorine content increases with increasing substrate bias. The SiCl LD-LIF signal is almost independent of rf power, while the ion density and etch rate increase by an order of magnitude over the range of rf power studied. In the investigation of Ge etching in a Cl2 ICP, 308 nm radiation from a XeCl excimer laser is used for LD-LIF of GeCl. The LD-LIF of GeCl is also independent of rf power, as for Si etching, but the rate of chlorination is faster than that during Si etching. The GeCl LD-LIF signal remains almost constant as dc substrate bias is increased from 0 V to over -100 V. The transient increase in plasma-induced emission following laser-induced thermal desorption (LD-PIE) is also used to analyze the surface adlayer during Si and InP etching by a Cl2 plasma. Several different species are monitored during Si etching by a Cl2 plasma, including Si, SiCl and SiCl2. The LD-PIE intensities from all of these species increase with rf power. In order to properly interpret the LD-PIE signal to determine the level of surface chlorination, the LD-PIE signal is normalized by the electron density. The LD-PIE intensities during Si etching increase with the dc substrate bias as in the LD-LIF study. Both the LD-LIF and LD-PIE measurements of Si etching are consistent with each other for determining the adlayer

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

    PubMed

    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.

  5. 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

  6. Preparation of novel butyryl galactose ester-modified coix component microemulsions and evaluation on hepatoma-targeting in vitro and in vivo.

    PubMed

    Liu, Ming Jian; Qu, Ding; Chen, Yan; Liu, Cong Yan; Liu, Yu Ping; Ding, Xue Fang

    2016-11-01

    The butyryl galactose ester-modified coix component microemulsions (But-Gal-CMEs) was developed for enhanced liver tumor-specific targeting. The study was aimed to evaluate the hepatoma-targeting potential of But-Gal-CMEs in vitro and in vivo. But-Gal-CMEs with a uniform spherical shape exhibited a small particle size (56.68 ± 0.07 nm), a narrow polydispersity (PDI, 0.144 ± 0.005) and slightly negative surface charge (-0.102 ± 0.008 mV). In the cell uptake studies, But-Gal-CMEs showed a significant enhancement on the intracellular fluorescent intensity on HepG2 cells model, which was 1.93-fold higher relative to coix component microemulsions (CMEs). The IC50 of But-Gal-CMEs against HepG2 cells was 64.250 μg/mL, which was notably stronger than that of CMEs. In the cell apoptosis studies, compared with CMEs, But-Gal-CMEs (50 μg/mL) treatment resulted in a 1.34-fold rise in total apoptosis cells of HepG2. In the biodistribution studies in vivo, the intratumorous fluorescence of Cy5-loaded But-Gal-CMEs was 1.43-fold higher relative to that of Cy5-loaded CMEs, suggesting an obviously enhanced accumulation in the tumor sites. Taken as together, But-Gal could be incorporated into the coix component microemulsions as a novel ligand for realizing hepatoma-targeting drugs delivery.

  7. Adlayer structure of octa-alkoxy-substituted copper(II) phthalocyanine on Au(111) by electrochemical scanning tunneling microscopy.

    PubMed

    Wang, Li; Ou-Yang, Liangyue; Yau, Shueh-Lin

    2008-01-01

    Electrochemical scanning tunneling microscopy (ECSTM) has been used to examine the adlayer of octa-alkoxy-substituted copper(II) phthalocyanines (CuPc(OC(8)H(17))(8)) on Au(111) in 0.1 M HClO(4), where the molecular adlayer was prepared by spontaneous adsorption from a benzene solution containing this molecule. Topography STM scans revealed long-range ordered, interweaved arrays of CuPc(OC(8)H(17))(8) with coexistent rectangular and hexagonal symmetries. High-quality STM molecular resolution yielded the internal molecular structure and the orientation of CuPc(OC(8)H(17))(8) admolecules. These STM results could shed insight into the method of generating ordered molecular assemblies of phthalocyanine molecules with long-chained substitutes on metal surface.

  8. 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

  9. Periodic domain boundary ordering in a dense molecular adlayer: Sub-saturation carbon monoxide on Pd(111)

    NASA Astrophysics Data System (ADS)

    Xu, Pan; Liu, Shizhong; Hong, Sung-Young; Liu, Ping; White, Michael G.; Camillone, Nicholas

    2017-04-01

    We describe a previously unreported ordered phase of carbon monoxide adsorbed on the (111) facet of single crystal palladium at near-saturation coverage. The adlayer superstructure is identified from low energy electron diffraction to be c(16×2) with respect to the underlying Pd(111) surface net. The ideal coverage is determined to be 0.6875 ML, approximately 92% of the 0.75-ML saturation coverage. Density functional theory calculations support a model for the molecular packing characterized by strips of locally-saturated (2×2) regions, with the CO bound near high-symmetry surface sites, separated by antiphase domain boundaries. The structure exists in a narrow coverage range and is prepared by heating the saturated adlayer to desorb a small fraction of the CO. Comparison of the c(16×2) domain-boundary structure with structural motifs at lower coverages suggests that between 0.6 and 0.6875 ML the adlayer order may be more strongly influenced by interadsorbate repulsion than by adsorption-site-specific interactions. The system is an example of the structural complexity that results from the compromise between adsorbate-substrate and adsorbate-adsorbate interactions.

  10. The involvement of Opaque 2 on beta-prolamin gene regulation in maize and Coix suggests a more general role for this transcriptional activator.

    PubMed

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

    1995-03-01

    The maize opaque 2 (o2) mutation is known to have numerous pleiotropic effects. Some polypeptides have their expression depressed while others are enhanced. The best characterized effects of the o2 mutation are those exerted on endosperm genes encoding the storage protein class of the 22 kDa alpha-zeins and the ribosome inactivating protein b-32. The Opaque 2 (O2) locus encodes a basic domain-leucine zipper DNA-binding factor, O2, which transcriptionally regulates these genes. In the maize-related grass Coix lacryma-jobi, an O2-homologous protein regulates the 25 kDa alpha-coixin family. We show in this paper that O2 transcriptionally regulates the structurally and developmentally different class of the beta-prolamins. A new O2-binding box was identified in beta-prolamin genes from maize and Coix that, together with the boxes previously identified in other endosperm expressed genes, forms a curious collection of O2 cis elements. This may have regulatory implications on the role of O2 in the mechanism that controls coordinated gene expression in the developing endosperm. Considering that the O2 locus controls at least three distinct classes of genes in maize endosperm, we propose that the O2 protein may play a more general role in maize endosperm development than previously conceived.

  11. Effect of ultrasonic treatment on immunological activities of polysaccharides from adlay.

    PubMed

    Yao, Yang; Zhu, Yingying; Gao, Yue; Ren, Guixing

    2015-09-01

    Alkali-extractable polysaccharides from the seed of adlay and their two polysaccharide sub-fractions (AAP-1 and AAP-2) were isolated and purified by anion-exchange and gel filtration chromatography. Ultrasonic treatment was put in place to obtain AAP-1' and AAP-2'. Average molecular weights (Mws) of AAP-1, AAP-1', AAP-2, and AAP-2' were 94.2 kDa, 63.1 kDa, 82.3 kDa, and 60.4 kDa, respectively. Monosaccharides composition analysis indicated that AAP-1 and AAP-1' were composed of Rha, Ara, Glc, and Gal in a molar ratio of 1.1:0.4:0.7:0.5 and 1.4:1.6:0.4:0.7. AAP-2 and AAP-2' were composed of Xyl, Rha, Gal and Glc in a molar percent of 0.4:1.4:1.6:0.5 and 0.3:1.6:1.1:0.7. In vitro study showed that AAP-1, AAP-1', AAP-2, and AAP-2' were all able to encourage the production of secretory molecules (NO, TNF-α and IL-6) of RAW264.7 murine macrophages in concentrations determines manner. AAP-2' seemed to be the most potent and induced significantly higher the NO production. These findings suggest that the ultrasonic polysaccharides isolated in our study have immune potentiation effects on macrophages and should serve as a beneficial health food.

  12. Antiproliferative lactams and spiroenone from adlay bran in human breast cancer cell lines.

    PubMed

    Chung, Cheng-Pei; Hsu, Chih-Ying; Lin, Jing-Hui; Kuo, Yueh-Hsiung; Chiang, Wenchang; Lin, Yun-Lian

    2011-02-23

    Two new lactams, coixspirolactam D (1) and coixspirolactam E (2), and a new spiroenone, coixspiroenone (3), together with seven known compounds, coixspirolactam A (4), coixspirolactam B (5), coixspirolactam C (6), coixlactam (7), coixol (8), ethyl dioxindole-3-acetate (9), and isoindol-1-one (10), and two neolignans, zhepiresionol (11) and ficusal (12), were isolated from the bioactive subfraction of adlay bran ethanolic extract (ABE). Compounds 9 and 10 are the first isolates from natural resources. The structures of new compounds were identified by spectroscopic methods, including infrared (IR) spectrum, 1D and 2D nuclear magnetic resonance (NMR), and mass spectrum (MS). All of the isolated compounds were tested for antiproliferative effects on MCF-7, MDA-MB-231, and T-47D cells. Results showed that compounds 1, 3, 4, 6, and 7 at 50 μM significantly inhibited MCF-7 cell proliferation by 30.2, 19.2, 21.0, 13.5, and 32.4%, respectively; compounds 2, 4, and 7 significantly inhibited T-47D cells at 50 μM by 20.7, 24.8, and 28.9%; and compounds 1, 2, and 12 significantly inhibited MDA-MB-231 cells at 50 μM by 47.4, 25.3, and 69.3%, respectively. In conclusion, ABE has antiproliferative activities, and this effect is partially related to the presence of lactams and spiroenone.

  13. Organic adlayer on inorganic materials: XPS analysis selectivity to cope with adventitious contamination

    NASA Astrophysics Data System (ADS)

    Landoulsi, Jessem; Genet, Michel J.; Fleith, Sandrine; Touré, Yetioman; Liascukiene, Irma; Méthivier, Christophe; Rouxhet, Paul G.

    2016-10-01

    This work addresses the ubiquitous presence of organic contaminants at inorganic solid surfaces and the improvement of XPS analysis selectivity to cope with it. Water contact angle measurements showed that the adsorption of organic contaminants occurs readily in ambient air, and faster and more extensively under high vacuum. It is stronger on stainless steel (SS) compared to silica and is significantly reduced when SS is sterilized by autoclaving. The reliability of XPS data was evaluated (selectivity, precision, accuracy) by correlations between spectral data incorporating a large amount of results obtained with different XPS spectrometers on SS and glass samples cleaned in different ways and conditioned with several biomacromolecules. The methodology used allows a discrimination to be made between contaminants and deliberately adsorbed biomacromolecules, and offers perspectives for tracking the source of contamination. Furthermore, a discrimination can be made between oxygen from the organic adlayer and oxygen from the substrate, and the O 1s component above 532.0 eV observed for SS is shown to be due to organic contaminants rather than adsorbed water. This approach offers new perspectives to examine the interactions (displacement or not) between contaminants and compounds of interest, e.g. proteins, at the stage of the adsorption process.

  14. 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.

  15. 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

  16. 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.

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

    DOE PAGES

    Hong, Sung -Young; Xu, Pan; Camillone, Nina R.; ...

    2016-07-01

    Here, 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 probabilitymore » 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.« less

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

    SciTech Connect

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

    2016-07-01

    Here, 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.

  19. 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.

  20. Study of sulfur adlayers on Au(1 1 1) from basic hydrolysis of piperazine bis(dithiocarbamate) sodium salt

    NASA Astrophysics Data System (ADS)

    Martínez, Javier A.; Valenzuela, José; Hernandez-Tamargo, Carlos E.; Cao-Milán, Roberto; Herrera, José A.; Díaz, Jesús A.; Farías, Mario H.; Mikosch, Hans; Hernández, Mayra P.

    2015-08-01

    Sulfur adlayers on Au(1 1 1) were obtained after the interaction of a gold substrate with an alkaline solution of piperazine bis(dithiocarbamate) sodium salt. Characterization of the sulfur modified gold surface was performed by means of X-Ray Photoelectron Spectroscopy (XPS), Scanning Tunneling Microscopy (STM) and Density Functional Theory (DFT) calculations. XPS signals indicated the presence of S-Au bonds, monomeric and polymeric sulfur, and absence of nitrogen and sodium. Images from STM showed the formation of quasi-rectangular octomers in coexistence with another phase. A DFT model using the arrangement of sulfur dimers on the Au(1 1 1) surface effectively reproduced the experimental STM images.

  1. Octanoyl galactose ester-modified microemulsion system self-assembled by coix seed components to enhance tumor targeting and hepatoma therapy

    PubMed Central

    Qu, Ding; Liu, Mingjian; Huang, Mengmeng; Wang, Lixiang; Chen, Yan; Liu, Congyan; Liu, Yuping

    2017-01-01

    A nanosized drug delivery platform with a combination of rational components and tumor targeting is significant for enhancement of anticancer therapy and reduction of side effects. In this study, we developed a octanoyl galactose ester-modified microemulsion system self-assembled by coix seed components (Gal(oct)-C-MEs), which improved the tumor accumulation through asialoglycoprotein receptor-mediated endocytosis and promoted the antitumor efficacy through multicomponent-mediated synergistic effect. Octanoyl galactose ester (Gal(oct)) with a yield of 82.3% was synthesized through a green enzymatic reaction and multidimensional characterization. Gal(oct)-C-MEs with a spherical shape had a small and uniform particle size (58.49±1.03 nm), narrow polydispersity index (0.09±0.01) and neutral surface charge (−5.82±0.57 mV). In the cellular uptake studies, the internalized Gal(oct)-C-ME was 2.28-fold higher relative to that of coix seed component-based microemulsions (C-MEs). The half-maximal inhibitory concentration of Gal(oct)-C-MEs against HepG2 cells was 46.5±2.4 μg/mL, which was notably higher than that of C-MEs. Importantly, the intratumor fluorescence of HepG2 xenograft-bearing nude mice treated with Cy5/Gal(oct)-C-MEs was 1.9-fold higher relative to treatment with Cy5/C-MEs. In the study of antitumor efficacy in vivo, HepG2 xenograft-bearing nude mice intragastrically administered Gal(oct)-C-MEs for 14 days exhibited the strongest inhibition of tumor growth and the lowest toxicity against liver and kidney among all the treatments. In summary, Gal(oct)-C-ME, as a highly effective and safe anticancer drug delivery system, showed promising potential for hepatoma therapy. PMID:28352174

  2. 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.

  3. 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

  4. 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.

  5. Effects of crude adlay hull acetone extract on corticosterone release from rat zona fasciculata-reticularis cells.

    PubMed

    Chang, Ling-Ling; Wun, Alfred Wan-Song; Hung, Chien-Te; Hsia, Shih-Min; Chiang, Wenchang; Wang, Paulus S

    2006-11-01

    Adlay is a grass crop which has been used in traditional Chinese medicine and also as a nourishing food. It has been shown to posses anti-allergic, antimutagenic and hypolipemic effects. However, the effects and action mechanisms of crude adlay hull acetone extract (AHA) on adrenal zona fasciculata-reticularis (ZFR) cells are still unclear. This study explored the effects of AHA on corticosterone release. ZFR cells were incubated with AHA in the presence or absence of adrenocorticotropin (ACTH), 8-bromo-cyclic 3': 5'- adenosine monophosphate (8-Br-cAMP), forskolin (FSK), 25-hydroxy cholesterol (25-OH-cholesterol), pregnenolone, progesterone or deoxycorticosterone. The concentrations of corticosterone or pregnenolone in the media were measured by radioimmunoassay (RIA). The cells were used to measure the expression of steroidogenic acute regulatory (StAR) protein by Western blot. The present data demonstrated that: (1) AHA inhibited ACTH-, 8-Br-cAMP-, forskolin-, 25-OH-cholesterol-, pregnenolone-, progesterone- or deoxycorticosterone-stimulated corticosterone release; (2) AHA (800 microg/ml) caused more pregnenolone release in control group, but not in 25-OH-cholesterol, trilostane or 25-OH-cholesterol+trilostane group; (3) kinetic study showed an uncompetitive inhibition model of AHA to P450 side chain cleavage enzyme (P450scc); (4) kinetic study showed a noncompetitive inhibition model of AHA to 11beta-hydroxylase; and (5) AHA inhibited the expression of StAR protein. These results suggest that AHA acts directly upon rat ZFR cells to diminish corticosterone release. These results indicate the inhibitory mechanism of AHA mediates through an inhibition of the activities of the post-cAMP corticosterone synthesis enzymes, i.e. 3beta-HSD, 21-hydroxylase, 11beta-hydroxylase, and inhibition of StAR protein expression.

  6. Overpotential deposition of Ag monolayer and bilayer on Au(1 1 1) mediated by Pb adlayer underpotential deposition/stripping cycles

    NASA Astrophysics Data System (ADS)

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

    2003-08-01

    Ultra-thin Ag films on the Au(1 1 1) surface were prepared via overpotential deposition (OPD) in the presence of Pb 2+ ions. By carrying out repetitive Pb adlayer underpotential deposition (UPD) and stripping cycles during Ag bulk deposition, the two-dimensional growth of Ag films was significantly enhanced in high OPD. The Ag monolayer sample was made by comparing the voltammetry curves, in which the signatures for Pb adlayer UPD on Au(1 1 1) changed to that on Ag(1 1 1). As demonstrated by the X-ray specular reflectivity measurements, nearly complete monolayer and bilayer films can be made with optimized deposition procedures. On subatomic scale, however, we found that these films have significant higher root-mean-square displacement amplitudes than those underpotentially deposited Ag monolayer and bilayer on either Au(1 1 1) or Pt(1 1 1).

  7. Dietary Monascus adlay supplements facilitate suppression of cigarette smoke-induced pulmonary endoplasmic reticulum stress, autophagy, apoptosis and emphysema-related PLGF in the rat.

    PubMed

    Li, Ping-Chia; Tsai, Wen-Hsin; Chien, Chiang-Ting

    2013-01-15

    Cigarette smoke (CS) exposure may cause oxidative stress in the lung, leading to cell death and long-term injury. Monascus adlay (MA) with antioxidant components produced by inoculating adlay (Cois lachrymal-jobi L. var. ma-yuen Stapf) with Monascus purpureus may protect lung against CS-induced lung injuries in rats. MA and lovastatin had higher antioxidant activities than either M. purpureus or adlay. CS exposure caused significant lung damage, as evidenced by higher levels of reactive oxygen species (ROS), neutrophil infiltration, dityrosine and 4-HNE, as well as lower levels of Mn-superoxide dismutase and catalase expression. Lung tissues with CS exposure had higher levels of ER stress, apoptosis, autophagy and emphysema-related placenta growth factor (PlGF) expressions. All CS-induced injuries were significantly suppressed by MA supplements. MA would be a beneficial nutritional therapy to ameliorate CS-induced lung injury via preserving antioxidant defense mechanisms, decreasing oxidative stress and inhibiting ER stress, autophagy, apoptosis and emphysema-related risk factor.

  8. Growth and electronic structure of alkali-metal adlayers on icosahedral Al{sub 70.5}Pd{sub 21}Mn{sub 8.5}

    SciTech Connect

    Shukla, A. K.; Dhaka, R. S.; Biswas, C.; Banik, S.; Barman, S. R.; Horn, K.; Ebert, Ph.; Urban, K.

    2006-02-01

    We report x-ray photoelectron spectroscopy (XPS) study of Na and K adlayers on icosahedral Al{sub 70.5}Pd{sub 21}Mn{sub 8.5} (i-Al-Pd-Mn) quasicrystal. The Na 1s core-level exhibits a continuous linear shift of 0.8 eV towards lower binding energies (BE) with increasing coverage up to one monolayer (ML) saturation coverage. In the case of K/i-Al-Pd-Mn, a similar linear shift in the K 2p spectra towards lower BE is observed. In both cases, the plasmon related loss features are observed only above 1 ML. The substrate core-level peaks, such as Al 2p, do not exhibit any shift with the adlayer deposition up to the highest coverage. Based on these experimental observations and previous studies of alkali metal growth on metals, we conclude that below 1 ML, both Na and K form a dispersed phase on i-Al-Pd-Mn and there is hardly any charge transfer to the substrate. The variation of the adlayer and substrate core-level intensities with coverage indicates layer by layer growth.

  9. Application of the solvent extraction technique to investigation of the anti-inflammatory activity of adlay bran.

    PubMed

    Huang, Din-Wen; Wu, Chi-Hao; Shih, Chun-Kuang; Liu, Chia-Yu; Shih, Ping-Hsiao; Shieh, Tzong-Ming; Lin, Ching-I; Chiang, Wenchang; Hsia, Shih-Min

    2014-02-15

    The current study utilised a bioassay-directed chemical analysis scheme to screen the anti-inflammatory activity of fractions and compounds from adlay bran (AB). Liquid-liquid extraction couple with liquid chromatography-mass spectrometry (LC-MS) was applied to the isolation, analysis and identification of active components in AB samples. Ethanol extracts of AB (ABE) and ethyl acetate extracts AB (ABEa) were obtained and further partitioned with different solvents. The results showed that among all 16 kinds of fractions from ABE and ABEa, ABEa-Ea-B (80% Ea/n-hexane sub-fraction from ABE-Ea) had the most potent inhibitory effects on NO production, iNOS and COX-2 expressions, and proinflammatory IL-6 and TNF-α secretion in lipopolysaccharide-activated RAW264.7 cells system. Mechanistic data from luciferase reporter-gene assay revealed that the anti-inflammatory action of ABEa-Ea-B may be associated with inhibition of NF-kB transcriptional activity. Notably, tangeretin, nobiletin, and p-hydroxybenzoic acid were found to be the main active compounds for the anti-inflammatory properties in ABEa-Ea-B.

  10. Antagonism of free-radical-induced damage of adlay seed and its antiproliferative effect in human histolytic lymphoma U937 monocytic cells.

    PubMed

    Kuo, C C; Shih, M C; Kuo, Y H; Chiang, W

    2001-03-01

    The goal of our current research was to investigate the antioxidative effects of methanolic extracts from different parts of adlay seed and their antiproliferative activity in malignant human cells. The methanolic extracts from different parts of adlay seeds were from the hull (AHM), testa (ATM), bran (ABM), and polished adlay (PAM). AHM exhibited greater capacity to scavenge superoxide anion radicals in the PMS-NADH system than ATM, ABM, or PAM. The scavenging capacities of AHM and ATM on hydrogen peroxides were about 20% at a dose of 250 microg/mL. Using the method of deoxyribose degradation to assess damage caused by hydroxyl radicals, AHM was found to inhibit damage in deoxyribose at a higher concentration. However, ATM, ABM, and PAM exhibited prooxidative activity at the same concentration. The inhibitory effect on enzymatic oxidation of xanthine to uric acid was found to follow the order AHM > ATM =. ABM. However, PAM was inactive. All test samples were positive for inhibition of TPA-induced free radical formation on neutrophil-like leukocytes and were found to follow the order AHM > ATM > ABM > PAM. When human histolytic lymphoma U937 monocytic cells were exposed to tert-butyl hydroperoxide, AHM protected the cells against the cytotoxicity caused by tert-butyl hydroperoxide. In addition, AHM exhibited antiproliferative activity against human histolytic lymphoma U937 monocytic cells in a dose-dependent manner. The antiproliferative properties of AHM appear to be attributable to its induction of apoptotic cell death as determined by flow cytometry. These results show that AHM displays multiple antioxidant effects and induces apoptosis of malignant human cells.

  11. Effects of adlay, buckwheat, and barley on transit time and the antioxidative system in obesity induced rats

    PubMed Central

    Kim, Jung Yun; Son, Bo Kyung

    2012-01-01

    In the present study, we examined whether four grains including adlay (AD), buckwheat (BW), glutinous barley (GB), and white rice (WR) affect the duration of food residence in the gastrointestinal tract and hepatic enzyme activities in rats fed different combinations of the grains. The rats were raised for 4 weeks on a high fat diet based on the American Institute of Nutrition-93 (AIN-93G) diets containing 1% cholesterol and 20% dietary lipids. Forty male rats were divided into four groups and raised for 4 weeks with a diet containing one of the grains. Corresponding to the dietary fiber contents of the experimental grains, gut transit time was shortest in the rats fed GB and increased in the order of BW, AD, and WR. In addition, the accumulated shortest transit time occurred in the GB group. Gut transit time affected weight gain and major organ weight, as it was closely related to the absorption of nutrients. The level of thiobarbituric acid reactive substance (TBARS) in liver was higher in rats fed WR, AD, BW, and GB, indicating that the other grains decreased oxidative stress in vivo more than WR. Glutathione, glutathione peroxidase, and glutathione S-transferase levels in the AD, BW, and GB groups were significantly higher than those in the WR group. In conclusion, reduced colonic transit time has been implicated in reducing the incidence of colon cancer, as evidenced by populations consuming diets rich in fiber. Whole grains such as AD, BW, and GB may contribute to a significant supply of antioxidants to prevent oxidative stress if they are consumed in large amounts. PMID:22808344

  12. Effects of adlay, buckwheat, and barley on transit time and the antioxidative system in obesity induced rats.

    PubMed

    Kim, Jung Yun; Son, Bo Kyung; Lee, Sang Sun

    2012-06-01

    In the present study, we examined whether four grains including adlay (AD), buckwheat (BW), glutinous barley (GB), and white rice (WR) affect the duration of food residence in the gastrointestinal tract and hepatic enzyme activities in rats fed different combinations of the grains. The rats were raised for 4 weeks on a high fat diet based on the American Institute of Nutrition-93 (AIN-93G) diets containing 1% cholesterol and 20% dietary lipids. Forty male rats were divided into four groups and raised for 4 weeks with a diet containing one of the grains. Corresponding to the dietary fiber contents of the experimental grains, gut transit time was shortest in the rats fed GB and increased in the order of BW, AD, and WR. In addition, the accumulated shortest transit time occurred in the GB group. Gut transit time affected weight gain and major organ weight, as it was closely related to the absorption of nutrients. The level of thiobarbituric acid reactive substance (TBARS) in liver was higher in rats fed WR, AD, BW, and GB, indicating that the other grains decreased oxidative stress in vivo more than WR. Glutathione, glutathione peroxidase, and glutathione S-transferase levels in the AD, BW, and GB groups were significantly higher than those in the WR group. In conclusion, reduced colonic transit time has been implicated in reducing the incidence of colon cancer, as evidenced by populations consuming diets rich in fiber. Whole grains such as AD, BW, and GB may contribute to a significant supply of antioxidants to prevent oxidative stress if they are consumed in large amounts.

  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

    2011-10-06

    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.

  14. Potent in vivo anticancer activity and stability of liposomes encapsulated with semi-purified Job's tear (Coix lacryma-jobi Linn.) extracts on human colon adenocarcinoma (HT-29) xenografted mice.

    PubMed

    Sainakham, Mathukorn; Manosroi, Aranya; Abe, Masahiko; Manosroi, Worapaka; Manosroi, Jiradej

    2016-11-01

    The in vivo anticancer activity and stability of liposomes encapsulated with semi-purified Job's tear (Coix lacryma-jobi Linn.) extracts (S5L), prepared by supercritical carbon dioxide fluid technique, on human colon adenocarcinoma (HT29) xenografted mice were investigated. For the stability and the physicochemical characteristics, S5L showed a high stability of pH, good dispersibility, small particle size and stable zeta potential. Liposomes can protect linoleic acid in the extract comparing with the free S5. S5L kept at 4 °C for 3 months showed the highest linoleic acid content of 63.50%, whereas at 45 °C, the lowest linoleic acid content of 42.66% was observed. The anticancer activity and toxicity on xenografted mice were observed for 14 days. At the end of the experiment, the relative tumor volume (RTV) in the S5L-treated xenografted mice showed a significant RTV reduction. The high dose of S5 and S5L were potent with the highest inhibition of tumor growth of 48.67 and 54.75%, which was 86.94% and 97.81% of 5-fluorouracil, respectively. The apoptotic activity was shown in xenografted mice treated with S5 at medium and high dose, S5L, 5-fluorouracil and commercial product. All treated xenografted mice showed no toxic signs and symptoms, abnormality of internal organs histopathology and blood chemistry. This study has demonstrated the high physicochemical stability of liposomes encapsulated with semi-purified Job's tear extract and their potent anticancer activity on human colon adenocarcinoma xenografted model with the potential for further development to anticolon cancer drug.

  15. Electrochemical and FTIRS characterisation of NO adlayers on cyanide-modified Pt(111) electrodes: the mechanism of nitric oxide electroreduction on Pt.

    PubMed

    Cuesta, Angel; Escudero, María

    2008-07-07

    We report here a study, using cyclic voltammetry and FTIRS, of NO irreversibly adsorbed on a cyanide-modified Pt(111) electrode. NO adlayers were formed by immersion of the cyanide-modified Pt(111) electrode in an acidic solution of KNO(2). The behaviour of NO adsorbed on the cyanide-modified electrode is very similar to that of NO on the clean Pt(111) surface, suggesting that adsorbed cyanide (saturation coverage theta(CN) = 0.5) behaves simply as a third body, blocking some of the surface sites but leaving the free Pt sites unaffected. Comparison of the voltammetric profile for NO electroreduction on Pt(111) and on cyanide-modified Pt(111) electrodes has allowed us: (i) to confirm that the reduction of three-fold hollow NO and atop NO on Pt(111) electrodes occurs in two distinct reduction peaks, as previously proposed by Rosca et al. (Langmuir, 2005, 21, 1448); (ii) to suggest that the reduction of irreversibly adsorbed NO layers on Pt electrodes can proceed through two possible paths, one involving an EE mechanism in which the rate-determining step (rds) is an Eley-Rideal reaction, with a direct proton transfer from the solution to adsorbed NO, and the other involving an EC mechanism in which the rds is a Langmuir-Hinshelwood reaction of adsorbed NO with adsorbed H. The availability of adsorbed hydrogen determines which path is followed by the reaction; (iii) to identify the smallest atomic ensemble for the reduction of NO on Pt as being composed of two adjacent Pt atoms.

  16. Surface modification of piezoelectric aluminum nitride with functionalizable organosilane adlayers

    NASA Astrophysics Data System (ADS)

    Chan, Edmund; Jackson, Nathan; Mathewson, Alan; Galvin, Paul; Alamin Dow, Ali B.; Kherani, Nazir P.; Blaszykowski, Christophe; Thompson, Michael

    2013-10-01

    The world of biosensors is expanding at a rapid pace with an ever-increasing demand for more sensitive miniaturized devices. Acoustic wave biosensors are not spared from this trend. In this domain, the search for enhanced sensitivity is increasingly oriented toward the rational design of new piezoelectric materials with superior properties to substitute for prevalent quartz. With respect to surface chemistry, construction of the biorecognition element, more often than not, requires the use of bifunctional molecules that can spontaneously assemble on the substrate and form organic surfaces readily biofunctionalizable in a subsequent, ideally single step. In this context, we present herein the surface modification of aluminum nitride (AlN) with alkyltrichlorosilane cross-linking molecules bearing a functionalizable benzenethiosulfonate moiety. This latter feature is next demonstrated through the straightforward, preactivation-free immobilization of thiolated biotin probes. To date, AlN has only received little attention in the field of piezoelectric biosensors despite its many attractive properties and the perspective to operate devices at ultra-high frequencies (GHz) with unprecedented sensitivity. To our knowledge, this work describes one of the first examples of direct surface derivatization of AlN with bifunctional trichlorosilane molecules. It also constitutes a first step toward the development of electrodeless GHz piezoelectric biosensing platforms based on AlN and trichlorosilane surface chemistry.

  17. Phylogenetic relationship of zeins and coixins as determined by immunological cross-reactivity and Southern blot analysis.

    PubMed

    Leite, A; Ottoboni, L M; Targon, M L; Silva, M J; Turcinelli, S R; Arruda, P

    1990-05-01

    Zeins from Zea mays L cv. Maya and coixins from Coix lacryma-jobi L. cv. Adlay were fractionated to obtain alpha-, beta-, and gamma-zein and alpha-, beta-, and gamma-coixin. The alpha-coixins were composed of 4 polypeptide classes of 27 kDa (C1), 25 kDa (C2), 17 kDa (C4) and 15 kDa (C5) with solubility properties very similar to those of the 22 kDa and 19 kDa alpha-zeins. Like the alpha-zeins, the C1 and C2 alpha-coixins corresponded to 80% of total Coix prolamins. The fraction corresponding to gamma-coixin contained only one protein band of 22 kDa (C3). This coixin fraction has solubility properties similar to those of gamma-zein and represents 15% of the total coixin. The beta-zein fraction was composed of a major 17 kDa protein band, while the beta-coixin fraction consisted of a mixture of alpha- and gamma-coixins. Polyclonal antibodies raised against C1 recognized C1 and C2 and cross-reacted strongly with the 22 kDa alpha-zein, as did C4 and C5 antisera. The antiserum against gamma-coixin showed strong cross-reaction with gamma-zein. The homology between coixins and zeins was further investigated by using Southern hybridization analyses. The genomic DNA of maize and Coix were digested with several restriction enzymes and probed with cDNA clones representing 19 and 22 kDa alpha-zeins as well as the 28 and 16 kDa gamma-zeins. The Coix genome showed complex cross-hybridization sequences with the 22 kDa alpha-zein cDNA, while no cross-hybridization was observed with the 19 kDa cDNA clone.(ABSTRACT TRUNCATED AT 250 WORDS)

  18. Collective concerted motion in a molecular adlayer visualized through the surface diffusion of isolated vacancies

    NASA Astrophysics Data System (ADS)

    Urban, Christian; Otero, Roberto; Écija, David; Trelka, Marta; Martín, Nazario; Gallego, José M.; Miranda, Rodolfo

    2016-10-01

    We have measured STM movies to study the diffusion of individual vacancies in a self-assembled layer of a tetrathiafulvalene derivative (exTTF) on Au(111) at room temperature. The diffusion is anisotropic, being faster along the compact direction of the molecular lattice. A detailed analysis of the anisotropic displacement distribution of the single vacancies shows that the relative abundance of double jumps (that is, the collective motion of molecular dimers) with respect to single jumps is rather large, the number of double jumps being more than 20% of the diffusion events. We conjecture that the relative abundances of long jumps might be related to the strength of the intermolecular bonding and the misfit of the molecular overlayer with the substrate lattice.

  19. 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.

  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. Electrochemical properties of palladium adlayers on Pt(1 0 0) substrates

    NASA Astrophysics Data System (ADS)

    Álvarez, B.; Berná, A.; Rodes, A.; Feliu, J. M.

    2004-12-01

    The formation of submonolayers of palladium on well-defined Pt(1 0 0) electrodes is described. It has been found that the adsorption of NO at open circuit and its further reductive stripping enable the possibility to prepare Pt(1 0 0) electrodes fully covered by the first palladium layer, without contributions coming from palladium in the subsequent layers. This method enables a better characterization of the palladium islands formed in the submonolayer range. The CO displacement method points out that hydrogen and anion adsorption play a role in the charge transfer processes involved in the voltammetric profile. The analysis of the charge-potential curves is used to determine the values of the potentials of zero total charge (pztc) of the different adelectrodes. The pztc diminishes almost linearly with palladium coverage, this shift being related to increasing anion adsorption at low potentials. Adsorbed palladium does not electrocatalyze the oxidation of adsorbed CO.

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

    SciTech Connect

    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.

  4. Origin of Multiple Peaks in the Potentiodynamic Oxidation of CO Adlayers on Pt and Ru-Modified Pt Electrodes.

    PubMed

    Wang, Hongsen; Abruña, Héctor D

    2015-05-21

    The study of the electrooxidation mechanism of CO(ad) on Pt based catalysts is very important for designing more effective CO-tolerant electrocatalysts for fuel cells. We have studied the origin of multiple peaks in the cyclic voltammograms of CO stripping from polycrystalline Pt and Ru modified polycrystalline Pt (Pt/Ru) surfaces in both acidic and alkaline media by differential electrochemical mass spectrometry (DEMS), DFT calculations, and kinetic Monte Carlo (KMC) simulations. A new CO(ad) electrooxidation kinetic model on heterogeneous Pt and Pt/Ru catalysts is proposed to account for the multiple peaks experimentally observed. In this model, OH species prefer to adsorb at low-coordination sites or Ru sites and, thus, suppress CO repopulation from high-coordination sites onto these sites. Therefore, CO(ad) oxidation occurs on different facets or regions, leading to multiplicity of CO stripping peaks. This work provides a new insight into the CO electrooxidation mechanism and kinetics on heterogeneous catalysts.

  5. 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.

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

    DOE PAGES

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

    2016-04-11

    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 bentmore » 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. Furthermore, energy barriers for diffusion along island edges can be determined with the aid of both conventional and unconventional interactions.« less

  7. 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.

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

    SciTech Connect

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

    2016-04-11

    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. Furthermore, energy barriers for diffusion along island edges can be determined with the aid of both conventional and unconventional interactions.

  9. Hydroxy monounsaturated fatty acids as agonists for peroxisome proliferator-activated receptors.

    PubMed

    Yokoi, Hiroshi; Mizukami, Hajime; Nagatsu, Akito; Tanabe, Hiroki; Inoue, Makoto

    2010-01-01

    The physiological and pathological role of oxidized polyunsaturated fatty acids (PUFAs) has been extensively studied, whereas those of hydroxy monounsaturated fatty acids (MUFAs) are not well understood. This study demonstrated that 11-hydroxy-(9Z)-octadecenoic acid ((9Z)-11-HOE), which was isolated from adlay seeds (Coix lacryma-jobi L. var. ma-yuen STAF.), can activate peroxisome proliferator-activated receptor (PPAR)alpha, delta and gamma in luciferase reporter assays more efficiently than (9Z)-octadecenoic acid (oleic acid), and to the same degree as linoleic acid. (9Z)-11-HOE increased the mRNA levels of UCP2 and CD36 in C2C12 myotubes and THP- 1 cells, respectively, and these effects were blocked by the PPARdelta- and gamma-specific antagonists GSK0660 and T0070907, respectively. Evaluation of the structure.activity relationship between hydroxy MUFAs and PPAR activation revealed that (9E)-11-HOE, the geometrical isomer of (9Z)-11-HOE, activated PPARs more potently than (9Z)-11-HOE, and that PPAR activation by hydroxyl MUFAs was not markedly influenced by the position of the hydroxy group or the double bond, although PPARdelta seemed to possess ligand specificity different to that of PPARalpha or gamma . Additionally, the finding that 11-hydroxy octadecanoic acid, the hydrogenated product of (9E)-11- HOE, was also capable of activating PPARs to a similar extent as (9E)-11-HOE indicates that the double bond in hydroxy MUFAs is not essential for PPAR activation. In conclusion, (9Z)-11-HOE derived from alday seeds and hydroxy MUFAs with a chain length of 16 or 18 acted as PPAR agonists. Hydroxylation of MUFAs may change these compounds from silent PPAR ligands to active PPAR agonists.

  10. Interaction between CO and NH 3 coadsorbed on Ru(001): its effects on the ordering in mixed adlayers and the ammonia dissociation

    NASA Astrophysics Data System (ADS)

    Sasaki, Takehiko; Aruga, Tetsuya; Kuroda, Haruo; Iwasawa, Yasuhiro

    1990-12-01

    The coadsorption of CO and ammonia on Ru(001) has been investigated by low-energy electron diffraction (LEED), temperature-programmed desorption (TPD) and high-resolution electron energy-loss spectroscopy (HREELS). The main focus has been on the interaction between different admolecules on the surface and its important role in surface reaction. Exposing CO-precovered Ru(001) to ammonia at 100 K leads to the formation of mixed ordered layers with a (2 × 2) periodicity. It was found that two types of (2 × 2) structures are formed depending on the CO precoverage. One of the (2 × 2) structures (α-phase) contains one CO and two ammonia molecules per (2 × 2) unit cell and the other (β-phase) contains two CO and one ammonia. Structure models for the two phases are proposed based on vibrational spectra measured for the coadsorbed phases of CO and ammonia ( 15NH 3 or ND 3). TPD results suggest that the ammonia dissociation takes place on clean and CO-precovered Ru(001). The amount of dissociated ammonia decreased initially with increasing CO precoverage, passed a minimum at θCO = 0.25, increased with a further increase of CO coverage, and eventually reached a saturation value above θCO = 0.5. The dissociation of ammonia in the β-(2 × 2) structure was found to be enhanced by a factor of 4-6 as compared with the dissociation in the α-(2 × 2) structure. The HREEL spectra indicated that the C 3v molecular axis of ammonia is tilted in the coadsorbed layers, the tilting being most pronounced in the β-(2 × 2) phase with a high CO partial coverage. This observation suggests that the tilting of ammonia due to the interaction with CO facilitates electron donation from Ru 4d to LUMO of ammonia, leading to the N-H bond dissociation. The microscopic model for the CO-NH 3 interaction on metal surfaces is presented.

  11. Deposition of lead iodide films on Rh( 1 0 0 ) electrodes from colloidal solutions--the effect of an iodine adlayer

    NASA Astrophysics Data System (ADS)

    Yang, Chia-Huei; Yau, Shueh-Lin; Fan, Liang-Jen; Yang, Yaw-Wen

    2003-08-01

    The growth of PbI 2 precipitates on single crystal substrates from colloidal solutions has been investigated with in air scanning tunneling microscopy and synchrotron-based X-ray photoelectron spectroscopy. The PbI 2 growth on Rh(1 0 0) results in nano-clusters with lateral dimensions between 30 and 60 Å, consistent with earlier reports. However, the growth of PbI 2 on a well-ordered iodinated Rh(1 0 0), denoted as (√2×√2) R45°-I, leads to atomically smooth PbI 2 films having a hexagonal symmetry with lattice constant identical to the bulk value of 4.5 Å. The heteroepitaxy is believed to be effected by the atomic iodine monolayer that helps to accommodate large lattice mismatch between PbI 2 and Rh surface with short-range van der Waals interaction.

  12. 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.

  13. 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.

  14. Laser Induced Surface Chemical Epitaxy

    DTIC Science & Technology

    1990-03-01

    eV was observed in this study for DMTe adlay ,,;s annealed at 423 K, a condition which is likely to produce a metallic Te adlayer , the Cd 3d5 /2...processes were studied by irradiating the adlayer with ultraviolet photons produced by a Questek excimer laser. These were introduced into the deposition...binding energy observed for similarly annealed DMCd adlayers was 405.1 eV. Based on room temperature measurements and ligand shift and electronegativity

  15. Surface Science at the Solid Liquid Interface

    DTIC Science & Technology

    1993-10-06

    Monolayers on the Au(111) and Ag(111) Surfaces 13 0760 Eric Stuve Coadsorption of Hydrofluoric Acid with Water and Oxygen on Ag(110): Adlayer Solution...saturated CO adlayers on low-index platinum and rhodium electrodes in aqueous and nonaqueous media. The central role of the surface potential in...controlling the CO adlayer structure is discussed on the basis of in situ IRAS data, especially in comparison with the properties of corresponding metal

  16. Calculation of Ray Paths in the Ionosphere Using an Analytic Raytracing Technique

    DTIC Science & Technology

    1986-07-01

    could have been intercented, the delay time DLAY is stored in the array ADLAY (ITHET. 1FREQ) which it; subse- quently plotted in the subroutine DLAYPL...870 and all rays whose final height XX(MAXR) is within 10 km of the satellite height SXAT are accepted and stored in ADLAY for plotting. Wm mm mm

  17. Compositional fingerprint of soy sauces via hydrophobic surface interaction.

    PubMed

    Jakobi, Victoria; Salmen, Paul; Paulus, Michael; Tolan, Metin; Rosenhahn, Axel

    2017-03-01

    In this work, the interaction of soy sauces with hydrophobic surfaces has been analyzed. Hydrophobic self-assembled monolayers on gold or silicon dioxide were used to harvest conditioning layers from soy sauce products with varying amounts of additives. The data was compared to adsorption of soy protein and glutamic acid as common ingredients. Spectral ellipsometry revealed that all tested sauces led to the formation of thin overlayers on hydrophobic surfaces. Products with less additives yielded adlayers in the same thickness range as pure soy protein. In contrast, sauces with more ingredients create distinctly thicker films. Using water contact angle goniometry, it is shown that all adlayers render the substrate more hydrophilic. Infrared spectroscopy provided a deeper insight into the adlayer chemistry and revealed that the adlayer composition is dominated by protein rich components. X-ray reflectivity on selected films provided further insight into the density profiles within the adlayers on the molecular scale.

  18. Dynamic evolution of bz orthologous regions in the Andropogoneae and other grasses.

    PubMed

    Wang, Qinghua; Dooner, Hugo K

    2012-10-01

    Genome structure exhibits remarkable plasticity within Zea mays. To examine how haplotype structure has evolved within the Andropogoneae tribe, we have analyzed the bz gene-rich region of maize (Zea mays), the Zea teosintes mays ssp. mexicana, luxurians and diploperennis, Tripsacum dactyloides, Coix lacryma-jobi and Sorghum propinquum. We sequenced and annotated BAC clones from these species and re-annotated the orthologous Sorghum bicolor region. Gene colinearity in the region is well conserved within the genus Zea. However, the orthologous regions of Coix and Sorghum exhibited several micro-rearrangements relative to Zea, including addition, truncation and deletion of genes. The stc1 gene, involved in the production of a terpenoid insect defense signal, is evolving particularly fast, and its progressive disappearance from some species is occurring by microhomology-mediated recombination. LTR retrotransposons are the main contributors to the dynamic evolution of the bz region. Common transposon insertion sites occur among haplotypes from different Zea mays sub-species, but not outside the species. As in Zea, different patterns of interspersion between genes and retrotransposons are observed in Sorghum. We estimate that the mean divergence times between maize and Tripsacum, Coix and Sorghum are 8.5, 12.1 and 12.4 million years ago, respectively, and that between Coix and Sorghum is 9.3 million years ago. A comparison of the bz orthologous regions of Zea, Sorghum and Coix with those of Brachypodium, Setaria and Oryza allows us to infer how the region has evolved by addition and deletion of genes in the approximately 50 million years since these genera diverged from a common progenitor.

  19. Self-Assembled Structures of Benzoic Acid on Au(111) Surface

    NASA Astrophysics Data System (ADS)

    Vu, Thu-Hien; Wandlowski, Thomas

    2017-02-01

    Electrochemical scanning tunneling microscopy combined with cyclic voltammetry were employed to explore the self-assembly of benzoic acid (BA) on a Au(111) substrate surface in a 0.1-M HClO4 solution. At the negatively charged surface, BA molecules form two highly ordered physisorbed adlayers with their phenyl rings parallel to the substrate surface. High-resolution scanning tunneling microscopy images reveal the packing arrangement and internal molecular structures. The striped pattern and zigzag structure of the BA adlayers are composed of parallel rows of dimers, in which two BA molecules are bound through a pair of O-H···O hydrogen bonds. Increasing the electrode potential further to positive charge densities of Au(111) leads to the desorption of the physisorbed hydrogen-bonded networks and the formation of a chemisorbed adlayer. BA molecules change their orientation from planar to upright fashion, which is accompanied by the deprotonation of the carboxyl group. Furthermore, potential-induced formation and dissolution of BA adlayers were also investigated. Structural transitions between the various types of ordered adlayers occur according to a nucleation and growth mechanism.

  20. 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.

  1. In-situ STM studies of thallium underpotential deposition on Au(111) single-crystal electrode in acid solution

    NASA Astrophysics Data System (ADS)

    Polewska, Wanda; Adzic, Radoslav

    1999-04-01

    The structure of electrodeposited Tl adlayers on Au(111) in 0.1 M. HClO4 has been investigated using in-situ scanning tunneling microscopy method. Incommensurate, rotated hexagonal (RHCP) Tl adlayer was found, within a wide potential window, between Tl bulk deposition at -0.7 V and -0.4 V. This adlayer is closely packed with Tl interatomic distance of 3.4 +/- 0.2 angstroms, its rotation from the gold substrate axis is 60 +/- 10 and its coverage is 0.74. At slightly more positive potentials, between -0.45 V and -0.37 V, low coverage 2 X 2 phase of Tl was found, coexisting together with RHCP monolayer. At the potential region between -0.35 V and 0.8 V both ordered Tl phases disappeared and instead the formation of considerable amount of pits at the surface has been observed.

  2. Microemulsion-based synergistic dual-drug codelivery system for enhanced apoptosis of tumor cells

    PubMed Central

    Qu, Ding; Ma, Yihua; Sun, Wenjie; Chen, Yan; Zhou, Jing; Liu, Congyan; Huang, Mengmeng

    2015-01-01

    A microemulsion-based synergistic dual-drug codelivery system was developed for enhanced cell apoptosis by transporting coix seed oil and etoposide into A549 (human lung carcinoma) cells simultaneously. Results obtained by dynamic light scattering showed that an etoposide (VP16)-loaded coix seed oil microemulsion (EC-ME) delivery system had a small size around 35 nm, a narrow polydispersity index, and a slightly negative surface charge. The encapsulating efficiency and total drug loading rate were 97.01% and 45.48%, respectively, by high-performance liquid chromatography. The release profiles at various pH values showed an obvious pH-responsive difference, with the accumulated amount of VP16 released at pH 4.5 (and pH 5.5) being 2.7-fold higher relative to that at pH 7.4. Morphologic alteration (particle swelling) associated with a mildly acidic pH environment was found on transmission electron microscopy. In the cell study, the EC-ME system showed a significantly greater antiproliferative effect toward A549 cells in comparison with free VP16 and the mixture of VP16 and coix seed oil. The half-maximal inhibitory concentration of the EC-ME system was 3.9-fold and 10.4-fold lower relative to that of free VP16 and a mixture of VP16 and coix seed oil, respectively. Moreover, fluorescein isothiocyanate and VP16 (the green fluorescent probe and entrapped drug, respectively) were efficiently internalized into the cells by means of coix seed oil microemulsion through intuitive observation and quantitative measurement. Importantly, an EC-ME system containing 20 μg/mL of VP16 showed a 3.3-fold and 3.5-fold improvement in induction of cell apoptosis compared with the VP-16-loaded microemulsion and free VP16, respectively. The EC-ME combination strategy holds promise as an efficient drug delivery system for induction of apoptosis and treatment of lung cancer. PMID:25709440

  3. In situ STM study of Cu(111) surface structure and corrosion in pure and benzotriazole-containing sulfuric acid solution

    SciTech Connect

    Polewska, W.; Vogt, M.R.; Magnussen, O.M.; Behm, R.J.

    1999-11-25

    The authors present results of an in situ STM study on the surface structure and anodic dissolution of Cu(111) electrodes in pure 0.01 M H{sub 2}SO{sub 4} solution and in solution containing the corrosion inhibitor benzotriazole (BTAH), which is aimed at an atomistic understanding of the dissolution process and the inhibitor effects. The initial stages of Cu dissolution as well as the adsorption of BTAH are pronouncedly influenced by the presence of the ordered sulfate adlayer, which forms in the double layer potential regime and induces a reconstruction of the underlying Cu surface layer, together with a reorientation of the steps along the close-packed lattice directions. Cu dissolution in pure H{sub 2}SO{sub 4} solution proceeds by a step flow mechanism. The onset of dissolution is critically affected by the relative orientation of the sulfate adlayer on the lower terrace side, with the stability being highest for steps running perpendicular to the close-packed sulfate rows. The retracting steps often expose apparently disordered areas, which are attributed to a disordered sulfate adlayer on a Cu surface where, because of kinetic limitations, a well-ordered reconstruction has not yet reformed. BTAH adsorption is only observed in the potential regime of the ordered sulfate adlayer. The BTAH adlayer is highly defective, which is attributed to the removal of the reconstruction due to sulfate adlayer displacement. Islands with poorly ordered 1D chain structures are surrounded by areas with no resolved structure. Cu dissolution inhibition is manifested by an anodic shift in the onset of dissolution as well as by the blocking of the step flow etch mechanism, reflecting a stabilization of the Cu steps by adsorbed BTAH. Dissolution at higher potentials proceeds predominantly via formation of monolayer etch pits. When the potential is reversed back into the double layer regime, smoothening of the surface is observed with a rate that increases strongly with decreasing

  4. Single-Molecule Imaging of Iron-Phthalocyanine-Catalyzed Oxygen Reduction Reaction by in Situ Scanning Tunneling Microscopy.

    PubMed

    Gu, Jing-Ying; Cai, Zhen-Feng; Wang, Dong; Wan, Li-Jun

    2016-09-27

    We report herein an in situ electrochemical scanning tunneling microscopy (ECSTM) investigation of iron-phthalocyanine (FePc)-catalyzed oxygen reduction reaction (ORR). A highly ordered FePc adlayer is revealed on a Au(111) electrode. The center ions in the FePc adlayer show uniform high contrast in an oxygen-saturated electrolyte, which is attributed to the formation of an FePc-O2 complex. In situ STM results reveal the sharp contrast change upon shifting the electrode potential to trigger the ORR. Theoretical simulation has supplied further evidence for the contrast difference of the adsorbed FePc species.

  5. Combined optical second harmonic generation/quartz crystal microbalance study of underpotential deposition processes: copper electrodeposition on polycrystalline gold.

    PubMed

    Lakkaraju, S; Bennahmias, M J; Borges, G L; Gordon Ii, J G; Lazaga, M; Stone, B M; Ashley, K

    1990-11-20

    Optical second harmonic generation and quartz crystal microbalance techniques are used as in situ probes of copper underpotential deposition on polycrystalline gold surfaces in sulfuric acid electrolyte. The second harmonic signal from a polished bulk gold substrate is observed to decrease by >60% as a result of copper underpotential deposition on gold. Also, the mass of an underpotentially deposited copper adlayer is monitored in situ by an oscillating quartz crystal microbalance, yielding an estimated coverage of ~8.0 x 10(-10) mol cm(-2) and an electrosorption valency of 1.5 for a copper adlayer on the surface of vapor-deposited polycrystalline gold.

  6. Evanescent field response to immunoassay layer thickness on planar waveguides

    NASA Astrophysics Data System (ADS)

    Yan, Rongjin; Yuan, Guangwei; Stephens, Matthew D.; He, Xinya; Henry, Charles S.; Dandy, David S.; Lear, Kevin L.

    2008-09-01

    The response of a compact photonic immunoassay biosensor based on a planar waveguide to variation in antigen (C-reactive protein) concentration as well as waveguide ridge height has been investigated. Near-field scanning optical microscope measurements indicate 1.7%/nm and 3.3%/nm top surface optical intensity modulation due to changes in effective adlayer thickness on waveguides with 16.5 and 10nm ridge heights, respectively. Beam propagation method simulations are in good agreement with the experimental sensitivities as well as the observation of leaky mode interference both within and after the adlayer region.

  7. Finite-temperature properties of ultra-thin lead films on gold (110) surfaces

    NASA Astrophysics Data System (ADS)

    De'Bell, K.; Imeson, D.

    1997-07-01

    At low coverages, lead adatoms form a single layer on the gold (110) surface. However, if a critical coverage 0953-8984/9/27/005/img1 is exceeded, a second adlayer forms. At zero temperature, various properties such as the energy and atomic spacing of atoms in the first adlayer are discontinuous at 0953-8984/9/27/005/img1. The effects of temperature on the discontinuities and location of 0953-8984/9/27/005/img1 are reported. Results for clean Au(110) and Pb(110) surfaces are also reported.

  8. Structural Imaging of Surface Oxidation and Oxidation Catalysis on Ru(0001)

    SciTech Connect

    Flege, J.; Hrbek, J; Sutter, P

    2008-01-01

    Using simultaneous imaging and structural fingerprinting under reaction conditions, we probe the initial oxidation pathway and CO oxidation catalysis on Ru(0001). Oxidation beyond an initial (1 x 1)-O adlayer phase produces a heterogeneous surface, comprising a disordered trilayerlike surface oxide and an ordered RuO{sub 2}(110) thin-film oxide, which form independently and exhibit similar stability. The surface oxide and RuO{sub 2} phases both show high intrinsic catalytic activity. The oxygen adlayer is inactive in isolation but becomes active due to cooperative effects in close proximity to the surface oxide.

  9. Preparation of culinary-medicinal king oyster mushroom Pleurotus eryngii-fermented products with high ergothioneine content and their taste quality.

    PubMed

    Chen, Shih-Yu; Ho, Kung-Jui; Liang, Chih-Hung; Tsai, Ching-Hsuan; Huang, Ling-Yi; Mau, Jeng-Leun

    2012-01-01

    Pleurotus eryngii (DC. : Fr.) Ouel. was used in solid-state fermentation to develop novel mushroom products with a high amount of ergothioneine. The correlation coefficients between ergothioneine content and biomass were 0.8878 and 0.9206 for fermented adlay and buckwheat, respectively. Using optimal conditions, Pleurotus-fermented adlay and buckwheat (PFA and PFB) with the ergothioneine contents of 795.5 and 786.1 mg/ kg, respectively, were prepared. However, mycelia contained the highest ergothioneine content of 1514.6 mg/kg. As a result of SSF by P. eryngii, PFA and PFB contained more taste components than adlay and buckwheat, as evidenced by higher contents of total sugars and polyols, total free amino acids and monosodium glutamate-like components, and total and flavor 5'-nucleotides. In addition, PFB and buckwheat showed comparable equivalent umami concentration (EUC) values, whereas PFA showed a higher EUC value than adlay. Overall, Pleurotus-fermented products with a high amount of ergothioneine will be a novel functional food.

  10. On the possible mechanism of the W(001) surface reconstruction with adsorbed hydrogen

    NASA Astrophysics Data System (ADS)

    Egorushkin, V. E.; Savushkin, E. V.

    1990-12-01

    The reconstruction of the (001) face of tungsten is treated as a Jahn-Teller transition connected with two narrow surface electronic bands along the Γ M lines. The surface periodic lattice distortion is found to be accompanied by the occurence of the hydrogen ordering in an adlayer with the result that the reconstruction temperature raises.

  11. Electroreduction of Peroxide on Au(100) Surface Modified with Underpotentially Deposited Bismuth

    NASA Astrophysics Data System (ADS)

    Hara, Masanori; Nagahara, Yoshiki; Yoshimoto, Soichiro; Inukai, Junji; Itaya, Kingo

    2004-10-01

    The adlayer structure of Bi underpotentially deposited on Au(100) was investigated in a HClO4 solution using in-situ scanning tunneling microscopy. The underpotential deposition of Bi was found to occur in three steps. The electrochemical reduction rate of H2O2 on the Bi-modified Au(100) surface was the highest for an intermediate coverage of Bi.

  12. Interfacial interactions of pectin with bovine serum albumin studied by quartz crystal microbalance with dissipation monitoring: effect of ionic strength.

    PubMed

    Wang, Xiaoyong; Ruengruglikit, Chada; Wang, Yu-Wen; Huang, Qingrong

    2007-12-12

    The effect of ionic strength ( I) on the interfacial interactions between pectin and the bovine serum albumin (BSA) surface has been investigated using the quartz crystal microbalance with dissipation monitoring (QCM-D). As I increases from 0.01 to 0.02 M, the frequency shift (Delta F) decreases, whereas the energy dissipation shift (Delta D) changes toward a higher value. Further increase of I from 0.02 to 0.5 M causes both Delta F and Delta D to gradually return to almost zero. The adsorbed mass and thickness of the pectin adlayer estimated from the Voigt model confirm that the adsorption of pectin and the formation of thicker pectin adlayers on a BSA surface are favored by the increase of ionic strength at I = 0.01 approximately 0.02 M. An increase of I above 0.02 M hinders pectin adsorption and causes the formation of a thinner pectin adlayer. The ionic strength-enhanced effect at I values lower than 0.02 M is explained as an increase of ionic strength that can screen the electrostatic repulsion to a larger extent than the electrostatic attraction between pectin and BSA. However, when I is higher than 0.02 M, both electrostatic repulsion and attraction can be significantly screened by the increasing ionic strength, resulting in the ionic strength-reduced effect. On the other hand, the high viscoelasticity of the pectin adlayer revealed by the Voigt model suggests the formation of a network-structured pectin adlayer on the BSA surface, which contains two steps for higher pectin adsorptions at I = 0.0125 approximately 0.1 M by the indication of two slopes in Delta D-Delta F plots.

  13. 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

  14. Interactive effect of herbivory and competition on the invasive plant Mikania micrantha.

    PubMed

    Li, Junmin; Xiao, Tao; Zhang, Qiong; Dong, Ming

    2013-01-01

    A considerable number of host-specific biological control agents fail to control invasive plants in the field, and exploring the mechanism underlying this phenomenon is important and helpful for the management of invasive plants. Herbivory and competition are two of the most common biotic stressors encountered by invasive plants in their recipient communities. We predicted that the antagonistic interactive effect between herbivory and competition would weaken the effect of herbivory on invasive plants and result in the failure of herbivory to control invasive plants. To examine this prediction, thus, we conducted an experiment in which both invasive Mikania micrantha and native Coix lacryma-job i were grown together and subjected to herbivory-mimicking defoliation. Both defoliation and competition had significantly negative effects on the growth of the invader. However, the negative effect of 75% respective defoliation on the above- and below-ground biomass of Mikania micrantha was alleviated by presence of Coix lacryma-jobi. The negative effect of competition on the above- and below-ground biomass was equally compensated at 25%, 50% and 100% defoliation and overcompensated at 75% defoliation. The interactive effect was antagonistic and dependent on the defoliation intensity, with the maximum effect at 75% defoliation. The antagonistic interaction between defoliation and competition appears to be able to release the invader from competition, thus facilitating the invasiveness of Mikania, a situation that might make herbivory fail to inhibit the growth of invasive Mikania in the invaded community.

  15. Interactive Effect of Herbivory and Competition on the Invasive Plant Mikania micrantha

    PubMed Central

    Li, Junmin; Xiao, Tao; Zhang, Qiong; Dong, Ming

    2013-01-01

    A considerable number of host-specific biological control agents fail to control invasive plants in the field, and exploring the mechanism underlying this phenomenon is important and helpful for the management of invasive plants. Herbivory and competition are two of the most common biotic stressors encountered by invasive plants in their recipient communities. We predicted that the antagonistic interactive effect between herbivory and competition would weaken the effect of herbivory on invasive plants and result in the failure of herbivory to control invasive plants. To examine this prediction, thus, we conducted an experiment in which both invasive Mikania micrantha and native Coix lacryma-jobi were grown together and subjected to herbivory-mimicking defoliation. Both defoliation and competition had significantly negative effects on the growth of the invader. However, the negative effect of 75% respective defoliation on the above- and below-ground biomass of Mikania micrantha was alleviated by presence of Coix lacryma-jobi. The negative effect of competition on the above- and below-ground biomass was equally compensated at 25%, 50% and 100% defoliation and overcompensated at 75% defoliation. The interactive effect was antagonistic and dependent on the defoliation intensity, with the maximum effect at 75% defoliation. The antagonistic interaction between defoliation and competition appears to be able to release the invader from competition, thus facilitating the invasiveness of Mikania, a situation that might make herbivory fail to inhibit the growth of invasive Mikania in the invaded community. PMID:23737942

  16. 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.

  17. Real-time investigations of Pt(111) surface transformations in sulfuric acid solutions.

    PubMed

    Braunschweig, Björn; Mukherjee, Prabuddha; Dlott, Dana D; Wieckowski, Andrzej

    2010-10-13

    We present the first broadband sum-frequency generation (SFG) spectra of adlayers from sulfuric acid solutions on Pt(111) surfaces and reveal surface transformations of (bi)sulfate anions in unprecedented detail. SFG amplitudes, bandwidth, and electrochemical Stark tuning of (bi)sulfate vibrational bands centered at 1250-1290 cm(-1) strongly depend on the applied potential and are correlated with prominent voltammetric features. (Bi)sulfate adlayers on Pt(111) are important model systems for weak, specific adsorption of anions on catalytically active surfaces. Although the existence of surface transformations on Pt(111) in dilute H(2)SO(4) solutions has been established by previous studies, so far they have not been observed with surface vibrational spectroscopy. Our results confirm previous reports of a surface transformation at 0.21 V and provide new information on a second transformation at 0.5 V due to surface hydroxyl formation and rearrangement of the electric double layer.

  18. Versatile UHV compatible Knudsen type effusion cell

    SciTech Connect

    Shukla, A.K.; Banik, S.; Dhaka, R.S.; Biswas, C.; Barman, S.R.; Haak, H.

    2004-11-01

    A versatile Knudsen type effusion cell has been fabricated for growing nanostructures and epitaxial layers of metals and semiconductors. The cell provides excellent vacuum compatibility (10{sup -10} mbar range during operation), efficient water cooling, uniform heating, and moderate input power consumption (100 W at 1000 deg. C). The thermal properties of the cell have been determined. The performance of the cell has been assessed by x-ray photoemission spectroscopy (XPS) for Mn adlayer growth on Al(111). We find that this Knudsen cell has a stable deposition rate of 0.17 monolayer per minute at 550 deg. C. From the XPS spectra, we show that the Mn adlayers are completely clean, i.e., devoid of any surface contamination.

  19. 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

    2015-12-02

    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.

  20. Surface Functionalization of Piezoelectric Aluminum Nitride with Selected Amino Acid and Peptides

    NASA Astrophysics Data System (ADS)

    Chan, Edmund Ho Man

    In the present contribution, we elaborate on the covalent attachment of the amino acid cysteine and selected cysteine-bearing peptides, in aqueous buffered media, onto AlN surfaces modified with adlayers of one of our homemade bifunctional alkyltrichlorosilane cross-linking molecules bearing the benzenethiosulfonate head group. Surface characterizations confirmed the successful covalent immobilization of cysteine in buffered media, whereas the attachment of the peptides proved to be difficult as the undesired partial destruction of the adlayer on AlN by hydrolysis in aqueous/buffered solvent systems, which was confirmed in a separate study, appeared to have interfered with the covalent attachment and resulted in one of the peptides failing to immobilize. Future directions from this will focus on optimizing the solvent conditions for the cysteine/peptide immobilizations and the implementation of the surface chemistry to the covalent functionalization of AlN with biologically significant protein fragments, among them the antigen-binding fragment of antibodies.

  1. 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

  2. Probing Electrochemical Adsorbate Structure and Reactions with In-Situ Atomic-Resolution Scanning Microscopy: Some Progress and Prospects

    DTIC Science & Technology

    1992-10-01

    counterion would be of substantial value. An interesting example, examined recently by in-situ AFM, concerns underpotential deposited (upd) silver on...Au(lll)[31]. Markedly different symmetries of the deposited metal adlayer were observed, depending upon the nature of the electrolyte counteranion...with the common use of Au(lll) surfaces prepared by 19 vacuum metal deposition on mica or other suitable templates. The examination of ordered

  3. In-Situ Surface EXAFS at Chemically Modified Electrodes.

    DTIC Science & Technology

    1987-07-28

    characterization of underpotentially deposited copper on gold(ll) electrodes. [12] We now present an in-situ surface EXAFS study of electropolymerized... deposition or adsorption of metallic adlayers (6] or transition metal complexes. [7] In addition the electrode can act as a simple electron shuttle to...structure at all stages of polymer deposition . These values correlate very well with the known coordination member of six and a Ru-N distance of 2.056 A

  4. Fibronectin and bovine serum albumin adsorption and conformational dynamics on inherently conducting polymers: a QCM-D study.

    PubMed

    Molino, Paul J; Higgins, Michael J; Innis, Peter C; Kapsa, Robert M I; Wallace, Gordon G

    2012-06-05

    Quartz crystal microbalance with dissipation monitoring (QCM-D) was employed to characterize the adsorption of the model proteins, bovine serum albumin (BSA) and fibronectin (FN), to polypyrrole doped with dextran sulfate (PPy-DS) as a function of DS loading and surface roughness. BSA adsorption was greater on surfaces of increased roughness and was above what could be explained by the increase in surface area alone. Furthermore, the additional mass adsorbed on the rough films was concomitant with an increase in the rigidity of the protein layer. Analysis of the dynamic viscoelastic properties of the protein adlayer reveal BSA adsorption on the rough films occurs in two phases: (1) arrival and initial adsorption of protein to the polymer surface and (2) postadsorption molecular rearrangement to a more dehydrated and compact conformation that facilitates further recruitment of protein to the polymer interface, likely forming a multilayer. In contrast, FN adsorption was independent of surface roughness. However, films prepared from solutions containing the highest concentration of DS (20 mg/mL) demonstrated both an increase in adsorbed mass and adlayer viscoelasticity. This is attributed to the higher DS loading in the conducting polymer film resulting in presentation of a more hydrated molecular structure indicative of a more unfolded and bioactive conformation. Modulating the redox state of the PPy-DS polymers was shown to modify both the adsorbed mass and viscoelastic nature of FN adlayers. An oxidizing potential increased both the total adsorbed mass and the adlayer viscoelasticity. Our findings demonstrate that modification of polymer physicochemical and redox condition alters the nature of protein-polymer interaction, a process that may be exploited to tailor the bioactivity of protein through which interactions with cells and tissues may be controlled.

  5. Mn deposition on Ni{sub 2}MnGa(100)

    SciTech Connect

    Nayak, J.; Rai, Abhishek; D'Souza, S. W.; Maniraj, M.; Barman, S. R.

    2012-06-05

    We report the study of Mn adlayers on a Mn deficient Ni{sub 2}MnGa(100) surface by using low energy electron diffraction (LEED). The spot profile analysis indicates that after 0.2 monolayer (ML) deposition, the LEED spots become very sharp. This pattern indicates the removal of Mn vacancies formed on the surface due to Mn deficiency. But with further growth of Mn layers on this surface, the LEED spots become broad.

  6. Atomic-Level Structure and Dynamics of Ordered Metal Electrodes as Probed by Infrared Spectroscopy and Scanning Tunneling Microscopy

    DTIC Science & Technology

    1992-02-28

    modified Pt(lll), two major oxidation products, oxalic acid and C02, are formed via distinct reaction pathways (39). The presence of predosed bismuth...the expense of the oxalic acid yield (39). These results suggest that larger ensembles of contiguous active sites are required for the partial...oxidation of ethylene glycol to form oxalic acid than for exhaustive electrooxidation to yield CO2. COMBINED STM-FTIR EXAMINATIONS OF CO ADLAYER STRUCTURES

  7. Improved production, purification and bioactivity of a polysaccharide from submerged cultured Ganoderma lucidum.

    PubMed

    Zhou, Huabin; Liu, Gaoqiang; Huang, Furu; Wu, Xiangting; Yang, Hailong

    2014-12-01

    Polysaccharides from Ganoderma lucidum showed multiple biological activities, such as immuno-modulating, antitumor, antioxidant, and hepatoprotective activity, etc. Adlay oil was added into the media to enhance polysaccharide production by submerged culture of G. lucidum in this work. The results revealed the optimal concentration of adlay oil was 1.5 % for polysaccharide production of G. lucidum. Analysis of the polysaccharide components confirmed that no novel components were biosynthesized by the addition of adlay oil. The main fraction of extracellular polysaccharide, GLEP-2, was isolated from the submerged culture broth of G. lucidum by ethanol precipitation, filtration, DEAE cellulose-52 and Sepharose CL-6B chromatography. GLEP-2, which was composed of glucose, galactose, mannose, arabinose, and rhamnose in a ratio of 332:55:32:13:3 respectively, had an average molecular weight of ~2.08 × 10(4) Da. The bioactivity tests demonstrated that GLEP-2 enhanced the T lymphocyte proliferation significantly at a concentration of 200 μg/mL and B lymphocyte proliferation at lower concentrations of 50 μg/mL. The results suggest polysaccharides from the submerged culture of G. lucidum are potential candidates for further development and possible commercial applications, especially in the pharmaceutical and functional foods industries.

  8. In situ stress and nanogravimetric measurements during underpotential deposition of bismuth on (111)-textured Au.

    PubMed

    Stafford, G R; Bertocci, U

    2006-08-10

    The surface stress associated with the underpotential deposition (upd) of bismuth on (111)-textured Au is examined, using the wafer curvature method, in acidic perchlorate and nitrate supporting electrolyte. The surface stress is correlated to Bi coverage by independent nanogravimetric measurements using an electrochemical quartz crystal nanobalance. The mass increase measured in the presence of perchlorate is consistent with the (2 x 2) and (p x square root 3)-2Bi adlayers reported in the literature. ClO(4)(-) does not play a significant role in the upd process. The complete Bi monolayer causes an overall surface stress change of about -1.4 N m(-1). We attribute this compressive stress to the formation of Bi-Au bonds which partially satisfy the bonding requirements of the Au surface atoms, thereby reducing the tensile surface stress inherent to the clean Au surface. At higher Bi coverage, an additional contribution to the compressive stress is due to the electrocompression of the (p x square root 3)-2Bi adlayer. In nitric acid electrolyte, NO(3)(-) coadsorbs with Bi over the entire upd region but has little fundamental impact on adlayer structure and stress.

  9. Toward the microscopic identification of anions and cations at the ionic liquid|Ag(111) interface: a combined experimental and theoretical investigation.

    PubMed

    Buchner, Florian; Forster-Tonigold, Katrin; Uhl, Benedikt; Alwast, Dorothea; Wagner, Nadja; Farkhondeh, Hanieh; Gross, Axel; Behm, R Jürgen

    2013-09-24

    The interaction between an adsorbed 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [BMP][TFSA], ionic liquid (IL) layer and a Ag(111) substrate, under ultrahigh-vacuum conditions, was investigated in a combined experimental and theoretical approach, by high-resolution scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and dispersion-corrected density functional theory calculations (DFT-D). Most importantly, we succeeded in unambiguously identifying cations and anions in the adlayer by comparing experimental images with submolecular resolution and simulated STM images based on DFT calculations, and these findings are in perfect agreement with the 1:1 ratio of anions and cations adsorbed on the metal derived from XPS measurements. Different adlayer phases include a mobile 2D liquid phase at room temperature and two 2D solid phases at around 100 K, i.e., a 2D glass phase with short-range order and some residual, but very limited mobility and a long-range ordered 2D crystalline phase. The mobility in the different adlayer phases, including melting of the 2D crystalline phase, was evaluated by dynamic STM imaging. The DFT-D calculations show that the interaction with the substrate is composed of mainly van der Waals and weak electrostatic (dipole-induced dipole) interactions and that upon adsorption most of the charge remains at the IL, leading to attractive electrostatic interactions between the adsorbed species.

  10. Mobility and Oxidation of Adsorbed CO on Shape-Controlled Pt Nanoparticles in Acidic Medium.

    PubMed

    Farias, Manuel J S; Busó-Rogero, Carlos; Vidal-Iglesias, Francisco J; Solla-Gullón, José; Camara, Giuseppe A; Feliu, Juan M

    2017-01-31

    The knowledge about how CO occupies and detaches from specific surface sites on well-structured Pt surfaces provides outstanding information on both dynamics/mobility of COads and oxidation of this molecule under electrochemical conditions. This work reports how the potentiostatic growth of different coverage CO adlayers evolves with time on both cubic and octahedral Pt nanoparticles in acidic medium. Data suggest that during the growth of the CO adlayer, COads molecules slightly shift toward low coordination sites only on octahedral Pt nanoparticles, so that these undercoordinated sites are the first filled on octahedral Pt nanoparticles. Conversely, on cubic Pt nanoparticles, adsorbed CO behaves as an immobile species, and low coordinated sites as well as (100) terraces are apparently filled uniformly and simultaneously. However, once the adlayer is complete, irrespectively of whether the CO is oxidized in a single step or in a sequence of different potential steps, results suggest that COads behaves as an immobile species during its oxidation on both octahedral and cubic Pt nanoparticles.

  11. Nature of the electrochemical HClO4/Pt(111) interface

    NASA Astrophysics Data System (ADS)

    Liu, Shan Ping; Zhao, Ming; Gao, Wang; Jacob, Timo; Jiang, Qing

    2017-04-01

    It is crucial to understand the electrochemical HClO4/Pt(111) interface in the field of electrochemistry, which is unfortunately still disputed. To reveal the fundamental properties of this interface, we have studied co-adsorption of possible species at the HClO4/Pt(111) interface using density functional theory (DFT). Our calculations demonstrate that HClO4* is most likely to dissociate into ClO4* on Pt(111) surface, leading to an adlayer of ClO4* co-adsorbed with H3O* and H2O* molecules. Interestingly, these co-adsorbed H3O* molecules exhibit the nature of hydronium ions with highly localized positive charge states. On the other hand, the stability of this ClO4* co-adsorbed adlayer is almost equal to that of a H2O* + H3O* bilayer. This competition would prohibit the formation of periodic ClO4* + H2O* + H3O* adlayer on Pt(111), yielding a weak adsorption of ClO4* in electrochemical condition as the experiments found. In addition, the electrostatic potential along the direction that is perpendicular to the substrate exhibits clearly distinguishable peaks for the different interfacial structures. These results provide deep insights into this fundamental electrochemical interface and offer promising clues for future experimental studies.

  12. Functionalization of nanostructured cerium oxide films with histidine.

    PubMed

    Tsud, Nataliya; Bercha, Sofiia; Acres, Robert G; Vorokhta, Mykhailo; Khalakhan, Ivan; Prince, Kevin C; Matolín, Vladimír

    2015-01-28

    The surfaces of polycrystalline cerium oxide films were modified by histidine adsorption under vacuum and characterized by the synchrotron based techniques of core and valence level photoemission, resonant photoemission and near edge X-ray absorption spectroscopy, as well as atomic force microscopy. Histidine is strongly bound to the oxide surface in the anionic form through the deprotonated carboxylate group, and forms a disordered molecular adlayer. The imidazole ring and the amino side group do not form bonds with the substrate but are involved in the intermolecular hydrogen bonding which stabilizes the molecular adlayer. The surface reaction with histidine results in water desorption accompanied by oxide reduction, which is propagated into the bulk of the film. Previously studied, well-characterized surfaces are a guide to the chemistry of the present polycrystalline surface and histidine bonds via the carboxylate group in both cases. In contrast, bonding via the imidazole group occurs on the well-ordered surface but not in the present case. The morphology and structure of the cerium oxide are decisive factors which define the adsorption geometry of the histidine adlayer.

  13. Predictive beyond-mean-field rate equations for multisite lattice–gas models of catalytic surface reactions: CO oxidation on Pd(100)

    DOE PAGES

    Liu, Da -Jiang; Zahariev, Federico; Gordon, Mark S.; ...

    2016-11-29

    Tailored multisite lattice–gas (msLG) models are developed for CO oxidation on Pd(100) at low-pressures. These models include multiple adsorption site types and superlattice adlayer ordering due to short-range exclusion for highly mobile reactant adspecies. However, they are simplified to neglect longer-range weaker adspecies interactions, so that the key energetic parameters are the CO desorption barrier and the reaction barrier. We discuss existing density functional theory results for these energies and present additional analysis for CO adsorption. After also including an appropriate nontrivial specification of the dynamics of adsorption onto mixed reactant adlayers, we develop rate equations for the reaction kinetics.more » Our formulation goes beyond traditional mean-field (MF) Langmuirian treatments by accounting for multiple adsorption sites and for the strong spatial correlations associated with superlattice ordering. Specifically, we utilize factorization approximations based on appropriate site motifs, and also Padé resummation of exact low-coverage expansions for sticking coefficients. Our beyond-MF rate equations are successful in accurately predicting key aspects of reactive steady-state behavior, and thus expand the utility of rate equation formulations in surface chemistry. This is confirmed by comparison with precise kinetic Monte Carlo simulation results. Furthermore, we not only assess bistability and criticality observed for CO oxidation but also find more complex multistability associated with symmetry-breaking transitions in high-coverage CO adlayers.« less

  14. Predictive beyond-mean-field rate equations for multisite lattice–gas models of catalytic surface reactions: CO oxidation on Pd(100)

    SciTech Connect

    Liu, Da -Jiang; Zahariev, Federico; Gordon, Mark S.; Evans, James W.

    2016-11-29

    Tailored multisite lattice–gas (msLG) models are developed for CO oxidation on Pd(100) at low-pressures. These models include multiple adsorption site types and superlattice adlayer ordering due to short-range exclusion for highly mobile reactant adspecies. However, they are simplified to neglect longer-range weaker adspecies interactions, so that the key energetic parameters are the CO desorption barrier and the reaction barrier. We discuss existing density functional theory results for these energies and present additional analysis for CO adsorption. After also including an appropriate nontrivial specification of the dynamics of adsorption onto mixed reactant adlayers, we develop rate equations for the reaction kinetics. Our formulation goes beyond traditional mean-field (MF) Langmuirian treatments by accounting for multiple adsorption sites and for the strong spatial correlations associated with superlattice ordering. Specifically, we utilize factorization approximations based on appropriate site motifs, and also Padé resummation of exact low-coverage expansions for sticking coefficients. Our beyond-MF rate equations are successful in accurately predicting key aspects of reactive steady-state behavior, and thus expand the utility of rate equation formulations in surface chemistry. This is confirmed by comparison with precise kinetic Monte Carlo simulation results. Furthermore, we not only assess bistability and criticality observed for CO oxidation but also find more complex multistability associated with symmetry-breaking transitions in high-coverage CO adlayers.

  15. Two-dimensional material confined water.

    PubMed

    Li, Qiang; Song, Jie; Besenbacher, Flemming; Dong, Mingdong

    2015-01-20

    CONSPECTUS: The interface between water and other materials under ambient conditions is of fundamental importance due to its relevance in daily life and a broad range of scientific research. The structural and dynamic properties of water at an interface have been proven to be significantly difference than those of bulk water. However, the exact nature of these interfacial water adlayers at ambient conditions is still under debate. Recent scanning probe microscopy (SPM) experiments, where two-dimensional (2D) materials as ultrathin coatings are utilized to assist the visualization of interfacial water adlayers, have made remarkable progress on interfacial water and started to clarify some of these fundamental scientific questions. In this Account, we review the recently conducted research exploring the properties of confined water between 2D materials and various surfaces under ambient conditions. Initially, we review the earlier studies of water adsorbed on hydrophilic substrates under ambient conditions in the absence of 2D coating materials, which shows the direct microscopic results. Subsequently, we focus on the studies of water adlayer growth at both hydrophilic and hydrophobic substrates in the presence of 2D coating materials. Ice-like water adlayers confined between hydrophobic graphene and hydrophilic substrates can be directly observed in detail by SPM. It was found that the packing structure of the water adlayer was determined by the hydrophilic substrates, while the orientation of intercalation water domains was directed by the graphene coating. In contrast to hydrophilic substrates, liquid-like nanodroplets confined between hydrophobic graphene and hydrophobic substrates appear close to step edges and atomic-scale surface defects, indicating that atomic-scale surface defects play significant roles in determining the adsorption of water on hydrophobic substrates. In addition, we also review the phenomena of confined water between 2D hydrophilic MoS2 and

  16. (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

  17. 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

  18. Surface Confined Metallosupramolecular Architectures: Formation and STM Characterization

    PubMed Central

    Li, Shan-Shan; Northrop, Brian H.; Yuan, Qun-Hui; Wan, Li-Jun; Stang, Peter J.

    2009-01-01

    CONSPECTUS Metallosupramolecular compounds have attracted a great deal of attention over the past two decades largely because of their unique, highly-complex structural characteristics, the fact that they can be prepared with relative ease using coordination-driven self-assembly techniques, and their potential electronic, magnetic, optical, and catalytic properties. In particular, the use of electron-poor square planar Pt(II) transition metals in conjunction with rigid, electron-rich pyridyl donors had enabled the spontaneous self-assembly of a rich library of 2D metallacyclic and 3D metallacage assemblies via the directional-bonding approach. With the tremendous progress that has been made in the preparation and characterization of metallosupramolecules, much attention is now being turned toward fully exploring and developing their materials properties. Assembling metallosupramolecular compounds on solid supports represents a vitally important step toward developing their materials properties. Surfaces provide a means of uniformly aligning and orienting these highly symmetric metallacycles and metallacages, which increases the level of coherence between molecules above that which can be achieved in the solution phase and affords a means of integrating adlayers into a solid-state materials setting. The dynamic nature of kinetically labile Pt(II)-N coordination bonds, however, requires that deposition and imaging conditions be appropriate to retain the assemblies' stability. Toward these aims it is imperative to understand the factors that govern surface self-assembly and the interactions that influence the structure and stability of the resulting adlayer. Such insight can be obtained from Scanning Tunneling Microscopy (STM), which has emerged as a powerful technique for the imaging and characterization of self-assembled adlayers. This account describes the means by which 2D rectangular and square metallacycles and 3D trigonal bipyrimidal and chiral trigonal prism

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

    PubMed

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

    2016-06-07

    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.

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

    PubMed Central

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

    2016-01-01

    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

  2. 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

  3. 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

  4. 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.

  5. In situ STM imaging of bis-3-sodiumsulfopropyl-disulfide molecules adsorbed on copper film electrodeposited on Pt(111) single crystal electrode.

    PubMed

    Tu, HsinLing; Yen, PoYu; Chen, Sihzih; Yau, ShuehLin; Dow, Wei-Ping; Lee, Yuh-Lang

    2011-06-07

    The adsorption of bis-3-sodiumsulfopropyldi-sulfide (SPS) on metal electrodes in chloride-containing media has been intensively studied to unveil its accelerating effect on Cu electrodeposition. Molecular resolution scanning tunneling microscopy (STM) imaging technique was used in this study to explore the adsorption and decomposition of SPS molecules concurring with the electrodeposition of copper on an ordered Pt(111) electrode in 0.1 M HClO(4) + 1 mM Cu(ClO(4))(2) + 1 mM KCl. Depending on the potential of Pt(111), SPS molecules could react, adsorb, and decompose at chloride-capped Cu films. A submonolayer of Cu adatoms classified as the underpotential deposition (UPD) layer at 0.4 V (vs Ag/AgCl) was completely displaced by SPS molecules, possibly occurring via RSSR (SPS) + Cl-Cu-Pt → RS(-)-Pt(+) + RS(-) (MPS) + Cu(2+) + Cl(-), where MPS is 3-mercaptopropanesulfonate. By contrast, at 0.2 V, where a full monolayer of Cu was presumed to be deposited, SPS molecules were adsorbed in local (4 × 4) structures at the lower ends of step ledges. Bulk Cu deposition driven by a small overpotential (η < 50 mV) proceeded slowly to yield an atomically smooth Cu deposit at the very beginning (<5 layers). On a bilayer Cu deposit, the chloride adlayer was still adsorbed to afford SPS admolecules arranged in a unique 1D striped phase. SPS molecules could decompose into MPS upon further Cu deposition, as a (2 × 2)-MPS structure was observed with prolonged in situ STM imaging. It was possible to visualize either SPS admolecules in the upper plane or chloride adlayer sitting underneath upon switching the imaging conditions. Overall, this study established a MPS molecular film adsorbed to the chloride adlayer sitting atop the Cu deposit.

  6. Underpotential deposition of Cu on iodine-modified Au(1 1 1): an in situ scanning tunneling microscopy study

    NASA Astrophysics Data System (ADS)

    Martínez-Ruiz, A.; Valenzuela-Benavides, J.; Morales de la Garza, L.; Batina, N.

    2001-04-01

    The electrochemical deposition of Cu on iodine-modified Au(1 1 1) surfaces has been investigated by in situ electrochemical scanning tunneling microscopy (ECSTM) and cyclic voltammetry (CV) in sulfuric acid solutions. In situ ECSTM studies reveal different iodine adlayer structures before and during the process of copper underpotential deposition (UPD). At the beginning of the cathodic scan and for potentials higher than the onset of UPD a c( p×√3 R-30°) iodine structure is observed on wide terraces. For lower potentials this iodine structure transforms to a more compact (3×3) structure characterized by two different structural variations (symmetric and asymmetric) sometimes observed coexisting in the same terrace. Charge transfer analysis from CV measurements reveals that the amount of copper deposited at these potentials is not sufficient to account for this structure in the framework of a hard-ball structural model. During the UPD process itself other iodine structures are also observed as a function of copper deposition, together with an additional compression of the iodine adlayer associated with the formation of a CuI bilayer, in agreement with previously reported X-ray diffraction data. At the end of the UPD process a Cu(1×1) monolayer is formed with a lattice parameter equal to that of Au(1 1 1). The same course of structural changes was also observed during the anodic scan where stripping of the copper layer takes place, returning to the initial iodine c( p×√3 R-30°) structure. Our results strongly suggest that the iodine adlayer is constantly present as the top layer during the process of electrodeposition and stripping of Cu with no noticeable loss of iodine in the process. The observed structures are discussed in terms of iodine-copper interactions.

  7. 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.

  8. Quenching of the luminescence intensity of GaN nanowires under electron beam exposure: impact of C adsorption on the exciton lifetime.

    PubMed

    Lähnemann, Jonas; Flissikowski, Timur; Wölz, Martin; Geelhaar, Lutz; Grahn, Holger T; Brandt, Oliver; Jahn, Uwe

    2016-11-11

    Electron irradiation of GaN nanowires in a scanning electron microscope strongly reduces their luminous efficiency as shown by cathodoluminescence imaging and spectroscopy. We demonstrate that this luminescence quenching originates from a combination of charge trapping at already existing surface states and the formation of new surface states induced by the adsorption of C on the nanowire sidewalls. The interplay of these effects leads to a complex temporal evolution of the quenching, which strongly depends on the incident electron dose per area. Time-resolved photoluminescence measurements on electron-irradiated samples reveal that the carbonaceous adlayer affects both the nonradiative and the radiative recombination dynamics.

  9. Aflatoxin contamination in foods and foodstuffs in Tokyo: 1986-1990.

    PubMed

    Tabata, S; Kamimura, H; Ibe, A; Hashimoto, H; Iida, M; Tamura, Y; Nishima, T

    1993-01-01

    Aflatoxins were determined in 3054 samples of foods or foodstuffs, including cereals, nuts, beans, spices, dairy products, dry fruits, and edible oil. Samples were collected in Tokyo from 1986 to 1990. Aflatoxins were found in rice products, adlay, corn, crude sugar, peanut products, pistachio nuts, brazil nuts, sesame products, butter beans, white pepper, red pepper, paprika, nutmeg, and mixed spices. The highest incidence of aflatoxin contamination was observed in nutmeg (80%), and the highest level of aflatoxin B1 was observed in pistachio nuts (1382 ppb).

  10. 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

  11. Influence of sp-d hybridization on the electronic structure of Al-Mn alloys

    SciTech Connect

    Shukla, A. K.; Biswas, C.; Dhaka, R. S.; Das, S. C.; Barman, S. R.; Krueger, P.

    2008-05-15

    The influence of sp-d hybridization on the electronic structure of different Al-Mn alloys has been studied by photoelectron spectroscopy. Experimental evidence of a pseudogap in a crystalline binary Hume-Rothery alloy is provided. The pseudogap varies systematically with Mn concentration. The sp-d hybridization alone, even in the absence of Hume-Rothery mechanism, can produce the pseudogap. Existence of the pseudogap, suppression of the Mn 2p satellite, and decrease in the Doniach-Sunjic asymmetry parameter are the consequences of the sp-d hybridization. An in situ method of preparing these alloys by annealing a Mn adlayer on Al(111) is presented.

  12. Anion promoted Ni-underpotential deposition on Au(111)

    NASA Astrophysics Data System (ADS)

    Bubendorff, J. L.; Cagnon, L.; Costa-Kieling, V.; Bucher, J. P.; Allongue, P.

    1997-07-01

    In situ scanning tunneling microscopy (STM) and cyclic voltammetry show that a Ni monolayer can be deposited from a sulfamate solution on Au(111) at positive potentials with respect to the Nernst potential of the {Ni}/{Ni2+} couple. This process is specific to H 2NSO -3 anions since it could not be observed in the presence of sulfates. High resolution STM images suggest that the Ni layer builds up on the surface due to a complexation of Ni 2+ by the sulfamate adlayer on the gold surface.

  13. The (3 × 2) β -SiC(001) surface reconstruction investigated by photoelectron diffraction in the backscattering regime

    NASA Astrophysics Data System (ADS)

    Michel, E. G.; Dunham, D.; Tejeda, A.; Soukiassian, P.; Rotenberg, E.; Denlinger, J. D.

    2006-03-01

    The atomic positions of the (3× 2) reconstruction of the cubic polytype of SiC(001) are determined by using photoelectron diffraction in the backscattering regime. The comparison of multiple scattering spherical wave calculations with experimental data favours a modified version of the two-adlayer asymmetric dimer model. The atomic positions in the reconstructed layers are obtained from an R-factor refinement analysis. Atoms in the outermost layer form asymmetric dimers with a corrugation of (0.25 ± 0.10) Å. The second layer is also dimerized and originates rows of long and short dimers.

  14. New functionalizable alkyltrichlorosilane surface modifiers for biosensor and biomedical applications.

    PubMed

    Blaszykowski, Christophe; Sheikh, Sonia; Benvenuto, Pasquale; Thompson, Michael

    2012-02-07

    We report herein three unprecedented alkyltrichlorosilane surface modifiers bearing pentafluorophenyl ester (PFP), benzothiosulfonate (BTS), or novel β-propiolactone (BPL) functionalizable terminal groups. Evidence is provided that these molecules can be prepared in very high purity (as assessed by NMR) through a last synthetic step of Pt-catalyzed alkene hydrosilylation then directly employed, without further purification, for the surface modification of quartz and medical grade stainless steel. Subsequent on-surface functionalizations with amine and thiol model molecules demonstrate the potential of these molecular adlayers to be important platforms for future applications in the bioanalytical and biomedical fields.

  15. Surface modification of diamond-like carbon films with protein via polydopamine inspired coatings

    NASA Astrophysics Data System (ADS)

    Tao, Caihong; Yang, Shengrong; Zhang, Junyan; Wang, Jinqing

    2009-10-01

    In this paper, we report a facile two-step approach to immobilize proteins onto DLC surfaces. The first step was a simple immersion of DLC in a solution of dopamine. Polydopamine was deposited on DLC as a stable anchor to present protein molecules. Then the protein ad-layer was deposited on it. The chemical components of the modified DLC surfaces were characterized by Fourier transform infrared spectra and X-ray photoelectron spectroscopy. The biocompatibility of it was evaluated in vitro by the tetrazolium salt method. And it was indicated that the BSA modified surface had good haemocompatibility properties, and was cytocompatible to PC-12 cells.

  16. Mussel-Inspired Surface Chemistry for Multifunctional Coatings

    NASA Astrophysics Data System (ADS)

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

    2007-10-01

    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.

  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. Influence of sp-d hybridization on the electronic structure of Al-Mn alloys

    NASA Astrophysics Data System (ADS)

    Shukla, A. K.; Biswas, C.; Dhaka, R. S.; Das, S. C.; Krüger, P.; Barman, S. R.

    2008-05-01

    The influence of sp-d hybridization on the electronic structure of different Al-Mn alloys has been studied by photoelectron spectroscopy. Experimental evidence of a pseudogap in a crystalline binary Hume-Rothery alloy is provided. The pseudogap varies systematically with Mn concentration. The sp-d hybridization alone, even in the absence of Hume-Rothery mechanism, can produce the pseudogap. Existence of the pseudogap, suppression of the Mn2p satellite, and decrease in the Doniach-Šunjić asymmetry parameter are the consequences of the sp-d hybridization. An in situ method of preparing these alloys by annealing a Mn adlayer on Al(111) is presented.

  19. 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.

  20. Intrinsic electronic properties of high-quality wurtzite InN

    NASA Astrophysics Data System (ADS)

    Eisele, H.; Schuppang, J.; Schnedler, M.; Duchamp, M.; Nenstiel, C.; Portz, V.; Kure, T.; Bügler, M.; Lenz, A.; Dähne, M.; Hoffmann, A.; Gwo, S.; Choi, S.; Speck, J. S.; Dunin-Borkowski, R. E.; Ebert, Ph.

    2016-12-01

    Recent reports suggested that InN is a highly unusual III-V semiconductor, whose behavior fundamentally differs from that of others. We therefore analyzed its intrinsic electronic properties on the highest available quality InN layers, demonstrating the absence of electron accumulation at the (10 1 ¯0 ) cleavage surface and in the bulk. The bulk electron density is governed solely by dopants. Hence, we conclude that InN acts similarly to the other III-V semiconductors and previously reported intriguing effects are related to low crystallinity, surface decomposition, nonstoichiometry, and/or In adlayers.

  1. 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.

  2. Dynamic screening and electron electron scattering in low-dimensional metallic systems

    NASA Astrophysics Data System (ADS)

    Silkin, V. M.; Quijada, M.; Muiño, R. Díez; Chulkov, E. V.; Echenique, P. M.

    2007-09-01

    The modification of dynamic screening in the electron-electron interaction in systems with reduced dimensionality and tunable one-particle electronic structure is studied. Two examples of such systems are considered, namely, the adsorbate-induced quantum well states at the Na adlayer covered Cu(1 1 1) surface, and metal clusters of sizes up to few nanometers. The dependence of the electron-electron decay rates on the Na coverage in the former case and on the cluster size in the latter is investigated. The role played by the dynamical screened interaction in such processes is addressed as well.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. Sulfidation of a Cu submonolayer at the Au(1 1 1)/electrolyte interface An in situ STM study

    NASA Astrophysics Data System (ADS)

    Friebel, Daniel; Schlaup, Christian; Broekmann, Peter; Wandelt, Klaus

    2006-07-01

    We describe the electrochemical preparation of an ultrathin copper sulfide film on Au(1 1 1) and its structural characterization by in situ STM. The first step, underpotential deposition of a Cu submonolayer from CuSO 4/H 2SO 4 solution, is followed by two electrolyte exchanges for (i) Cu-free (blank) H 2SO 4 solution and (ii) NaOH/Na 2S solution. The well-known (√3 × √3) R30° structure of the upd Cu layer is stable in the blank electrolyte for at least 2 h. After exposure to bisulfide, the Cu layer contracts and forms two-dimensional islands of two distinct ordered surface phases, i.e. a rectangular and, at higher potentials, a hexagonal phase, with Cu-free Au(1 1 1) regions between them, the latter exhibiting the characteristic (√3 × √3) R30°-S adlayer structure. Potential changes lead to a complex phase behaviour including HS - ⇆ S x oxidation/reduction and, at strongly anodic potentials, dissolution of the Cu adlayer.

  8. Underpotential deposition of Cd on Ag(1 1 1): an in situ STM study

    NASA Astrophysics Data System (ADS)

    García, S. G.; Salinas, D. R.; Staikov, G.

    2005-02-01

    The kinetics and mechanism of Cd underpotential deposition (UPD) and involved surface alloy formation processes in the system Ag(1 1 1)/Cd 2+, SO42-, are studied by means of combined electrochemical measurements and in situ scanning tunneling microscopy (STM). The results show that the UPD process starts with a formation of an expanded (diluted) adlayer with a superlattice structure Ag(1 1 1)- (√{3}×√{19})R23.4°. In the underpotential range 50 mV < Δ E < 80 mV this adlayer transforms to a condensed close packed Cd monolayer via a first order phase transition. At long polarization times the condensed monolayer undergoes structural changes involving place exchange processes between Cd atoms and surface Ag atoms. A formation of a second Cd monolayer and a significant Ag-Cd surface alloying take place at lower underpotentials (Δ E < 50 mV). The kinetics of surface alloying are analyzed on the basis of a recently proposed diffusion model including a relatively fast initial formation of a very thin surface alloy film and a subsequent slow alloy growth controlled by solid state diffusion. The anodic dealloying results in an appearance of monatomically deep pits, which disappear quickly at relatively high underpotentials (Δ E > 550 mV) indicating a high mobility of surface Ag atoms.

  9. Reconstructions and origin of surface states on AlN polar and nonpolar surfaces

    NASA Astrophysics Data System (ADS)

    Miao, M. S.; Janotti, A.; van de Walle, C. G.

    2009-10-01

    The AlN (0001), (0001¯) , (101¯0) , and (112¯0) surfaces and their electronic structures are studied based on density-functional theory using the generalized gradient approximation as well as the hybrid functional approach. The stable reconstructions generally satisfy the electron-counting rule, except for cases where Al adlayers are present. We find that the transitions between different reconstructions exhibit a distinct trend for group-III nitrides. For all surfaces, Al dangling-bond states tend to be close to the conduction-band minimum (CBM) and N dangling-bond states close to the valence-band maximum (VBM). Al-N bonding states also occur near the VBM, while Al-Al bonding states occur in the middle of the gap. We find that Al dangling-bond states on the Al-polar (0001) surface can pin the Fermi level of n -type AlN at 1.0 eV below the CBM at moderate Al/N growth ratios. At high Al/N ratios, metallic Al adlayers form which pin the Fermi level in the middle of the gap. The lack of a surface donor state in the upper part of the gap suggests that the surface states on clean AlGaN surfaces are unlikely to be the source of carriers in the two-dimensional electron gas in AlGaN/GaN high-electron-mobility transistors.

  10. Preparation and characterization of dopamine-decorated hydrophilic carbon black

    NASA Astrophysics Data System (ADS)

    Zhu, Lijun; Lu, Yonglai; Wang, Yiqing; Zhang, Liqun; Wang, Wencai

    2012-05-01

    Inspired by the bio-adhesive proteins secreted by mussels for attachment to almost all wet substrates, a facile method involving oxidative polymerization of dopamine was proposed to prepare highly hydrophilic carbon black (CB) particles. A self-assembled polydopamine (PDA) ad-layer was formed via the oxidative polymerization of dopamine on the surface of CB simply by dipping the CB into an alkaline dopamine solution and mildly stirring at room temperature. The process is simple, controllable, and environment-friendly. The surface composition and structure of the CB were characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The surface morphology of the CB was observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results showed that the PDA ad-layer was successfully deposited on the CB surfaces. The PDA-functionalized CB (CB-PDA) gave a stable colloidal dispersion in water. Contact angle measurement results indicated that the hydrophilicity of CB was significantly improved after dopamine modification. TGA results confirmed that the modified CB maintained good heat resistance. The method provided a facile route to prepare hydrophilic CB having terminal hydroxyl groups.

  11. 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

  12. Systematic characterization of spectral surface plasmon resonance sensors with absorbance measurement

    NASA Astrophysics Data System (ADS)

    Qi, Zhi-Mei; Xia, Shanhong; Wei, Mingdeng; Matsuda, Hirofumi; Zhou, Haoshen

    2007-11-01

    Spectral surface plasmon resonance (SPR) sensors with absorbance measurement were prepared. Resonant wavelengths (λ R ) versus effective refractive indexes of the SPR mode were measured with different media in contact with the gold layer. An investigation into the refractive-index sensitivity of the sensor at a fixed angle reveals a linear dependence of λ R on the refractive index of the solution (nc), with Δλ R /Δnc=3553.6 nm in a small range of 1.333≤nc≤1.347. It was observed that the effective refractive index slowly decreases with increasing nc, attributable to wavelength-induced modulation of optical dielectric constant for the gold layer. Adsorption of bromothymol blue (BTB) on the gold layer leads to a redshift of Δλ R =3.7 nm, larger than Δλ R =2.5 nm induced by myoglobin (Mb) adsorption. On the basis of Fresnel equations, calculations with d~1 nm and n=1.69 for BTB and d~3 nm and n=1.40 for Mb also demonstrate that the SPR band shift induced by full-monolayer adsorption of BTB is larger than that for full-monolayer Mb adsorption. The combination of both measured and calculated results suggests that the contribution of the adlayer index of refraction to the sensitivity of the sensor is greater than that of the adlayer thickness.

  13. 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

  14. Investigation of adsorption behavior of (-)-epigallocatechin gallate on bovine serum albumin surface using quartz crystal microbalance with dissipation monitoring.

    PubMed

    Wang, Xiaoyong; Ho, Chi-Tang; Huang, Qingrong

    2007-06-27

    Quartz crystal microbalance with dissipation monitoring (QCM-D) has been employed to study the interactions between (-)-epigallocatechin gallate (EGCG) and bovine serum albumin (BSA) surface. The adsorbed mass, thickness, and viscoelastic properties of EGCG adlayer on BSA surface at various EGCG concentrations, temperatures, sodium chloride concentrations, and pH values have been determined by QCM-D in combination with the Voigt model. The adsorption isotherm of EGCG on BSA surfaces can be better described by the Freundlich model than the Langmuir model, indicating that EGCG adsorption on BSA surfaces is dominated by nonspecific hydrophobic interactions, as supported by stronger EGCG adsorption at higher temperature. Shifts in the Fourier transform infrared spectra of the BSA surface with and without EGCG adsorption disclose that hydrogen bonding might also be involved in EGCG adsorption on BSA surfaces. The addition of salt and change of pH can also influence the EGCG adsorption on BSA surfaces. Usually, higher EGCG adsorption leads to higher values of viscosity and shear elastic modulus of EGCG adlayer, which can be explained by the aggregation of BSA through EGCG bridges. Compared with EGCG, nongalloylated (+)-catechin shows much lower adsorption capacity on BSA surfaces, suggesting the importance of the galloyl group in polyphenol/protein interactions.

  15. 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.

  16. 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.

  17. 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.

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

    DOE PAGES

    St. John, Samuel; Atkinson, Robert W.; Unocic, Kinga A.; ...

    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

  19. Structure and function evolution of thiolate monolayers on gold

    SciTech Connect

    Edwards, Grant Alvin

    2006-01-01

    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 (infrared 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.

  20. Structure and Function Evolution of Thiolate Monolayers on Gold

    SciTech Connect

    Edwards, Grant Alvin

    2006-01-01

    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.

  1. Double layer effects in electrocatalysis: the oxygen reduction reaction and ethanol oxidation reaction on Au(111), Pt(111) and Ir(111) in alkaline media containing Na and Li cations.

    SciTech Connect

    Lopes, Pietro P.; Strmcnik, Dusan; Jirkovsky, Jakub S.; Connell, Justin G.; Stamenkovic, Vojislav; Markovic, Nenad

    2016-03-15

    Oxygen reduction and ethanol oxidation reactions were studied on Au(111), Pt(111) and Ir(111) in alkaline solutions containing sodium and/or lithium cations. By keeping the same (111) surface orientation and exploring oxophilicity trends and non-covalent interactions between OHad and alkali metal cations (AMCn+), we were able to gain deep insights into the multiple roles that OHad plays in these important electrocatalytic reactions. Cyclic voltammetry experiments revealed that OHad formation initiates at distinct electrode potentials, governed by the oxophilicity of the specific metal surface, with further OHad adlayer stabilization by non-covalent alkali-cation interactions and affecting the formation of a “true oxide” layer at higher electrode potentials. Although OHad is a simple spectator for the ORR, it promotes the ethanol oxidation reaction (EOR) at lower potentials and act as spectator at high OHad coverages. By changing the alkali metal cation at the interface (Li+) on more oxophilic surfaces, it was possible to promote the EOR even more, relative to Na+, without changing the product distribution for the reaction. This cation effect suggests that OHad---Li+(H2O)x clusters can stabilize the ethoxide adlayer, thus improving the EOR activity. Our results indicate the importance of the entire electrochemical interface in determining the electrocatalytic activity during reaction.

  2. Work of Adhesion of a Sessile Drop to a Clean Surface.

    PubMed

    Schroder

    1999-05-15

    According to the Young-Dupré equation, as interpreted by Bangham and Razouk, the work of adhesion of a sessile drop to a smooth solid surface is given by WS(V)L = gammaL (1 + cos θ), where θ is the equilibrium contact angle measured at equilibrium of the system with the saturated vapor of the liquid, and WS(V)L is the work of adhesion of that drop to the solid surface which is in equilibrium with that vapor and may contain an adlayer of the vapor. For calculation of WSL, the work of adhesion of a sessile drop to a clean solid surface, the equation WSL = gammaL (1 + cos θ) + Pie is generally used (although Bangham and Razouk never proposed it). Pie is the negative of the free energy of formation of the adlayer, sometimes called the spreading pressure. In the present work it is shown that the latter equation cannot be accurate. Copyright 1999 Academic Press.

  3. Cycloadditions on diamond (100) 2 x 1: observation of lowered electron affinity due to hydrocarbon adsorption.

    PubMed

    Ouyang, Ti; Gao, Xingyu; Qi, Dongchen; Wee, Andrew Thye Shen; Loh, Kian Ping

    2006-03-23

    The adsorption of allyl alcohol, acrylic acid, and allyl chloride, as well as unsaturated organic molecules such as acetylene and 1,3 butadiene, on reconstructed diamond (100) 2 x 1 have been investigated using high-resolution electron energy loss (HREELS) spectroscopy and synchrotron radiation spectroscopy. The cycloadditions of these organic molecules produce chemically adsorbed adlayers with varying degree of coverages on the clean diamond. The organic adsorbed surface has a lowered electron affinity and shows a secondary electron yield that varies between 12 and 40% of the yield obtained from a fully hydrogenated diamond surface. The diamond surface can be functionalized with hydroxyl, carboxylic, and chlorine functionalities by the adsorption of these allyl organics. The [2 + 2] adduct of acetylene on the diamond (100) 2 x 1 surface can be observed. 1,3-butadiene attains a higher coverage as well as forms a thermally more stable adlayer on the diamond surface compared to the other organic molecules, due to its ability to undergo [4 + 2] cycloaddition.

  4. Temperature Dependence in Femtosecond Desorption at Metal Surfaces

    NASA Astrophysics Data System (ADS)

    Misewich, James

    1998-03-01

    Femtosecond laser induced desorption at metal surfaces is distinguished by two salient observations: the high yield of the reaction and the short correlation time in pump-probe measurements. This has led to the proposal of a model for desorption induced by multiple electronic transitions (DIMET). (J.A. Misewich, T.F. Heinz, and D.M. Newns, Phys. Rev. Lett. v.68 (1992) 3737.) The effect of the adsorbate temperature in DIMET has been studied using stochastic trajectory calculations with initial adsorbate vibrational quantum state occupation. We find that initial vibrational excitation substantially increases the desorption yield. These findings are related to two experimental observations. The long time-scale wings found in femtosecond time-resolved correlation measurements are thought to reflect the residual vibrational excitation left in the undesorbed adlayer following the first laser pulse. (J.A. Misewich, A. Kalamarides, T.F. Heinz, U. Hoefer, and M.M.T. Loy, J. Chem. Phys. v.100 (1994) 736.) Also, the wavelength dependence of femtosecond desorption experiments (S. Deliwala, R.J. Finlay, J.R. Goldman, T.H. Her, W.D. Mieher, and E. Mazur, Chem. Phys. Lett. v.242 (1995) 617 and D.G. Busch and W. Ho, Phys. Rev. Lett. v.77 (1996) 1338.) suggests a role for nonthermalized electrons which is interpreted in terms of the vibrational excitation left in the adlayer from unsuccessful DIET (single excitation) events as a result of the wavelength dependent nonthermalized electron distribution.

  5. An ambient FTIR study of small molecules on MgO(100) as a model for dust interactions in the troposphere

    NASA Astrophysics Data System (ADS)

    Foster, Michelle

    2005-03-01

    Magnesium oxide is a model basic oxide, having a simple rock-salt structure, a single valence state, only one stable low-index surface orientation-the (100) face, and most importantly, it is transparent in the infrared. So while MgO is not a common mineral found in tropospheric dust, it can be used as a model substrate for studies of adsorption and reactions on tropospheric dust particles. I have investigated the dynamic equilibrium occurring between MgO(100) surfaces and a series of small molecules, including water, methanol and acetic acid, in an attempt to model the role played by metal oxide surfaces in heterogeneous tropospheric chemistry. A sample cell has been constructed such that many of these infrared transparent surfaces are investigated. The adsorbate of interest is introduced at the desired pressure and allowed to establish a dynamic equilibrium with the MgO(100). The adlayer formed on the crystal faces is observed by transmission-FTIR spectroscopy, and a quantitative determination of adlayer coverages is determined using a modified Beer-Lambert Law. The substrates have also been inspected with atomic force microscopy (AFM) both before and after each series of experiments. The interactions of these adsorbates with MgO(100) under room temperature conditions and pressures on the order of 10 Torr vary from physisorbed, as is the case with methanol all the way up to dissociatively chemisorbed, as is the case with acetic acid.

  6. 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.

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

    PubMed

    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 (V(P)) 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 V(P) shift (>1 V) and a steeper subthreshold slope ( approximately 80 mVdecade), whereas "dummy" RNA induced a small positive V(P) shift ( approximately 0.3 V) without a significant change in subthreshold slopes ( approximately 330 mVdecade). 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.

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

    SciTech Connect

    Bergren, Adam Johan

    2006-01-01

    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

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

    SciTech Connect

    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 exceeding 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.

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

    DOE PAGES

    Zhang, Tingting; Liu, Ping; Lei, Wanying; ...

    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

  11. Growth and nutrient removal of three macrophytes in response to concentrations and ratios of N and P.

    PubMed

    Liao, JianXiong; Zhang, DeNan; Mallik, Azim; Huang, YuQing; He, ChengXin; Xu, GuangPing

    2017-01-13

    Wastewater from different sources show great differences in concentrations and ratios of N and P. In order to choose suitable plant species to remove excess N and/or P from polluted waters, it is important to know the performances of these plants under different N and P concentrations. In this study, we investigated the growth and N and P removal of three macrophytes, Coix lacryma-jobi, Iris wilsonii and Arundo donax under six N and P combination treatments. C. lacryma-jobi preferred higher N and P concentrations (16 mg N L(-1) and 3.2 mg P L(-1)), and increasing N supply could increase its P removal rate. I. wilsonii exhibited a growth preference at a combination of moderate N and P concentrations (8 mg N L(-1) and 0.8 mg P L(-1)). A. donax could grow well at all combinations of N and P and had significantly higher relative growth rate (RGR) and N and P removal rates than the other two species. These results showed A. donax is a promising species to treat various polluted waters and the other two species can be used specifically to treat certain types of wastewater.

  12. 2-hydroxy-4,7-dimethoxy-1,4-benzoxazin-3-one (N-O-Me-DIMBOA), a possible toxic factor in corn to the southwestern corn borer.

    PubMed

    Hedin, P A; Davis, F M; Williams, W P

    1993-03-01

    The southwestern corn borer (SWCB),Diatraea grandiosella Dyar, is a major pest of corn,Zea mays L., in the southern United States. The damage to corn is caused primarily by larval feeding on leaf, ear, and stem tissues. In this study, 2-hydroxy-4,7-dimethoxy-1,4-benzoxazin-3-one (N-O-Me-DIMBOA) was identified by MS and NMR as present in corn whorl surface waxes. This compound has evidently not been isolated previously, but its glucoside has been reported in corn, wheat, andCoix lachryma. It is present in the waxes in a higher concentration than DIMBOA (2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one) and 6-MBOA (6-methoxybenzoxazolinone). It was toxic to the SWCB in a stress diet, but it was less toxic to this insect than 6-MBOA when incorporated in the standard rearing diet. Nevertheless, it may have some role in the resistance of corn to the SWCB because the total surface wax content is higher in resistant lines than in susceptible lines.

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

    PubMed

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

    2014-11-04

    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.

  14. Correct targeting of proinsulin in protein storage vacuoles of transgenic soybean seeds.

    PubMed

    Cunha, N B; Araújo, A C G; Leite, A; Murad, A M; Vianna, G R; Rech, E L

    2010-06-22

    Soybean plants are promising bioreactors for the expression of biochemically complex proteins that cannot be produced in a safe and/or economically viable way in microorganisms, eukaryotic culture cells or secreted by transgenic animal glands. Soybeans present many desirable agronomic characteristics for high scale protein production, such as high productivity, short reproductive cycle, photoperiod sensitivity, and natural organs destined for protein accumulation in the seeds. The significant similarities between plant and human cells in terms of protein synthesis processes, folding, assembly, and post-translational processing are important for efficient accumulation of recombinant proteins. We obtained two transgenic lines using biolystics, incorporating the human proinsulin gene under control of the monocot tissue-specific promoter from sorghum gamma-kafirin seed storage protein gene and the alpha-coixin cotyledonary vacuolar signal peptide from Coix lacryma-jobi (Poaceae). Transgenic plants expressed the proinsulin gene and accumulated the polypeptide in mature seeds. Protein targeting to cotyledonary protein storage vacuoles was successfully achieved and confirmed with immunocytochemistry assays. The combination of different regulatory sequences was apparently responsible for high stability in protein accumulation, since human proinsulin was detected after seven years under room temperature storage conditions.

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

    PubMed Central

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

    2014-01-01

    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. PMID:25367357

  16. Occurrence of toxigenic fungi and determination of mycotoxins by HPLC-FLD in functional foods and spices in China markets.

    PubMed

    Kong, Weijun; Wei, Riwei; Logrieco, Antonio F; Wei, Jianhe; Wen, Jing; Xiao, Xiaohe; Yang, Meihua

    2014-03-01

    Twenty-four samples including 14 functional foods and 10 spices obtained from Chinese markets were examined for their mould profile. The mycotoxin contamination levels were also determined by an optimized HPLC-FLD method. 124 fungal isolates belonging to four different genera were recovered with Aspergillus and Penicillium as predominant fungi, with an incidence of 66.1% and 15.3%, respectively. In functional foods Aspergillus niger section (57.1%) was isolated more frequently, followed by Aspergillus flavi section (50.0%) and Aspergillus ochraceus section (21.4%), with the most contaminated samples being Coix seeds. Similar fungal presence and frequency were encountered in spice with A. niger section group (60.0%) and A. flavi section (40.0%) as main fungi. Cumin and Pricklyash peel samples showed the highest fungal contamination. Four functional foods and three spices were found to be positive at low levels for mycotoxins including aflatoxin B1 (up to 0.26μg/kg) and ochratoxin A (OTA) (5.0μg/kg). The more frequently detected mycotoxin was AFB1 (16.7%).

  17. A cell-based high-throughput protocol to screen entry inhibitors of highly pathogenic viruses with Traditional Chinese Medicines.

    PubMed

    Yang, Yong; Cheng, Han; Yan, Hui; Wang, Peng-Zhan; Rong, Rong; Zhang, Ying-Ying; Zhang, Cheng-Bo; Du, Rui-Kun; Rong, Li-Jun

    2017-05-01

    Emerging viruses such as Ebola virus (EBOV), Lassa virus (LASV), and avian influenza virus H5N1 (AIV) are global health concerns. Since there is very limited options (either vaccine or specific therapy) approved for humans against these viruses, there is an urgent need to develop prophylactic and therapeutic treatments. Previously we reported a high-throughput screening (HTS) protocol to identify entry inhibitors for three highly pathogenic viruses (EBOV, LASV, and AIV) using a human immunodeficiency virus-based pseudotyping platform which allows us to perform the screening in a BSL-2 facility. In this report, we have adopted this screening protocol to evaluate traditional Chinese Medicines (TCMs) in an effort to discover entry inhibitors against these viruses. Here we show that extracts of the following Chinese medicinal herbs exhibit potent anti-Ebola viral activities: Gardenia jasminoides Ellis, Citrus aurantium L., Viola yedoensis Makino, Prunella vulgaris L., Coix lacryma-jobi L. var. mayuen (Roman.) Stapf, Pinellia ternata (Thunb.) Breit., and Morus alba L. This study represents a proof-of-principle investigation supporting the suitability of this assay for rapid screening TCMs and identifying putative entry inhibitors for these viruses. J. Med. Virol. 89:908-916, 2017. © 2016 Wiley Periodicals, Inc.

  18. 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.

  19. 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

  20. 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.

  1. Detection of aflatoxin B1 in imported food products into Japan by enzyme-linked immunosorbent assay and high performance liquid chromatography.

    PubMed

    Adachi, Y; Hara, M; Kumazawa, N H; Hirano, K; Ueno, I; Egawa, K

    1991-02-01

    In order to detect the presence of aflatoxin B1 (AFB1), the use of the enzyme-linked immunosorbent assay (ELISA) and recovery test was evaluated. The detection limit of ELISA for AFB1 was 1 pg/assay and the recovery from maize spiked with AFB1 exceeded 80%. AFB1 was detected by ELISA in seven out of twelve samples of imported food products including peanut, almond, red pepper, cocoa bean, black pepper, buckwheat, walnut, adlay, soybean, popcorn, and pistachio nut, and by high performance liquid chromatography (HPLC) in four of the samples. However, the content of AFB1 in these samples was less than 10 ng/g of the minimum value authorized by the Japanese sanitation law. These results demonstrate that ELISA is more sensitive than HPLC and imported food products are broadly contaminated with AFB1.

  2. 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.

  3. Facile synthesis of AgCl/polydopamine/Ag nanoparticles with in-situ laser improving Raman scattering effect

    NASA Astrophysics Data System (ADS)

    Zhang, Yan; Zhang, Wenqi; Wang, Lin; Wang, Feng; Yang, Haifeng

    2017-01-01

    We reported a simple and fast method to prepare a composite material of polydopamine (PDA) adlayer covered cubic AgCl core, which was inlaid with Ag nanoparticles (NPs), shortly named as AgCl/PDA/AgNPs. The resultant AgCl/PDA/AgNPs could be employed as surface-enhanced Raman scattering (SERS) substrate for in-situ detection and the SERS activity could be further greatly improved due to the production of more AgNPs upon laser irradiation. With 4-mercaptopyridine (4-Mpy) as the probe molecule, the enhancement factor could reach 107. Additionally, such SERS substrate shows good reproducibility with relative standard deviation of 7.32% and long term stability (after storage for 100 days under ambient condition, SERS intensity decay is less than 25%). In-situ elevating SERS activity of AgCl/PDA/AgNPs induced by laser may be beneficial to sensitive analysis in practical fields.

  4. 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.

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

    PubMed

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

    2016-02-17

    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.

  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. In situ STM investigation of spinodal decomposition and surface alloying during underpotential deposition of Cd on Au(111) from an ionic liquid.

    PubMed

    Pan, Ge-Bo; Freyland, Werner

    2007-07-07

    The electrodeposition and anodic dissolution of Cd on Au(111) in an acidic chloroaluminate ionic liquid (MBIC-AlCl(3), 42 : 58 mol%) have been investigated by cyclic voltammetry and in situ STM. In the Cd underpotential deposition region, various nanostructures can be distinguished. At a potential of 0.95 V vs. Al/Al(iii), a transformation from a well ordered AlCl(4)(-) adlayer to a ( radical3 x radical19) superstructure, presumably due to Cd-AlCl(4)(-) coadsorption, is observed. Reducing the potential to 0.45 V, surface alloying of Cd and Au occurs, which is evidenced for the first time by typical spinodal structures occurring both during deposition and dissolution of the surface alloy layer having a hexagonal structure. At still lower potentials below 0.21 V, a layer-by-layer growth of bulk Cd sets in.

  8. Study of copper underpotential deposition on Au(111) surfaces

    NASA Astrophysics Data System (ADS)

    Xu, J. G.; Wang, X. W.

    1998-06-01

    First-principles total energy calculations are carried out to study the structure of copper underpotential deposition on Au(111) surfaces in sulfuric acid solutions. The norm-conserving method is used to construct the pseudopotentials of all the elements involved. The copper adlayer structure under various copper coverage is investigated. The results show that the proposed honeycomb structure with 2/3 monolayer copper coverage is unstable without the co-adsorption of sulfate. The co-adsorbed sulfate is found to bind to copper. The calculated structural parameters are in general agreement with those obtained from a recent X-ray experiment. In addition, the sulfate adsorption on clean Au(111) surface is studied. The results show that sulfate molecule binds much more weakly with clean Au(111) surfaces. Total energy calculations for bisulfate adsorption suggest that even though it is the dominant species in acidic electrolyte, the adsorbed bisulfate may dissociate thus leave sulfate adsorbed on the surface.

  9. Photoelectron diffraction study of the Si -rich 3C-SiC(001)-(3×2) structure

    NASA Astrophysics Data System (ADS)

    Tejeda, A.; Dunham, D.; García de Abajo, F. J.; Denlinger, J. D.; Rotenberg, E.; Michel, E. G.; Soukiassian, P.

    2004-07-01

    The structure of the Si -rich 3C-SiC(001)-(3×2) surface reconstruction is determined using soft x-ray photoelectron diffraction. Photoelectrons are detected along a full hemispherical sector for different photon energies. A comparison between the experimental data and multiple scattering calculations of the competing models favors a modified version of the two-adlayer asymmetric dimer model. An R -factor analysis has been employed to refine this model. We determine the interlayer spacings of the last six atomic layers and find a corrugation of (0.25±0.10) Å for the atoms in the outermost dimer. Atoms in the second layer dimerize as well, forming rows of long and short dimers.

  10. Self-referenced spectroscopy using plasmon waveguide resonance biosensor

    PubMed Central

    Bahrami, Farshid; Maisonneuve, Mathieu; Meunier, Michel; Aitchison, J. Stewart; Mojahedi, Mo

    2014-01-01

    A plasmon waveguide resonance (PWR) sensor is designed, fabricated, and tested for self-referenced biosensing. The PWR sensor is able to support two different polarizations, TM and TE. The TM polarization has a large sensitivity to variations in the background refractive index while the TE polarization is more sensitive to the surface properties. The ability of the PWR sensor to simultaneously operate in both TM and TE modes is used to decouple the background index variations (bulk effects) from the changes in adlayer thickness (surface effects) via multimode spectroscopy. To benchmark the performance of the PWR, a conventional surface plasmon resonance (SPR) sensor is fabricated and tested under the same conditions. PMID:25136479

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. In situ investigation of growth modes during plasma-assisted molecular beam epitaxy of (0001) GaN

    SciTech Connect

    Koblmueller, G.; Fernandez-Garrido, S.; Calleja, E.; Speck, J. S.

    2007-10-15

    Real-time analysis of the growth modes during homoepitaxial (0001) GaN growth by plasma-assisted molecular beam epitaxy was performed using reflection high energy electron diffraction. A growth mode map was established as a function of Ga/N flux ratio and growth temperature, exhibiting distinct transitions between three-dimensional (3D), layer-by-layer, and step-flow growth modes. The layer-by-layer to step-flow growth transition under Ga-rich growth was surfactant mediated and related to a Ga adlayer coverage of one monolayer. Under N-rich conditions the transition from 3D to layer-by-layer growth was predominantly thermally activated, facilitating two-dimensional growth at temperatures of thermal decomposition.

  16. Surface structure of SiC formed by C60 molecules on a Si(001)-2×1 surface at 800 °C

    NASA Astrophysics Data System (ADS)

    Cheng, C.-P.; Huang, J.-W.; Pi, T.-W.; Lee, H.-H.

    2006-06-01

    Formation of silicon carbide upon deposition of C60 onto Si(001) at an elevated temperature of 800 °C was studied via synchrotron-radiation photoemission and low electron energy diffraction. The molecules are completely decomposed upon hitting on the hot surface, giving rise to a well-order 2×1 pattern. The C 1s and Si 2p core-level spectra, and valence-band spectra indicate characteristics of a Si-terminated β-SiC(001) 2×1 film. Two surface components corresponding to the terminated and ad-dimer Si atoms are well resolved in the Si 2p cores. By the spectral area ratio of both components, the adlayer atoms cover half of the surface, which agrees with the missing-row structure model [W. Lu et al., Phys. Rev. Lett. 81, 2292 (1998)].

  17. Conversion of Langmuir–Blodgett monolayers and bilayers of poly(amic acid) through polyimide to graphene

    NASA Astrophysics Data System (ADS)

    Jo, Hye Jin; Lyu, Ji Hong; Ruoff, Rodney S.; Lim, Hyunseob; In Yoon, Seong; Jeong, Hu Young; Shin, Tae Joo; Bielawski, Christopher W.; Shin, Hyeon Suk

    2017-03-01

    Various solid carbon sources, particularly poly(methyl methacrylate), have been used as precursors to graphene. The corresponding growth process generally involves the decomposition of the solids to hydrocarbon gases followed by their adsorption on metallic substrates (e.g., Cu). We report a different approach that uses a thermally-resistant polyimide (PI) as a carbon precursor. Langmuir–Blodgett films of poly(amic acid) (PAA) were transferred to copper foils and then converted to graphene via a PI intermediate. The Cu foil substrate was also discovered to facilitate the orientation of aromatic moieties upon carbonization process of the PI. As approximately 50% of the initial quantity of the PAA was found to remain at 1000 °C, thermally-stable polymers may reduce the quantity of starting material required to prepare high quality films of graphene. Graphene grown using this method featured a relatively large domain size and an absence of adventitious adlayers.

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

    DOE PAGES

    Walen, Holly; Liu, Da -Jiang; Oh, Junepyo; ...

    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

  19. 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.

  20. 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.

  1. Incorporation of pyrene in polypyrrole/polystyrene magnetic beads.

    PubMed

    Głowala, Paulina; Budniak, Adam; Krug, Pamela; Wysocka, Barbara; Berbeć, Sylwia; Dec, Robert; Dołęga, Izabela; Kacprzak, Kamil; Wojciechowski, Jarosław; Kawałko, Jakub; Kępka, Paweł; Kępińska, Daria; Kijewska, Krystyna; Mazur, Maciej

    2014-10-15

    Pyrene, a fluorescent dye, was incorporated into polystyrene particles coated with polypyrrole. The incorporation was achieved by treating the polypyrrole/polystyrene (PPy/PS) beads in a tetrahydrofuran (THF) solution of the pyrene fluorophore followed by rinsing with methanol. The polystyrene cores of the beads swell in THF, allowing penetration of pyrene molecules into the polystyrene structure. The addition of methanol causes contraction of the swollen polystyrene, which encapsulates the dye molecules inside the beads. It is shown that the polypyrrole coating is permeable with respect to both the dye and the solvent, allowing the transport of molecules between the polystyrene cores and the contacting solution. The polypyrrole adlayer can be used as a matrix for the incorporation of magnetic nanoparticles. Embedded particles provide magnetic functionality to the PPy/PS beads. It is demonstrated that the pyrene-loaded beads can be manipulated with an external magnetic field.

  2. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    SciTech Connect

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Willinger, Marc-Georg; Schloegl, R.

    2016-10-19

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.

  3. 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.

  4. 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.

  5. 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

  6. 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.

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

    PubMed

    Sen, Tapas; Bruce, Ian J

    2012-01-01

    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.

  8. Strong and stable doping of carbon nanotubes and graphene by MoOx for transparent electrodes.

    PubMed

    Hellstrom, Sondra L; Vosgueritchian, Michael; Stoltenberg, Randall M; Irfan, Irfan; Hammock, Mallory; Wang, Yinchao Bril; Jia, Chuancheng; Guo, Xuefeng; Gao, Yongli; Bao, Zhenan

    2012-07-11

    MoO(x) has been used for organic semiconductor doping, but it had been considered an inefficient and/or unstable dopant. We report that MoO(x) can strongly and stably dope carbon nanotubes and graphene. Thermally annealed MoO(x)-CNT composites can form durable thin film electrodes with sheet resistances of 100 Ω/sq at 85% transmittance plain and 85 Ω/sq at 83% transmittance with a PEDOT:PSS adlayer. Sheet resistances change less than 10% over 20 days in ambient and less than 2% with overnight heating to 300 °C in air. The MoO(x) can be easily deposited either by thermal evaporation or from solution-based precursors. Excellent stability coupled with high conductivity makes MoO(x)-CNT composites extremely attractive candidates for practical transparent electrodes.

  9. 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.

  10. 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.

  11. Interactions of Oxygen and Ethylene with Submonolayer Ag Films Supported on Ni(111)

    SciTech Connect

    Alamgir, F.M.; Senanayake, S.; Rettew, R.E.; Meyer, A.; Chen, T.-L.; Petersburg, C.; Flege, J.I.; Falta, J.

    2011-06-01

    We investigate the oxidation of, and the reaction of ethylene with, Ni(111) with and without sub-monolayer Ag adlayers as a function of temperature. The addition of Ag to Ni(111) is shown to enhance the activity towards the ethylene epoxidation reaction, and increase the temperature at which ethylene oxide is stable on the surface. We present a systematic study of the formation of chemisorbed oxygen on the Ag-Ni(111) surfaces and correlate the presence and absence of O{sup 1-} and O{sup 2-} surface species with the reactivity towards ethylene. By characterizing the samples with low-energy electron microscopy (LEEM) in combination with X-ray photoelectron spectroscopy (XPS), we have identified specific growth of silver on step-edge sites and successfully increased the temperature at which the produced ethylene oxide remains stable, a trait which is desirable for catalysis.

  12. Interactions of Oxygen and Ethylene with Submonolayer Ag Films Supported on Ni(111)

    SciTech Connect

    R Rettew; A Meyer; S Senanayake; T Chen; C Petersburg; J Flege; J Falta; F Alamgir

    2011-12-31

    We investigate the oxidation of, and the reaction of ethylene with, Ni(111) with and without sub-monolayer Ag adlayers as a function of temperature. The addition of Ag to Ni(111) is shown to enhance the activity towards the ethylene epoxidation reaction, and increase the temperature at which ethylene oxide is stable on the surface. We present a systematic study of the formation of chemisorbed oxygen on the Ag-Ni(111) surfaces and correlate the presence and absence of O{sup 1-} and O{sup 2-} surface species with the reactivity towards ethylene. By characterizing the samples with low-energy electron microscopy (LEEM) in combination with X-ray photoelectron spectroscopy (XPS), we have identified specific growth of silver on step-edge sites and successfully increased the temperature at which the produced ethylene oxide remains stable, a trait which is desirable for catalysis.

  13. High fidelity neuronal networks formed by plasma masking with a bilayer membrane: analysis of neurodegenerative and neuroprotective processes.

    PubMed

    Hardelauf, Heike; Sisnaiske, Julia; Taghipour-Anvari, Amir Ali; Jacob, Peter; Drabiniok, Evelyn; Marggraf, Ulrich; Frimat, Jean-Philippe; Hengstler, Jan G; Neyer, Andreas; van Thriel, Christoph; West, Jonathan

    2011-08-21

    Spatially defined neuronal networks have great potential to be used in a wide spectrum of neurobiology assays. We present an original technique for the precise and reproducible formation of neuronal networks. A PDMS membrane comprising through-holes aligned with interconnecting microchannels was used during oxygen plasma etching to dry mask a protein rejecting poly(ethylene glycol) (PEG) adlayer. Patterns were faithfully replicated to produce an oxidized interconnected array pattern which supported protein adsorption. Differentiated human SH-SY5Y neuron-like cells adhered to the array nodes with the micron-scale interconnecting tracks guiding neurite outgrowth to produce neuronal connections and establish a network. A 2.0 μm track width was optimal for high-level network formation and node compliance. These spatially standardized neuronal networks were used to analyse the dynamics of acrylamide-induced neurite degeneration and the protective effects of co-treatment with calpeptin or brain derived neurotrophic factor (BDNF).

  14. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    NASA Astrophysics Data System (ADS)

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Schloegl, R.; Willinger, Marc-Georg

    2016-10-01

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene-graphene and graphene-substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.

  15. 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.

  16. Cardioprotective effects of diet with different grains on lipid profiles and antioxidative system in obesity-induced rats.

    PubMed

    Kim, Jung Yun; Shin, Ji Hye; Lee, Sang Sun

    2012-04-01

    In the present study, the nutritional quality of four grains including adlay (AD), buckwheat (BW), glutinous barley (GB), and white rice (WR) were evaluated in terms of plasma lipid parameters, gut transit time, and thickness of the aortic wall in rats. The rats were then raised for 4 weeks on the high-fat diet based on the American Institute of Nutrition-93 (AIN-93 G) diets containing 1 % cholesterol and 20 % dietary lipids. Forty male rats were divided into 4 groups and raised for 4 weeks with a diet containing one of the following grains: WR, AD, BW, or WB. The level of thiobarbituric acid-reactive substances (TBARS) in liver was shown to be higher in rats by the order of those fed WR, AD, GB, and BW. This indicates that other grains decreased oxidative stress in vivo more than WR. The superoxide dismutase, glutathione, glutathione peroxidase, and glutathione reductase levels in the AD, BW, and GB groups were significantly higher than those in the WR group (p < 0.05). Plasma lipid profiles differed significantly according to grain combination, and decreased aortic wall thickness was consistent with the finding of decreased plasma low-density lipoprotein cholesterol (LDL-C) (p < 0.05) and increased high-density lipoprotein (HDL-C) in rats fed AD, BW, and GB (p < 0.001). The antioxidant and hypolipidemic capacities of grains are quite high, especially those of adlay, buckwheat, and glutinous barley. In conclusion, this study has demonstrated that the whole grains had a cardioprotective effect. This effect was related to several mechanisms that corresponded to lowering plasma lipids, decreasing TBARS, and increasing antioxidant activities.

  17. H2O on Pt(111): structure and stability of the first wetting layer

    NASA Astrophysics Data System (ADS)

    Standop, Sebastian; Morgenstern, Markus; Michely, Thomas; Busse, Carsten

    2012-03-01

    We study the structure and stability of the first water layer on Pt(111) by variable-temperature scanning tunneling microscopy. We find that a high Pt step edge density considerably increases the long-range order of the equilibrium \\sqrt{37}\\times \\sqrt{37}{R25.3}°- and \\sqrt{39}\\times \\sqrt{39}{R16.1}°-superstructures, presumably due to the capability of step edges to trap residual adsorbates from the surface. Passivating the step edges with CO or preparing a flat metal surface leads to the formation of disordered structures, which still show the same structural elements as the ordered ones. Coadsorption of Xe and CO proves that the water layer covers the metal surface completely. Moreover, we determine the two-dimensional crystal structure of Xe on top of the chemisorbed water layer which exhibits an Xe-Xe distance close to the one in bulk Xe and a rotation angle of 90° between the close-packed directions of Xe and the close-packed directions of the underlying water layer. CO is shown to replace H2O on the Pt(111) surface as has been deduced previously. In addition, we demonstrate that tunneling of electrons into the antibonding state or from the bonding state of H2O leads to dissociation of the molecules and a corresponding reordering of the adlayer into a \\sqrt{3}\\times \\sqrt{3}{R30}°-structure. Finally, a so far not understood restructuring of the adlayer by an increased tunneling current has been observed.

  18. Observation and control of the surface kinetics of InGaN for the elimination of phase separation

    NASA Astrophysics Data System (ADS)

    Moseley, Michael; Gunning, Brendan; Greenlee, Jordan; Lowder, Jonathan; Namkoong, Gon; Alan Doolittle, W.

    2012-07-01

    The growth of InGaN alloys via Metal-Modulated Epitaxy has been investigated. Transient reflection high-energy electron diffraction intensities for several modulation schemes during the growth of 20% InGaN were analyzed, and signatures associated with the accumulation, consumption, and segregation of excess metal adlayers were identified. A model for shuttered, metal-rich growth of InGaN was then developed, and a mechanism for indium surface segregation was elucidated. It was found that indium surface segregation only occurs after a threshold of excess metal is accumulated, and a method of quantifying this indium surface segregation onset dose is presented. The onset dose of surface segregation was found to be indium-composition dependent and between 1 and 2 monolayers of excess metal. Below this surface threshold off excess metal, metal-rich growth can occur without indium surface segregation. Since at least 2 monolayers of excess metal will accumulate in the case of metal-rich, unshuttered growth of InGaN at the low temperatures required to suppress thermal and spinodal decomposition, this study reveals that some form of modulation must be employed to maintain this adlayer thickness. These theories were applied in the growth of InGaN with varying compositions using Metal-Modulated Epitaxy. Single-phase, high-quality InGaN films with compositions throughout the miscibility gap with root mean square roughnesses less than 0.8 nm were obtained, demonstrating the feasibility of shuttered, metal-rich InGaN growth.

  19. Monitoring the binding processes of black tea thearubigin to the bovine serum albumin surface using quartz crystal microbalance with dissipation monitoring.

    PubMed

    Chitpan, Monthana; Wang, Xiaoyong; Ho, Chi-Tang; Huang, Qingrong

    2007-12-12

    The binding processes of thearubigin, which is one of the two major polyphenols (the other one is theaflavin) that gives black tea its characteristic color and taste, to the bovine serum albumin (BSA) surface have been investigated by quartz crystal microbalance with dissipation monitoring (QCM-D). The mass and thickness of the thearubigin adlayer on BSA surfaces at various thearubigin concentrations, salt concentrations, and pH values have been determined by QCM-D using the Voigt model. Our results show that the adsorption isotherm of thearubigin on the BSA surface can be better described by the Langmuir model than the Freundlich model, suggesting that the thearubigin adsorption on the BSA surface is dominated by specific interactions, such as electrostatic interaction and hydrogen bonding, as evidenced by the stronger thearubigin adsorption at pH below the isoelectric point (pI) of BSA and shifts in the positions of both amide bands in the FTIR spectra of the BSA surface with and without thearubigin adsorption. The addition of salt can also influence the thearubigin binding to BSA surfaces. The salt concentration-enhanced effect at a salt concentration lower than 0.1 M is explained as that an increase of salt concentration can screen the electrostatic repulsion to a larger extent than the electrostatic attraction between thearubigin and BSA. On the other hand, when the salt concentration is higher than 0.1 M, both electrostatic repulsion and attraction can be significantly screened by the higher salt concentration, resulting in the salt concentration-reduced effect. However, when the salt concentration is further increased to 0.4 M, the addition of thearubigin may promote the formation of a certain type of complex with BSA, resulting in the increases of both thickness and mass of the thearubigin adlayer.

  20. Ordered molecular assemblies of substituted bis(phthalocyaninato) rare earth complexes on Au(111): in situ scanning tunneling microscopy and electrochemical studies.

    PubMed

    Ma, Houyi; Yang, Liang-Yueh Ou; Pan, Na; Yau, Shueh-Lin; Jiang, Jianzhuang; Itaya, Kingo

    2006-02-28

    Substituted bis(phthalocyaninato) rare earth complexes ML2 (M = Y and Ce; L = [Pc(OC8H17)8]2, where Pc = phthalocyaninato) were adsorbed onto single crystalline Au(111) electrodes from benzene saturated with either YL2 or CeL2 complex at room temperature. In situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV) were used to examine the structures and the redox reactions of these admolecules on Au(111) electrodes in 0.1 mol dm(-3) HClO4. The CVs obtained with YL2- and CeL2-coated Au(111) electrodes respectively contained two and three pairs of redox peaks between 0 and 1.0 V (versus reversible hydrogen electrode). STM molecular resolution revealed that YL2 and CeL2 admolecules were imaged as spherical protrusions separated by 2.3 nm, which suggests that they were oriented with their molecular planes parallel to the unreconstructed Au(111)-(1 x 1). Both molecules when adsorbing from approximately micromolar benzene dosing solutions produced mainly ordered arrays characterized as (8 x 5 radical3)rect (theta = 0.0125). The redox reactions occurring between 0.2 and 1.0 V caused no change in the adlayer, but they were desorbed or oxidized at the negative and positive potential limits. The processes of adsorption and desorption at the negative potentials were reversible to the modulation of potential. Electrochemical impedance spectroscopy (EIS) and CV measurements showed that YL2 and CeL2 adlayers could block the adsorption of perchlorate anions and mediating electron transfer at the Au(111) electrode, leading to the enhancement of charge transfer for the ferro/ferricyanide redox couple.

  1. Controlling adsorption and passivation properties of bovine serum albumin on silica surfaces by ionic strength modulation and cross-linking.

    PubMed

    Park, Jae Hyeon; Sut, Tun Naw; Jackman, Joshua A; Ferhan, Abdul Rahim; Yoon, Bo Kyeong; Cho, Nam-Joon

    2017-03-15

    Understanding the physicochemical factors that influence protein adsorption onto solid supports holds wide relevance for fundamental insights into protein structure and function as well as for applications such as surface passivation. Ionic strength is a key parameter that influences protein adsorption, although how its modulation might be utilized to prepare well-coated protein adlayers remains to be explored. Herein, we investigated how ionic strength can be utilized to control the adsorption and passivation properties of bovine serum albumin (BSA) on silica surfaces. As protein stability in solution can influence adsorption kinetics, the size distribution and secondary structure of proteins in solution were first characterized by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), and circular dichroism (CD) spectroscopy. A non-monotonic correlation between ionic strength and protein aggregation was observed and attributed to colloidal agglomeration, while the primarily α-helical character of the protein in solution was maintained in all cases. Quartz crystal microbalance-dissipation (QCM-D) experiments were then conducted in order to track protein adsorption onto silica surfaces as a function of ionic strength, and the measurement responses indicated that total protein uptake at saturation coverage is lower with increasing ionic strength. In turn, the QCM-D data and the corresponding Voigt-Voinova model analysis support that the surface area per bound protein molecule is greater with increasing ionic strength. While higher protein uptake under lower ionic strengths by itself did not result in greater surface passivation under subsequent physiologically relevant conditions, the treatment of adsorbed protein layers with a gluteraldehyde cross-linking agent stabilized the bound protein in this case and significantly improved surface passivation. Collectively, our findings demonstrate that ionic strength modulation influences BSA adsorption

  2. 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.

  3. Mussel inspired preparation of MoS2 based polymer nanocomposites: The case of polyPEGMA

    NASA Astrophysics Data System (ADS)

    Zeng, Guangjian; Liu, Meiying; Liu, Xinhua; Huang, Qiang; Xu, Dazhuang; Mao, Liucheng; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2016-11-01

    In this work, we report a facile strategy to prepare PEGylated MoS2 nanosheets through the combination of mussel inspired chemistry and Michael addition reaction. The MoS2 nanosheets were obtained from lithium intercalation and exfoliation method. Meanwhile, the amino-contained poly((polyethylene glycol) methyl ether methacrylate) (PPEGMA) were obtained via chain transfer free radical polymerization using cysteamine hydrochloride as the chain transfer agents and PEGMA as the monomer. To introduce PPEGMA on MoS2 nanosheets, polydopamine (PDA) thin films were first coated on the surface of MoS2 nanosheets through self polymerization of dopamine as the ad-layers, which can react with amino-terminated PPEGMA through Michael addition reaction. The structure, morphology and chemical compositions of MoS2 nanosheets and MoS2-PDA-PPEGMA have been characterized by various characterization techniques. The results demonstrated that the amino-terminated PPEGMA can be successfully immobilized on MoS2 nanosheets via PDA thin films as the ad-layers. More importantly, the strategy described in this work could also be utilized for surface immobilization of various polymers on many other materials and surfaces because of the universal adhesion of PDA and the good monomer applicability of chain transfer free radical polymerization. Taken together, we developed a facile and versatile method to fabricate multifunctional MoS2 based polymer nanocomposites with designable properties and applications via combination of mussel inspired and chain transfer free radical polymerization. The resultant composites are expected to be potentially used for drug delivery and photothermal cancer treatment.

  4. 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.

  5. 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.

  6. A survey for isoenzymes of glucosephosphate isomerase, phosphoglucomutase, glucose-6-phosphate dehydrogenase and 6-Phosphogluconate dehydrogenase in C3-, C 4-and crassulacean-acid-metabolism plants, and green algae.

    PubMed

    Herbert, M; Burkhard, C; Schnarrenberger, C

    1979-01-01

    Two isoenzymes each of glucosephosphate isomerase (EC 5.3.1.9), phosphoglucomutase (EC 2.7.5.1), glucose-6-phosphate dehydrogenase (EC 1.1.1.49) and 6-phosphogluconate dehydrogenase (EC 1.1.1.43) were separated by (NH4)2SO4 gradient solubilization and DEAE-cellulose ion-exchange chromatography from green leaves of the C3-plants spinach (Spinacia oleracea L.), tobacco (Nicotiana tabacum L.) and wheat (Triticum aestivum L.), of the Crassulacean-acid-metabolism plants Crassula lycopodioides Lam., Bryophyllum calycinum Salisb. and Sedum rubrotinctum R.T. Clausen, and from the green algae Chlorella vulgaris and Chlamydomonas reinhardii. After isolation of cell organelles from spinach leaves by isopyenic centrifugation in sucrose gradients one of two isoenzymes of each of the four enzymes was found to be associated with whole chloroplasts while the other was restricted to the soluble cell fraction, implying the same intracellular distribution of these isoenzymes also in the other species.Among C4-plants, glucose-6-phosphate dehydrogenase and 6-phosphogluconate dehydrogenase were found in only one form in corn (Zea mays L.), sugar cane (Saccharum officinarum L.) and Coix lacrymajobi L., but as two isoenzymes in Atriplex spongiosa L. and Portulaca oleracea L. In corn, the two dehydrogenases were mainly associated with isolated mesophyll protoplasts while in Atriplex spongiosa they were of similar specific activity in both mesophyll protoplasts and bundle-sheath strands. In all five C4-plants three isoenzymes of glucosephosphate isomerase and phosphoglucomutase were found. In corn two were localized in the bundle-sheath strands and the third one in the mesophyll protoplasts. The amount of activity of the enzymes was similar in each of the two cell fractions. Apparently, C4 plants have isoenzymes not only in two cell compartments, but also in physiologically closely linked cell types such as mesophyll and bundle-sheath cells.

  7. Southern rice black-streaked dwarf virus: a white-backed planthopper-transmitted fijivirus threatening rice production in Asia.

    PubMed

    Zhou, Guohui; Xu, Donglin; Xu, Dagao; Zhang, Maoxin

    2013-09-09

    Southern rice black-streaked dwarf virus (SRBSDV), a non-enveloped icosahedral virus with a genome of 10 double-stranded RNA segments, is a novel species in the genus Fijivirus (family Reoviridae) first recognized in 2008. Rice plants infected with this virus exhibit symptoms similar to those caused by Rice black-streaked dwarf virus. Since 2009, the virus has rapidly spread and caused serious rice losses in East and Southeast Asia. Significant progress has been made in recent years in understanding this disease, especially about the functions of the viral genes, rice-virus-insect interactions, and epidemiology and control measures. The virus can be efficiently transmitted by the white-backed planthopper (WBPH, Sogatella furcifera) in a persistent circulative propagative manner but cannot be transmitted by the brown planthopper (Nilaparvata lugens) and small brown planthopper (Laodelphax striatellus). Rice, maize, Chinese sorghum (Coix lacryma-jobi) and other grass weeds can be infected via WBPH. However, only rice plays a major role in the virus infection cycle because of the vector's preference. In Southeast Asia, WBPH is a long-distance migratory rice pest. The disease cycle can be described as follows: SRBSDV and its WBPH vector overwinter in warm tropical or sub-tropical areas; viruliferous WBPH adults carry the virus from south to north via long-distance migration in early spring, transmit the virus to rice seedlings in the newly colonized areas, and lay eggs on the infected seedlings; the next generation of WBPHs propagate on infected seedlings, become viruliferous, disperse, and cause new disease outbreaks. Several molecular and serological methods have been developed to detect SRBSDV in plant tissues and individual insects. Control measures based on protection from WBPH, including seedbed coverage, chemical seed treatments, and chemical spraying of seedlings, have proven effective in China.

  8. Selectively labeling the heterologous protein in Escherichia coli for NMR studies: a strategy to speed up NMR spectroscopy.

    PubMed

    Almeida, F C; Amorim, G C; Moreau, V H; Sousa, V O; Creazola, A T; Américo, T A; Pais, A P; Leite, A; Netto, L E; 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 (1)H/(15)N heteronuclear correlation two-dimensional NMR spectrum (HMQC) of the selective (15)N-labeled thioredoxin without any purification is remarkably similar to the spectrum of the purified protein. The method has high yields and a good (1)H/(15)N 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 (15)N-edited spectrum of Opaque 2 LZ showed only the resonances of the protein of heterologous expression (Opaque 2 LZ) while the (1)H 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.

  9. 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.

  10. Nanostructured organic and inorganic thin films with novel molecular recognition properties

    NASA Astrophysics Data System (ADS)

    Twardowski, Mariusz Z.

    An important theme in surface/interface science is the development of molecular level understandings of interactions at solid-liquid interfaces. The study of molecular recognition at such interfaces is well suited for modeling with self-assembled monolayers of alkanethiols (SAMs). For optimal studies, the SAM must be defect-free. Towards this end, a chemical treatment of the gold substrate was developed, consisting of a sequential treatment in "piranha" followed by dilute aqua regia. We found that the SAMs assembled on these treated substrates had exceptional barrier properties as measured by cyclic voltammetry(CV). X-ray diffraction(XRD) indicated that oxidative treatment induces significant bulk recrystallization of the metal. The dynamics suggest that recrystallization results from preferential dissolution of Au and/or impurities present at grain boundaries, leading to unpinning and merger into larger grains. Supported lipid layers were formed via fusion of unilamellar vesicles of 1,2-dimyristoyl-sn-glycero-3-phosphocholine(DMPC) to mixed SAMs containing ferrocene-functionalized hexadecanethiol chains(FcCO 2C16SH). The structures were characterized by several methods, including CV, ellipsometry and surface plasmon resonance(SPR). Studies revealed that the adsorbed DMPC strongly influences the interactions of the tethered ferrocene groups with secondary aqueous molecular redox probes. Permselective properties are seen. We believe that molecular scale defect structures in the adsorbed DMPC layer confer these molecular discrimination properties. Unilamellar vesicles of DMPC and varying quantities of 1,2-dimyristoyl-sn-glycero-3-[phospho-rac-(1-glycerol)(sodium salt)(DMPG) were used to deposit lipid bilayer assemblies on SAMs. The coverages of the layers were measured with SPR and decreased with increasing DMPG. The assembly is reversible and the lipid adlayer removable with ethanol. Effects of the adsorbed lipid layer on the electrochemical interactions of the

  11. Growth and decay of the Pd(1 1 1)-Pd 5O 4 surface oxide: Pressure-dependent kinetics and structural aspects

    NASA Astrophysics Data System (ADS)

    Gabasch, Harald; Unterberger, Werner; Hayek, Konrad; Klötzer, Bernhard; Kresse, Georg; Klein, Christof; Schmid, Michael; Varga, Peter

    2006-01-01

    Growth and decomposition of the Pd 5O 4 surface oxide on Pd(1 1 1) were studied at sample temperatures between 573 and 683 K and O 2 gas pressures between 10 -7 and 6 × 10 -5 mbar, by means of an effusive O 2 beam from a capillary array doser, scanning tunnelling microscopy (STM) and thermal desorption spectrometry (TDS). Exposures beyond the p(2 × 2)O adlayer (saturation coverage 0.25) at 683 K (near thermodynamic equilibrium with respect to Pd 5O 4 surface oxide formation) lead to incorporation of additional oxygen into the surface. To initiate the incorporation, a critical pressure beyond the thermodynamic stability limit of the surface oxide is required. This thermodynamic stability limit is near 8.9 × 10 -6 mbar at 683 K, in good agreement with calculations by density functional theory. A controlled kinetic study was feasible by generating nuclei by only a short O 2 pressure pulse and then following further growth kinetics in the lower (10 -6 mbar) pressure range. Growth of the surface oxide layer at a lower temperature (573 K) studied by STM is characterized by a high degree of heterogeneity. Among various metastable local structures, a seam of disordered oxide formed at the step edges is a common structural feature characteristic of initial oxide growth. Further oxide nucleation appears to be favoured along the interface between the p(2 × 2)O structure and these disordered seams. Among the intermediate phases one specifically stable phase was detected both during growth and decomposition of the Pd 5O 4 layer. It is hexagonal with a distance of about 0.62 nm between the protrusions. Its well-ordered form is a (√{67}×√{67})R12.2° superstructure. Isothermal decay of the Pd 5O 4 oxide layer at 693 K involves at first a rearrangement into the (√{67}×√{67})R12.2° structure, indicating its high-temperature stability. This structure can break up into small clusters of uniform size and leaves a free metal surface area covered by a p(2 × 2)O adlayer

  12. 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

  13. ReaxFF Grand Canonical Monte Carlo simulation of adsorption and dissociation of oxygen on platinum (111)

    NASA Astrophysics Data System (ADS)

    Valentini, Paolo; Schwartzentruber, Thomas E.; Cozmuta, Ioana

    2011-12-01

    Atomic-level Grand Canonical Monte Carlo (GCMC) simulations equipped with a reactive force field (ReaxFF) are used to study atomic oxygen adsorption on a Pt(111) surface. The off-lattice GCMC calculations presented here rely solely on the interatomic potential and do not necessitate the pre-computation of surface adlayer structures and their interpolation. As such, they provide a predictive description of adsorbate phases. In this study, validation is obtained with experimental evidence (steric heats of adsorption and isotherms) as well as DFT-based state diagrams available in the literature. The ReaxFF computed steric heats of adsorption agree well with experimental data, and this study clearly shows that indirect dissociative adsorption of O2 on Pt(111) is an activated process at non-zero coverages, with an activation energy that monotonically increases with coverage. At a coverage of 0.25 ML, a highly ordered p(2 × 2) adlayer is found, in agreement with several low-energy electron diffraction observations. Isotherms obtained from the GCMC simulations compare qualitatively and quantitatively well with previous DFT-based state diagrams, but are in disagreement with the experimental data sets available. ReaxFF GCMC simulations at very high coverages show that O atoms prefer to bind in fcc hollow sites, at least up to 0.8 ML considered in the present work. At moderate coverages, little to no disorder appears in the Pt lattice. At high coverages, some Pt atoms markedly protrude out of the surface plane. This observation is in qualitative agreement with recent STM images of an oxygen covered Pt surface. The use of the GCMC technique based on a transferable potential is particularly valuable to produce more realistic systems (adsorbent and adsorbate) to be used in subsequent dynamical simulations (Molecular Dynamics) to address recombination reactions (via either Eley-Rideal or Langmuir-Hinshelwood mechanisms) on variously covered surfaces. By using GCMC and Molecular

  14. Aluminum and copper chemical vapor deposition on fluoropolymer dielectrics and subsequent interfacial interactions

    NASA Astrophysics Data System (ADS)

    Sutcliffe, Ronald David

    Fluoropolymers have been proposed as a low capacitance replacement for silica glasses currently used in the microelectronics industry as interlevel dielectrics (ILDs). Fluoropolymers are particularly attractive due to their low dielectric constants (2.4-1.9) and chemical inertness. However, there are a number of issues that need to be addressed before fluoropolymers can be successfully integrated into microelectronic devices. One such issue is the area of the metallization of fluoropolymers. Problems with adhesion and diffusion at the metal/fluoropolymer interface have thus far limited the use of fluoropolymer ILDs in integrated circuits (ICs). This study is an investigation of the chemical vapor deposition (CVD) of aluminum and copper on fluoropolymer surfaces and the subsequent inter-facial interactions. The fluoropolymers used are known commercially as Teflon-AF (a co-polymer of 2,2-bis(tetrafluoromethyl)-4,5-difluoro-1,3-dioxole and tetrafluoroethylene) and Parylene AF-4 (a homopolymer of alpha,alpha,alphasp', alphasp'-tetrafluoro-p-xylene). CVD was accomplished by condensing the organometallic precursors on the polymer surfaces at low temperatures (˜115 K) and subsequent annealing to higher temperatures in ultra-high vacuum. The interactions between deposition species and the polymer substrates were monitored by x-ray photoelectron spectroscopy (XPS). It was found that a reaction occurs between trimethylaluminum, the polymer surface, and physisorbed water at or below 300 K, producing Al-F, Al-O, and Al-C bonds. The reaction produces a thermally stable aluminum oxide film on the fluoropolymer surface. A fluoride concentration gradient exists across the aluminum adlayer with increasing fluorination towards the adlayer/polymer interface. Annealing to higher temperature results in further defluorination of the polymer surface and additional Al-F formation. Aluminum CVD on a Parylene AF-4 surface modified by exposure to *OH flux results in increased aluminum

  15. Impact of the growth on the stability instability transition at Si (111) during step bunching induced by electromigration

    NASA Astrophysics Data System (ADS)

    Métois, J. J.; Stoyanov, S.

    1999-10-01

    The central result of this work is the definite proof that the mechanisms of the direct current induced step bunching in the middle and high temperature domains are different. We used the recently developed technique for reflection electron microscopy (REM) observation of Si surfaces during equilibrium and during crystal growth to document the impact of the growth on the process of step bunching induced by direct current heating of an Si crystal. We found completely different effects of crystal growth on the stability of the vicinal surfaces in the two temperature domains 1160-1240°C and 1260-1320°C. In the high temperature domain step bunching takes place at step-down direction of the electric current during sublimation, equilibrium and growth; whereas in the 1160-1240°C domain bunching takes place at step-up current during sublimation and at step-down current during growth. These findings support the concept of local mass transport in the high temperature domain — the surface migration of adatoms is effectively interrupted at each step by a high rate exchange between the adlayer and the crystal phase. At 1160-1240°C the mass transport is global — adatoms easily cross the steps without taking part in the crystal-adlayer exchange. Since earlier studies of other researchers support the concept of local mass transport in the low temperature domain, 900-1050°C, a difficult question arises — why do the properties of the steps, with respect to the mass transport over the crystal surface, have a temperature dependence which is not monotonous? To explain the transition from local mass transport in the low temperature domain to global mass transport in the middle temperature domain we advance a hypothesis for a transition from a low temperature state of adsorption (Takayanagi-like adatoms, existing above the (7×7)↔(1×1) transition) to a high temperature state of adsorption (adatom with three dangling bonds) with much lower activation energy for desorption.

  16. Mixed DNA/Oligo(ethylene glycol) Functionalized Gold Surface Improve DNA Hybridization in Complex Media

    SciTech Connect

    Lee,C.; Gamble, L.; Grainger, D.; Castner, D.

    2006-01-01

    Reliable, direct 'sample-to-answer' capture of nucleic acid targets from complex media would greatly improve existing capabilities of DNA microarrays and biosensors. This goal has proven elusive for many current nucleic acid detection technologies attempting to produce assay results directly from complex real-world samples, including food, tissue, and environmental materials. In this study, we have investigated mixed self-assembled thiolated single-strand DNA (ssDNA) monolayers containing a short thiolated oligo(ethylene glycol) (OEG) surface diluent on gold surfaces to improve the specific capture of DNA targets from complex media. Both surface composition and orientation of these mixed DNA monolayers were characterized with x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS). XPS results from sequentially adsorbed ssDNA/OEG monolayers on gold indicate that thiolated OEG diluent molecules first incorporate into the thiolated ssDNA monolayer and, upon longer OEG exposures, competitively displace adsorbed ssDNA molecules from the gold surface. NEXAFS polarization dependence results (followed by monitoring the N 1s{yields}{pi}* transition) indicate that adsorbed thiolated ssDNA nucleotide base-ring structures in the mixed ssDNA monolayers are oriented more parallel to the gold surface compared to DNA bases in pure ssDNA monolayers. This supports ssDNA oligomer reorientation towards a more upright position upon OEG mixed adlayer incorporation. DNA target hybridization on mixed ssDNA probe/OEG monolayers was monitored by surface plasmon resonance (SPR). Improvements in specific target capture for these ssDNA probe surfaces due to incorporation of the OEG diluent were demonstrated using two model biosensing assays, DNA target capture from complete bovine serum and from salmon genomic DNA mixtures. SPR results demonstrate that OEG incorporation into the ssDNA adlayer improves surface resistance to both nonspecific DNA and protein

  17. 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

  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. Water accommodation on ice and organic surfaces: insights from environmental molecular beam experiments.

    PubMed

    Kong, Xiangrui; Thomson, Erik S; Papagiannakopoulos, Panos; Johansson, Sofia M; Pettersson, Jan B C

    2014-11-26

    Water uptake on aerosol and cloud particles in the atmosphere modifies their chemistry and microphysics with important implications for climate on Earth. Here, we apply an environmental molecular beam (EMB) method to characterize water accommodation on ice and organic surfaces. The adsorption of surface-active compounds including short-chain alcohols, nitric acid, and acetic acid significantly affects accommodation of D2O on ice. n-Hexanol and n-butanol adlayers reduce water uptake by facilitating rapid desorption and function as inefficient barriers for accommodation as well as desorption of water, while the effect of adsorbed methanol is small. Water accommodation is close to unity on nitric-acid- and acetic-acid-covered ice, and accommodation is significantly more efficient than that on the bare ice surface. Water uptake is inefficient on solid alcohols and acetic acid but strongly enhanced on liquid phases including a quasi-liquid layer on solid n-butanol. The EMB method provides unique information on accommodation and rapid kinetics on volatile surfaces, and these studies suggest that adsorbed organic and acidic compounds need to be taken into account when describing water at environmental interfaces.

  20. First-principles study of the adsorption of MgO molecules on a clean Fe(001) surface

    NASA Astrophysics Data System (ADS)

    Wiśnios, Damian; Kiejna, Adam; Korecki, Józef

    2015-10-01

    The adsorption of MgO molecules on a Fe(001) surface was studied using density functional theory and projector augmented-wave methods. The energetically most favored configurations for different adsorption sites considered were identified. The most preferable adsorption geometry is when the MgO molecules are parallel to the surface, with Mg in the interstitial site and O in the on-top site of the Fe atom. During the adsorption of subsequent MgO molecules in this geometry, a sharp, nonoxidized interface is formed between the MgO adlayer and the Fe(001) surface. The adsorption of MgO perpendicular to the surface, with oxygen incorporated in the topmost Fe layer, is less probable, but it may lead to the formation of the FeO layer when stabilized with an excess of oxygen atoms. Structural, electronic, and magnetic properties of both interface types were examined for the MgO coverage from 1/9 to 1 monolayer (ML). Electronic and magnetic properties are sensitive to the MgO coverage. For lower coverage of MgO, clear hybridization between the Fe 3 d and O 2 p states is shown. The average magnetic moment of the surface Fe atoms is reduced with coverage, achieving 2.78 μB for 1 ML of MgO.

  1. Infrared spectroscopy of molecular submonolayers on surfaces by infrared scanning tunneling microscopy: tetramantane on Au111.

    PubMed

    Pechenezhskiy, Ivan V; Hong, Xiaoping; Nguyen, Giang D; Dahl, Jeremy E P; Carlson, Robert M K; Wang, Feng; Crommie, Michael F

    2013-09-20

    We have developed a new scanning-tunneling-microscopy-based spectroscopy technique to characterize infrared (IR) absorption of submonolayers of molecules on conducting crystals. The technique employs a scanning tunneling microscope as a precise detector to measure the expansion of a molecule-decorated crystal that is irradiated by IR light from a tunable laser source. Using this technique, we obtain the IR absorption spectra of [121]tetramantane and [123]tetramantane on Au(111). Significant differences between the IR spectra for these two isomers show the power of this new technique to differentiate chemical structures even when single-molecule-resolved scanning tunneling microscopy (STM) images look quite similar. Furthermore, the new technique was found to yield significantly better spectral resolution than STM-based inelastic electron tunneling spectroscopy, and to allow determination of optical absorption cross sections. Compared to IR spectroscopy of bulk tetramantane powders, infrared scanning tunneling microscopy (IRSTM) spectra reveal narrower and blueshifted vibrational peaks for an ordered tetramantane adlayer. Differences between bulk and surface tetramantane vibrational spectra are explained via molecule-molecule interactions.

  2. 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.

  3. Antioxidant properties of certain cereals as affected by food-grade bacteria fermentation.

    PubMed

    Wang, Chung-Yi; Wu, Sz-Jie; Shyu, Yuan-Tay

    2014-04-01

    The effects of fermentation by 2 food-grade bacteria (Bacillus subtilis and Lactobacillus plantarum) on antioxidant activities and the contents of phenolics and flavonoids in 4 cereals (specifically adlay, chestnut, lotus seed, and walnut) were determined and compared with those of their non-fermented counterparts. Results showed that antioxidant properties observed in the fermented and non-fermented cereals may vary with fermented starters. Fermentation was observed to increase the phenolic and flavonoid contents of the extracts. The effects on Bacillus-fermented cereals were stronger than on Lactobacillus-fermented cereals. In IC50 values (mg/mL) of extracts, the extracts of fermented cereal showed a stronger DPPH radical scavenging and ferric-reducing activities. Fermentation did not significantly alter the Fe(2+)-chelating activity in the extracts of chestnuts and lotus seeds. All cereals were shown significantly inhibited the production of LPS-induced intracellular reactive oxygen species (ROS) without creating obvious cytotoxic effects in the macrophage cells. These results suggest that the fermentation process enables cereal-based foods with enhanced antioxidant capacities to contribute to health and nutritional improvements in consumers.

  4. Influence of poly(ethylene oxide)-based copolymer on protein adsorption and bacterial adhesion on stainless steel: modulation by surface hydrophobicity.

    PubMed

    Yang, Yi; Rouxhet, Paul G; Chudziak, Dorota; Telegdi, Judit; Dupont-Gillain, Christine C

    2014-06-01

    The aim of the present work is to study the adhesion of Pseudomonas NCIMB 2021, a typical aerobic marine microorganism, on stainless steel (SS) substrate. More particularly, the potential effect on adhesion of adsorbed poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer is investigated. Bacterial attachment experiments were carried out using a modified parallel plate flow chamber, allowing different surface treatments to be compared in a single experiment. The amount of adhering bacteria was determined via DAPI staining and fluorescence microscopy. X-ray photoelectron spectroscopy (XPS) was used to characterize the surface chemical composition of SS and hydrophobized SS before and after PEO-PPO-PEO adsorption. The adsorption of bovine serum albumin (BSA), a model protein, was investigated to test the resistance of PEO-PPO-PEO layers to protein adsorption. The results show that BSA adsorption and Pseudomonas 2021 adhesion are significantly reduced on hydrophobized SS conditioned with PEO-PPO-PEO. Although PEO-PPO-PEO is also found to adsorb on SS, it does not prevent BSA adsorption nor bacterial adhesion, which is attributed to different PEO-PPO-PEO adlayer structures on hydrophobic and hydrophilic surfaces. The obtained results open the way to a new strategy to reduce biofouling on metal oxide surfaces using PEO-PPO-PEO triblock copolymer.

  5. 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.

  6. Density functional theory study of water dissociation in a double water bilayer with or without coadsorption of CO on Pt(111)

    NASA Astrophysics Data System (ADS)

    Wang, J. G.; Hammer, B.

    2006-05-01

    Using density functional theory, we investigate the structure of the double water bilayer with or without coadsorption of CO on Pt(111). The double water bilayer consists of two bilayers. Each bilayer is buckled with every second water molecule being closer to the surface than every other water molecule. CO is found to adsorb most strongly when substituting in the first bilayer, the water molecule closest to the surface. Dissociation of H2O in the water bilayer (with or without CO) is further considered. A great number of pathways for the dissociation are studied. These include homolytic pathways where both dissociation products end up adsorbed on the Pt surface and heterolytic pathways where only the OH is adsorbed, while a proton is transferred to the water adlayers. We find that the heterolytic dissociation pathways are energetically more favorable than the homolytic ones, yet they are all rather endothermic. The most favorable pathways found have reaction energies of 0.60 and 0.52eV without and with CO present. The corresponding activation energies are 0.99 and 0.53eV, respectively.

  7. A novel gas-vacuum interface for environmental molecular beam studies

    NASA Astrophysics Data System (ADS)

    Johansson, Sofia M.; Kong, Xiangrui; Papagiannakopoulos, Panos; Thomson, Erik S.; Pettersson, Jan B. C.

    2017-03-01

    Molecular beam techniques are commonly used to obtain detailed information about reaction dynamics and kinetics of gas-surface interactions. These experiments are traditionally performed in vacuum and the dynamic state of surfaces under ambient conditions is thereby excluded from detailed studies. Herein we describe the development and demonstration of a new vacuum-gas interface that increases the accessible pressure range in environmental molecular beam (EMB) experiments. The interface consists of a grating close to a macroscopically flat surface, which allows for experiments at pressures above 1 Pa including angularly resolved measurements of the emitted flux. The technique is successfully demonstrated using key molecular beam experiments including elastic helium and inelastic water scattering from graphite, helium and light scattering from condensed adlayers, and water interactions with a liquid 1-butanol surface. The method is concluded to extend the pressure range and flexibility in EMB studies with implications for investigations of high pressure interface phenomena in diverse fields including catalysis, nanotechnology, environmental science, and life science. Potential further improvements of the technique are discussed.

  8. Studies of high coverage oxidation of the Cu(100) surface using low energy positrons

    NASA Astrophysics Data System (ADS)

    Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

    2012-02-01

    The study of oxidation of single crystal metal surfaces is important in understanding the corrosive and catalytic processes associated with thin film metal oxides. The structures formed on oxidized transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which result from the diffusion of oxygen into subsurface regions. In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. The results of calculations of positron binding energy, positron work function, and annihilation characteristics of surface trapped positrons with relevant core electrons as function of oxygen coverage are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES).

  9. 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.

  10. 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

  11. Comparative investigation of underpotential deposition of Ag from aqueous and ionic electrolytes: An electrochemical and in situ STM study.

    PubMed

    Borissov, D; Aravinda, C L; Freyland, W

    2005-06-16

    Underpotential deposition (UPD) of Ag on Au(111) has been studied with two different electrolytes: aqueous 0.1 M H2SO4 solution in comparison with the ionic liquid 1-butyl-3-methylimidazolium chloride BMICl + AlCl3. Of particular interest is the distinct behavior of 2D phase formation at both interfaces, which has been investigated by cyclic and linear sweep voltammetry in combination with in situ electrochemical scanning tunneling microscopy (STM). It is found that one monolayer (ML) of Ag is formed in the UPD region in both electrolytes. In aqueous solution, atomically resolved STM images at 500 mV versus Ag/Ag+ show a (3 x 3) adlayer of Ag, whereas after sweeping the potential just before the commencement of the bulk Ag deposition, a transition from expanded (3 x 3) to pseudomorphic ML of Ag on Au(111) occurs. In BMICl-AlCl3, the first UPD process of Ag exhibits two peaks at 410 and 230 mV indicating that two distinct processes on the surface take place. For the first time, STM images with atomic resolution reveal a transition from an inhomogeneous to an ordered phase with a (square root of 3 x square root of 3)R30 degrees structure and an adsorption of AlCl4- anions having a superlattice of (1.65 x square root of 3)R30 degrees preceding the deposition of Ag.

  12. Microgravimetric and voltammetric study of Zn underpotential deposition on platinum in alkaline medium

    NASA Astrophysics Data System (ADS)

    Calegaro, M. L.; Santos, M. C.; Miwa, D. W.; Machado, S. A. S.

    2005-03-01

    The microgravimetric and voltammetric responses of a polycrystalline Pt electrode in 0.1 mol L -1 NaOH solution in the presence and the absence of 1.6 × 10 -4 Zn 2+, at 0.1 V s -1 were analyzed. During the positive potential sweep, the water molecules are progressively substituted by OH - ions, prior to PtO formation. The voltammetric charges obtained under the Zn ads dissolution peaks suggest that 0.7 monolayers are deposited, with each Zn ad-atom occupying one active site and transferring two electrons. The total loss of mass due to the dissolution of the Zn ad-layer was 136.6 ng cm -2 and the mass increase due to PtO formation was found to be only 12 ng cm -2 less than the theoretical ones, 157.5 and 37.4 ng cm -2, respectively, indicating that both processes are overlapped. In this way it is proposed that an adsorbed by-layer of Zn and OH - ions is formed.

  13. Self-assembly of thiophene derivatives on highly oriented pyrolytic graphite: hydrogen bond effect.

    PubMed

    Xu, Li-Ping; Liu, Yibiao; Zhao, Jing; Wang, Shuqi; Lin, Chen-Sheng; Zhang, Rui-Qin; Wen, Yongqiang; Du, Hongwu; Zhang, Xueji

    2013-02-01

    In this paper, to elucidate the hydrogen bond effect on the assembly behavior, we studied the assembly structures of two carboxylic substituted thiophene derivatives on highly oriented pyrolytic graphite (HOPG) by scanning tunneling microscopy. Here thiophene-2-carboxylic acid (TCA) and thiophene-2,5-dicarboxylic acid (TDA) were employed. TDA molecules spontaneously adsorb on the HOPG surface and self-organize into a two-dimensional (2D) assembly with well-defined structure. Two types of domain could be observed. Each TDA molecule appears as a round circle with two small faint dots and forms hydrogen bonds with neighbours. Besides monolayer structure, a bilayer structure of TDA adlayer on HOPG was also observed in this research. Remnant TDA molecules adsorb on the monolayer of TDA and bilayer structure is formed. In contrast to TDA, no ordered structure of TCA on HOPG can be observed. TCA molecules have high propensity to form dimers through H-bond between carboxylic groups. But TCA dimer is not stable enough for either adsorption or imaging. Our result provides a new example for understanding hydrogen effect on stabilizing and controlling two-dimensional assembly structure and is helpful for surface nanofabrication and development of electric nanodevices.

  14. Scattering, Adsorption, and Langmuir-Hinshelwood Desorption Models for Physisorptive and Chemisorptive Gas-Surface Systems

    NASA Astrophysics Data System (ADS)

    Bentley, Brook I.

    Surface effects limit the performance of hypersonic vehicles, micro-electro-mechanical devices, and directed energy systems. This research develops methods to predict adsorption, scattering, and thermal desorption of molecules on a surface. These methods apply to physisorptive (adsorption and scattering) and chemisorptive (thermal desorption) gas-surface systems. Engineering and design applications will benefit from these methods, hence they are developed under the Direct Simulation Monte Carlo construct. The novel adsorption and scattering contribution, the Modified Kisliuk with Scattering method, predicts angular and energy distributions, and adsorption probabilities. These results agree more closely with experiment than the state-of-the-art Cercignani-Lampis-Lord scattering kernel. Super-elastic scattering is predicted. Gas-adlayer interactions are included for the first time. Accommodation coefficents can be determined by fitting simulations to experimental data. The new thermal desorption model accurately calculates angular, translational, rotational, and vibrational distributions, and the rotational alignment parameter. The model is validated by comparing with experiments. Multiple transition states are considered in a set of non-dimensionalized equations of motion, linked with temporally-accurate event timing. Initial conditions are chosen from a new truncated Maxwell-Boltzmann distribution. Run times are improved by eliminating the Gaussian Weighting of desorbing products. The absorption energy barrier is shown to significantly contribute only to the translational energy of desorbing molecules by contributing energy to each adatom in a similar manner.

  15. 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.

  16. High-resolution electron spectroscopy of different adsorption states of ethylene on Pd(1 1 1)

    NASA Astrophysics Data System (ADS)

    Sock, M.; Eichler, A.; Surnev, S.; Andersen, J. N.; Klötzer, B.; Hayek, K.; Ramsey, M. G.; Netzer, F. P.

    2003-11-01

    The adsorption of ethylene at 100 K on clean and oxygen precovered Pd(1 1 1) surfaces and the thermal evolution of the ethylene adsorbate layers have been investigated experimentally by high-resolution electron energy loss spectroscopy (HREELS), high-resolution X-ray photoelectron spectroscopy with synchrotron radiation, thermal desorption spectroscopy and theoretically by ab initio density functional theory (DFT) calculations. On the clean Pd(1 1 1) surface at 100 K ethylene is adsorbed in a di-σ bonding state, whereas on the oxygen precovered Pd(1 1 1)2 × 2-O surface the π-bonded configuration is more stable; this has been established both experimentally and theoretically. Upon adsorption at room temperature ethylidyne adspecies are formed on both surfaces, but neither di-σ nor π-bonded ethylene transform into ethylidyne on heating from low temperature up to 450 K. Complete molecular desorption of ethylene is observed in both cases, with no signs of dehydrogenation. The spectroscopic data recorded during the thermal evolution of the low temperature adsorbate phase have been analysed with the help of DFT and indicate that π-bonded ethylene adsorption states may become populated upon heating the low temperature adlayer to 350 K.

  17. 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.

  18. 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.

  19. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    PubMed Central

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Schloegl, R.; Willinger, Marc-Georg

    2016-01-01

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene–graphene and graphene–substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite. PMID:27759024

  20. Anisotropic mechanical amorphization drives wear in diamond.

    PubMed

    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 sp(3)-sp(2) 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.

  1. 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.

  2. Interaction of acetonitrile with thin films of solid water

    SciTech Connect

    Bahr, S.; Kempter, V.

    2009-06-07

    Thin films of water were prepared on Ag at 124 K. Their properties were studied with metastable impact electron spectroscopy, reflection absorption infrared spectroscopy, and temperature programmed desorption. The interaction of acetonitrile (ACN) with these films was studied with the abovementioned techniques. From the absence of any infrared activity in the initial adsorption stage, it is concluded that ACN adsorbs linearly and that the C{identical_to}N axis is aligned parallel to the water surface (as also found on neat Ag). Initially, the interaction with water surface species involves their dangling OD groups. During the completion of the first adlayer the ACN-ACN lateral interaction becomes of importance as well, and the ACN molecules become tilted with respect to the water surface. ACN shows propensity to stay at the surface after surface adsorption even during annealing up to the onset of desorption. The present results for the ACN-water interaction are compared with available classical molecular dynamics calculations providing the orientation profile for ACN on water as well as the ACN bonding properties.

  3. Characterization of oxidized platinum surfaces by X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Peuckert, M.; Bonzel, H. P.

    1984-09-01

    Various adlayers were grown on the (111) surface of a platinum crystal by four different oxidizing treatments. The resulting surface phases were characterized by X-ray photoelectron spectroscopy. According to the Pt 4f and O 1s XPS spectra, treatment in 0.1 MPa O 2 at 900 K yielded about two monolayers of PtO 2; anodic polarization in 0.5M H 2SO 4 acid electrolyte at 3 V versus standard hydrogen electrode gave a thick (> 5 nm) layer of Pt(OH) 4, while by polarization in 1M NaOH base electrolyte at 3 V versus Ag/AgCl reference electrode a thick film of an oxyhydroxide (approximately PtO(OH) 2) was formed. Etching in boiling conc. HNO 3 led to a thin layer of about 1 nm of a hydrated oxide, PtO 2 · xH 2O. Identification of the different surface phases was supported by comparative experiments with bulk PtO 2. The thermal stability of all compounds was investigated by heating the samples in ultrahigh vacuum. They all decomposed at about 400 K. Initially, not a pure metal phase was formed, but a mixed phase containing Pt metal and oxide, which was stable over a wide temperature range. No oxygen could be detected on the surface at 1070 K by XPS or Auger spectroscopy.

  4. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    DOE PAGES

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; ...

    2016-10-19

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy andmore » density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.« less

  5. An XPS and UPS investigation of the adsorption of ethylene on the (111) surface of silver

    NASA Astrophysics Data System (ADS)

    Felter, T. E.; Weinberg, W. H.; Zhdan, P. A.; Boreskov, G. K.

    1980-07-01

    Monolayer adsorption of pure ethylene on the (111) surface of saver at 80 K has been studied by X-ray ( hv = 1486.6 eV) and ultraviolet ( hv = 21.2 and 40.8 eV) photoelectron spectroscopy. The density of the adlayer is approximately 5 × 10 14 molecules/cm 2 at saturation, multilayer formation being prohibited by the ultrahigh vacuum of the spectrometer. The molecular orbitals designated σ ∗CH, σ CC, σ CH and 2ss ∗ by Demuth are observed at 7.0, 9.0, 10.3 and 13.6 eV below the Fermi level, respectively, but the higher lying π level is obscured by the silver d-band emission. The data are consistent with an undistorted molecule, adsorbed with the molecular axis parallel to the surface. Desorption occurs below 200 K without significant decomposition products remaining on the surface in agreement with the conventional notion that clean silver is relatively inert with respect to olefin adsorption.

  6. 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

  7. Stability and Electronic Properties of Two-Dimensional Silicene and Germanene on Graphene

    NASA Astrophysics Data System (ADS)

    Chuu, Chih-Piao; Cai, Yongmao; Wei, C.-M.; Chou, M.-Y.

    2014-03-01

    Recently, there have been experimental attempts to synthesize silicene, a two-dimensional (2D) graphene-like form of silicon on metal surfaces such as Ag(111) and Ir(0001). The possibility of preparing silicene on ZrB2 thin films grown on silicon wafers has also been reported. This suggests new perspectives for the applications of massless fermions in materials that are compatible with Si-based electronics. It is expected that many of the unique electronic properties of graphene can also be realized in this new 2D system. However, the interaction between the 2D silicon structure and the metal substrate is found to be quite strong, leading to distortion in the adlayer and consequently the disappearance of the Dirac cone. Therefore, finding a suitable substrate that interacts with silicene weakly and preserves the sublattice symmetry is of ultimate importance. We have performed first-principles calculations of silicene and germanene on graphene in order to understand the effect of substrate interaction on the physical properties of these systems. Of particular interest is the induced change in the electronic structure, the modification of the Fermi velocity, the gap opening, the charge doping from the substrate, and the stability of the combined system. The energetics of forming the 2D silicone structure on a substrate is carefully evaluated in comparison with possible three-dimensional cluster structures.

  8. Templated bilayer self-assembly of fully conjugated π-expanded macrocyclic oligothiophenes complexed with fullerenes.

    PubMed

    Cojal González, José D; Iyoda, Masahiko; Rabe, Jürgen P

    2017-03-10

    Fully conjugated macrocyclic oligothiophenes exhibit a combination of highly attractive structural, optical and electronic properties, and multifunctional molecular thin film architectures thereof are envisioned. However, control over the self-assembly of such systems becomes increasingly challenging, the more complex the target structures are. Here we show a robust self-assembly based on hierarchical non-covalent interactions. A self-assembled monolayer of hydrogen-bonded trimesic acid at the interface between an organic solution and graphite provides host-sites for the epitaxial ordering of Saturn-like complexes of fullerenes with oligothiophene macrocycles in mono- and bilayers. STM tomography verifies the formation of the templated layers. Molecular dynamics simulations corroborate the conformational stability and assign the adsorption sites of the adlayers. Scanning tunnelling spectroscopy determines their rectification characteristics. Current-voltage characteristics reveal the modification of the rectifying properties of the macrocycles by the formation of donor-acceptor complexes in a densely packed all-self-assembled supramolecular nanostructure.

  9. Templated bilayer self-assembly of fully conjugated π-expanded macrocyclic oligothiophenes complexed with fullerenes

    NASA Astrophysics Data System (ADS)

    Cojal González, José D.; Iyoda, Masahiko; Rabe, Jürgen P.

    2017-03-01

    Fully conjugated macrocyclic oligothiophenes exhibit a combination of highly attractive structural, optical and electronic properties, and multifunctional molecular thin film architectures thereof are envisioned. However, control over the self-assembly of such systems becomes increasingly challenging, the more complex the target structures are. Here we show a robust self-assembly based on hierarchical non-covalent interactions. A self-assembled monolayer of hydrogen-bonded trimesic acid at the interface between an organic solution and graphite provides host-sites for the epitaxial ordering of Saturn-like complexes of fullerenes with oligothiophene macrocycles in mono- and bilayers. STM tomography verifies the formation of the templated layers. Molecular dynamics simulations corroborate the conformational stability and assign the adsorption sites of the adlayers. Scanning tunnelling spectroscopy determines their rectification characteristics. Current-voltage characteristics reveal the modification of the rectifying properties of the macrocycles by the formation of donor-acceptor complexes in a densely packed all-self-assembled supramolecular nanostructure.

  10. Blue-violet InGaN laser diodes grown on bulk GaN substrates by plasma-assisted molecular-beam epitaxy

    SciTech Connect

    Skierbiszewski, C.; Wasilewski, Z.R.; Siekacz, M.; Feduniewicz, A.; Perlin, P.; Wisniewski, P.; Borysiuk, J.; Grzegory, I.; Leszczynski, M.; Suski, T.; Porowski, S.

    2005-01-03

    We report on the InGaN multiquantum laser diodes (LDs) made by rf plasma-assisted molecular beam epitaxy (PAMBE). The laser operation at 408 nm is demonstrated at room temperature with pulsed current injections using 50 ns pulses at 0.25% duty cycle. The threshold current density and voltage for the LDs with cleaved uncoated mirrors are 12 kA/cm{sup 2} (900 mA) and 9 V, respectively. High output power of 0.83 W is obtained during pulse operation at 3.6 A and 9.6 V bias with the slope efficiency of 0.35 W/A. The laser structures are deposited on the high-pressure-grown low dislocation bulk GaN substrates taking full advantage of the adlayer enhanced lateral diffusion channel for adatoms below the dynamic metallic cover. Our devices compare very favorably to the early laser diodes fabricated using the metalorganic vapor phase epitaxy technique, providing evidence that the relatively low growth temperatures used in this process pose no intrinsic limitations on the quality of the blue optoelectronic components that can be fabricated using PAMBE.

  11. 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%.

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

    PubMed

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

    2014-01-01

    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.

  13. 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

  14. Adsorption of glycinin and β-conglycinin on silica and cellulose: surface interactions as a function of denaturation, pH, and electrolytes.

    PubMed

    Salas, Carlos; Rojas, Orlando J; Lucia, Lucian A; Hubbe, Martin A; Genzer, Jan

    2012-02-13

    Soybean proteins have found uses in different nonfood applications due to their interesting properties. We report on the kinetics and extent of adsorption on silica and cellulose surfaces of glycinin and β-conglycinin, the main proteins present in soy. Quartz crystal microgravimetry (QCM) experiments indicate that soy protein adsorption is strongly affected by changes in the physicochemical environment. The affinity of glycinin and the mass adsorbed on silica and cellulose increases (by ca. 13 and 89%, respectively) with solution ionic strength (as it increases from 0 to 100 mM NaCl) due to screening of electrostatic interactions. In contrast, β-conglycinin adsorbs on the same substrates to a lower extent and the addition of electrolyte reduces adsorption (by 25 and 57%, respectively). The addition of 10 mM 2-mercaptoethanol, a denaturing agent, reduces the adsorption of both proteins with a significant effect for glycinin. This observation is explained by the cleavage of disulfide bonds which allows unfolding of the molecules and promotes dissociation into subunits that favors more compact adsorbed layer structures. In addition, adsorption of glycinin onto cellulose decreases with lowering the pH from neutral to pH 3 due to dissociation of the macromolecules, resulting in flatter adsorbed layers. The respective adsorption isotherms fit a Langmuir model and QCM shifts in energy dissipation and frequency reveal multiple-step kinetic processes indicative of changes in adlayer structure.

  15. Growth-induced polarity formation in solid solutions of organic molecules: Markov mean-field model and Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Wüst, Thomas; Hulliger, Jürg

    2005-02-01

    A layer-by-layer growth model is presented for the theoretical investigation of growth-induced polarity formation in solid solutions H1-XGX of polar (H) and nonpolar (G) molecules (X: molar fraction of G molecules in the solid, 0adlayers, with respect to the up and down orientation of the dipoles of H molecules and to an exchange of H and G molecules, while previously attached layers are kept frozen. The model is analyzed by means of a Markov mean-field description and Monte Carlo simulations. In solid solutions, polarity results from a combined effect of orientational selectivity by H and G molecules with respect to the alignment of the dipoles of H molecules and miscibility between the two components. Even though both native structures (H,G) may be centrosymmetric, polarity can arise just from the admixture of G molecules in the H crystal upon growth. An overview of possible phenomena is given by random selection of molecular interaction energies within an assumed but realistic energy range. The analytical approach describes sufficiently basic phenomena and is in good agreement with simulations. High probabilities for significant vectorial alignment of H molecules are found for low (X⩽0.2) and high (X⩾0.8) fractions of G molecules, respectively, as well as for ordered HG compounds (X=0.5).

  16. Sulfur-induced mobilization of Au surface atoms on Au(1 1 1) studied by real-time STM

    NASA Astrophysics Data System (ADS)

    Biener, Monika M.; Biener, Juergen; Friend, Cynthia M.

    2007-04-01

    The interaction of sulfur with gold surfaces has attracted considerable interest due to numerous technological applications such as the formation of self-assembled monolayers and as a chemical sensor. Here, we report on the interaction of sulfur with Au(1 1 1) at two different temperatures (300 K and 420 K) studied by real-time scanning tunnelling microscopy, low energy electron diffraction and Auger electron spectroscopy. In the low coverage regime (<0.1 ML), S adsorption lifts the herringbone reconstruction of the clean Au(1 1 1) surface indicating a lateral expansion of the surface layer. An ordered (√3 × √3) R30° sulfur adlayer develops as the coverage reaches ˜0.3 ML. At higher S coverages (>0.3 ML) gold surface atoms are removed from regular terrace sites and incorporated into a growing gold sulfide phase. At 300 K this process leads to the formation of a rough pit and mound surface morphology. This gold sulfide exhibits short-range order and an incommensurate, long-range ordered AuS phase develops upon annealing at 450-525 K. In contrast, formation of an ordered AuS phase via rapid step-retraction rather than etch pit formation is observed during S-interaction with Au(1 1 1) surfaces at 420 K. Our results shed new light on the S-Au(1 1 1) interaction.

  17. MBE Growth of InN/GaN(0001) and Shape Transitions of InN islands

    NASA Astrophysics Data System (ADS)

    Cao, Yongge; Xie, Maohai; Liu, Ying; Ng, Y. F.

    2003-03-01

    Plasma-assisted molecular-beam epitaxial growth of InN on GaN(0001) is investigated. Both layer-by-layer and Stranski-Krastanov (SK) growth modes are observed under different growth windows. Strain relaxation is studied by real-time recording of the in-plane lattice spacing evolutions on RHEED pattern, which suggest a gradual relaxation of the strain in InN film commenced during the first bilayer (BL) deposition and almost completed after 2-4 BLs. For SK growth, 3D islanding initiates after the strain has mostly been relieved, presumably by dislocations. Based on statistical analysis, the shape transitions of 3D islands are firstly observed in the III-nitrides system. The InN islands transform gradually from pyramids to platelets with increasing of In flux. Under In-rich growth condition, the reverse trend of island shape evolution dependence on volume size, compared with Equilibrium Crystal Shape (ECS) theory, is induced by the Indium self-surfactant effects, in which Indium adlayer on the top surface of InN islands will depress the thermodynamic driving force for the vertical growth of 3D islands. Lateral growth of 3D islands is not only the result of kinetic process but also favored by thermodynamics while Indium self-surfactant exist.

  18. Vibrations of alkali metal overlayers on metal surfaces

    NASA Astrophysics Data System (ADS)

    Rusina, G. G.; Eremeev, S. V.; Echenique, P. M.; Benedek, G.; Borisova, S. D.; Chulkov, E. V.

    2008-06-01

    We review the current progress in the understanding of vibrations of alkalis adsorbed on metal surfaces. The analysis of alkali vibrations was made on the basis of available theoretical and experimental results. We also include in this discussion our recent calculations of vibrations in K/Pt(111) and Li(Na)/Cu(001) systems. The dependence of alkali adlayer localized modes on atomic mass, adsorption position and coverage as well as the dependence of vertical vibration frequency on the substrate orientation is discussed. The square root of atomic mass dependence of the vertical vibration energy has been confirmed by using computational data for alkalis on the Al(111) and Cu(001) substrates. We have confirmed that in a wide range of submonolayer coverages the stretch mode energy remains nearly constant while the energy of in-plane polarized modes increases with the increase of alkali coverage. It was shown that the spectrum of both stretch and in-plane vibrations can be very sensitive to the adsorption position of alkali atoms and substrate orientation.

  19. 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.

  20. Hole-mediated Photodecomposition of Trimehtyl Acetate on a TiO2(001) Anatase Epitaxial Thin Film Surface

    SciTech Connect

    Ohsawa, Takeo; Lyubinetsky, Igor; Henderson, Michael A.; Chambers, Scott A.

    2008-12-18

    Surfaces of titanium dioxide in both rutile and anatase polymorphs have attracted significant attention in catalysis and photochemistry. The (110) orientation of rutile, and to a lesser extent other rutile orientations, have been studied on an atomic scale, yielding information on surface structure and chemical reactivity. In contrast, the thermal and photochemistry of well-defined, single-crystal anatase surfaces had not been investigated, largely because of the metastable nature of anatase , as well as the lack of availability of high-quality surfaces. Here we describe a study of the adsorption and photoreactivity of an organic adlayer, trimethyl acetate (TMA), on structurally-excellent anatase (001) epitaxial thin films grown by oxygen plasma assisted molecular beam epitaxy (OPAMBE). High-resolution scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), and photodesorption spectrometry have been used to study the chemisorptions and ultraviolet (UV) light-induced photodecomposition of TMA in ultrahigh vacuum. UV light promotes hole-mediated photodecomposition of TMA, resulting in decarboxylation to yield tert-butyl radical and CO2. The photochemical rate constant is equal to that measured for OPAMBE grown rutile TiO2(110) surfaces.

  1. 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.

  2. Scanning tunneling microscopy investigation of copper phthalocyanine and truxenone derivative binary superstructures on graphite.

    PubMed

    Liu, Jia; Wang, Dong; Wang, Jie-Yu; Pei, Jian; Wan, Li-Jun

    2011-02-01

    The binary self-assembly of copper phthalocyanine (CuPc) and 2,3,7,8,12,13-hexahexyloxy-truxenone (TrO23) at the solid/liquid interface of highly oriented pyrolytic graphite (HOPG) was investigated by using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Pseduohexagonal and linear patterned superstructures of CuPc are obtained by co-adsorbing with TrO23. High-resolution STM images reveal the structural details of the arrangement of TrO23 and CuPc in the binary assembly structures. The molecular ratio between CuPc and TrO23 in the adlayer can be modulated by the CuPc concentration in liquid phase. The electronic properties of CuPc and TrO23 in the co-adsorbed self-assembly are investigated by STS. The results presented here are helpful to the design and fabrication of multi-component functional molecular nanostructures.

  3. Particle attraction effects on the centrifugal casting and extrusion of alumina

    SciTech Connect

    Schilling, C.H.; Bergstroem, L.; Ker, H.L.; Aksay, I.A.

    1993-04-01

    Interparticle attraction forces were empirically related to the centrifugal casting and extrusion behavior of flocculated alumina suspensions. Attractive forces were altered by two approaches: Salt flocculation, which entails regulating the electrical double-layer thickness through electrolyte additions; and screening of van der Waals attraction by steric interactions of surface-adsorbed fatty acids. Specimens produced by both compressibility at a critical maximum density that increased with decreasing interparticle attraction. Gradients in packing density during centrifugal casting were alleviated using both methods as long as spatial variations of the effective stress were within the low-compressibility range. We hypothesized that the reduced interparticle attraction in both methods may also raise the threshold packing density at which ductile-to-brittle transitions occur during plastic shear. Specimens prepared with oleic acid adlayers were highly plastic and easily extrudable at solids contents of up to 59 vol%, although salt-flocculated samples at 55 vol% density extruded at creeping flow rates that were insensitive to the applied pressure. Results suggested that particle rearrangement during shear, is a rate-limiting process, with an average relaxation time that is lowered by reducing interparticle attraction.

  4. Particle attraction effects on the centrifugal casting and extrusion of alumina

    SciTech Connect

    Schilling, C.H. ); Bergstroem, L. ); Ker, H.L.; Aksay, I.A. )

    1993-01-01

    Interparticle attraction forces were empirically related to the centrifugal casting and extrusion behavior of flocculated alumina suspensions. Attractive forces were altered by two approaches: Salt flocculation, which entails regulating the electrical double-layer thickness through electrolyte additions; and screening of van der Waals attraction by steric interactions of surface-adsorbed fatty acids. Specimens produced by both compressibility at a critical maximum density that increased with decreasing interparticle attraction. Gradients in packing density during centrifugal casting were alleviated using both methods as long as spatial variations of the effective stress were within the low-compressibility range. We hypothesized that the reduced interparticle attraction in both methods may also raise the threshold packing density at which ductile-to-brittle transitions occur during plastic shear. Specimens prepared with oleic acid adlayers were highly plastic and easily extrudable at solids contents of up to 59 vol%, although salt-flocculated samples at 55 vol% density extruded at creeping flow rates that were insensitive to the applied pressure. Results suggested that particle rearrangement during shear, is a rate-limiting process, with an average relaxation time that is lowered by reducing interparticle attraction.

  5. 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.

  6. 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.

  7. Templated bilayer self-assembly of fully conjugated π-expanded macrocyclic oligothiophenes complexed with fullerenes

    PubMed Central

    Cojal González, José D.; Iyoda, Masahiko; Rabe, Jürgen P.

    2017-01-01

    Fully conjugated macrocyclic oligothiophenes exhibit a combination of highly attractive structural, optical and electronic properties, and multifunctional molecular thin film architectures thereof are envisioned. However, control over the self-assembly of such systems becomes increasingly challenging, the more complex the target structures are. Here we show a robust self-assembly based on hierarchical non-covalent interactions. A self-assembled monolayer of hydrogen-bonded trimesic acid at the interface between an organic solution and graphite provides host-sites for the epitaxial ordering of Saturn-like complexes of fullerenes with oligothiophene macrocycles in mono- and bilayers. STM tomography verifies the formation of the templated layers. Molecular dynamics simulations corroborate the conformational stability and assign the adsorption sites of the adlayers. Scanning tunnelling spectroscopy determines their rectification characteristics. Current–voltage characteristics reveal the modification of the rectifying properties of the macrocycles by the formation of donor–acceptor complexes in a densely packed all-self-assembled supramolecular nanostructure. PMID:28281557

  8. Surface tectonics of nanoporous networks of melamine-capped molecular building blocks formed through interface Schiff-base reactions.

    PubMed

    Liu, Xuan-He; Wang, Dong; Wan, Li-Jun

    2013-10-01

    Control over the assembly of molecules on a surface is of great importance for the fabrication of molecule-based miniature devices. Melamine (MA) and molecules with terminal MA units are promising candidates for supramolecular interfacial packing patterning, owing to their multiple hydrogen-bonding sites. Herein, we report the formation of self-assembled structures of MA-capped molecules through a simple on-surface synthetic route. MA terminal groups were successfully fabricated onto rigid molecular cores with 2-fold and 3-fold symmetry through interfacial Schiff-base reactions between MA and aldehyde groups. Sub-molecular scanning tunneling microscopy (STM) imaging of the resultant adlayer revealed the formation of nanoporous networks. Detailed structural analysis indicated that strong hydrogen-bonding interactions between the MA groups persistently drove the formation of nanoporous networks. Herein, we demonstrate that functional groups with strong hydrogen-bond-formation ability are promising building blocks for the guided assembly of nanoporous networks and other hierarchical 2D assemblies.

  9. Facile immobilization of biomolecules onto various surfaces using epoxide-containing antibiofouling polymers.

    PubMed

    Sung, Daekyung; Park, Sangjin; Jon, Sangyong

    2012-03-06

    The surface modifications of plastic or glass substrate and the subsequent immobilization of biomolecules onto the surfaces has been a central feature of the fabrication of biochips. To this end, we designed and synthesized new epoxide-containing random copolymers that form stable polymer adlayers on plastic or glass surface and subsequently react with amine or sulfhydryl functional groups of biomolecules under aqueous conditions. Epoxide-containing random copolymers were synthesized by radical polymerization of three functional monomers: a monomer acting as an anchor to the surfaces, a PEG group for preventing nonspecific protein adsorption, and an epoxide group for conjugating to biomolecules. Polymer coating layers were facilely formed on cyclic olefin copolymer (COC) or glass substrate by simply dipping each substrate into a solution of each copolymer. The polymer-coated surfaces characterized by a contact angle analyzer and X-ray photoelectron spectroscopy (XPS) showed very low levels of nonspecific immunoglobulin G (IgG) adsorption compared to the uncoated bare surface (control). Using a microcontact printing (μCP) method, antibodies as representative biomolecules could be selectively attached onto the copolymers-coated glass or COC surface with high signal-to-noise ratios.

  10. Modeling of 1,4-cyclohexadiene adsorption thermodynamics on Si(001)-2 × 1 surface

    NASA Astrophysics Data System (ADS)

    Gorbunov, V. A.; Myshlyavtsev, A. V.; Myshlyavtseva, M. D.; Fefelov, V. F.

    2015-06-01

    The adsorption thermodynamics of 1,4-cyclohexadiene on Si(001)-2 × 1 are studied in the framework of the lattice gas model with the Monte Carlo and transfer-matrix methods. Adsorption isotherms, heat capacity, entropy as function of chemical potential and adlayer density were calculated. It is shown that there are two ordered phases for the model under consideration. The first phase consists of the tetra-σ complexes and there is a low surface concentration of the adsorbed molecules. The second phase consists of the π-complexes and there is a high surface concentration. The ordered phase consisting of the di-σ complexes is absent within the constructed model. The obtained set of ordered phases and the sequence of its arising with growth of chemical potential are in close correspondence with the experimental data. In the framework of the model under consideration the observed behavior of 1,4-cyclohexadiene adsorption layer on Si(001)-2 × 1 is explained by the presence of three adsorption states with different surface area per molecule and repulsive lateral interactions. Thus, the transition between π- and di-σ configurations and the formation of the π-complex phase can be the thermodynamically driven effect.

  11. 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.

  12. Layer by layer self-assembly of poly[2-(methacryloyloxy) ethyl phosphorylcholine] multilayer via the ionic complexation with zirconium.

    PubMed

    Pang, Shaopeng; Zhu, Congshan; Xu, Fangming; Chen, Chaojian; Ji, Jian

    2012-06-01

    Zirconium-phosphonate (Zr-P) ionic complexation chemistry is explored as a new approach to fabricate poly[2-(methacryloyloxy) ethyl phosphorylcholine] (PMPC) multilayer film by layer-by-layer self-assembly method. Quartz crystal microbalance with dissipation (QCM-D) and optical ellipsometry measurements demonstrated that PMPC layer can be fully absorbed on each Zr(4+) layer. The thickness of the multilayer film with a good linear relationship was followed by the ellipsometry in situ adlayer characterization. The influence of pH of the PMPC and Zr(4+) solutions on the multilayer deposition were investigated by optical ellipsometry. QCM-D results indicated that the multilayer film is stable in a PBS flowing chamber at a high flow rate of 5.2×10(-3)m/s. The ellipsometry data demonstrated that 67.2% of the film still remained on the silicon wafer after being strong shaken in PBS at 80 rpm for 12h. The adsorption of bovine serum albumin (BSA) and fetal bovine serum (FBS) on the PMPC surface was monitored by the QCM-D and spectroscopic ellipsometry, and the results showed the multilayer film have excellent protein resistance.

  13. Ultrathin suspended nanopores with surface plasmon resonance fabricated by combined colloidal lithography and film transfer.

    PubMed

    Junesch, Juliane; Sannomiya, Takumi

    2014-05-14

    Suspended plasmonic nanopores in ultrathin film layers were fabricated through a simple and widely applicable method combining colloidal lithography and thin film transfer, which allows mass production of short-range ordered nanopore arrays on a large scale. By this combined method, mechanically stable and flexible free-standing nanopore membranes with a thickness down to 15-30 nm were produced. The plasmon resonances of the ultrathin plasmonic nanopores fabricated in AlN/Au/AlN trilayer and single layer Au membranes were tuned to lie in the vis-NIR wavelength range by properly designing their dimensions. The optical responses to the refractive index changes were tested and applied to adlayer sensing. The trilayer nanopore membrane showed a unique property to support water only on one side of the membrane, which was confirmed by the resonance shift and comparison with numerical simulation. Pore size reduction down to 10 nm can be achieved through additional material deposition. The filtering function of such pore-size-reduced conical shaped nanofunnels has also been demonstrated. The presented nanopore fabrication method offers new platforms for ultrathin nanopore sensing or filtering devices with controlled pore-size and optical properties. The film transfer technique employed in this work would enable the transformation of any substrate-based nanostructures to free-standing membrane based devices without complicated multiple etching processes.

  14. Interaction of acetonitrile with thin films of solid water.

    PubMed

    Bahr, S; Kempter, V

    2009-06-07

    Thin films of water were prepared on Ag at 124 K. Their properties were studied with metastable impact electron spectroscopy, reflection absorption infrared spectroscopy, and temperature programmed desorption. The interaction of acetonitrile (ACN) with these films was studied with the abovementioned techniques. From the absence of any infrared activity in the initial adsorption stage, it is concluded that ACN adsorbs linearly and that the C identical withN axis is aligned parallel to the water surface (as also found on neat Ag). Initially, the interaction with water surface species involves their dangling OD groups. During the completion of the first adlayer the ACN-ACN lateral interaction becomes of importance as well, and the ACN molecules become tilted with respect to the water surface. ACN shows propensity to stay at the surface after surface adsorption even during annealing up to the onset of desorption. The present results for the ACN-water interaction are compared with available classical molecular dynamics calculations providing the orientation profile for ACN on water as well as the ACN bonding properties.

  15. Interaction of acetonitrile with thin films of solid water

    NASA Astrophysics Data System (ADS)

    Bahr, S.; Kempter, V.

    2009-06-01

    Thin films of water were prepared on Ag at 124 K. Their properties were studied with metastable impact electron spectroscopy, reflection absorption infrared spectroscopy, and temperature programmed desorption. The interaction of acetonitrile (ACN) with these films was studied with the abovementioned techniques. From the absence of any infrared activity in the initial adsorption stage, it is concluded that ACN adsorbs linearly and that the C≡N axis is aligned parallel to the water surface (as also found on neat Ag). Initially, the interaction with water surface species involves their dangling OD groups. During the completion of the first adlayer the ACN-ACN lateral interaction becomes of importance as well, and the ACN molecules become tilted with respect to the water surface. ACN shows propensity to stay at the surface after surface adsorption even during annealing up to the onset of desorption. The present results for the ACN-water interaction are compared with available classical molecular dynamics calculations providing the orientation profile for ACN on water as well as the ACN bonding properties.

  16. In/GaN(0001)- ( √{ 3 } × √{ 3 } ) R 30 ° adsorbate structure as a template for embedded (In, Ga)N/GaN monolayers and short-period superlattices

    NASA Astrophysics Data System (ADS)

    Chèze, C.; Feix, F.; Anikeeva, M.; Schulz, T.; Albrecht, M.; Riechert, H.; Brandt, O.; Calarco, R.

    2017-02-01

    We explore an alternative way to fabricate (In, Ga)N/GaN short-period superlattices on GaN(0001) by plasma-assisted molecular beam epitaxy. We exploit the existence of an In adsorbate structure manifesting itself by a ( √{ 3 } × √{ 3 } ) R 30 ° surface reconstruction observed in-situ by reflection high-energy electron diffraction. This In adlayer accommodates a maximum of 1/3 monolayer of In on the GaN surface and, under suitable conditions, can be embedded into GaN to form an In0.33Ga0.67N quantum sheet whose width is naturally limited to a single monolayer. Periodically inserting these quantum sheets, we synthesize (In,Ga)N/GaN short-period superlattices with abrupt interfaces and high periodicity as demonstrated by x-ray diffractometry and scanning transmission electron microscopy. The embedded quantum sheets are found to consist of single monolayers with an In content of 0.25-0.29. For a barrier thickness of 6 monolayers, the superlattice gives rise to a photoluminescence band at 3.16 eV, close to the theoretically predicted values for these structures.

  17. 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.

  18. Effect of bromine and substituted alkyl chain on the interfacial self-assembly of bromobenzene derivatives by scanning tunneling microscopy.

    PubMed

    Li, Yijing; Miao, Xinrui; Liu, Gang; Li, Zhuomin; Xu, Li; Deng, Wenli

    2012-01-01

    The self-assemblies of four compounds, 1-bromo-4-(hexadecyloxy)benzene (BHB-16), 1-bromo-4-(octadecyloxy)benzene (BOB-18), 1-bromo-4-(pentadecyloxy)benzene (BPB-15) and 1,4-dibromo-2,5-(dioctadecyloxy)benzene (DDB-18), have been studied on highly oriented pyrolytic graphite (HOPG) under ambient conditions by scanning tunneling microscopy (STM), with the aim of understanding the influence of the molecular structure and functional groups on the arrangements. It is found that the bromine atoms of the four molecules are in bright contrast and can be identified in STM images. The neighbouring phenyl head groups of the BHB-16, BOB-18 and BPB-15 molecules in one lamella, with an anti-parallel orientation, are interdigitated with different offset distance, while the aromatic cores of DDB-18 molecules in the same row are in a parallel orientation. Moreover, an odd-even effect is observed in the self-assemblies of the former three molecules as expected. The STM images of the four molecules resemble the calculated HOMO electron density contours somewhat with positive surface bias voltage. On the basis of comparative analysis between the STM images, it is suggested that the electrostatic attractions between the neighbouring molecules play an important role in the self-assemblies of BHB-16, BOB-18 and BPB-15, while it is the van der Waals force and the non-covalent halogen-halogen interaction that dominate the structure of DDB-18 adlayer.

  19. Scanning tunneling microscopy of the formation, transformation, and property of oligothiophene self-organizations on graphite and gold surfaces

    PubMed Central

    Yang, Zhi-Yong; Zhang, Hui-Min; Yan, Cun-Ji; Li, Shan-Shan; Yan, Hui-Juan; Song, Wei-Guo; Wan, Li-Jun

    2007-01-01

    Two alkyl-substituted dual oligothiophenes, quarterthiophene (4T)-trimethylene (tm)-octithiophene (8T) and 4T-tm-4T, were used to fabricate molecular structures on highly oriented pyrolytic graphite and Au(111) surfaces. The resulted structures were investigated by scanning tunneling microscopy. The 4T-tm-8T and 4T-tm-4T molecules self-organize into long-range ordered structures with linear and/or quasi-hexagonal patterns on highly oriented pyrolytic graphite at ambient temperature. Thermal annealing induced a phase transformation from quasi-hexagonal to linear in 4T-tm-8T adlayer. The molecules adsorbed on Au(111) surface in randomly folded and linear conformation. Based on scanning tunneling microscopy results, the structural models for different self-organizations were proposed. Scanning tunneling spectroscopy measurement showed the electronic property of individual molecules in the patterns. These results are significant in understanding the chemistry of molecular structure, including its formation, transformation, and electronic properties. They also help to fabricate oligothiophene assemblies with desired structures for future molecular devices. PMID:17360417

  20. 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.

  1. 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.

  2. The analysis of time-resolved optical waveguide absorption spectroscopy based on positive matrix factorization.

    PubMed

    Liu, Ping; Li, Zhu; Li, Bo; Shi, Guolong; Li, Minqiang; Yu, Daoyang; Liu, Jinhuai

    2013-08-01

    Time-resolved optical waveguide absorption spectroscopy (OWAS) makes use of an evanescent field to detect the polarized absorption spectra of sub-monomolecular adlayers. This technique is suitable for the investigation of kinetics at the solid/liquid interface of dyes, pigments, fluorescent molecules, quantum dots, metallic nanoparticles, and proteins with chromophores. In this work, we demonstrate the application of positive matrix factorization (PMF) to analyze time-resolved OWAS for the first time. Meanwhile, PCA is researched to compare with PMF. The absorption/desorption kinetics of Rhodamine 6G (R6G) onto a hydrophilic glass surface and the dynamic process of Meisenheimer complex between Cysteine and TNT are selected as samples to verify experimental system and analytical methods. The results are shown that time-resolved OWAS can well record the absorption/desorption of R6G onto a hydrophilic glass surface and the dynamic formation process of Meisenheimer complexes. The feature of OWAS extracted by PMF is dynamic and consistent with the results analyzed by the traditional function of time/wavelength-absorbance. Moreover, PMF prevents the negative factors from occurring, avoids contradicting physical reality, and makes factors more easily interpretable. Therefore, we believe that PMF will provide a valuable analysis route to allow processing of increasingly large and complex data sets.

  3. Potential-dependent structures investigated at the perchloric acid solution/iodine modified Au(111) interface by electrochemical frequency-modulation atomic force microscopy.

    PubMed

    Utsunomiya, Toru; Tatsumi, Shoko; Yokota, Yasuyuki; Fukui, Ken-ichi

    2015-05-21

    Electrochemical frequency-modulation atomic force microscopy (EC-FM-AFM) was adopted to analyze the electrified interface between an iodine modified Au(111) and a perchloric acid solution. Atomic resolution imaging of the electrode was strongly dependent on the electrode potential within the electrochemical window: each iodine atom was imaged in the cathodic range of the electrode potential, but not in the more anodic range where the tip is retracted by approximately 0.1 nm compared to the cathodic case for the same imaging parameters. The frequency shift versus tip-to-sample distance curves obtained in the electric double layer region on the iodine adlayer indicated that the water structuring became weaker at the anodic potential, where the atomic resolution images could not be obtained, and immediately recovered at the original cathodic potential. The reversible hydration structures were consistent with the reversible topographic images and the cyclic voltammetry results. These results indicate that perchlorate anions concentrated at the anodic potential affect the interface hydration without any irreversible changes to the interface under these conditions.

  4. Manifestations of non-planar adsorption geometries of lead pyrenocyanine at the liquid-solid interface.

    PubMed

    Mali, Kunal S; Zöphel, Lukas; Ivasenko, Oleksandr; Müllen, Klaus; De Feyter, Steven

    2013-10-01

    In this work, we provide evidence for multiple non-planar adsorption geometries of a novel pyrenocyanine derivative at the liquid-solid interface under ambient conditions. When adsorbed at the organic liquid-solid interface, lead pyrenocyanine forms well-ordered monolayers that exhibit peculiar non-periodic contrast variation. The different contrast of the adsorbed molecules is attributed to dissimilar adsorption geometries which arise from the non-planar conformation of the molecules. The non-planarity of the molecular backbone in turn arises due to a combination of the angularly extended pyrene subunits and the presence of the large lead ion, which is too big to fit inside the central cavity and thus is located out of the aromatic plane. The two possible locations of the lead atom, namely below and above the aromatic plane, could be identified as depression and protrusion in the central cavity, respectively. The manifestation of such multiple adsorption geometries on the structure of the resultant monolayer is discussed in detail. The packing density of these 2D arrays of molecules could be tuned by heating of the sample wherein the molecular packing changes from a low-density, pseudo six-fold symmetric to a high-density, two-fold symmetric arrangement. Finally, a well-ordered two-component system could be constructed by incorporating C60 molecules in the adlayer of lead pyrenocyanine at the liquid-solid interface.

  5. Giant perpendicular magnetic anisotropy of an Ir monolayer on a NiAl(001) surface

    NASA Astrophysics Data System (ADS)

    Kim, Dongyoo; Yang, Jeonghwa; Hong, Jisang

    2009-08-01

    Using the state-of-the-art full potential linearized augmented plane-wave method, we have investigated the magnetic properties of Os and Ir monolayer (ML) film on NiAl(001) surface. It has been found that the one ML of Os and Ir film can have ferromagnetic ground state with magnetic moment of 0.35 and 0.64μB on Ni terminated surface, whereas both films display no sign of magnetic state on Al terminated surface. In addition, the surface Ni atom has an induced magnetic moment of 0.26μB in Ir/NiAl(001), while only 0.09μB is observed in Os/NiAl(001). We attribute the existence of magnetism to the interaction between 5d of adlayer and 3d of surface Ni. Moreover, we have obtained that the Os/NiAl(001) and Ir/NiAl(001) films show a perpendicular magnetic anisotropy (PMA). Surprisingly, it appears that the Ir/NiAl(001) has a giant PMA energy of 7.18 meV.

  6. Observation of multiple vibrational modes in ultrahigh vacuum tip-enhanced Raman spectroscopy combined with molecular-resolution scanning tunneling microscopy.

    PubMed

    Jiang, N; Foley, E T; Klingsporn, J M; Sonntag, M D; Valley, N A; Dieringer, J A; Seideman, T; Schatz, G C; Hersam, M C; Van Duyne, R P

    2012-10-10

    Multiple vibrational modes have been observed for copper phthalocyanine (CuPc) adlayers on Ag(111) using ultrahigh vacuum (UHV) tip-enhanced Raman spectroscopy (TERS). Several important new experimental features are introduced in this work that significantly advance the state-of-the-art in UHV-TERS. These include (1) concurrent sub-nm molecular resolution STM imaging using Ag tips with laser illumination of the tip-sample junction, (2) laser focusing and Raman collection optics that are external to the UHV-STM that has two cryoshrouds for future low temperature experiments, and (3) all sample preparation steps are carried out in UHV to minimize contamination and maximize spatial resolution. Using this apparatus we have been able to demonstrate a TERS enhancement factor of 7.1 × 10(5). Further, density-functional theory calculations have been carried out that allow quantitative identification of eight different vibrational modes in the TER spectra. The combination of molecular-resolution UHV-STM imaging with the detailed chemical information content of UHV-TERS allows the interactions between large polyatomic molecular adsorbates and specific binding sites on solid surfaces to be probed with unprecedented spatial and spectroscopic resolution.

  7. 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

    2016-09-05

    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.

  8. Surface chemistry and catalysis confined under two-dimensional materials.

    PubMed

    Fu, Qiang; Bao, Xinhe

    2016-10-07

    Two-dimensional (2D) materials are characterised by their strong intraplanar bonding but weak interplanar interaction. Interfaces between neighboring 2D layers or between 2D overlayers and substrate surfaces provide intriguing confined spaces for chemical processes, which have stimulated a new area of "chemistry under 2D cover". In particular, well-defined 2D material overlayers such as graphene, hexagonal boron nitride, and transition metal dichalcogenides have been deposited on solid surfaces, which can be used as model systems to understand the new chemistry. In the present review, we first show that many atoms and molecules can intercalate ultrathin 2D materials supported on solid surfaces and the space under the 2D overlayers has been regarded as a 2D nanocontainer. Moreover, chemical reactions such as catalytic reactions, surface adlayer growth, chemical vapor deposition, and electrochemical reactions occur in the 2D confined spaces, which further act as 2D nanoreactors. It has been demonstrated that surface chemistry and catalysis are strongly modulated by the 2D covers, resulting in weakened molecule adsorption and enhanced surface reactions. Finally, we conclude that the confinement effect of the 2D cover leads to new chemistry in a small space, such as "catalysis under cover" and "electrochemistry under cover". These new concepts enable us to design advanced nanocatalysts encapsulated with 2D material shells which may present improved performance in many important processes of heterogeneous catalysis, electrochemistry, and energy conversion.

  9. Cooperation and competition between halogen bonding and van der Waals forces in supramolecular engineering at the aliphatic hydrocarbon/graphite interface: position and number of bromine group effects.

    PubMed

    Zha, Bao; Dong, Meiqiu; Miao, Xinrui; Peng, Shan; Wu, Yican; Miao, Kai; Hu, Yi; Deng, Wenli

    2017-01-07

    Herein, the photophysical properties of two π-conjugated thienophenanthrene derivatives (6,9- and 5,10-DBTD) are reported. Their self-assembled monolayers in aliphatic hydrocarbon solvents under different concentrations were investigated by scanning tunneling microscopy on a graphite surface. The STM results revealed that the self-assembled structures of the two geometrical isomers exhibited absolutely different behaviors. At the aliphatic solvent/graphite interface, 6,9-DBTD produced almost a single stable coassembled linear structure, except for that with n-tridecane as the solvent. However, the self-assembly of 5,10-DBTD showed structural diversity, and it presented a gradient variety through increasing the chain length of the aliphatic solvents as well as the solution concentration. All ordered self-assembled adlayers critically depend on not only the interchain van der Waals (vdW) interactions, but also on multiple intermolecular interactions, including BrO[double bond, length as m-dash]C and BrS hetero-halogen bonds, homo-BrBr interactions, and HBr and HO hydrogen bonds. We proposed that the cooperation and competition of the intermolecular interactions involving a Br atom and interchain vdW forces induce this structural variety. Density functional theory calculations support to unravel the different elementary structural units based on halogen bonds and hydrogen bonds and were useful tools to dissect and explain the formation mechanism.

  10. Adsorption of the ionic liquid [BMP][TFSA] on Au(111) and Ag(111): substrate effects on the structure formation investigated by STM

    PubMed Central

    Alwast, Dorothea; Wagner, Nadja

    2013-01-01

    Summary In order to resolve substrate effects on the adlayer structure and structure formation and on the substrate–adsorbate and adsorbate–adsorbate interactions, we investigated the adsorption of thin films of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium-bis(trifluoromethylsulfonyl)imide [BMP][TFSA] on the close-packed Ag(111) and Au(111) surfaces by scanning tunneling microscopy, under ultra high vacuum (UHV) conditions in the temperature range between about 100 K and 293 K. At room temperature, highly mobile 2D liquid adsorbate phases were observed on both surfaces. At low temperatures, around 100 K, different adsorbed IL phases were found to coexist on these surfaces, both on silver and gold: a long-range ordered (‘2D crystalline’) phase and a short-range ordered (‘2D glass’) phase. Both phases exhibit different characteristics on the two surfaces. On Au(111), the surface reconstruction plays a major role in the structure formation of the 2D crystalline phase. In combination with recent density functional theory calculations, the sub-molecularly resolved STM images allow to clearly discriminate between the [BMP]+ cation and [TFSA]− anion. PMID:24367760

  11. Amination of surfaces via self-assembly of dopamine.

    PubMed

    Liu, Ying; Yu, Bo; Hao, Jingcheng; Zhou, Feng

    2011-10-01

    Catechols can strongly bind to a variety of substrates so as to functionalize the target surfaces by forming self-assembled monolayer. However, catecholic amine might self-oxidize and polymerize at high pH since the amine is susceptible to nucleophilic addition reaction that results in polymerized oligomers on surfaces. Therefore, the availability of amines for further derivation reaction would be restricted to a large extent. Herein, by controlling pH values to avoid self-oxidative polymerization, dopamine (DA) forms thin and surface-adherent monolayers onto a wide range of inorganic and organic materials, including mica, silica, and Au surface, allowing amination of the surfaces that resemble commercially used aminosilanization. The self-assembly process was traced by surface topography and elemental composition analysis using atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS), and electrochemical characterization (electrochemical impedance spectroscopy and cyclic voltammetry measurements). Then, the aminated surfaces were used for secondary derivation reactions to create a variety of ad-layers, including patterned streptavidin through specific binding interaction with biotin and ferrocene surface via amidation reaction. The surface and interface properties of the obtained surfaces were tested by electrochemical measurements.

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

    PubMed Central

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

    2013-01-01

    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

  13. 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.

  14. Chemical grafting of poly(ethylene glycol) methyl ether methacrylate onto polymer surfaces by atmospheric pressure plasma processing.

    PubMed

    D'Sa, Raechelle A; Meenan, Brian J

    2010-02-02

    This article reports the use of atmospheric pressure plasma processing to induce chemical grafting of poly(ethylene glycol) methyl ether methacrylate (PEGMA) onto polystyrene (PS) and poly(methyl methacrylate) (PMMA) surfaces with the aim of attaining an adlayer conformation which is resistant to protein adsorption. The plasma treatment was carried out using a dielectric barrier discharge (DBD) reactor with PEGMA of molecular weights (MW) 1000 and 2000, PEGMA(1000) and PEGMA(2000), being grafted in a two step procedure: (1) reactive groups are generated on the polymer surface followed by (2) radical addition reactions with the PEGMA. The surface chemistry, coherency, and topography of the resulting PEGMA grafted surfaces were characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and atomic force microscopy (AFM), respectively. The most coherently grafted PEGMA layers were observed for the 2000 MW PEGMA macromolecule, DBD processed at an energy dose of 105.0 J/cm(2) as indicated by ToF-SIMS images. The effect of the chemisorbed PEGMA layer on protein adsorption was assessed by evaluating the surface response to bovine serum albumin (BSA) using XPS. BSA was used as a model protein to determine the grafted macromolecular conformation of the PEGMA layer. Whereas the PEGMA(1000) surfaces showed some protein adsorption, the PEGMA(2000) surfaces appeared to absorb no measurable amount of protein, confirming the optimum surface conformation for a nonfouling surface.

  15. 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

  16. Organic molecules as tools to control the growth, surface structure, and redox activity of colloidal quantum dots.

    PubMed

    Weiss, Emily A

    2013-11-19

    In order to achieve efficient and reliable technology that can harness solar energy, the behavior of electrons and energy at interfaces between different types or phases of materials must be understood. Conversion of light to chemical or electrical potential in condensed phase systems requires gradients in free energy that allow the movement of energy or charge carriers and facilitate redox reactions and dissociation of photoexcited states (excitons) into free charge carriers. Such free energy gradients are present at interfaces between solid and liquid phases or between inorganic and organic materials. Nanostructured materials have a higher density of these interfaces than bulk materials. Nanostructured materials, however, have a structural and chemical complexity that does not exist in bulk materials, which presents a difficult challenge: to lower or eliminate energy barriers to electron and energy flux that inevitably result from forcing different materials to meet in a spatial region of atomic dimensions. Chemical functionalization of nanostructured materials is perhaps the most versatile and powerful strategy for controlling the potential energy landscape of their interfaces and for minimizing losses in energy conversion efficiency due to interfacial structural and electronic defects. Colloidal quantum dots are semiconductor nanocrystals synthesized with wet-chemical methods and coated in organic molecules. Chemists can use these model systems to study the effects of chemical functionalization of nanoscale organic/inorganic interfaces on the optical and electronic properties of a nanostructured material, and the behavior of electrons and energy at interfaces. The optical and electronic properties of colloidal quantum dots have an intense sensitivity to their surface chemistry, and their organic adlayers make them dispersible in solvent. This allows researchers to use high signal-to-noise solution-phase spectroscopy to study processes at interfaces. In this

  17. 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.

  18. A colorimetric method for the molecular weight determination of polyethylene glycol using gold nanoparticles

    PubMed Central

    2013-01-01

    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 (〈h2〉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 〈h2〉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 〈h2〉1/2 using a mathematical relationship between 〈h2〉1/2 and MW of PEG molecule. Applying this approach, we determined the 〈h2〉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. PMID:24359120

  19. Bidentate surface structures of glycylglycine on Si(111)7×7 by high-resolution scanning tunneling microscopy: site-specific adsorption via N-H and O-H or double N-H dissociation.

    PubMed

    Chatterjee, A; Zhang, L; Leung, K T

    2012-08-28

    The early adsorption stage of glycylglycine on Si(111)7×7 surface has been studied by scanning tunneling microscopy (STM). Filled-state imaging shows that glycylglycine adsorbs dissociatively in a bidentate fashion on two adjacent Si adatoms across a dimer wall or an adatom-restatom pair, with the dissociated H atoms on neighboring restatoms. The present STM result validates our hypothesis that both bidentate configurations involving N-H and O-H dissociation and double N-H dissociation are equally probable. Our STM results further show that the relative surface concentrations of the five bidentate configurations follow a specific ordering. This suggests that N-H dissociation at a center adatom site would likely be followed by N-H dissociation at an adjacent restatom, while N-H dissociation at a corner adatom site would be succeeded by O-H dissociation at an adatom across the dimer wall. Evidently, the strong bidentate interactions also inhibit surface diffusion of the adsorbed glycylglycine fragment, and the adsorption apparently follows random sequential adsorption statistics. The random nature of adsorption is also supported by the similar relative occupancies of the center adatom and corner adatom sites, indicating that the relative reactivities of these adatom sites do not play a significant role. Our DFT computational study shows that all three bidentate (Si-)NHCH(2)CONHCH(2)COO(-Si) adatom-adatom configurations (center-center, corner-corner, center-corner) have similar adsorption energies for a double adatom-adatom pair across the dimer wall, while the (Si-)NHCH(2)CON(-Si)CH(2)COOH bidentate adatom-restatom configuration is energetically favorable. The free -CONH- and -COOH groups remaining on the respective bidentate adstructures could facilitate adsorption of the second adlayer through the formation of hydrogen bonding.

  20. Electrocatalytic oxidation of dihydronicotineamide adenine dinucleotide on gold electrode modified with catechol-terminated alkanethiol self-assembly.

    PubMed

    Nakano, Koji; Ohkubo, Kimihiko; Taira, Hiroaki; Takagi, Makoto; Imato, Toshihiko

    2008-06-30

    Synthesis of a mercaptoundecaneamide derivative having a terminus of catechol is described. FT-IR spectroscopic characterization showed that the new molecular entry simply undergoes molecular self-assembly on Au substrate surfaces promoting intra- and intermolecular hydrogen bonds to form well-packed monolayers. Cyclic voltammetric (CV) measurements on the monolayer-modified Au electrode revealed that the surface adlayer possesses specific electrochemical activity due to the reversible catechol/o-quinone redox reaction having characteristics of a surface process and also pH-dependence in its formal potential (59 mV per pH). Detailed analysis of CVs gave fundamental electrochemical parameters including the electroactive surface coverage (0.20-0.24 nmol cm(-2)), the transfer coefficients (0.24 in oxidation and 0.81 in reduction), and also the electron transfer rate constant (1.10-2.76 s(-1)). These data were almost consistent to those seen in literature. We have also found that the catechol monolayer modified electrode exhibits an electrocatalytic function in NADH oxidation. That is, the faradaic current appeared reinforcingly at around the same potential where catechol function is oxidized in the monolayer and increased with an increase in the NADH concentration from 1 to 5 mM, and then reached to a plateau indicating a catalyzed reaction pathway. Detailed analyses revealed that the present system could be characterized by its weak stability of the intermediate compound formed and prompt reaction rate compared with the previously reported chemically modified electrode (CME) systems. We think this type of achievement should be important for the basics of biosensors that rely on dehydrogenase enzymes.

  1. CONDENSED MATTER: ELECTRONIC STRUCTURE, ELECTRICAL, MAGNETIC, AND OPTICAL PROPERTIES: Characterization of Ag adsorption on TiC(001) substrate: an ab initio study

    NASA Astrophysics Data System (ADS)

    Ma, Shang-Yi; Wang, Shao-Qing

    2008-10-01

    Ag adsorptions at 0.25-3 monolayer (ML) coverage on a perfect TiC(001) surface and at 0.25 ML coverage on C vacancy are separately investigated by using the pseudopotential-based density functional theory. The preferential adsorption sites and the adsorption-induced modifications of electronic structures of both the substrate and adsorbate are analysed. Through the analyses of adsorption energy, ideal work of separation, interface distance, projected local density of states, and the difference electron density, the characteristic evolution of the adatom-surface bonding as a function of the amount of deposited silver is studied. The nature of the Ag/TiC bonding changes as the coverage increases from 0.25 to 3 MLs. Unlike physisorption in an Ag/MgO system, polar covalent component contributes to the Ag/TiC interfacial adhesion in most cases, however, for the case of 1-3 ML coverage, an additional electrostatic interaction between the absorption layer and the substrate should be taken into account. The value of ideal work of separation, 1.55 J/m2 for a 3-ML-thick adlayer accords well with other calculations. The calculations predict that Ag does not wet TiC(001) surface and prefers a three-dimensional growth mode in the absence of kinetic factor. This work reports on a clear site and coverage dependence of the measurable physical parameters, which would benefit the understanding of Ag/TiC (001) interface and the analysis of experimental data.

  2. 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.

  3. 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.

  4. Facet-Dependent Interactions of Islet Amyloid Polypeptide with Gold Nanoparticles: Implications for Fibril Formation and Peptide-Induced Lipid Membrane Disruption

    PubMed Central

    2017-01-01

    A comprehensive understanding of the mechanisms of interaction between proteins or peptides and nanomaterials is crucial for the development of nanomaterial-based diagnostics and therapeutics. In this work, we systematically explored the interactions between citrate-capped gold nanoparticles (AuNPs) and islet amyloid polypeptide (IAPP), a 37-amino acid peptide hormone co-secreted with insulin from the pancreatic islet. We utilized diffusion-ordered spectroscopy, isothermal titration calorimetry, localized surface plasmon resonance spectroscopy, gel electrophoresis, atomic force microscopy, transmission electron microscopy (TEM), and molecular dynamics (MD) simulations to systematically elucidate the underlying mechanism of the IAPP–AuNP interactions. Because of the presence of a metal-binding sequence motif in the hydrophilic peptide domain, IAPP strongly interacts with the Au surface in both the monomeric and fibrillar states. Circular dichroism showed that AuNPs triggered the IAPP conformational transition from random coil to ordered structures (α-helix and β-sheet), and TEM imaging suggested the acceleration of IAPP fibrillation in the presence of AuNPs. MD simulations revealed that the IAPP–AuNP interactions were initiated by the N-terminal domain (IAPP residues 1–19), which subsequently induced a facet-dependent conformational change in IAPP. On a Au(111) surface, IAPP was unfolded and adsorbed directly onto the Au surface, while for the Au(100) surface, it interacted predominantly with the citrate adlayer and retained some helical conformation. The observed affinity of AuNPs for IAPP was further applied to reduce the level of peptide-induced lipid membrane disruption. PMID:28260837

  5. 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.

  6. The structure of adsorbed bromide concurrent with the underpotential deposition (UPD) of Cu on Pt(111)

    NASA Astrophysics Data System (ADS)

    Marković, Nenad M.; Lucas, Chris A.; Gasteiger, Hubert A.; Ross, Philip N.

    1997-02-01

    The adsorption of bromide anions concurrent with the underpotential deposition (UPD) of Cu on Pt(111) was examined utilizing ex-situ LEED and in-situ surface X-ray scattering for structure determination, in combination with coverage determination by rotating ring disk flux measurements with the Pt(111) single crystal as the disk electrode. The results show definitively that Cu UPD on Pt(111) in the presence of bromide is a two-step process, with the total amount of Cu deposited at underpotentials ˜0.95 ± 5% ML (1 ML = 1 adatom per Pt atom). The results also indicate that the surface coverage by adsorbed bromide undergoes only a small (<0.05 ML) change upon the deposition of Cu, even up to a nominal monolayer. We propose a model wherein the first stage of deposition occurs by displacement of the close-packed hexagonal layer of Br adatoms by Cu adatoms through a "turn-over" process, in which Cu is sandwiched between the Pt surface and the Br overlayer, leading to the formation of an ordered Pt(111)CuBr bilayer intermediate phase which closely resembles the (111) planes of the Cu(I)Br crystal. The coverage of both Cu and Br in this intermediate phase is ˜0.5 ML. The second stage is the filling-in of the Cu plane of the bilayer to form a pseudomorphic (1 × 1) Cu monolayer and a disordered Br adlayer with a coverage of ˜0.4 ML. The same mechanism is suggested for Cu UPD on Pt(111) in solutions containing chloride anions.

  7. Optical Diagnostics of the Plasma and Surface during Inductively Coupled Plasma Etching

    NASA Astrophysics Data System (ADS)

    Herman, Irving P.

    1999-10-01

    The use of optical diagnostics to analyze the etching of Si, Ge, and InP by chlorine in an inductively coupled plasma (ICP) is investigated. Optical probes, along with other conventional plasma diagnostics, are used to characterize the process through measurements of the constituents of the plasma and the surface composition to obtain a more complete picture of the etching process. Neutral Cl2 and Cl densities are determined by optical emission actinometry by following optical emission from Cl_2. The absolute densities of Cl_2^+ and Cl^+ are determined by laser- induced fluorescence (LIF) of Cl_2^+ and Langmuir probe measurements of the total positive ion density. The surface is probed by using laser-induced thermal desorption with an XeCl laser (308 nm) to desorb the steady-state adlayer and optical methods to detect these desorbed species. The development of a new method to detect optically these laser desorbed (LD) species is detailed, that of examining transient changes in the plasma-induced emission (PIE). This LD-PIE method is more universal than the previously reported detection by LIF (LD-LIF), but requires more calibration due to varying electron density and temperature with varying plasma conditions. This is detailed for Si etching, for which LD-PIE and LD-LIF results are compared. The calibration methods are seen to be valid when the surface is analyzed as the rf power supplied to the reactor is varied. The electron density - needed for LD-PIE calibration - is measured by microwave interferometry. An improved understanding of the etching mechanism is obtained by combining the results of each of these measurements. This work was supported by NSF Grant No. DMR-98-15846. note

  8. Interface effects between germanene and Au(1 1 1) from first principles

    NASA Astrophysics Data System (ADS)

    Li, Fengping; Wei, Wei; Yu, Lin; Huang, Baibiao; Dai, Ying

    2017-03-01

    We study two-dimensional (2D) germanene supported on Au(1 1 1) to determine the structural, electronic and interface interaction properties on the basis of first-principles electronic calculations. In light of the lattice commensurability, (2  ×  2)/(√7  ×  √7) and (√3  ×  √3)/(√7  ×  √7) germanene/Au(1 1 1) superstructures are obtained with low-binding energy. We find that the interface effects between germanene and Au(1 1 1) break the inversion symmetry of germanene to a significant extent. The electron accumulation layer between germanene and Au(1 1 1) bonds the adlayer and substrate together, indicating strong adsorption behavior. Charge transfer occurs from Au(1 1 1) to germanene with the formation of a dipole layer. In addition, the intense electronic orbital hybridization effects between germanene and Au(1 1 1) are revealed through the atomic projected band structures. Clearly, resonant behavior occurs between germanene p orbitals and Au(1 1 1) s orbitals. As germanene is peeled off from Au(1 1 1), the band structures are characterized as metallic, and in the absence of the Au(1 1 1) substrate the band structure of (√3  ×  √3) single layer germanene demonstrates a lower effective mass due to its higher geometrical symmetry, which is similar to that of planar graphene. This paper shows that Au(1 1 1) is a suitable candidate for the growth of germanene, and our results offer useful information for the application of germanene in electronic devices.

  9. Coexistence of ice clusters and liquid-like water clusters on the Ru(0001) surface.

    PubMed

    Liu, Feng; Sturm, J M; Lee, Chris J; Bijkerk, Fred

    2017-03-10

    The RAIRS spectra of water adsorbed on Ru(0001) at 85 K are recorded from 600 cm(-1) to 4000 cm(-1). Measured at water coverages from 0.13 ML to 2.0 ML, the RAIRS spectra suggest that chemisorption of water on Ru(0001) depends on coverage. Water adsorbs on a clean Ru surface as chemisorbed ice-like clusters (likely through an O-Ru bond) up to 0.33 ML. Above this coverage, the chemisorbed layer saturates. Upon more exposure, water adsorbs as a liquid-like H-bonded layer without bonding to the Ru substrate. The chemisorbed water absorbs 7 times less IR per molecule than the liquid-like structure, which indicates that the orientation of the chemisorbed water is more parallel to the surface. Additionally, the influence of water-Ru bonding on H-bonding is reflected in the OH symmetric stretching mode. Under perturbation from water-Ru bonding, a large red shift (40 cm(-1)) in the free OH stretching frequency is observed in the chemisorbed clusters. By deconvoluting the main H-bonded OH stretching peak into five Gaussian sub-bands at 2945 ± 5 cm(-1), 3210 ± 5 cm(-1), 3300 ± 15 cm(-1), 3430 ± 5 cm(-1) and 3570 ± 10 cm(-1), changes in the H-bonding network are rationalized in terms of H-bonding motifs. The donor-acceptor-acceptor motif is significant only in the chemisorbed clusters. On the other hand, the donor-acceptor motif dominates in the liquid-like structure, which increases the disorder present in the adlayer. Although chemisorption is suppressed above 0.33 ML, no structural changes in the ice-like clusters are observed up to multilayer coverage. Therefore, ice-like and liquid-like water coexist in a meta-stable state at 85 K.

  10. 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

  11. 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

  12. 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.

  13. 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.

  14. Nitroxide malonate methanofullerene as biomimetic model of interaction of nitroxide species with antioxidants.

    PubMed

    Melnikova, N B; Korobko, V M; Gulenova, M V; Gubskaya, V P; Fazlleeva, G M; Zhiltsova, O E; Kochetkov, E N; Poddel'sky, A I; Nuretdinov, I A

    2015-12-01

    Bis-nitroxide malonate methanofullerene (NO)2-MF was studied as a biomimetic model of reduction-oxidation activity with natural compounds-cytochrome c (cyt c), dihydroquercetin (DHQ), ascorbic acid (AA) and synthetic drug-1-(β-oxyethyl)-4,6-dimethyl-1,2-dihydro-2-oxopyrimidine (xymedon(®)). (NO)2-MF may be used as the component of Langmuir monolayers on an aqueous subphase and as the adsorbate on silica gel. The activity of (NO)2-MF in the reaction with cyt c was compared with the effect of nitroxide species such as gaseous nitric oxide, 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) by using UV-vis and EPR-spectra. It has been shown, that iron(III) in cyt c(3+) under action (NO)2-MF was reduced up to iron(II), similar effect was observed under the influence of gaseous NO in aqueous solution, but reduction of iron(III) in heme cyt c was reversible in the presence of TEMPO. Therefore, the state of Fe-heme in cyt c can be used as the indicator of the interaction of cyt c with nitroxide species in vitro. The interaction of cyt c, DHQ, xymedon(®) with (NO)2-MF monolayers was confirmed by the increasing of limiting area А0 from 0.88 nm(2) up to 1.70 nm(2) of (NO)2-MF on the aqueous subphase, by the paramagnetism and UV-vis spectral data changes. These results can be explained by appearance of oxoammonium ion (NO(+))2-MF adlayers and monolayers. The antioxidant and regenerating effects were shown when treating wounds by xymedon(®) in the presence of additives (0.001%) of (NO)2-MF in the experiments on the rats.

  15. Determination of configuration of arsenite-glutathione complexes using ECSTM.

    PubMed

    Han, Mei-Juan; Meng, Xiaoguang; Lippincott, Lee

    2007-12-10

    Inorganic arsenicals such as arsenite [As(III)] and arsenate [As(V)] are known human carcinogens. The interactions of As(III) with sulfhydryl groups of peptides and proteins are very important mechanisms for the toxicity and metabolism of arsenic in mammals. The present study was designed to explore the application of electrochemical scanning tunneling microscopy (ECSTM) for determining the configuration of complexes formed between As(III) and glutathione (GSH) in solution. The configurations of GSH and As(III)-GSH complexes were imaged on the Au(111) surface in a 0.1M NaClO(4) solution. High-resolution STM images revealed that the As(III) and GSH formed a As(GS)(3) complex. The orientation and packing arrangement of the molecular adlayers were also seen clearly from the images and molecular models constructed using the Chemical Window and Hyperchem software package. The configuration of GSH in As(GS)(3) was found to be different from single GSH. UV-vis spectra indicated the emergence of an absorption shoulder in the range 250-280 nm for the aged As(III)-GSH solution, compared to the spectra of single As(III) and GSH solutions. MS spectra showed the presence of a new peak for the aged As(III)-GSH solution at m/z 992 corresponding to the As(GS)(3) complex. The results obtained by the last two methods verify the compound imaged by using STM is As(GS)(3). Studying the interactions of As(III) and peptides and knowing the structure details of the complexes are a significant step toward a better understanding of the interactions between As(III) and proteins and the mechanism of arsenic toxicology. ECSTM will be especially valuable for the determination of competitive interactions of GSH and proteins with arsenic.

  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. Manipulating cluster size of polyanion-stabilized Fe3O4 magnetic nanoparticle clusters via electrostatic-mediated assembly for tunable magnetophoresis behavior

    NASA Astrophysics Data System (ADS)

    Yeap, Swee Pin; Ahmad, Abdul Latif; Ooi, Boon Seng; Lim, JitKang

    2015-10-01

    We report in this article an approach for manipulating the size of magnetic nanoparticle clusters (MNCs) via electrostatic-mediated assembly technique using an electrolyte as a clustering agent. The clusters were surface-tethered with poly(sodium 4-styrenesulfonate) (PSS) through electrostatic compensation to enhance their colloidal stability. Dynamic light scattering was employed to trace the evolution of cluster size. Simultaneously, electrophoretic mobility and Fourier transform infrared spectroscopy analyses were conducted to investigate the possible schemes involved in both cluster formation and PSS grafting. Results showed that the average hydrodynamic cluster size of the PSS/MNCs and their corresponding size distributions were successfully shifted by means of manipulating the suspension pH, the ionic nature of the electrolyte, and the electrolyte concentration. More specifically, the electrokinetic behavior of the particles upon interaction with the electrolyte plays a profound role in the formation of the PSS/MNCs. Nonetheless, the solubility of the polymer in electrolyte solution and the purification of the particles from residual ions should not be omitted in determining the effectiveness of this clustering approach. The PSS adlayer makes the resultant entities highly water-dispersible and provides electrosteric stabilization to shield the PSS/MNCs from aggregation. In this study, the experimental observations were analyzed and discussed on the basis of existing fundamental colloidal theories. The strategy of cluster size manipulation proposed here is simple and convenient to implement. Furthermore, manipulating the size of the MNCs also facilitates the tuning of magnetophoresis kinetics on exposure to low magnetic field gradient, which makes this nano-entity useful for engineering applications, specifically in separation processes.

  19. 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.

  20. Annealing-Induced Bi Bilayer on Bi2Te3 Investigated via Quasi-Particle-Interference Mapping.

    PubMed

    Schouteden, Koen; Govaerts, Kirsten; Debehets, Jolien; Thupakula, Umamahesh; Chen, Taishi; Li, Zhe; Netsou, Asteriona; Song, Fengqi; Lamoen, Dirk; Van Haesendonck, Chris; Partoens, Bart; Park, Kyungwha

    2016-09-27

    Topological insulators (TIs) are renowned for their exotic topological surface states (TSSs) that reside in the top atomic layers, and hence, detailed knowledge of the surface top atomic layers is of utmost importance. Here we present the remarkable morphology changes of Bi2Te3 surfaces, which have been freshly cleaved in air, upon subsequent systematic annealing in ultrahigh vacuum and the resulting effects on the local and area-averaging electronic properties of the surface states, which are investigated by combining scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and Auger electron spectroscopy (AES) experiments with density functional theory (DFT) calculations. Our findings demonstrate that the annealing induces the formation of a Bi bilayer atop the Bi2Te3 surface. The adlayer results in n-type doping, and the atomic defects act as scattering centers of the TSS electrons. We also investigated the annealing-induced Bi bilayer surface on Bi2Te3 via voltage-dependent quasi-particle-interference (QPI) mapping of the surface local density of states and via comparison with the calculated constant-energy contours and QPI patterns. We observed closed hexagonal patterns in the Fourier transform of real-space QPI maps with secondary outer spikes. DFT calculations attribute these complex QPI patterns to the appearance of a "second" cone due to the surface charge transfer between the Bi bilayer and the Bi2Te3. Annealing in ultrahigh vacuum offers a facile route for tuning of the topological properties and may yield similar results for other topological materials.

  1. 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.

  2. Atomic oxygen adsorption and absorption on Rh(111) and Ag(111)

    NASA Astrophysics Data System (ADS)

    Derouin, Jonathan D.

    A central question in the field of heterogeneous catalysis is how surface structure and subsurface species influence catalytic behavior. One key to answering that question is determining which surface structures and subsurface species are present under catalytically relevant conditions. This dissertation presents results of Auger electron spectroscopy, low energy electron diffraction, temperature programmed desorption, and scanning tunneling microscopy experiments on oxidized Rh(111) and Ag(111) crystals. Exposing Rh(111) to O2 produced a predominately (2 x 1) adlayer, but even after extended dosing, (2 x 2) domains were also present. Exposing Rh(111) to atomic oxygen yielded O coverages greater than 0.5 ML and (1 x 1) domains were observed to form along terrace step edges. However, (2 x 1) and (2 x 2) domains were still present. Atomic oxygen was used to oxidize Ag(111) in order to study the effect of sample temperature as well as oxygen flux and energy. When atomic oxygen was generated using a lower temperature thermal cracker, a variety of previously reported surface structures were observed. When O was generated using a higher filament temperature, the surface became highly corrugated, layers of Ag 2O appeared to form, and little subsurface oxygen was observed. To investigate the role of sample temperature, the Ag(111) sample was held at various temperatures while being exposed to atomic oxygen. For short doses, sample temperature had minimal effect on surface reconstruction. For longer doses, changes in sample temperature in the range of 490 K to 525 K had a substantial impact on surface reconstruction and subsurface oxygen absorption. Higher temperature dosing yielded the same surface structures which were observed after short doses. Lower temperature dosing with atomic oxygen resulted in subsurface oxygen formation and new structures which covered the surface. The results indicate the rich complexity of oxygen/transition metal interactions and illustrate how

  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. Anion adsorption induced surface reconstructions

    NASA Astrophysics Data System (ADS)

    Tang, Lei

    2005-11-01

    Surface stress plays an important role in the behavior of solid surfaces. Potential-controlled anion adsorption in electrolytes alters the surface stress of the electrode and results in morphology changes to the surfaces. With a combination of potential-induced surface stress measurement and in situ electrochemical scanning tunneling microscopy (STM), it is demonstrated that anion adsorption induces changes in structure of thin films and modifies the growth morphology and stress evolution in epitaxially grown films. Surface structural transitions in the heteroepitaxial system consisting of one to two gold monolayers on platinum substrates were observed. By increasing the potential, structural transitions, from (1 x 1), to a striped phase, to a hexagonal structure, occurred in the gold bilayer. This hexagonal structure was related to the formation of an ordered sulfate adlayer with a ( 3x7 ) structure. Such transitions were repeatable by cycling the potential. Furthermore, the transitions between various dislocation structures were affected by anion adsorption. The surface composition of the gold bilayer on Pt was measured by underpotential deposition of copper. By subtracting the contribution of a pure Pt surface from the gold bi-layer on Pt, a stress change of -2.4 N/m was observed, which agrees with the stress change of -2.46 N/m predicted to accompany formation of 1.5 MLs of coherent Au on Pt(111) from epitaxy theory. The Cu monolayer deposited on Au(111) from an acid sulfate electrolyte was found to be pseudomorphic while the Cu monolayer formed on Au(111) in vacuum was incoherent. The stress-thickness change associated with the coherent monolayer of copper on Au(111) in electrolyte was -0.6 N/m, while conventional epitaxy theories predict a value of +7.76 N/m. STM results elucidated the sulfate adsorption on the copper monolayer caused an expansion of the layer as evidenced by a Moire Structure. For the Cu monolayer on Au(111), the sulfate-induced expansion

  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. 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

  8. Potential-induced structural transitions of DL-homocysteine monolayers on Au(1 1 1) electrode surfaces

    NASA Astrophysics Data System (ADS)

    Zhang, Jingdong; Demetriou, Anna; Welinder, Anne Christina; Albrecht, Tim; Nichols, Richard J.; Ulstrup, Jens

    2005-12-01

    Monolayers of homocysteine on Au(1 1 1)-surfaces have been investigated by voltammetry, in situ scanning tunnelling microscopy (STM) and subtractively normalised interfacial Fourier transform spectroscopy (SNIFTIRS). A pair of sharp voltammetric peaks build up in the potential range 0 to -0.1 V (vs. SCE) in phosphate buffer pH 7.7. The peak half-widths are about 25 mV at a scan rate of 10 mV s -1. This is much smaller than for a one-electron Faradaic process (90.6 mV) under similar conditions. The coverage of homocysteine is 6.1 (±0.2) × 10 -10 mol cm -2, or 5.9 × 10 -5 C cm -2, from Au-S reductive desorption at -0.8 V (SCE) in 0.1 M NaOH, while the charge is only about 8 × 10 -6 C cm -2 (pH 7.7) for the 0 to -0.1 V peak. This suggests a capacitive origin. The peak potential and shape depend on pH. At pH 7.7 both cathodic and anodic peak currents reach a maximum, but drop at both higher and lower pH. The midpoint potential shows biphasic behaviour, decreasing linearly with increasing pH until pH 10.4 towards a constant value at higher pH. The cathodic and anodic peak charges decay at pH both higher and lower than 7.7. The homocysteine monolayer was investigated by in situ STM at different potentials at pH 7.7. The molecules pack into highly ordered domains around the peak potential. High-resolution in situ STM reveals a (√3 × 5) R30° lattice with three homocysteine molecules in each unit cell. The adlayer changes into disordered structures on either side of the peak potential. This process is reversible. We propose that the voltammetric peaks are capacitive. The ordered domains are formed only around the potential of zero charge (pzc) and dissipate at potentials on either side of the peak, inducing mirror charge flow in the metallic electrode as the charged -COO - and -NH3+ groups approach the surface. No bands for carboxylate coordinated to the surface were observed in SNIFTIRS implying more subtle orientation changes of the charged groups on transcending

  9. The Organic LED Surface:. a Synchrotron Radiation Photoemission Study

    NASA Astrophysics Data System (ADS)

    Pi, Tun-Wen; Yu, T. C.

    Tris(8-hydroxyquinolato) aluminum (Alq3), a prototypical molecule for organic light-emitting devices, has been studied via synchrotron radiation photoemission to investigate (1) the surface electronic structure of the molecules at room temperature and at elevated temperatures, (2) adsorption onto the inorganic Si(001)-2×1 surface, and (3) doping with the alkaline metal Mg. For case (1), three chemical environments of carbon are resolved. Moreover, the shake-up satellite structures are detected in all the N 1s, C 1s, O 1s, and Al 2p core-level spectra, but with different magnitudes. Annealing allows for a charge redistribution within Alq3 itself. As to case (2), the organic molecules not only passivate the dangling bonds, but also rupture the dimer bonds. The wave function of the surface dangling bonds and of the pyridyl side of an 8-quinolinol ligand overlaps greatly so that charge is polarized towards, the organic adlayer. However, the polarization diminishes at greater coverage. With regard to case (3), the N 1s core-level spectra appear as an Mg-induced charge-transfer component with a binding energy lower than the original component. This new component grows gradually in intensity with increasing concentration of the dopant. Moreover, Mg also affects the O 1s core, as manifested by a component lying at a +1.09 eV higher binding energy than the original component. The Mg 2p core-level spectra, although rather broad, exhibit a shift toward a lower binding energy with increasing Mg vapor. Upon examining all these experimental results, we propose that Mg in the surface Alq3 molecules forms clusters. Each cluster attaches to a pyridyl ring, affecting not only the nitrogen atom at that ring, but also the oxygen atom in the adjacent phenoxide ring. The depleted charge in the affected oxygen then flows about its adherent ligand and resides on the pyridyl ring at that ligand, resulting in a high Alq3 anion state.

  10. Charge Transfer as a Probe for the Interfacial Properties of Quantum Dot-Ligand Complexes

    NASA Astrophysics Data System (ADS)

    Weinberg, David Joseph

    This dissertation describes the study of charge transfer interactions between colloidal quantum dots (QDs) and molecular redox partners in the context of both fundamental investigations of charge recombination mechanisms in nanocrystal-molecule systems, and as a technique to probe the properties of the QD ligand shell. Charge separation in a system of CdS nanocrystals and organic hole acceptors results in the formation of a spin-correlated radical ion pair. Interrogating this photogenerated species with EPR and magnetic field effect transient absorption techniques reveals that the charge recombination dynamics of this donor-acceptor system are dictated by the radical pair intersystem crossing mechanism on the nanosecond timescale. These experiments also indicate that the photoinjected electron localizes at a CdS QD surface trap state, and the coupling between the electron and hole in this spin-correlated system is low. Additional studies involving the CdS QDs and organic hole acceptors are proposed which would investigate the exchange of charge and energy within the nanocrystal organic adlayer. Collisional charge transfer interactions between substituted benzoquinone molecules and PbS QDs coated with mixed monolayers of oleic acid and perfluorodecanethiol are monitored via photoluminescence and transient absorption spectroscopies. These experiments reveal that partially fluorinated ligand shells are less permeable to solution phase molecules and offer greater protection of the nanocrystal surface than their aliphatic counterparts. Only a small amount of fluorinated surfactant ( 20% surface coverage) is necessary to profoundly change the permeability of the ligand shell, and the protective nature of these fluorinated molecules is likely a combination of the molecular volume and oleophobicity of these ligands. Follow up work is discussed which would elucidate the influence of solvent and extent of surfactant fluorination on the permeability of these ligand shells, as

  11. A passive microfluidic hydrogen-air fuel cell with exceptional stability and high performance.

    PubMed

    Mitrovski, Svetlana M; Nuzzo, Ralph G

    2006-03-01

    We describe an advanced microfluidic hydrogen-air fuel cell (FC) that exhibits exceptional durability and high performance, most notably yielding stable output power (>100 days) without the use of an anode-cathode separator membrane. This FC embraces an entirely passive device architecture and, unlike conventional microfluidic designs that exploit laminar hydrodynamics, no external pumps are used to sustain or localize the reagent flow fields. The devices incorporate high surface area/porous metal and metal alloy electrodes that are embedded and fully immersed in liquid electrolyte confined in the channels of a poly(dimethylsiloxane) (PDMS)-based microfluidic network. The polymeric network also serves as a self-supporting membrane through which oxygen and hydrogen are supplied to the cathode and alloy anode, respectively, by permeation. The operational stability of the device and its performance is strongly dependent on the nature of the electrolyte used (5 M H2SO4 or 2.5 M NaOH) and composition of the anode material. The latter choice is optimized to decrease the sensitivity of the system to oxygen cross-over while still maintaining high activity towards the hydrogen oxidation reaction (HOR). Three types of high surface area anodes were tested in this work. These include: high-surface area electrodeposited Pt (Pt); high-surface area electrodeposited Pd (Pd); and thin palladium adlayers supported on a "porous" Pt electrode (Pd/Pt). The FCs display their best performance in 5 M H2SO4 using the Pd/Pt anode. This exceptional stability and performance was ascribed to several factors, namely: the high permeabilities of O2, H2, and CO2 in PDMS; the inhibition of the formation of insoluble carbonate species due to the presence of a highly acidic electrolyte; and the selectivity of the Pd/Pt anode toward the HOR. The stability of the device for long-term operation was modeled using a stack of three FCs as a power supply for a portable display that otherwise uses a 3 V

  12. 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

  13. Surface Morphology and Overlayer Formation Kinetics of OXYGEN/SILVER(110) Studied by Scanning Tunneling Microscopy

    NASA Astrophysics Data System (ADS)

    Pai, Woei Wu.

    1995-01-01

    I have applied scanning tunneling microscopy (STM) to study clean and oxygen-covered vicinal Ag(110) surfaces at room temperature. Experimental results of surface morphology/stability, surface mass transport and surface chemical reactivity are presented. On clean vicinal Ag(110) surfaces, the steps distribute under the influence of step-step interactions. The terrace width distributions indicate an additional oscillatory component besides an l^{-2} interaction term. If the surface is contaminated slightly (quasi-clean), isolated "pinning sites" impede the motion of steps. The interactions between steps push the steps across the pinning site, resulting in a curved step front. When oxygen atoms adsorb on stepped Ag(110), a dramatic change in surface morphology occurs. The surface separates into two distinct phases--step bunches and large terraces (facets). The orientational instability is closely related to the linear "added-row" structure of the oxygen overlayer, as the long O chains push steps into bunches. The O chains do not push the steps effectively when O chains orient perpendicular to steps, and the faceting proceeds through nucleation. If the O chains orient near parallel to steps, however, O chains push the steps easily and the faceting proceeds through spinodal decomposition. To understand the mass transport during faceting, I quantify the thermal step fluctuations by employing a Langevin statistical analysis. The mass transport mechanism at the step edge is shown to be by atomic exchange between steps and terraces, making the step an effective source or sink for Ag adatoms. This Ag source also proves essential in O overlayer formation, since both Ag and O atoms are incorporated into the "added -row" overlayer structure. Because an Ag source must be found during the adlayer formation, I show the surface morphology is sensitive to oxygen dosing pressure. Above a critical O pressure of 10^{-5} mbar, vacancy islands on terraces provide a second source of Ag

  14. 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

  15. 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

  16. 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

  17. 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.

  18. Core-Exciton Decay in Photoemission and the Nonmetal - Transition.

    NASA Astrophysics Data System (ADS)

    Zhang, Jiandi

    , and free clusters in which a metallization process exhibits with changing cluster size, we conclude that the average coordination numbers of 6 (or larger) or a hexagonal adlayer for mercury is required for the onset of metallicity. On the other hand, the Hg overlayers on Si(111)--a semiconductor surface, exhibit always metallic even in low coverages. This completely different behavior has been found to be caused by the strong surface bonding between the Hg adatoms and silicon substrate. A nonmetal to metal transition in alkali earth metal monolayers on transition metal surfaces has also been observed. The intensity change of the resonances related to Ba 5pto5d/4f and 5s to6p excitations suggests that there exists a nonmetal-metal transition in the Ba overlayers on Ni(111) though the overlayer structure is not clearly identified. On the other hand, for the magnesium overlayers on Mo(112), the dramatic changes of the density of states, the dispersion of the bands near E_{F}, and screening, have been observed across the nonmetal to metal transition in the overlayers. The changes of the resonance photon energy and the intensity of Mg to epsilond excitation with different coverages indicate a obvious correlation between the electronic structure (particularly final state screening effects) and the overlayer structure. The commensurate to incommensurate transition beyond 0.5 monolayer of coverage corresponds to the overlayer nonmetal-metal transition, which is due to the hybridization of Mg s and p bands and represents a transition from a localized (bondlike) to a delocalized (bandlike) phase for divalent atoms.

  19. PREFACE: Functionalized Liquid Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Girault, Hubert; Kornyshev, Alexei A.; Monroe, Charles W.; Urbakh, Michael

    2007-09-01

    Most natural processes take place at interfaces. For this reason, surface science has been a focal point of modern research. At solid-liquid interfaces one can induce various species to adsorb or react, and thus may study interactions between the substrate and adsorbates, kinetic processes, optical properties, etc. Liquid-liquid interfaces, formed by immiscible liquids such as water and oil, have a number of distinctive features. Both sides of the interface are amenable to detailed physical and chemical analysis. By chemical or electrochemical means, metal or semiconductor nanoparticles can be formed or localised at the interface. Surfactants can be used to tailor surface properties, and also to place organic molecular or supermolecular constructions at the boundary between the liquids. Electric fields can be used to drive ions from one fluid to another, or even change the shape of the interface itself. In many cases, both liquids are optically transparent, making functionalized liquid-liquid interfaces promising for various optical applications based on the transmission or reflection of light. An advantage common to most of these systems is self-assembly; because a liquid-liquid interface is not mechanically constrained like a solid-liquid interface, it can easily access its most stable state, even after it has been driven far from equilibrium. This special issue focuses on four modes of liquid-liquid interfacial functionalization: the controlled adsorption of molecules or nanoparticles, the formation of adlayers or films, electrowetting, and ion transfer or interface-localized reactions. Interfacial adsorption can be driven electrically, chemically, or mechanically. The liquid-liquid interface can be used to study how anisotropic particles orient at a surface under the influence of a field, how surfactants interact with other adsorbates, and how nanoparticles aggregate; the transparency of the interface also makes the chirality of organic adsorbates amenable to