Structural and Chemical Biology of Terpenoid Cyclases

PubMed Central

2017-01-01

The year 2017 marks the twentieth anniversary of terpenoid cyclase structural biology: a trio of terpenoid cyclase structures reported together in 1997 were the first to set the foundation for understanding the enzymes largely responsible for the exquisite chemodiversity of more than 80000 terpenoid natural products. Terpenoid cyclases catalyze the most complex chemical reactions in biology, in that more than half of the substrate carbon atoms undergo changes in bonding and hybridization during a single enzyme-catalyzed cyclization reaction. The past two decades have witnessed structural, functional, and computational studies illuminating the modes of substrate activation that initiate the cyclization cascade, the management and manipulation of high-energy carbocation intermediates that propagate the cyclization cascade, and the chemical strategies that terminate the cyclization cascade. The role of the terpenoid cyclase as a template for catalysis is paramount to its function, and protein engineering can be used to reprogram the cyclization cascade to generate alternative and commercially important products. Here, I review key advances in terpenoid cyclase structural and chemical biology, focusing mainly on terpenoid cyclases and related prenyltransferases for which X-ray crystal structures have informed and advanced our understanding of enzyme structure and function. PMID:28841019

Chemical Evolution of Interstellar Methanol Ice Analogs upon Ultraviolet Irradiation: The Role of the Substrate

NASA Astrophysics Data System (ADS)

Ciaravella, A.; Jiménez-Escobar, A.; Cosentino, G.; Cecchi-Pestellini, C.; Peres, G.; Candia, R.; Collura, A.; Barbera, M.; Di Cicca, G.; Varisco, S.; Venezia, A. M.

2018-05-01

An important issue in the chemistry of interstellar ices is the role of dust materials. In this work, we study the effect of an amorphous water-rich magnesium silicate deposited onto ZnSe windows on the chemical evolution of ultraviolet-irradiated methanol ices. For comparison, we also irradiate similar ices deposited onto bare ZnSe windows. Silicates are produced at relatively low temperatures exploiting a sol–gel technique. The chemical composition of the synthesized material reflects the forsterite stoichiometry. Si–OH groups and magnesium carbonates are incorporated during the process. The results show that the substrate material does affect the chemical evolution of the ice. In particular, the CO2/CO ratio within the ice is larger for methanol ices deposited onto the silicate substrate as a result of concurrent effects: the photolysis of carbonates present in the adopted substrate as a source of CO2, CO, and carbon and oxygen atoms; reactions of water molecules and hydroxyl radicals released from the substrate with the CO formed in the ice by the photolysis of the methanol ice; and changes in the structure and energy of the silicate surface by ultraviolet irradiation, leading to more favorable conditions for chemical reactions or catalysis at the grain surface. The results of our experiments allow such chemical effects contributed by the various substrate material components to be disentangled.

Communication: Enhanced chemical reactivity of graphene on a Ni(111) substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ambrosetti, Alberto; Silvestrelli, Pier Luigi

2016-03-21

Due to the unique combination of structural, mechanical, and transport properties, graphene has emerged as an exceptional candidate for catalysis applications. The low chemical reactivity caused by sp{sup 2} hybridization and strongly delocalized π electrons, however, represents a main challenge for straightforward use of graphene in its pristine, free-standing form. Following recent experimental indications, we show that due to charge hybridization, a Ni(111) substrate can enhance the chemical reactivity of graphene, as exemplified by the interaction with the CO molecule. While CO only physisorbs on free-standing graphene, chemisorption of CO involving formation of ethylene dione complexes is predicted in Ni(111)-graphene.more » Higher chemical reactivity is also suggested in the case of oxidized graphene, opening the way to a simple and efficient control of graphene chemical properties, devoid of complex defect patterning or active metallic structures deposition.« less

Review of Recent Progress of Plasmonic Materials and Nano-Structures for Surface-Enhanced Raman Scattering

PubMed Central

Wang, Alan X.; Kong, Xianming

2015-01-01

Surface-enhanced Raman scattering (SERS) has demonstrated single-molecule sensitivity and is becoming intensively investigated due to its significant potential in chemical and biomedical applications. SERS sensing is highly dependent on the substrate, where excitation of the localized surface plasmons (LSPs) enhances the Raman scattering signals of proximate analyte molecules. This paper reviews research progress of SERS substrates based on both plasmonic materials and nano-photonic structures. We first discuss basic plasmonic materials, such as metallic nanoparticles and nano-rods prepared by conventional bottom-up chemical synthesis processes. Then, we review rationally-designed plasmonic nano-structures created by top-down approaches or fine-controlled synthesis with high-density hot-spots to provide large SERS enhancement factors (EFs). Finally, we discuss the research progress of hybrid SERS substrates through the integration of plasmonic nano-structures with other nano-photonic devices, such as photonic crystals, bio-enabled nanomaterials, guided-wave systems, micro-fluidics and graphene. PMID:26900428

Review of Recent Progress of Plasmonic Materials and Nano-Structures for Surface-Enhanced Raman Scattering.

PubMed

Wang, Alan X; Kong, Xianming

2015-06-01

Surface-enhanced Raman scattering (SERS) has demonstrated single-molecule sensitivity and is becoming intensively investigated due to its significant potential in chemical and biomedical applications. SERS sensing is highly dependent on the substrate, where excitation of the localized surface plasmons (LSPs) enhances the Raman scattering signals of proximate analyte molecules. This paper reviews research progress of SERS substrates based on both plasmonic materials and nano-photonic structures. We first discuss basic plasmonic materials, such as metallic nanoparticles and nano-rods prepared by conventional bottom-up chemical synthesis processes. Then, we review rationally-designed plasmonic nano-structures created by top-down approaches or fine-controlled synthesis with high-density hot-spots to provide large SERS enhancement factors (EFs). Finally, we discuss the research progress of hybrid SERS substrates through the integration of plasmonic nano-structures with other nano-photonic devices, such as photonic crystals, bio-enabled nanomaterials, guided-wave systems, micro-fluidics and graphene.

Direct growth of ZnO tetrapod on glass substrate by Chemical Vapor Deposition Technique

NASA Astrophysics Data System (ADS)

Fadzil, M. F. M.; Rahman, R. A.; Azhar, N. E. A.; Aziz, T. N. T. A.; Zulkifli, Z.

2018-03-01

This research demonstrates the growth of ZnO tetrapod structure on glass substrate for different types of flow gas and at different growth temperatures. The study on the morphological structure and electrical properties of ZnO thin film growth by Chemical Vapour Deposition (CVD) technique showed that the optimum growth temperature was obtained at 750°C with ZnO nanotetrapod morphological structure. Introducing Nitrogen gas flow during the growth process exhibited leg-to-leg linking ZnO tetrapods morphology. The electrical properties of ZnO tetrapods film were measured by using two point probes and it shows that, the sample growth in Ar and O2 atmosphere have better I-V characteristic.

Anion-induced reconstitution of a self-assembling system to express a chloride-binding Co10L15 pentagonal prism.

PubMed

Riddell, Imogen A; Smulders, Maarten M J; Clegg, Jack K; Hristova, Yana R; Breiner, Boris; Thoburn, John D; Nitschke, Jonathan R

2012-09-01

Biochemical systems are adaptable, capable of reconstitution at all levels to achieve the functions associated with life. Synthetic chemical systems are more limited in their ability to reorganize to achieve new functions; they can reconfigure to bind an added substrate (template effect) or one binding event may modulate a receptor's affinity for a second substrate (allosteric effect). Here we describe a synthetic chemical system that is capable of structural reconstitution on receipt of one anionic signal (perchlorate) to create a tight binding pocket for another anion (chloride). The complex, barrel-like structure of the chloride receptor is templated by five perchlorate anions. This second-order templation phenomenon allows chemical networks to be envisaged that express more complex responses to chemical signals than is currently feasible.

Process for forming exoergic structures with the use of a plasma

DOEpatents

Kelly, Michael D.

1989-02-21

A method of forming exoergic structures, as well as exoergic structures produced by the method, is provided. The method comprises the steps of passing a plasma-forming gas through a plasma spray gun, forming a plasma spray, introducing exoergic material into the plasma spray and directing the plasma spray toward a substrate, and allowing the exoergic material to become molten, without chemically reacting in the plasma spray and to thereafter impinge on the substrate to form a solid mass of exoergic material, the shape of which corresponds to the shape of the substrate.

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

NASA Astrophysics Data System (ADS)

McBriarty, Martin E.

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

Mechanistic Insights into the Specificity of Human Cytosolic Sulfotransferase 2A1 (hSULT2A1) for Hydroxylated Polychlorinated Biphenyls Through the Use of Fluoro-tagged Probes

PubMed Central

Ekuase, E.J.; van ’t Erve, T.J.; Rahaman, A.; Robertson, L.W.; Duffel, M.W.; Luthe, G.

2015-01-01

Determining the relationships between the structures of substrates and inhibitors and their interactions with drug-metabolizing enzymes is of prime importance in predicting the toxic potential of new and legacy xenobiotics. Traditionally, quantitative structure activity relationship (QSAR) studies are performed with many distinct compounds. Based on the chemical properties of the tested compounds, complex relationships can be established so that models can be developed to predict toxicity of novel compounds. In this study, the use of fluorinated analogues as supplemental QSAR compounds was investigated. Substituting fluorine induces changes in electronic and steric properties of the substrate without substantially changing the chemical backbone of the substrate. In vitro assays were performed using purified human cytosolic sulfotransferase hSULT2A1 as a model enzyme. A mono-hydroxylated polychlorinated biphenyl (4-OH PCB 14) and its four possible mono-fluoro analogues were used as test compounds. Remarkable similarities were found between this approach and previously published QSAR studies for hSULT2A1. Both studies implicate the importance of dipole moment and dihedral angle as being important to PCB structure in respect to being substrates for hSULT2A1. We conclude that mono-fluorinated analogues of a target substrate can be a useful tool to study the structure activity relationships for enzyme specificity. PMID:26165989

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Yu; School of Mechanical and Electrical Engineering, Wuhan Institute of Technology, Wuhan 430073; Guo, Zhiguang, E-mail: zguo@licp.cas.cn

Graphical abstract: A double-metal-assisted chemical etching method is employed to fabricate superhydrophobic surfaces, showing a good superhydrophobicity with the contact angle of about 170°, and the sliding angle of about 0°. Meanwhile, the potential formation mechanism about it is also presented. Highlights: ► A double-metal-assisted chemical etching method is employed to fabricate superhydrophobic surfaces. ► The obtained surfaces show good superhydrophobicity with a high contact angle and low sliding angle. ► The color of the etched substrate dark brown or black and it is so-called black silicon. -- Abstract: Silicon substrates treated by metal-assisted chemical etching have been studied formore » many years since they could be employed in a variety of electronic and optical devices such as integrated circuits, photovoltaics, sensors and detectors. However, to the best of our knowledge, the chemical etching treatment on the same silicon substrate with the assistance of two or more kinds of metals has not been reported. In this paper, we mainly focus on the etching time and finally obtain a series of superhydrophobic silicon surfaces with novel etching structures through two successive etching processes of Cu-assisted and Ag-assisted chemical etching. It is shown that large-scale homogeneous but locally irregular wire-like structures are obtained, and the superhydrophobic surfaces with low hysteresis are prepared after the modifications with low surface energy materials. It is worth noting that the final silicon substrates not only possess high static contact angle and low hysteresis angle, but also show a black color, indicating that the superhydrophobic silicon substrate has an extremely low reflectance in a certain range of wavelengths. In our future work, we will go a step further to discuss the effect of temperature, the size of Cu nanoparticles and solution concentration on the final topography and superhydrophobicity.« less

Wet-chemical passivation of atomically flat and structured silicon substrates for solar cell application

NASA Astrophysics Data System (ADS)

Angermann, H.; Rappich, J.; Korte, L.; Sieber, I.; Conrad, E.; Schmidt, M.; Hübener, K.; Polte, J.; Hauschild, J.

2008-04-01

Special sequences of wet-chemical oxidation and etching steps were optimised with respect to the etching behaviour of differently oriented silicon to prepare very smooth silicon interfaces with excellent electronic properties on mono- and poly-crystalline substrates. Surface photovoltage (SPV) and photoluminescence (PL) measurements, atomic force microscopy (AFM) and scanning electron microscopy (SEM) investigations were utilised to develop wet-chemical smoothing procedures for atomically flat and structured surfaces, respectively. Hydrogen-termination as well as passivation by wet-chemical oxides were used to inhibit surface contamination and native oxidation during the technological processing. Compared to conventional pre-treatments, significantly lower micro-roughness and densities of surface states were achieved on mono-crystalline Si(100), on evenly distributed atomic steps, such as on vicinal Si(111), on silicon wafers with randomly distributed upside pyramids, and on poly-crystalline EFG ( Edge-defined Film-fed- Growth) silicon substrates. The recombination loss at a-Si:H/c-Si interfaces prepared on c-Si substrates with randomly distributed upside pyramids was markedly reduced by an optimised wet-chemical smoothing procedure, as determined by PL measurements. For amorphous-crystalline hetero-junction solar cells (ZnO/a-Si:H(n)/c-Si(p)/Al) with textured c-Si substrates the smoothening procedure results in a significant increase of short circuit current Isc, fill factor and efficiency η. The scatter in the cell parameters for measurements on different cells is much narrower, as compared to conventional pre-treatments, indicating more well-defined and reproducible surface conditions prior to a-Si:H emitter deposition and/or a higher stability of the c-Si surface against variations in the a-Si:H deposition conditions.

Structural characteristics of a non-polar ZnS layer on a ZnO buffer layer formed on a sapphire substrate by mist chemical vapor deposition

NASA Astrophysics Data System (ADS)

Okita, Koshi; Inaba, Katsuhiko; Yatabe, Zenji; Nakamura, Yusui

2018-06-01

ZnS is attractive as a material for low-cost light-emitting diodes. In this study, a non-polar ZnS layer was epitaxially grown on a sapphire substrate by inserting a ZnO buffer layer between ZnS and sapphire. The ZnS and ZnO layers were grown by a mist chemical vapor deposition system with a simple setup operated under atmospheric pressure. The sample was characterized by high-resolution X-ray diffraction measurements including 2θ/ω scans, rocking curves, and reciprocal space mapping. The results showed that an m-plane wurtzite ZnS layer grew epitaxially on an m-plane wurtzite ZnO buffer layer formed on the m-plane sapphire substrate to provide a ZnS/ZnO/sapphire structure.

Medicinal Chemistry and Molecular Modeling: An Integration to Teach Drug Structure-Activity Relationship and the Molecular Basis of Drug Action

ERIC Educational Resources Information Center

Carvalho, Ivone; Borges, Aurea D. L.; Bernardes, Lilian S. C.

2005-01-01

The use of computational chemistry and the protein data bank (PDB) to understand and predict the chemical and molecular basis involved in the drug-receptor interactions is discussed. A geometrical and chemical overview of the great structural similarity in the substrate and inhibitor is provided.

Determination of conformation and orientation of immobilized peptides and proteins at buried interfaces

NASA Astrophysics Data System (ADS)

Shen, Lei; Ulrich, Nathan W.; Mello, Charlene M.; Chen, Zhan

2015-01-01

Surface immobilized peptides/proteins have important applications such as antimicrobial coating and biosensing. We report a study of such peptides/proteins using sum frequency generation vibrational spectroscopy and ATR-FTIR. Immobilization on surfaces via physical adsorption and chemical coupling revealed that structures of chemically immobilized peptides are determined by immobilization sites, chemical environments, and substrate surfaces. In addition, controlling enzyme orientation by engineering the surface immobilization site demonstrated that structures can be well-correlated to measured chemical activity. This research facilitates the development of immobilized peptides/proteins with improved activities by optimizing their surface orientation and structure.

Arginine Kinase. Joint Crystallographic & NMR RDC Analyses link Substrate-Associated Motions to Intrinsic Flexibility

PubMed Central

Niu, Xiaogang; Brüschweiler-Li, Lei; Davulcu, Omar; Skalicky, Jack J.; Brüschweiler, Rafael; Chapman, Michael S.

2010-01-01

The phosphagen kinase family, including creatine and arginine kinases, catalyze the reversible transfer of a “high energy” phosphate between ATP and a phospho-guanidino substrate. They have become a model for the study of both substrate-induced conformational change and intrinsic protein dynamics. Prior crystallographic studies indicated large substrate-induced domain rotations, but differences among a recent set of arginine kinase structures was interpreted as a plastic deformation. Here, the structure of Limulus substrate-free arginine kinase is refined against high resolution crystallographic data and compared quantitatively with NMR chemical shifts and residual dipolar couplings (RDCs). This demonstrates the feasibility of this type of RDC analysis of proteins that are large by NMR standards (42 kDa), and illuminates the solution structure, free from crystal-packing constraints. Detailed comparison of the 1.7 Å resolution substrate-free crystal structure against the 1.2 Å transition state analog complex shows large substrate-induced domain motions which can be broken down into movements of smaller quasi-rigid bodies. The solution state structure of substrate-free arginine kinase is most consistent with an equilibrium of substrate-free and –bound structures, with the substrate-free form dominating, but with varying displacements of the quasi-rigid groups. Rigid-group rotations evident from the crystal structures are about axes previously associated with intrinsic millisecond dynamics using NMR relaxation dispersion. Thus, “substrate-induced” motions are along modes that are intrinsically flexible in the substrate-free enzyme, and likely involve some degree of conformational selection. PMID:21075117

Laser Microperforated Biodegradable Microbial Polyhydroxyalkanoate Substrates for Tissue Repair Strategies: An Infrared Microspectroscopy Studey

DOE Office of Scientific and Technical Information (OSTI.GOV)

G Ellis; P Cano; M Jadraque

Flexible and biodegradable film substrates prepared by solvent casting from poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) solutions in chloroform were microperforated by ultraviolet laser ablation and subsequently characterized using infrared (IR) microspectroscopy and imaging techniques and scanning electron microscopy (SEM). Both transmission synchrotron IR microspectroscopy and attenuated total reflectance microspectroscopy measurements demonstrate variations in the polymer at the ablated pore rims, including evidence for changes in chemical structure and crystallinity. SEM results on microperforated PHBHV substrates after cell culture demonstrated that the physical and chemical changes observed in the biomaterial did not hinder cell migration through the pores.

Graphene-Based Electrode for a Supercapacitor

NASA Technical Reports Server (NTRS)

Chen, Bin (Inventor); Meyyappan, Meyya (Inventor)

2015-01-01

A supercapacitor electrode mechanism comprising an electrically conductive, porous substrate, having one or more metallic oxides deposited on a first surface and a chemically reduced graphene oxide deposited on a second surface, to thereby provide an electrical double layer associated with the substrate. The substrate may be carbon paper or a similar substance. The layers of the supercapacitor are optionally rolled into an approximately cylindrical structure.

Complex, multi-scale small intestinal topography replicated in cellular growth substrates fabricated via chemical vapor deposition of Parylene C.

PubMed

Koppes, Abigail N; Kamath, Megha; Pfluger, Courtney A; Burkey, Daniel D; Dokmeci, Mehmet; Wang, Lin; Carrier, Rebecca L

2016-08-22

Native small intestine possesses distinct multi-scale structures (e.g., crypts, villi) not included in traditional 2D intestinal culture models for drug delivery and regenerative medicine. The known impact of structure on cell function motivates exploration of the influence of intestinal topography on the phenotype of cultured epithelial cells, but the irregular, macro- to submicron-scale features of native intestine are challenging to precisely replicate in cellular growth substrates. Herein, we utilized chemical vapor deposition of Parylene C on decellularized porcine small intestine to create polymeric intestinal replicas containing biomimetic irregular, multi-scale structures. These replicas were used as molds for polydimethylsiloxane (PDMS) growth substrates with macro to submicron intestinal topographical features. Resultant PDMS replicas exhibit multiscale resolution including macro- to micro-scale folds, crypt and villus structures, and submicron-scale features of the underlying basement membrane. After 10 d of human epithelial colorectal cell culture on PDMS substrates, the inclusion of biomimetic topographical features enhanced alkaline phosphatase expression 2.3-fold compared to flat controls, suggesting biomimetic topography is important in induced epithelial differentiation. This work presents a facile, inexpensive method for precisely replicating complex hierarchal features of native tissue, towards a new model for regenerative medicine and drug delivery for intestinal disorders and diseases.

Mechanisms of the micro-crack generation in an ultra-thin AlN/GaN superlattice structure grown on Si(110) substrates by metalorganic chemical vapor deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, X. Q., E-mail: xq-shen@aist.go.jp; Takahashi, T.; Ide, T.

2015-09-28

We investigate the generation mechanisms of micro-cracks (MCs) in an ultra-thin AlN/GaN superlattice (SL) structure grown on Si(110) substrates by metalorganic chemical vapor deposition. The SL is intended to be used as an interlayer (IL) for relaxing tensile stress and obtaining high-quality crack-free GaN grown on Si substrates. It is found that the MCs can be generated by two different mechanisms, where large mismatches of the lattice constant (LC) and the coefficient of thermal expansion (CTE) play key roles in the issue. Different MC configurations (low-density and high-density MCs) are observed, which are considered to be formed during the differentmore » growth stages (SL growth and cooling down processes) due to the LC and the CTE effects. In-situ and ex-situ experimental results support the mechanism interpretations of the MCs generation. The mechanism understanding makes it possible to optimize the SL IL structure for growing high-quality crack-free GaN films on Si substrates for optical and electronic device applications.« less

Nanostructured Diamond Device for Biomedical Applications.

PubMed

Fijalkowski, M; Karczemska, A; Lysko, J M; Zybala, R; KozaneckI, M; Filipczak, P; Ralchenko, V; Walock, M; Stanishevsky, A; Mitura, S

2015-02-01

Diamond is increasingly used in biomedical applications because of its unique properties such as the highest thermal conductivity, good optical properties, high electrical breakdown voltage as well as excellent biocompatibility and chemical resistance. Diamond has also been introduced as an excellent substrate to make the functional microchip structures for electrophoresis, which is the most popular separation technique for the determination of analytes. In this investigation, a diamond electrophoretic chip was manufactured by a replica method using a silicon mold. A polycrystalline 300 micron-thick diamond layer was grown by the microwave plasma-assisted CVD (MPCVD) technique onto a patterned silicon substrate followed by the removal of the substrate. The geometry of microstructure, chemical composition, thermal and optical properties of the resulting free-standing diamond electrophoretic microchip structure were examined by CLSM, SFE, UV-Vis, Raman, XRD and X-ray Photoelectron Spectroscopy, and by a modified laser flash method for thermal property measurements.

Chemical vapor deposition growth

NASA Technical Reports Server (NTRS)

Ruth, R. P.; Manasevit, H. M.; Campbell, A. G.; Johnson, R. E.; Kenty, J. L.; Moudy, L. A.; Shaw, G. L.; Simpson, W. I.; Yang, J. J.

1978-01-01

The objective was to investigate and develop chemical vapor deposition (CVD) techniques for the growth of large areas of Si sheet on inexpensive substrate materials, with resulting sheet properties suitable for fabricating solar cells that would meet the technical goals of the Low Cost Silicon Solar Array Project. The program involved six main technical tasks: (1) modification and test of an existing vertical-chamber CVD reactor system; (2) identification and/or development of suitable inexpensive substrate materials; (3) experimental investigation of CVD process parameters using various candidate substrate materials; (4) preparation of Si sheet samples for various special studies, including solar cell fabrication; (5) evaluation of the properties of the Si sheet material produced by the CVD process; and (6) fabrication and evaluation of experimental solar cell structures, using impurity diffusion and other standard and near-standard processing techniques supplemented late in the program by the in situ CVD growth of n(+)/p/p(+) sheet structures subsequently processed into experimental cells.

Tungsten as a Chemically-Stable Electrode Material on Ga-Containing Piezoelectric Substrates Langasite and Catangasite for High-Temperature SAW Devices

PubMed Central

Rane, Gayatri K.; Seifert, Marietta; Menzel, Siegfried; Gemming, Thomas; Eckert, Jürgen

2016-01-01

Thin films of tungsten on piezoelectric substrates La3Ga5SiO14 (LGS) and Ca3TaGa3Si2O14 (CTGS) have been investigated as a potential new electrode material for interdigital transducers for surface acoustic wave-based sensor devices operating at high temperatures up to 800 °C under vacuum conditions. Although LGS is considered to be suitable for high-temperature applications, it undergoes chemical and structural transformation upon vacuum annealing due to diffusion of gallium and oxygen. This can alter the device properties depending on the electrode nature, the annealing temperature, and the duration of the application. Our studies present evidence for the chemical stability of W on these substrates against the diffusion of Ga/O from the substrate into the film, even upon annealing up to 800 °C under vacuum conditions using Auger electron spectroscopy and energy-dispersive X-ray spectroscopy, along with local studies using transmission electron microscopy. Additionally, the use of CTGS as a more stable substrate for such applications is indicated. PMID:28787898

Chemical vapor deposition growth

NASA Technical Reports Server (NTRS)

Ruth, R. P.; Manasevit, H. M.; Kenty, J. L.; Moudy, L. A.; Simpson, W. I.; Yang, J. J.

1976-01-01

The chemical vapor deposition (CVD) method for the growth of Si sheet on inexpensive substrate materials is investigated. The objective is to develop CVD techniques for producing large areas of Si sheet on inexpensive substrate materials, with sheet properties suitable for fabricating solar cells meeting the technical goals of the Low Cost Silicon Solar Array Project. Specific areas covered include: (1) modification and test of existing CVD reactor system; (2) identification and/or development of suitable inexpensive substrate materials; (3) experimental investigation of CVD process parameters using various candidate substrate materials; (4) preparation of Si sheet samples for various special studies, including solar cell fabrication; (5) evaluation of the properties of the Si sheet material produced by the CVD process; and (6) fabrication and evaluation of experimental solar cell structures, using standard and near-standard processing techniques.

Resonance assignments for the substrate binding domain of Hsp70 chaperone Ssa1 from Saccharomyces cerevisiae.

PubMed

Hu, Wanhui; Wu, Huiwen; Zhang, Hong; Gong, Weibin; Perrett, Sarah

2015-10-01

Hsp70 chaperone proteins play crucial roles in the cell. Extensive structural and functional studies have been performed for bacterial and mammalian Hsp70s. Ssa1 from Saccharomyces cerevisiae is a member of the Hsp70 family. In vivo and biochemical studies on Ssa1 have revealed that it regulates prion propagation and the cell cycle. However, no structural data has been obtained for Ssa1 up to now. Here we report the almost complete (96 %) (1)H, (13)C, (15)N backbone and side chain NMR assignment of the 18.8 kDa Ssa1 substrate binding domain. The construct includes residues 382-554, which corresponds to the entire substrate binding domain and two following α-helices in homologous structures. The secondary structure predicted from the assigned chemical shifts is consistent with that of homologous Hsp70 substrate binding domains.

A chemical proteomics approach for global analysis of lysine monomethylome profiling.

PubMed

Wu, Zhixiang; Cheng, Zhongyi; Sun, Mingwei; Wan, Xuelian; Liu, Ping; He, Tieming; Tan, Minjia; Zhao, Yingming

2015-02-01

Methylation of lysine residues on histone proteins is known to play an important role in chromatin structure and function. However, non-histone protein substrates of this modification remain largely unknown. An effective approach for system-wide analysis of protein lysine methylation, particularly lysine monomethylation, is lacking. Here we describe a chemical proteomics approach for global screening for monomethyllysine substrates, involving chemical propionylation of monomethylated lysine, affinity enrichment of the modified monomethylated peptides, and HPLC/MS/MS analysis. Using this approach, we identified with high confidence 446 lysine monomethylation sites in 398 proteins, including three previously unknown histone monomethylation marks, representing the largest data set of protein lysine monomethylation described to date. Our data not only confirms previously discovered lysine methylation substrates in the nucleus and spliceosome, but also reveals new substrates associated with diverse biological processes. This method hence offers a powerful approach for dynamic study of protein lysine monomethylation under diverse cellular conditions and in human diseases. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Effect of deposition pressure on the morphology and structural properties of carbon nanotubes synthesized by hot-filament chemical vapor deposition.

PubMed

Arendse, C J; Malgas, G F; Scriba, M R; Cummings, F R; Knoesen, D

2007-10-01

Hot-filament chemical vapor deposition has developed into an attractive method for the synthesis of various carbon nanostructures, including carbon nanotubes. This is primarily due to its versatility, low cost, repeatability, up-scalability, and ease of production. The resulting nano-material synthesized by this technique is dependent on the deposition conditions which can be easily controlled. In this paper we report on the effect of the deposition pressure on the structural properties and morphology of carbon nanotubes synthesized by hot-filament chemical vapor deposition, using Raman spectroscopy and high-resolution scanning electron microscopy, respectively. A 10 nm-thick Ni layer, deposited on a SiO2/Si substrate, was used as catalyst for carbon nanotube growth. Multi-walled carbon nanotubes with diameters ranging from 20-100 nm were synthesized at 500 degrees C with high structural perfection at deposition pressures between 150 and 200 Torr. Raman spectroscopy measurements confirm that the carbon nanotube deposit is homogeneous across the entire substrate area.

NMR Crystallography of Enzyme Active Sites: Probing Chemically-Detailed, Three-Dimensional Structure in Tryptophan Synthase

PubMed Central

Dunn, Michael F.

2013-01-01

Conspectus NMR crystallography – the synergistic combination of X-ray diffraction, solid-state NMR spectroscopy, and computational chemistry – offers unprecedented insight into three-dimensional, chemically-detailed structure. From its initial role in refining diffraction data of organic and inorganic solids, NMR crystallography is now being developed for application to active sites in biomolecules, where it reveals chemically-rich detail concerning the interactions between enzyme site residues and the reacting substrate that is not achievable when X-ray, NMR, or computational methodologies are applied in isolation. For example, typical X-ray crystal structures (1.5 to 2.5 Å resolution) of enzyme-bound intermediates identify possible hydrogen-bonding interactions between site residues and substrate, but do not directly identify the protonation state of either. Solid-state NMR can provide chemical shifts for selected atoms of enzyme-substrate complexes, but without a larger structural framework in which to interpret them, only empirical correlations with local chemical structure are possible. Ab initio calculations and molecular mechanics can build models for enzymatic processes, but rely on chemical details that must be specified. Together, however, X-ray diffraction, solid-state NMR spectroscopy, and computational chemistry can provide consistent and testable models for structure and function of enzyme active sites: X-ray crystallography provides a coarse framework upon which models of the active site can be developed using computational chemistry; these models can be distinguished by comparison of their calculated NMR chemical shifts with the results of solid-state NMR spectroscopy experiments. Conceptually, each technique is a puzzle piece offering a generous view of the big picture. Only when correctly pieced together, however, can they reveal the big picture at highest resolution. In this Account, we detail our first steps in the development of NMR crystallography for application to enzyme catalysis. We begin with a brief introduction to NMR crystallography and then define the process that we have employed to probe the active site in the β-subunit of tryptophan synthase with unprecedented atomic-level resolution. This approach has resulted in a novel structural hypothesis for the protonation state of the quinonoid intermediate in tryptophan synthase and its surprising role in directing the next step in the catalysis of L-Trp formation. PMID:23537227

Direct synthesis of large area graphene on insulating substrate by gallium vapor-assisted chemical vapor deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murakami, Katsuhisa, E-mail: k.murakami@bk.tsukuba.ac.jp; Hiyama, Takaki; Kuwajima, Tomoya

2015-03-02

A single layer of graphene with dimensions of 20 mm × 20 mm was grown directly on an insulating substrate by chemical vapor deposition using Ga vapor catalysts. The graphene layer showed highly homogeneous crystal quality over a large area on the insulating substrate. The crystal quality of the graphene was measured by Raman spectroscopy and was found to improve with increasing Ga vapor density on the reaction area. High-resolution transmission electron microscopy observations showed that the synthesized graphene had a perfect atomic-scale crystal structure within its grains, which ranged in size from 50 nm to 200 nm.

Advances in silicon carbide Chemical Vapor Deposition (CVD) for semiconductor device fabrication

NASA Technical Reports Server (NTRS)

Powell, J. Anthony; Petit, Jeremy B.; Matus, Lawrence G.

1991-01-01

Improved SiC chemical vapor deposition films of both 3C and 6H polytypes were grown on vicinal (0001) 6H-SiC wafers cut from single-crystal boules. These films were produced from silane and propane in hydrogen at one atmosphere at a temperature of 1725 K. Among the more important factors which affected the structure and morphology of the grown films were the tilt angle of the substrate, the polarity of the growth surface, and the pregrowth surface treatment of the substrate. With proper pregrowth surface treatment, 6H films were grown on 6H substrates with tilt angles as small as 0.1 degrees. In addition, 3C could be induced to grow within selected regions on a 6H substrate. The polarity of the substrate was a large factor in the incorporation of dopants during epitaxial growth. A new growth model is discussed which explains the control of SiC polytype in epitaxial growth on vicinal (0001) SiC substrates.

Electric field induced microstructures in thin films on physicochemically heterogeneous and patterned substrates.

PubMed

Srivastava, Samanvaya; Reddy, P Dinesh Sankar; Wang, Cindy; Bandyopadhyay, Dipankar; Sharma, Ashutosh

2010-05-07

We study by nonlinear simulations the electric field induced pattern formation in a thin viscous film resting on a topographically or chemically patterned substrate. The thin film microstructures can be aligned to the substrate patterns within a window of parameters where the spinodal length scale of the field induced instability is close to the substrate periodicity. We investigate systematically the change in the film morphology and order when (i) the substrate pattern periodicity is varied at a constant film thickness and (ii) the film thickness is varied at a constant substrate periodicity. Simulations show two distinct pathway of evolution when the substrate-topography changes from protrusions to cavities. The isolated substrate defects generate locally ordered ripplelike structures distinct from the structures on a periodically patterned substrate. In the latter case, film morphology is governed by a competition between the pattern periodicity and the length scale of instability. Relating the thin film morphologies to the underlying substrate pattern has implications for field induced patterning and robustness of inter-interface pattern transfer, e.g., coding-decoding of information printed on a substrate.

Solution structural ensembles of substrate-free cytochrome P450(cam).

PubMed

Asciutto, Eliana K; Young, Matthew J; Madura, Jeffry; Pochapsky, Susan Sondej; Pochapsky, Thomas C

2012-04-24

Removal of substrate (+)-camphor from the active site of cytochrome P450(cam) (CYP101A1) results in nuclear magnetic resonance-detected perturbations in multiple regions of the enzyme. The (1)H-(15)N correlation map of substrate-free diamagnetic Fe(II) CO-bound CYP101A permits these perturbations to be mapped onto the solution structure of the enzyme. Residual dipolar couplings (RDCs) were measured for (15)N-(1)H amide pairs in two independent alignment media for the substrate-free enzyme and used as restraints in solvated molecular dynamics (MD) simulations to generate an ensemble of best-fit structures of the substrate-free enzyme in solution. Nuclear magnetic resonance-detected chemical shift perturbations reflect changes in the electronic environment of the NH pairs, such as hydrogen bonding and ring current shifts, and are observed for residues in the active site as well as in hinge regions between secondary structural features. RDCs provide information about relative orientations of secondary structures, and RDC-restrained MD simulations indicate that portions of a β-rich region adjacent to the active site shift so as to partially occupy the vacancy left by removal of the substrate. The accessible volume of the active site is reduced in the substrate-free enzyme relative to the substrate-bound structure calculated using the same methods. Both symmetric and asymmetric broadening of multiple resonances observed upon substrate removal as well as localized increased errors in RDC fits suggest that an ensemble of enzyme conformations are present in the substrate-free form.

Organometallic chemical vapor deposition and characterization of ZnGeP2/GaP multiple heterostructures on GaP substrates

NASA Technical Reports Server (NTRS)

Xing, G. C.; Bachmann, Klaus J.

1993-01-01

The growth of ZnGeP2/GaP double and multiple heterostructures on GaP substrates by organometallic chemical vapor deposition is reported. These epitaxial films were deposited at a temperature of 580 C using dimethylzinc, trimethylgallium, germane, and phosphine as source gases. With appropriate deposition conditions, mirror smooth epitaxial GaP/ZnGeP2 multiple heterostructures were obtained on (001) GaP substrates. Transmission electron microscopy (TEM) and secondary ion mass spectroscopy (SIMS) studies of the films showed that the interfaces are sharp and smooth. Etching study of the films showed dislocation density on the order of 5x10(exp 4)cm(sup -2). The growth rates of the GaP layers depend linearly on the flow rates of trimethylgallium. While the GaP layers crystallize in zinc-blende structure, the ZnGeP2 layers crystallize in the chalcopyrite structure as determined by (010) electron diffraction pattern. This is the first time that multiple heterostructures combining these two crystal structures were made.

Fabrication of robust hydrogel coatings on polydimethylsiloxane substrates using micropillar anchor structures with chemical surface modification.

PubMed

Zhang, Hongbin; Bian, Chao; Jackson, John K; Khademolhosseini, Farzad; Burt, Helen M; Chiao, Mu

2014-06-25

A durable hydrophilic and protein-resistant surface of polydimethylsiloxane (PDMS) based devices is desirable in many biomedical applications such as implantable and microfluidic devices. This paper describes a stable antifouling hydrogel coating on PDMS surfaces. The coating method combines chemical modification and surface microstructure fabrication of PDMS substrates. Three-(trimethoxysilyl)propyl methacrylates containing C═C groups were used to modify PDMS surfaces with micropillar array structures fabricated by a replica molding method. The micropillar structures increase the surface area of PDMS surfaces, which facilitates secure bonding with a hydrogel coating compared to flat PMDS surfaces. The adhesion properties of the hydrogel coating on PDMS substrates were characterized using bending, stretching and water immersion tests. Long-term hydrophilic stability (maintaining a contact angle of 55° for a month) and a low protein adsorption property (35 ng/cm(2) of adsorbed BSA-FITC) of the hydrogel coated PDMS were demonstrated. This coating method is suitable for PDMS modification with most crosslinkable polymers containing C═C groups, which can be useful for improving the anti-biofouling performance of PDMS-based biomedical microdevices.

Catalyst free growth of CNTs by CVD on nanoscale rough surfaces of silicon substrates

NASA Astrophysics Data System (ADS)

Damodar, D.; Sahoo, R. K.; Jacob, C.

2013-06-01

Catalyst free growth of carbon nanotubes (CNT) has been achieved using atmospheric pressure chemical vapor deposition (APCVD) on surface modified Si(111) substrates. The effect of the substrate surface has been observed by partially etching with KOH (potassium hydroxide) solution which is an anisotropic etchant. Scanning electron microscopy (SEM) confirmed the formation of CNTs over most of the area of the substrate where substrates were anisotropically etched. Transmission electron microscopy (TEM) was used to observe the internal structure of the CNTs. Raman spectroscopy further confirmed the formation of the carbon nanostructures and also their graphitic crystallinity.

Chemical structure of interfaces

NASA Technical Reports Server (NTRS)

Grunthaner, F. J.

1985-01-01

The interfacial structure of silicon/dielectric and silicon/metal systems is particularly amenable to analysis using a combination of surface spectroscopies together with a variety of chemical structures of Si/SiO2, Si/SiO2Si3N4, Si/Si2N2O, Si/SiO2/Al, and Si/Native Oxide interfaces using high resolution (0.350 eV FWHM) X ray photoelectron spectroscopy. The general structure of these dielectric interfaces entails a monolayer chemical transition layer at the Si/dielectric boundary. Amorphous Si substrates show a wide variety of hydrogenated Si and Si(OH) sub x states that are not observed in thermal oxidation of single crystal material. Extended SiO2 layers greater than 8 A in thickness are shown to be stoichiometric SiO2, but to exhibit a wide variety of local network structures. In the nitrogen containing systems, an approach to stoichiometric oxynitride compounds with interesting impurity and electron trapping properties are seen. In native oxides, substantial topographical nonuniformity in oxide thickness and composition are found. Analysis of metal/oxide interfacial layers is accomplished by analytical removal of the Si substrate by UHV XeF2 dry etching methods.

How Conformational Dynamics of DNA Polymerase Select Correct Substrates: Experiments and Simulations

PubMed Central

Kirmizialtin, Serdal; Nguyen, Virginia; Johnson, Kenneth A.; Elber, Ron

2012-01-01

Summary Nearly every enzyme undergoes a significant change in structure after binding it’s substrate. New experimental and theoretical analyses of the role of changes in HIV reverse transcriptase structure in selecting a correct substrate are presented. Atomically detailed simulations using the Milestoning method predict a rate and free energy profile of the conformational change commensurate with experimental data. A large conformational change occurring on a ms timescale locks the correct nucleotide at the active site, but promotes release of a mismatched nucleotide. The positions along the reaction coordinate that decide the yield of the reaction are not determined by the chemical step. Rather, the initial steps of weak substrate binding and protein conformational transition significantly enrich the yield of a reaction with a correct substrate, while the same steps diminish the reaction probability of an incorrect substrate. PMID:22483109

Understanding ligninase-mediated reactions of endocrine disrupting chemicals in water: reaction rates and quantitative structure-activity relationships.

PubMed

Mao, Liang; Colosi, Lisa M; Gao, Shixiang; Huang, Qingguo

2011-07-15

We have verified in our previous work that lignin peroxidase (LiP) mediates effective removal of selected natural and synthetic estrogens. The efficiency of these reactions was greatly enhanced in the presence of veratryl alcohol (VA), a chemical that is produced along with LiP by certain white rot fungi, for example, Phanerochaete chrysosporium. In this study, we systematically evaluated the kinetic behaviors of LiP-mediated reactions for six endocrine disrupting compounds (EDCs), that is, steroid estrogens and their structural analogs, in both the presence and absence of VA. Resulting kinetic parameters were then correlated with structural features of LiP/substrate binding complexes, as quantified using molecular simulation, to create quantitative structure-activity relationship (QSAR) equations. These equations suggest that binding distance between a substrate's phenolic proton and δN of HIS47's imidazole ring plays an important role in modulating substrate reactivity toward LiP in both the presence and absence of VA. This information provides insight into an important enzymatic reaction process that occurs in the natural environment affecting EDC transformation, a process that may be used in engineered systems to achieve EDC removal from water.

Structural, electronic and chemical properties of metal/oxide and oxide/oxide interfaces and thin film structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lad, Robert J.

1999-12-14

This project focused on three different aspects of oxide thin film systems: (1) Model metal/oxide and oxide/oxide interface studies were carried out by depositing ultra-thin metal (Al, K, Mg) and oxide (MgO, AlO{sub x}) films on TiO{sub 2}, NiO and {alpha}-Al{sub 2}O{sub 3} single crystal oxide substrates. (2) Electron cyclotron resonance (ECR) oxygen plasma deposition was used to fabricate AlO{sub 3} and ZrO{sub 2} films on sapphire substrates, and film growth mechanisms and structural characteristics were investigated. (3) The friction and wear characteristics of ZrO{sub 2} films on sapphire substrates in unlubricated sliding contact were studied and correlated with filmmore » microstructure. In these studies, thin film and interfacial regions were characterized using diffraction (RHEED, LEED, XRD), electron spectroscopies (XPS, UPS, AES), microscopy (AFM) and tribology instruments (pin-on-disk, friction microprobe, and scratch tester). By precise control of thin film microstructure, an increased understanding of the structural and chemical stability of interface regions and tribological performance of ultra-thin oxide films was achieved in these important ceramic systems.« less

Integration of GaAs vertical-cavity surface emitting laser on Si by substrate removal

NASA Astrophysics Data System (ADS)

Yeh, Hsi-Jen J.; Smith, John S.

1994-03-01

The successful integration of strained quantum well InGaAs vertical-cavity surface-emitting lasers (VCSELs) on both Si and Cu substrates was described using a GaAs substrate removal technique. The GaAs VCSEL structure was metallized and bonded to the Si substrate after growth. The GaAs substrate was then removed by selective chemical wet etching. Finally, the bonded GaAs film metallized on the top (emitting) side and separate lasers were defined. This is the first time a VCSEL had been integrated on a Si substrate with its substrate removed. The performance enhancement of GaAs VCSELs bonded on good thermal conductors are demonstrated.

AES study on the chemical composition of ferroelectric BaTiO3 thin films RF sputter-deposited on silicon

NASA Technical Reports Server (NTRS)

Dharmadhikari, V. S.; Grannemann, W. W.

1983-01-01

AES depth profiling data are presented for thin films of BaTiO3 deposited on silicon by RF sputtering. By profiling the sputtered BaTiO3/silicon structures, it was possible to study the chemical composition and the interface characteristics of thin films deposited on silicon at different substrate temperatures. All the films showed that external surface layers were present, up to a few tens of angstroms thick, the chemical composition of which differed from that of the main layer. The main layer had stable composition, whereas the intermediate film-substrate interface consisted of reduced TiO(2-x) oxides. The thickness of this intermediate layer was a function of substrate temperature. All the films showed an excess of barium at the interface. These results are important in the context of ferroelectric phenomena observed in BaTiO3 thin films.

Effect of tacticity on the structure and glass transition temperature of polystyrene adsorbed onto solid surfaces

NASA Astrophysics Data System (ADS)

Negash, Solomon; Tatek, Yergou B.; Tsige, Mesfin

2018-04-01

We have carried out atomistic (all-atom) molecular dynamics simulations to investigate the effect of tacticity on the structure and glass transition temperature (Tg) of polystyrene (PS) thin films adsorbed on two distinct types of solid substrates. The systems consist of thin films made of atactic, isotactic, and syndiotactic PS chains supported by graphite or hydroxylated α-quartz substrates, which are known to be atomically flat but chemically and structurally different. We have observed a marked dependence of the film structure on substrate type as well as on tacticity. For instance, rings' orientation near substrate surfaces depends on substrate type for atactic PS and isotactic PS films, while no such dependence is observed for syndiotactic PS films whose interfacial structure seems to result from their propensity to adopt the trans conformation rather than their specific interaction with the substrates. Moreover, our results indicate that glass transition temperatures of substrate supported polystyrene films are higher compared to those of the corresponding free-standing films. More specifically, PS films on graphite exhibit larger Tg values than those on α-quartz, and we have noticed that syndiotactic PS has the largest Tg irrespective of the substrate type. Furthermore, the local Tg in the region of the film in contact with the substrates shows a strong tacticity and substrate dependence, whereas no dependencies were found for the local Tg in the middle of the film. Substrate-film interaction energy and chains' dynamics near substrate-film interfaces were subsequently investigated in order to substantiate the obtained Tgs, and it was found that films with higher Tgs are strongly adsorbed on the substrates and/or exhibit smaller interfacial chains' dynamics essentially due to steric hindrance.

Local atomic and electronic structure of oxide/GaAs and SiO2/Si interfaces using high-resolution XPS

NASA Technical Reports Server (NTRS)

Grunthaner, F. J.; Grunthaner, P. J.; Vasquez, R. P.; Lewis, B. F.; Maserjian, J.; Madhukar, A.

1979-01-01

The chemical structures of thin SiO2 films, thin native oxides of GaAs (20-30 A), and the respective oxide-semiconductor interfaces, have been investigated using high-resolution X-ray photoelectron spectroscopy. Depth profiles of these structures have been obtained using argon ion bombardment and wet chemical etching techniques. The chemical destruction induced by the ion profiling method is shown by direct comparison of these methods for identical samples. Fourier transform data-reduction methods based on linear prediction with maximum entropy constraints are used to analyze the discrete structure in oxides and substrates. This discrete structure is interpreted by means of a structure-induced charge-transfer model.

Conformational and chemical selection by a trans-acting editing domain

PubMed Central

Danhart, Eric M.; Bakhtina, Marina; Cantara, William A.; Kuzmishin, Alexandra B.; Ma, Xiao; Sanford, Brianne L.; Vargas-Rodriguez, Oscar; Košutić, Marija; Goto, Yuki; Suga, Hiroaki; Nakanishi, Kotaro; Micura, Ronald; Musier-Forsyth, Karin

2017-01-01

Molecular sieves ensure proper pairing of tRNAs and amino acids during aminoacyl-tRNA biosynthesis, thereby avoiding detrimental effects of mistranslation on cell growth and viability. Mischarging errors are often corrected through the activity of specialized editing domains present in some aminoacyl-tRNA synthetases or via single-domain trans-editing proteins. ProXp-ala is a ubiquitous trans-editing enzyme that edits Ala-tRNAPro, the product of Ala mischarging by prolyl-tRNA synthetase, although the structural basis for discrimination between correctly charged Pro-tRNAPro and mischarged Ala-tRNAAla is unclear. Deacylation assays using substrate analogs reveal that size discrimination is only one component of selectivity. We used NMR spectroscopy and sequence conservation to guide extensive site-directed mutagenesis of Caulobacter crescentus ProXp-ala, along with binding and deacylation assays to map specificity determinants. Chemical shift perturbations induced by an uncharged tRNAPro acceptor stem mimic, microhelixPro, or a nonhydrolyzable mischarged Ala-microhelixPro substrate analog identified residues important for binding and deacylation. Backbone 15N NMR relaxation experiments revealed dynamics for a helix flanking the substrate binding site in free ProXp-ala, likely reflecting sampling of open and closed conformations. Dynamics persist on binding to the uncharged microhelix, but are attenuated when the stably mischarged analog is bound. Computational docking and molecular dynamics simulations provide structural context for these findings and predict a role for the substrate primary α-amine group in substrate recognition. Overall, our results illuminate strategies used by a trans-editing domain to ensure acceptance of only mischarged Ala-tRNAPro, including conformational selection by a dynamic helix, size-based exclusion, and optimal positioning of substrate chemical groups. PMID:28768811

Experimental and simulation study of growth of TiO2 films on different substrates and its applications

NASA Astrophysics Data System (ADS)

Ghogare, Trupti T.; Kartha, Moses J.; Kendre, Subhash D.; Pathan, Habib M.

2018-04-01

Monte-Carlo Ballistic Deposition simulations have done on substrates with different initial roughness. The grown films were observed to be porous. The initial growths of the films with seed like initiations are observed for substrate with high initial roughness. In order to confirm this effect TiO2 films were deposited on different substrates using chemical bath deposition. The surface morphological and optical properties were measured using scanning electron microscopy and a UV-Vis spectrophotometer. Flower like porous structure are obtained on glass substrate and continuous porous morphology is formed on ITO substrate. The morphology of the surfaces was successfully reconstructed and the surface porosity was calculated after digitalising images and reconstructed the surfaces. The TiO2 film formed on ITO is observed to be 10% more porous than on the film formed on glass substrate. Diffusion Limited Aggregation simulations with multiple seeds confirms that the observed flower like structure formed are due to the screening effects of the diffusing ion by already deposited particles.

Fabrication of Ti substrate grain dependent C/TiO2 composites through carbothermal treatment of anodic TiO2.

PubMed

Rüdiger, Celine; Favaro, Marco; Valero-Vidal, Carlos; Calvillo, Laura; Bozzolo, Nathalie; Jacomet, Suzanne; Hejny, Clivia; Gregoratti, Luca; Amati, Matteo; Agnoli, Stefano; Granozzi, Gaetano; Kunze-Liebhäuser, Julia

2016-04-07

Composite materials of titania and graphitic carbon, and their optimized synthesis are highly interesting for application in sustainable energy conversion and storage. We report on planar C/TiO2 composite films that are prepared on a polycrystalline titanium substrate by carbothermal treatment of compact anodic TiO2 with acetylene. This thin film material allows for the study of functional properties of C/TiO2 as a function of chemical composition and structure. The chemical and structural properties of the composite on top of individual Ti substrate grains are examined by scanning photoelectron microscopy and micro-Raman spectroscopy. Through comparison of these data with electron backscatter diffraction, it is found that the amount of generated carbon and the grade of anodic film crystallinity correlate with the crystallographic orientation of the Ti substrate grains. On top of Ti grains with ∼(0001) orientations the anodic TiO2 exhibits the highest grade of crystallinity, and the composite contains the highest fraction of graphitic carbon compared to Ti grains with other orientations. This indirect effect of the Ti substrate grain orientation yields new insights into the activity of TiO2 towards the decomposition of carbon precursors.

Strain-balanced InAs/GaSb type-II superlattice structures and photodiodes grown on InAs substrates by metalorganic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Huang, Yong; Ryou, Jae-Hyun; Dupuis, Russell D.; Zuo, Daniel; Kesler, Benjamin; Chuang, Shun-Lien; Hu, Hefei; Kim, Kyou-Hyun; Ting Lu, Yen; Hsieh, K. C.; Zuo, Jian-Min

2011-07-01

We propose and demonstrate strain-balanced InAs/GaSb type-II superlattices (T2SLs) grown on InAs substrates employing GaAs-like interfacial (IF) layers by metalorganic chemical vapor deposition (MOCVD) for effective strain management, simplified growth scheme, improved materials crystalline quality, and reduced substrate absorption. The in-plane compressive strain from the GaSb layers in the T2SLs on the InAs was completely balanced by the GaAs-like IF layers formed by controlled precursor carry-over and anion exchange effects, avoiding the use of complicated IF layers and precursor switching schemes that were used for the MOCVD growth of T2SLs on GaSb. An infrared (IR) p-i-n photodiode structure with 320-period InAs/GaSb T2SLs on InAs was grown and the fabricated devices show improved performance characteristics with a peak responsivity of ˜1.9 A/W and a detectivity of ˜6.78 × 109 Jones at 8 μm at 78 K. In addition, the InAs buffer layer and substrate show a lower IR absorption coefficient than GaSb substrates in most of the mid- and long-IR spectral range.

Electrical, structural and morphological properties of chemically sprayed F-doped ZnO films: effect of the ageing-time of the starting solution, solvent and substrate temperature

NASA Astrophysics Data System (ADS)

Guillén-Santiago, A.; Olvera, M. De La L.; Maldonado, A.; Asomoza, R.; Acosta, D. R.

2004-04-01

Conductive and highly transparent fluorine-doped zinc oxide (ZnO:F) thin films were deposited onto glass substrates by the chemical spray technique, using zinc acetate and hydrofluoric acid as precursors. Electrical, structural, morphological and optical characteristics were analyzed as a function of the ageing-time of the starting solution, alcoholic solvent type (methanol or ethanol) and the substrate temperature. The results show that these variables play a crucial role on the physical properties measured. The growth rates obtained were of 3 nm/s, showing that the chemical species involved are adequate for the film growth. The effect of the solution ageing-time on the electrical properties was monitored along three weeks. A gradual resistivity decrease with the ageing-time was observed, until a minimum value is reached, at 7 or 9 days depending on the alcohol employed. Films deposited after this time have resistivity values slightly higher. All the films were polycrystalline, with a hexagonal wurtzite structure whose preferential growth is strongly dependent on the deposition variables. Under optimal deposition conditions, ZnO:F films with a high transmittance in the visible spectrum (>85%), resistivity as low as 7 × 10-3 cm and maximum electronic mobility around of 4 cm2/(V-s) were obtained.

Large-Area Direct Hetero-Epitaxial Growth of 1550-nm InGaAsP Multi-Quantum-Well Structures on Patterned Exact-Oriented (001) Silicon Substrates by Metal Organic Chemical Vapor Deposition

NASA Astrophysics Data System (ADS)

Megalini, Ludovico; Cabinian, Brian C.; Zhao, Hongwei; Oakley, Douglas C.; Bowers, John E.; Klamkin, Jonathan

2018-02-01

We employ a simple two-step growth technique to grow large-area 1550-nm laser structures by direct hetero-epitaxy of III-V compounds on patterned exact-oriented (001) silicon (Si) substrates by metal organic chemical vapor deposition. Densely-packed, highly uniform, flat and millimeter-long indium phosphide (InP) nanowires were grown from Si v-grooves separated by silicon dioxide (SiO2) stripes with various widths and pitches. Following removal of the SiO2 patterns, the InP nanowires were coalesced and, subsequently, 1550-nm laser structures were grown in a single overgrowth without performing any polishing for planarization. X-ray diffraction, photoluminescence, atomic force microscopy and transmission electron microscopy analyses were used to characterize the epitaxial material. PIN diodes were fabricated and diode-rectifying behavior was observed.

Functional and Structural Impact of Target Uridine Substitutions on the H/ACA Ribonucleoprotein Particle Pseudouridine Synthase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Jing; Liang, Bo; Li, Hong

2010-09-17

Box H/ACA ribonucleoprotein protein particles catalyze the majority of pseudouridylation in functional RNA. Different from stand alone pseudouridine synthases, the RNP pseudouridine synthase comprises multiple protein subunits and an RNA subunit. Previous studies showed that each subunit, regardless its location, is sensitive to the step of subunit placement at the catalytic center and potentially to the reaction status of the substrate. Here we describe the impact of chemical substitutions of target uridine on enzyme activity and structure. We found that 3-methyluridine in place of uridine inhibited its isomerization while 2{prime}-deoxyuridine or 4-thiouridine did not. Significantly, crystal structures of an archaealmore » box H/ACA RNP bound with the nonreactive and the two postreactive substrate analogues showed only subtle structural changes throughout the assembly except for a conserved tyrosine and a substrate anchoring loop of Cbf5. Our results suggest a potential role of these elements and the subunit that contacts them in substrate binding and product release.« less

The neutron structure of urate oxidase resolves a long-standing mechanistic conundrum and reveals unexpected changes in protonation.

PubMed

Oksanen, Esko; Blakeley, Matthew P; El-Hajji, Mohamed; Ryde, Ulf; Budayova-Spano, Monika

2014-01-01

Urate oxidase transforms uric acid to 5-hydroxyisourate without the help of cofactors, but the catalytic mechanism has remained enigmatic, as the protonation state of the substrate could not be reliably deduced. We have determined the neutron structure of urate oxidase, providing unique information on the proton positions. A neutron crystal structure inhibited by a chloride anion at 2.3 Å resolution shows that the substrate is in fact 8-hydroxyxanthine, the enol tautomer of urate. We have also determined the neutron structure of the complex with the inhibitor 8-azaxanthine at 1.9 Å resolution, showing the protonation states of the K10-T57-H256 catalytic triad. Together with X-ray data and quantum chemical calculations, these structures allow us to identify the site of the initial substrate protonation and elucidate why the enzyme is inhibited by a chloride anion.

Krebs cycle metabolon: structural evidence of substrate channeling revealed by cross-linking and mass spectrometry.

PubMed

Wu, Fei; Minteer, Shelley

2015-02-02

It has been hypothesized that the high metabolic flux in the mitochondria is due to the self-assembly of enzyme supercomplexes (called metabolons) that channel substrates from one enzyme to another, but there has been no experimental confirmation of this structure or the channeling. A structural investigation of enzyme organization within the Krebs cycle metabolon was accomplished by in vivo cross-linking and mass spectrometry. Eight Krebs cycle enzyme components were isolated upon chemical fixation, and interfacial residues between mitochondrial malate dehydrogenase, citrate synthase, and aconitase were identified. Using constraint protein docking, a low-resolution structure for the three-enzyme complex was achieved, as well as the two-fold symmetric octamer. Surface analysis showed formation of electrostatic channeling upon protein-protein association, which is the first structural evidence of substrate channeling in the Krebs cycle metabolon. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fe Oxides on Ag Surfaces: Structure and Reactivity

DOE PAGES

Shipilin, M.; Lundgren, E.; Gustafson, J.; ...

2016-09-09

One layer thick iron oxide films are attractive from both applied and fundamental science perspectives. The structural and chemical properties of these systems can be tuned by changing the substrate, making them promising materials for heterogeneous catalysis. In the present work, we investigate the structure of FeO(111) monolayer films grown on Ag(100) and Ag(111) substrates by means of microscopy and diffraction techniques and compare it with the structure of FeO(111) grown on other substrates reported in literature. We also study the NO adsorption properties of FeO(111)/Ag(100) and FeO(111)/Ag(111) systems utilizing different spectroscopic techniques. Finally, we discuss similarities and differences inmore » the data obtained from adsorption experiments and compare it with previous results for FeO(111)/Pt(111).« less

Fe Oxides on Ag Surfaces: Structure and Reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shipilin, M.; Lundgren, E.; Gustafson, J.

One layer thick iron oxide films are attractive from both applied and fundamental science perspectives. The structural and chemical properties of these systems can be tuned by changing the substrate, making them promising materials for heterogeneous catalysis. In the present work, we investigate the structure of FeO(111) monolayer films grown on Ag(100) and Ag(111) substrates by means of microscopy and diffraction techniques and compare it with the structure of FeO(111) grown on other substrates reported in literature. We also study the NO adsorption properties of FeO(111)/Ag(100) and FeO(111)/Ag(111) systems utilizing different spectroscopic techniques. Finally, we discuss similarities and differences inmore » the data obtained from adsorption experiments and compare it with previous results for FeO(111)/Pt(111).« less

Preparation and Characterization of Biofunctionalized Inorganic Substrates.

PubMed

Dugger, Jason W; Webb, Lauren J

2015-09-29

Integrating the function of biological molecules into traditional inorganic materials and substrates couples biologically relevant function to synthetic devices and generates new materials and capabilities by combining biological and inorganic functions. At this so-called "bio/abio interface," basic biological functions such as ligand binding and catalysis can be co-opted to detect analytes with exceptional sensitivity or to generate useful molecules with chiral specificity under entirely benign reaction conditions. Proteins function in dynamic, complex, and crowded environments (the living cell) and are therefore appropriate for integrating into multistep, multiscale, multimaterial devices such as integrated circuits and heterogeneous catalysts. However, the goal of reproducing the highly specific activities of biomolecules in the perturbed chemical and electrostatic environment at an inorganic interface while maintaining their native conformations is challenging to achieve. Moreover, characterizing protein structure and function at a surface is often difficult, particularly if one wishes to compare the activity of the protein to that of the dilute, aqueous solution phase. Our laboratory has developed a general strategy to address this challenge by taking advantage of the structural and chemical properties of alkanethiol self-assembled monolayers (SAMs) on gold surfaces that are functionalized with covalently tethered peptides. These surface-bound peptides then act as the chemical recognition element for a target protein, generating a biomimetic surface in which protein orientation, structure, density, and function are controlled and variable. Herein we discuss current research and future directions related to generating a chemically tunable biofunctionalization strategy that has potential to successfully incorporate the highly specialized functions of proteins onto inorganic substrates.

Systematic Functional Analysis of Active-Site Residues in l-Threonine Dehydrogenase from Thermoplasma volcanium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Desjardins, Morgan; Mak, Wai Shun; O’Brien, Terrence E.

Enzymes have been through millions of years of evolution during which their active-site microenvironments are fine-tuned. Active-site residues are commonly conserved within protein families, indicating their importance for substrate recognition and catalysis. In this work, we systematically mutated active-site residues of l-threonine dehydrogenase from Thermoplasma volcanium and characterized the mutants against a panel of substrate analogs. Our results demonstrate that only a subset of these residues plays an essential role in substrate recognition and catalysis and that the native enzyme activity can be further enhanced roughly 4.6-fold by a single point mutation. Kinetic characterization of mutants on substrate analogs showsmore » that l-threonine dehydrogenase possesses promiscuous activities toward other chemically similar compounds not previously observed. Quantum chemical calculations on the hydride-donating ability of these substrates also reveal that this enzyme did not evolve to harness the intrinsic substrate reactivity for enzyme catalysis. Our analysis provides insights into connections between the details of enzyme active-site structure and specific function. Finally, these results are directly applicable to rational enzyme design and engineering.« less

Systematic Functional Analysis of Active-Site Residues in l-Threonine Dehydrogenase from Thermoplasma volcanium

DOE PAGES

Desjardins, Morgan; Mak, Wai Shun; O’Brien, Terrence E.; ...

2017-07-07

Enzymes have been through millions of years of evolution during which their active-site microenvironments are fine-tuned. Active-site residues are commonly conserved within protein families, indicating their importance for substrate recognition and catalysis. In this work, we systematically mutated active-site residues of l-threonine dehydrogenase from Thermoplasma volcanium and characterized the mutants against a panel of substrate analogs. Our results demonstrate that only a subset of these residues plays an essential role in substrate recognition and catalysis and that the native enzyme activity can be further enhanced roughly 4.6-fold by a single point mutation. Kinetic characterization of mutants on substrate analogs showsmore » that l-threonine dehydrogenase possesses promiscuous activities toward other chemically similar compounds not previously observed. Quantum chemical calculations on the hydride-donating ability of these substrates also reveal that this enzyme did not evolve to harness the intrinsic substrate reactivity for enzyme catalysis. Our analysis provides insights into connections between the details of enzyme active-site structure and specific function. Finally, these results are directly applicable to rational enzyme design and engineering.« less

Selective directed self-assembly of coexisting morphologies using block copolymer blends

NASA Astrophysics Data System (ADS)

Stein, A.; Wright, G.; Yager, K. G.; Doerk, G. S.; Black, C. T.

2016-08-01

Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. Here we expand on traditional DSA chemical patterning. A blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This is in contrast to the typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist.

X-ray diffraction study of the molecular propolis films deposited from an alcohol solution onto the cleavage surfaces of layered V2VI3 compounds

NASA Astrophysics Data System (ADS)

Drapak, S. I.; Gavrylyuk, S. V.; Kaminskii, V. M.; Kovalyuk, Z. D.

2008-09-01

The structures of the molecular propolis films deposited from an alcohol solution on the (0001) cleavage surface of layered bismuth selenide and telluride are studied by X-ray diffraction. Despite the chemical interaction between the semiconductor substrates and the organic-substance components, the molecular structural ordering of the propolis films is shown to be identical to that in the films of this substance on the surface of amorphous glass substrates. The chemical and deformation interaction between the organic substance and the layered V2VI3 compounds is found to result in the formation of an organic-inorganic sandwich nanostructure at a distance of ˜0.3 μm from the layered crystal-propolis film interface.

Mismatch repair factor MSH2-MSH3 binds and alters the conformation of branched DNA structures predicted to form during genetic recombination.

PubMed

Surtees, Jennifer A; Alani, Eric

2006-07-14

Genetic studies in Saccharomyces cerevisiae predict that the mismatch repair (MMR) factor MSH2-MSH3 binds and stabilizes branched recombination intermediates that form during single strand annealing and gene conversion. To test this model, we constructed a series of DNA substrates that are predicted to form during these recombination events. We show in an electrophoretic mobility shift assay that S. cerevisiae MSH2-MSH3 specifically binds branched DNA substrates containing 3' single-stranded DNA and that ATP stimulates its release from these substrates. Chemical footprinting analyses indicate that MSH2-MSH3 specifically binds at the double-strand/single-strand junction of branched substrates, alters its conformation and opens up the junction. Therefore, MSH2-MSH3 binding to its substrates creates a unique nucleoprotein structure that may signal downstream steps in repair that include interactions with MMR and nucleotide excision repair factors.

Structural and functional diversity of microbial communities from a lake sediment contaminated with trenbolone, an endocrine-disrupting chemical.

PubMed

Radl, Viviane; Pritsch, Karin; Munch, Jean Charles; Schloter, Michael

2005-09-01

Effects of trenbolone (TBOH), a hormone used in cattle production, on the structure and function of microbial communities in a fresh water sediment from a lake in Southern Germany were studied in a microcosm experiment. The microbial community structure and the total gene pool of the sediment, assessed by 16S rRNA/rDNA and RAPD fingerprint analysis, respectively, were not significantly affected by TBOH. In contrast, the N-acetyl-glucosaminidase activity was almost 50% lower in TBOH treated samples (P<0.05). Also, the substrate utilization potential, measured using the BIOLOG system, was reduced after TBOH treatment. Interestingly, this potential did not recover at the end of the experiment, i.e. 19 days after the addition of the chemical. Repeated application of TBOH did not lead to an additional reduction in the substrate utilization potential. Overall results indicate that microbial community function was more sensitive to TBOH treatment than the community structure and the total gene pool.

High efficiency epitaxial GaAs/GaAs and GaAs/Ge solar cell technology using OM/CVD

NASA Technical Reports Server (NTRS)

Wang, K. L.; Yeh, Y. C. M.; Stirn, R. J.; Swerdling, S.

1980-01-01

A technology for fabricating high efficiency, thin film GaAs solar cells on substrates appropriate for space and/or terrestrial applications was developed. The approach adopted utilizes organometallic chemical vapor deposition (OM-CVD) to form a GaAs layer epitaxially on a suitably prepared Ge epi-interlayer deposited on a substrate, especially a light weight silicon substrate which can lead to a 300 watt per kilogram array technology for space. The proposed cell structure is described. The GaAs epilayer growth on single crystal GaAs and Ge wafer substrates were investigated.

Self-organized semiconductor nano-network on graphene

NASA Astrophysics Data System (ADS)

Son, Dabin; Kim, Sang Jin; Lee, Seungmin; Bae, Sukang; Kim, Tae-Wook; Kang, Jae-Wook; Lee, Sang Hyun

2017-04-01

A network structure consisting of nanomaterials with a stable structural support and charge path on a large area is desirable for various electronic and optoelectronic devices. Generally, network structures have been fabricated via two main strategies: (1) assembly of pre-grown nanostructures onto a desired substrate and (2) direct growth of nanomaterials onto a desired substrate. In this study, we utilized the surface defects of graphene to form a nano-network of ZnO via atomic layer deposition (ALD). The surface of pure and structurally perfect graphene is chemically inert. However, various types of point and line defects, including vacancies/adatoms, grain boundaries, and ripples in graphene are generated by growth, chemical or physical treatments. The defective sites enhance the chemical reactivity with foreign atoms. ZnO nanoparticles formed by ALD were predominantly deposited at the line defects and agglomerated with increasing ALD cycles. Due to the formation of the ZnO nano-network, the photocurrent between two electrodes was clearly changed under UV irradiation as a result of the charge transport between ZnO and graphene. The line patterned ZnO/graphene (ZnO/G) nano-network devices exhibit sensitivities greater than ten times those of non-patterned structures. We also confirmed the superior operation of a fabricated flexible photodetector based on the line patterned ZnO/G nano-network.

Lift-off process with bi-layer photoresist patterns for conformal-coated superhydrophilic pulsed plasma chemical vapor deposition-SiOx on SiCx for lab-on-a-chip applications

NASA Astrophysics Data System (ADS)

Konishi, Satoshi; Nakagami, Chise; Kobayashi, Taizo; Tonomura, Wataru; Kaizuma, Yoshihiro

2015-04-01

In this work, a lift-off process with bi-layer photoresist patterns was applied to the formation of hydrophobic/hydrophilic micropatterns on practical polymer substrates used in healthcare diagnostic commercial products. The bi-layer photoresist patterns with undercut structures made it possible to peel the conformal-coated silicon oxide (SiOx) films from substrates. SiOx and silicon carbide (SiCx) layers were deposited by pulsed plasma chemical vapor deposition (PPCVD) method which can form roughened surfaces to enhance hydrophilicity of SiOx and hydrophobicity of SiCx. Microfluidic applications using hydrophobic/hydrophilic patterns were also demonstrated on low-cost substrates such as poly(ethylene terephthalate) (PET) and paper films.

Growth of pure ZnO thin films prepared by chemical spray pyrolysis on silicon

NASA Astrophysics Data System (ADS)

Ayouchi, R.; Martin, F.; Leinen, D.; Ramos-Barrado, J. R.

2003-01-01

Structural, morphological, optical and electrical properties of ZnO thin films prepared by chemical spray pyrolysis from zinc acetate (Zn(CH 3COO) 2 2H 2O) aqueous solutions, on polished Si(1 0 0), and fused silica substrates for optical characterization, have been studied in terms of deposition time and substrate temperature. The growth of the films present three regimes depending on the substrate temperature, with increasing, constant and decreasing growth rates at lower, middle, and higher-temperature ranges, respectively. Growth rate higher than 15 nm min -1 can be achieved at Ts=543 K. ZnO film morphological and electrical properties have been related to these growth regimes. The films have been characterized by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy.

Chemical bath deposited (CBD) CuO thin films on n-silicon substrate for electronic and optical applications: Impact of growth time

NASA Astrophysics Data System (ADS)

Sultana, Jenifar; Paul, Somdatta; Karmakar, Anupam; Yi, Ren; Dalapati, Goutam Kumar; Chattopadhyay, Sanatan

2017-10-01

Thin film of p-type cupric oxide (p-CuO) is grown on silicon (n-Si) substrate by using chemical bath deposition (CBD) technique and a precise control of thickness from 60 nm to 178 nm has been achieved. The structural properties and stoichiometric composition of the grown films are observed to depend significantly on the growth time. The chemical composition, optical properties, and structural quality are investigated in detail by employing XRD, ellipsometric measurements and SEM images. Also, the elemental composition and the oxidation states of Cu and O in the grown samples have been studied in detail by XPS measurements. Thin film of 110 nm thicknesses exhibited the best performance in terms of crystal quality, refractive index, dielectric constant, band-gap, and optical properties. The study suggests synthesis route for developing high quality CuO thin film using CBD method for electronic and optical applications.

Structural analysis of enzymes used for bioindustry and bioremediation.

PubMed

Tanokura, Masaru; Miyakawa, Takuya; Guan, Lijun; Hou, Feng

2015-01-01

Microbial enzymes have been widely applied in the large-scale, bioindustrial manufacture of food products and pharmaceuticals due to their high substrate specificity and stereoselectivity, and their effectiveness under mild conditions with low environmental burden. At the same time, bioremedial techniques using microbial enzymes have been developed to solve the problem of industrial waste, particularly with respect to persistent chemicals and toxic substances. And finally, structural studies of these enzymes have revealed the mechanistic basis of enzymatic reactions, including the stereoselectivity and binding specificity of substrates and cofactors. The obtained structural insights are useful not only to deepen our understanding of enzymes with potential bioindustrial and/or bioremedial application, but also for the functional improvement of enzymes through rational protein engineering. This review shows the structural bases for various types of enzymatic reactions, including the substrate specificity accompanying cofactor-controlled and kinetic mechanisms.

Substrate degradation by the proteasome: a single-molecule kinetic analysis

PubMed Central

Lu, Ying; Lee, Byung-hoon; King, Randall W; Finley, Daniel; Kirschner, Marc W

2015-01-01

To address how the configuration of conjugated ubiquitins determines the recognition of substrates by the proteasome, we analyzed the degradation kinetics of substrates with chemically defined ubiquitin configurations. Contrary to the view that a tetraubiquitin chain is the minimal signal for efficient degradation, we find that distributing the ubiquitins as diubiquitin chains provides a more efficient signal. To understand how the proteasome actually discriminates among ubiquitin configurations, we developed single-molecule assays that distinguished intermediate steps of degradation kinetically. The level of ubiquitin on a substrate drives proteasome-substrate interaction, whereas the chain structure of ubiquitin affects translocation into the axial channel on the proteasome. Together these two features largely determine the susceptibility of substrates for proteasomal degradation. PMID:25859050

Epoxy bond and stop etch fabrication method

DOEpatents

Simmons, Jerry A.; Weckwerth, Mark V.; Baca, Wes E.

2000-01-01

A class of epoxy bond and stop etch (EBASE) microelectronic fabrication techniques is disclosed. The essence of such techniques is to grow circuit components on top of a stop etch layer grown on a first substrate. The first substrate and a host substrate are then bonded together so that the circuit components are attached to the host substrate by the bonding agent. The first substrate is then removed, e.g., by a chemical or physical etching process to which the stop etch layer is resistant. EBASE fabrication methods allow access to regions of a device structure which are usually blocked by the presence of a substrate, and are of particular utility in the fabrication of ultrafast electronic and optoelectronic devices and circuits.

Enzyme Active Site Interactions by Raman/FTIR, NMR, and Ab Initio Calculations

PubMed Central

Deng, Hua

2017-01-01

Characterization of enzyme active site structure and interactions at high resolution is important for the understanding of the enzyme catalysis. Vibrational frequency and NMR chemical shift measurements of enzyme-bound ligands are often used for such purpose when X-ray structures are not available or when higher resolution active site structures are desired. This review is focused on how ab initio calculations may be integrated with vibrational and NMR chemical shift measurements to quantitatively determine high-resolution ligand structures (up to 0.001 Å for bond length and 0.01 Å for hydrogen bonding distance) and how interaction energies between bound ligand and its surroundings at the active site may be determined. Quantitative characterization of substrate ionic states, bond polarizations, tautomeric forms, conformational changes and its interactions with surroundings in enzyme complexes that mimic ground state or transition state can provide snapshots for visualizing the substrate structural evolution along enzyme-catalyzed reaction pathway. Our results have shown that the integration of spectroscopic studies with theoretical computation greatly enhances our ability to interpret experimental data and significantly increases the reliability of the theoretical analysis. PMID:24018325

High Sensitivity, Low Power Nano Sensors and Devices for Chemical Sensing

NASA Technical Reports Server (NTRS)

Li, Jing; Powell, Dan; Getty, Stephanie; Lu, Yi-Jiang

2004-01-01

The chemical sensor market has been projected to grow to better than $40 billion dollars worldwide within the next 10 years. Some of the primary motivations to develop nanostructured chemical sensors are monitoring and control of environmental pollution; improved diagnostics for consumption; improvement in measurement precision and accuracy; and improved detection limits for Homeland security, battlefield environments, and process and quality control of industrial applications. In each of these applications, there is demand for sensitivity, selectivity and stability of environmental and biohazard detection and capture beyond what is currently commercially available. Nanotechnology offers the ability to work at the molecular level, atom by atom, to create large structures with fundamentally new molecular organization. It is essentially concerned with materials, devices, and systems whose structures and components exhibit novel and significantly improved physical, chemical and biological properties, phenomena, and process control due to their nanoscale size. One such nanotechnology-enabled chemical sensor has been developed at NASA Ames leveraging nanostructures, such as single walled carbon nanotubes (SWNTs) and metal oxide nanobelts or nanowires, as a sensing medium bridging a pair of interdigitated electrodes (IDE) realized through a silicon-based microfabrication and micromachining technique. The DE fingers are fabricated on a silicon substrate using standard photolithography and thin film metallization techniques. It is noteworthy that the fabrication techniques employed are not confined to the silicon substrate. Through spin casting and careful substrate selection (i.e. clothing, glass, polymer, etc.), additional degrees of freedom can be exploited to enhance sensitivity or to conform to unique applications. Both in-situ growth of nanostructured materials and casting of nanostructured dispersions were used to produce analogous chemical sensing devices.

Structural and Functional Role of Acetyltransferase hMOF K274 Autoacetylation

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCullough, Cheryl E.; Song, Shufei; Shin, Michael H.

Many histone acetyltransferases undergo autoacetylation, either through chemical or enzymatic means, to potentiate enzymatic cognate substrate lysine acetylation, although the mode and molecular role of such autoacetylation is poorly understood. The MYST family of histone acetyltransferases is autoacetylated at an active site lysine residue to facilitate cognate substrate lysine binding and acetylation. Here, we report on a detailed molecular investigation of Lys-274 autoacetylation of the human MYST protein Males Absent on the First (hMOF). A mutational scan of hMOF Lys-274 reveals that all amino acid substitutions of this residue are able to bind cofactor but are significantly destabilized, both inmore » vitro and in cells, and are catalytically inactive for cognate histone H4 peptide lysine acetylation. The x-ray crystal structure of a hMOF K274P mutant suggests that the reduced stability and catalytic activity stems from a disordering of the residue 274-harboring a α2-β7 loop. We also provide structural evidence that a C316S/E350Q mutant, which is defective for cognate substrate lysine acetylation; and biochemical evidence that a K268M mutant, which is defective for Lys-274 chemical acetylation in the context of a K274-peptide, can still undergo quantitative K274 autoacetylation. Together, these studies point to the critical and specific role of hMOF Lys-274 autoacetylation in hMOF stability and cognate substrate acetylation and argues that binding of Ac-CoA to hMOF likely drives Lys-274 autoacetylation for subsequent cognate substrate acetylation.« less

Circularly polarized Raman study on diamond structure crystals

NASA Astrophysics Data System (ADS)

Lee, Je-Ho; Kim, Sera; Seong, Maeng-Je

2018-01-01

Circularly polarized Raman and/or photoluminescence (PL) analyses have recently been very important in studying physical properties of many layered materials that were either mechanically exfoliated or grown by chemical-vapor-deposition (CVD) on silicon substrates. Since silicon Raman signal is always accompanied by the circularly polarized Raman and/or PL signal from the layered materials, observation of proper circularly polarized Raman selection rules on silicon substrates would be extremely good indicator that the circularly polarized Raman and/or PL measurements on the layered materials were done properly. We have performed circularly polarized Raman measurements on silicon substrates and compared the results with the Raman intensities calculated by using Raman tensors of the diamond crystal structure. Our experimental results were in excellent agreement with the calculation. Similar circularly polarized Raman analysis done on germanium substrate also showed good agreement.

Large-area high-performance SERS substrates with deep controllable sub-10-nm gap structure fabricated by depositing Au film on the cicada wing

NASA Astrophysics Data System (ADS)

Jiwei, Qi; Yudong, Li; Ming, Yang; Qiang, Wu; Zongqiang, Chen; Wudeng, Wang; Wenqiang, Lu; Xuanyi, Yu; Jingjun, Xu; Qian, Sun

2013-10-01

Noble metal nanogap structure supports strong surface-enhanced Raman scattering (SERS) which can be used to detect single molecules. However, the lack of reproducible fabrication techniques with nanometer-level control over the gap size has limited practical applications. In this letter, by depositing the Au film onto the cicada wing, we engineer the ordered array of nanopillar structures on the wing to form large-area high-performance SERS substrates. Through the control of the thickness of the Au film deposited onto the cicada wing, the gap sizes between neighboring nanopillars are fine defined. SERS substrates with sub-10-nm gap sizes are obtained, which have the highest average Raman enhancement factor (EF) larger than 2 × 108, about 40 times as large as that of commercial Klarite® substrates. The cicada wings used as templates are natural and environment-friendly. The depositing method is low cost and high throughput so that our large-area high-performance SERS substrates have great advantage for chemical/biological sensing applications.

Simple Models for Tough Concepts

ERIC Educational Resources Information Center

Cavagnoi, Richard M.; Barnett, Thomas

1976-01-01

Describes the construction of teaching models made from a variety of materials such as poker chips and cardboard that illustrate many chemical phenomena, including subatomic particles, molecular structure, solvation and dissociation, and enzyme-substrate interactions. (MLH)

Sticking non-stick: Surface and Structure control of Diamond-like Carbon in Plasma Enhanced Chemical Vapour Deposition

NASA Astrophysics Data System (ADS)

Jones, B. J.; Nelson, N.

2016-10-01

This short review article explores the practical use of diamond-like carbon (DLC) produced by plasma enhanced chemical vapour deposition (PECVD). Using as an example issues relating to the DLC coating of a hand-held surgical device, we draw on previous works using atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, tensiometry and electron paramagnetic resonance. Utilising data from these techniques, we examine the surface structure, substrate-film interface and thin film microstructure, such as sp2/sp3 ratio (graphitic/diamond-like bonding ratio) and sp2 clustering. We explore the variations in parameters describing these characteristics, and relate these to the final device properties such as friction, wear resistance, and diffusion barrier integrity. The material and device characteristics are linked to the initial plasma and substrate conditions.

Superconducting structure

DOEpatents

Kwon, Chuhee; Jia, Quanxi; Foltyn, Stephen R.

2003-04-01

A superconductive structure including a dielectric oxide substrate, a thin buffer layer of a superconducting material thereon; and, a layer of a rare earth-barium-copper oxide superconducting film thereon the thin layer of yttrium-barium-copper oxide, the rare earth selected from the group consisting of samarium, gadolinium, ytterbium, erbium, neodymium, dysprosium, holmium, lutetium, a combination of more than one element from the rare earth group and a combination of one or more elements from the rare earth group with yttrium, the buffer layer of superconducting material characterized as having chemical and structural compatibility with the dielectric oxide substrate and the rare earth-barium-copper oxide superconducting film is provided.

Superconducting Structure

DOEpatents

Kwon, Chuhee; Jia, Quanxi; Foltyn, Stephen R.

2005-09-13

A superconductive structure including a dielectric oxide substrate, a thin buffer layer of a superconducting material thereon; and, a layer of a rare earth-barium-copper oxide superconducting film thereon the thin layer of yttrium-barium-copper oxide, the rare earth selected from the group consisting of samarium, gadolinium, ytterbium, erbium, neodymium, dysprosium, holmium, lutetium, a combination of more than one element from the rare earth group and a combination of one or more elements from the rare earth group with yttrium, the buffer layer of superconducting material characterized as having chemical and structural compatibility with the dielectric oxide substrate and the rare earth-barium-copper oxide superconducting film is provided.

Use of chemical-mechanical polishing for fabricating photonic bandgap structures

DOEpatents

Fleming, James G.; Lin, Shawn-Yu; Hetherington, Dale L.; Smith, Bradley K.

1999-01-01

A method is disclosed for fabricating a two- or three-dimensional photonic bandgap structure (also termed a photonic crystal, photonic lattice, or photonic dielectric structure). The method uses microelectronic integrated circuit (IC) processes to fabricate the photonic bandgap structure directly upon a silicon substrate. One or more layers of arrayed elements used to form the structure are deposited and patterned, with chemical-mechanical polishing being used to planarize each layer for uniformity and a precise vertical tolerancing of the layer. The use of chemical-mechanical planarization allows the photonic bandgap structure to be formed over a large area with a layer uniformity of about two-percent. Air-gap photonic bandgap structures can also be formed by removing a spacer material separating the arrayed elements by selective etching. The method is useful for fabricating photonic bandgap structures including Fabry-Perot resonators and optical filters for use at wavelengths in the range of about 0.2-20 .mu.m.

SERS detection of R6G based on a novel graphene oxide/silver nanoparticles/silicon pyramid arrays structure.

PubMed

Zhang, C; Jiang, S Z; Huo, Y Y; Liu, A H; Xu, S C; Liu, X Y; Sun, Z C; Xu, Y Y; Li, Z; Man, B Y

2015-09-21

We present a novel surface-enhanced Raman scattering (SERS) substrate based on graphene oxide/silver nanoparticles/silicon pyramid arrays structure (GO/Ag/PSi). The SERS behaviors are discussed and compared by the detection of R6G. Based on the contrast experiments with PSi, GO/PSi, Ag/PSi and GO/AgA/PSi as SERS substrate, the perfect bio-compatibility, good homogeneity and chemical stability were confirmed. We also calculated the electric field distributions using Finite-difference time-domain (FDTD) analysis to further understand the GO/Ag/PSi structure as a perfect SERS platform. These experimental and theoretical results imply that the GO/Ag/PSi with regular pyramids array is expected to be an effective substrate for label-free sensitive SERS detections in areas of medicine, food safety and biotechnology.

Self-Catalyzed Growth of Axial GaAs/GaAsSb Nanowires by Molecular Beam Epitaxy for Photodetectors

DTIC Science & Technology

2015-06-01

blende structure with mixture of stacking faults and twins and the presence of these faults were significantly reduced in the NWs grown on chemically...a) TEM image of the core NW (b) HR-TEM image displaying the stacking faults and twinning defects. (c)SAED pattern showing the ZB crystal structure...of stacking faults and twins and the presence of these faults were significantly reduced in the NWs grown on chemically etched substrates. For

Understanding transporter specificity and the discrete appearance of channel-like gating domains in transporters

PubMed Central

Diallinas, George

2014-01-01

Transporters are ubiquitous proteins mediating the translocation of solutes across cell membranes, a biological process involved in nutrition, signaling, neurotransmission, cell communication and drug uptake or efflux. Similarly to enzymes, most transporters have a single substrate binding-site and thus their activity follows Michaelis-Menten kinetics. Substrate binding elicits a series of structural changes, which produce a transporter conformer open toward the side opposite to the one from where the substrate was originally bound. This mechanism, involving alternate outward- and inward-facing transporter conformers, has gained significant support from structural, genetic, biochemical and biophysical approaches. Most transporters are specific for a given substrate or a group of substrates with similar chemical structure, but substrate specificity and/or affinity can vary dramatically, even among members of a transporter family that show high overall amino acid sequence and structural similarity. The current view is that transporter substrate affinity or specificity is determined by a small number of interactions a given solute can make within a specific binding site. However, genetic, biochemical and in silico modeling studies with the purine transporter UapA of the filamentous ascomycete Aspergillus nidulans have challenged this dogma. This review highlights results leading to a novel concept, stating that substrate specificity, but also transport kinetics and transporter turnover, are determined by subtle intramolecular interactions between a major substrate binding site and independent outward- or cytoplasmically-facing gating domains, analogous to those present in channels. This concept is supported by recent structural evidence from several, phylogenetically and functionally distinct transporter families. The significance of this concept is discussed in relationship to the role and potential exploitation of transporters in drug action. PMID:25309439

Sb-Te alloy nanostructures produced on a graphite surface by a simple annealing process

NASA Astrophysics Data System (ADS)

Kuwahara, Masashi; Uratsuji, Hideaki; Abe, Maho; Sone, Hayato; Hosaka, Sumio; Sakai, Joe; Uehara, Yoichi; Endo, Rie; Tsuruoka, Tohru

2015-08-01

We have produced Sb-Te alloy nanostructures from a thin Sb2Te3 layer deposited on a highly oriented pyrolytic graphite substrate using a simple rf-magnetron sputtering and annealing technique. The size, shape, and chemical composition of the structures were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), and energy dispersive X-ray spectrometry (EDX), respectively. The shape of the nanostructures was found to depend on the annealing temperature; nanoparticles appear on the substrate by annealing at 200 °C, while nanoneedles are formed at higher temperatures. Chemical composition analysis has revealed that all the structures were in the composition of Sb:Te = 1:3, Te rich compared to the target composition Sb2Te3, probably due to the higher movability of Te atoms on the substrate compared with Sb. We also tried to observe the production process of nanostructures in situ using SEM. Unfortunately, this was not possible because of evaporation in vacuum, suggesting that the formation of nanostructures is highly sensitive to the ambient pressure.

Optical and Structural Properties of Microcrystalline GaN on an Amorphous Substrate Prepared by a Combination of Molecular Beam Epitaxy and Metal-Organic Chemical Vapor Deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Min, Jung-Wook; Hwang, Hyeong-Yong; Kang, Eun-Kyu

2016-05-01

Microscale platelet-shaped GaN grains were grown on amorphous substrates by a combined epitaxial growth method of molecular beam epitaxy (MBE) and metal-organic chemical vapor deposition (MOCVD). First, MBE GaN was grown on an amorphous substrate as a pre-orienting layer and its structural properties were investigated. Second, MOCVD grown GaN samples using the different growth techniques of planar and selective area growth (SAG) were comparatively investigated by transmission electron microscopy (TEM), cathodoluminescence (CL), and photoluminescence (PL). In MOCVD planar GaN, strong bound exciton peaks dominated despite the high density of the threading dislocations (TDs). In MOCVD SAG GaN, on the othermore » hand, TDs were clearly reduced with bending, but basal stacking fault (BSF) PL peaks were observed at 3.42 eV. The combined epitaxial method not only provides a deep understanding of the growth behavior but also suggests an alternative approach for the growth of GaN on amorphous substances.« less

Strain-relaxed structure in (001)/(100)-oriented epitaxial PbTiO3 films grown on (100) SrTiO3 substrates by metal organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Nakaki, Hiroshi; Kim, Yong Kwan; Yokoyama, Shintaro; Ikariyama, Rikyu; Funakubo, Hiroshi; Nishida, Ken; Saito, Keisuke

2007-09-01

The authors grew (001)- and (001)/(100)-oriented epitaxial PbTiO3 films with various thicknesses on (100)SrTiO3 substrates. They used x-ray diffraction to measure the angles between surface normal [001] of (001)-oriented domains and [100] of (100)-oriented domains. The angles were found to be approximately 3.6° when the film thickness exceeded 1100nm. This value is consistent with the value obtained by a geometric calculation for strain-free PbTiO3. This result suggests that thick epitaxial PbTiO3 films grown on (100)SrTiO3 substrates have a fully strain-relaxed structure.

Technologies for thermal management of mid-IR Sb-based surface emitting lasers

NASA Astrophysics Data System (ADS)

Perez, J.-P.; Laurain, A.; Cerutti, L.; Sagnes, I.; Garnache, A.

2010-04-01

In this paper, for the first time to our knowledge, we report and demonstrate the technological steps dedicated to thermal management of antimonide-based surface emitting laser devices grown by molecular beam epitaxy. Key points of the technological process are firstly the bonding of the structure on the SiC host substrate and secondly the GaSb substrate removal to leave the Sb-based membrane. The structure design (etch stop layer, metallic mirror, etc), bonding process (metallic bonding via solid-liquid interdiffusion) and GaSb substrate removal process (selective wet-chemical etchants, etc) are presented. Optical characterizations together with external-cavity VCSEL laser emission at 2.3 µm at room temperature in continuous wave are presented.

On the growth mechanisms of polar (100) surfaces of ceria on copper (100)

NASA Astrophysics Data System (ADS)

Hackl, Johanna; Duchoň, Tomáš; Gottlob, Daniel M.; Cramm, Stefan; Veltruská, Kateřina; Matolín, Vladimír; Nemšák, Slavomír; Schneider, Claus M.

2018-05-01

We present a study of temperature dependent growth of nano-sized ceria islands on a Cu (100) substrate. Low-energy electron microscopy, micro-electron diffraction, X-ray absorption spectroscopy, and photoemission electron microscopy are used to determine the morphology, shape, chemical state, and crystal structure of the grown islands. Utilizing real-time observation capabilities, we reveal a three-way interaction between the ceria, substrate, and local oxygen chemical potential. The interaction manifests in the reorientation of terrace boundaries on the Cu (100) substrate, characteristic of the transition between oxidized and metallic surface. The reorientation is initiated at nucleation sites of ceria islands, whose growth direction is influenced by the proximity of the terrace boundaries. The grown ceria islands were identified as fully stoichiometric CeO2 (100) surfaces with a (2 × 2) reconstruction.

Electrically responsive microstructured polypyrrole-polyurethane composites for stimulated osteogenesis

NASA Astrophysics Data System (ADS)

Luculescu, Catalin Romeo; Acasandrei, Adriana Maria; Mustaciosu, Cosmin Catalin; Zamfirescu, Marian; Dinescu, Maria; Calin, Bogdan Stefanita; Popescu, Andrei; Chioibasu, Diana; Cristian, Dan; Paun, Irina Alexandra

2018-03-01

In this work, we demonstrate the efficiency of substrate-mediated electrical stimulation of micropatterned polypyrrole/polyurethane (PPy/PU) composites for enhancing the osteogenesis in osteoblast-like cells. The PPy/PU substrates were obtained by dispersing electrically conductive PPy nanograins within a mechanically resistant PU matrix. Spin-coated PPy/PU layers were micropatterned with predefined 3D geometries by ultrashort laser ablation. Then they were conformally coated by Matrix Assisted Pulsed Laser Evaporation, in order to restore their chemical and electrical integrity. The chemical structure of the laser-processed PPy/PU substrates was investigated by 2D and 3D mapping of the laser-processed areas, via Raman microspectroscopy. In vitro studies revealed that the micropatterned PPy/PU substrates facilitated the topological and electrical communication of the seeded osteoblasts. Specifically, we demonstrated the cells attachment on the predefined 3D micropatterns. More importantly, we found evidence about the cells mineralization inside the 3D micropatterns by investigating the calcium deposits by Energy-Dispersive X-Ray Spectroscopy (EDS) and Alizarin Red staining. We found that the substrate-mediated electrical stimulation of the PPy/PU substrates induced a twofold increase of the Ca deposits in the cultured cells.

Heparin/heparan sulfate 6-O-sulfatase from Flavobacterium heparinum: integrated structural and biochemical investigation of enzyme active site and substrate specificity.

PubMed

Myette, James R; Soundararajan, Venkataramanan; Shriver, Zachary; Raman, Rahul; Sasisekharan, Ram

2009-12-11

Heparin and heparan sulfate glycosaminoglycans (HSGAGs) comprise a chemically heterogeneous class of sulfated polysaccharides. The development of structure-activity relationships for this class of polysaccharides requires the identification and characterization of degrading enzymes with defined substrate specificity and enzymatic activity. Toward this end, we report here the molecular cloning and extensive structure-function analysis of a 6-O-sulfatase from the Gram-negative bacterium Flavobacterium heparinum. In addition, we report the recombinant expression of this enzyme in Escherichia coli in a soluble, active form and identify it as a specific HSGAG sulfatase. We further define the mechanism of action of the enzyme through biochemical and structural studies. Through the use of defined substrates, we investigate the kinetic properties of the enzyme. This analysis was complemented by homology-based molecular modeling studies that sought to rationalize the substrate specificity of the enzyme and mode of action through an analysis of the active-site topology of the enzyme including identifying key enzyme-substrate interactions and assigning key amino acids within the active site of the enzyme. Taken together, our structural and biochemical studies indicate that 6-O-sulfatase is a predominantly exolytic enzyme that specifically acts on N-sulfated or N-acetylated 6-O-sulfated glucosamines present at the non-reducing end of HSGAG oligosaccharide substrates. This requirement for the N-acetyl or N-sulfo groups on the glucosamine substrate can be explained through eliciting favorable interactions with key residues within the active site of the enzyme. These findings provide a framework that enables the use of 6-O-sulfatase as a tool for HSGAG structure-activity studies as well as expand our biochemical and structural understanding of this important class of enzymes.

Aqueous solution epitaxy of CdS layers on CuInSe 2

NASA Astrophysics Data System (ADS)

Furlong, M. J.; Froment, M.; Bernard, M. C.; Cortès, R.; Tiwari, A. N.; Krejci, M.; Zogg, H.; Lincot, D.

1998-09-01

Epitaxial CdS thin films have been deposited from an aqueous ammonia solution containing cadmium ions and thiourea as precursors on single crystalline CuInSe 2 films prepared by MBE on Si(1 1 1) and GaAs(1 0 0) substrates. The structure and quality of the films were investigated by RHEED, glancing angle XRD and HRTEM in cross-section. The films are cubic on (1 0 0) substrates, and mixed cubic and hexagonal on (1 1 1) substrates due to the presence of stacking faults parallel to the substrate. The growth is under surface kinetic control with an activation energy of 85 kJ mol -1. Epitaxy improves with increasing temperature and an epitaxial transition temperature at approx. 60°C is demonstrated in the selected experimental conditions. The epitaxy is very sensitive to the preparation of the surface. Beneficial effects of in situ or ex situ chemical etching are found. Similarities between aqueous solution and vapor-phase chemical depositions are pointed out.

Synthesis and characterization of structural, morphological and photosensor properties of Cu0.1Zn0.9S thin film prepared by a facile chemical method

NASA Astrophysics Data System (ADS)

Gubari, Ghamdan M. M.; Ibrahim Mohammed S., M.; Huse, Nanasaheb P.; Dive, Avinash S.; Sharma, Ramphal

2018-05-01

The Cu0.1Zn0.9S thin film was grown by facile chemical bath deposition (CBD) method on glass substrates at 60°C. The structural, morphological, photosensor properties of the as-grown thin film has been investigated. The structural and phase confirmation of the as-grown thin film was carried out by X-ray diffraction (XRD) technique and Raman spectroscopy. The FE-SEM images showed that the thin films are well covered with material on an entire glass substrate. From the optical absorption spectrum, the direct band gap energy for the Cu0.1Zn0.9S thin film was found to be ˜3.16 eV at room temperature. The electrical properties were measured at room temperature in the voltage range ±2.5 V, showed a drastic enhancement in current under light illumination with the highest photosensitivity of ˜72 % for 260 W.

Selective directed self-assembly of coexisting morphologies using block copolymer blends

PubMed Central

Stein, A.; Wright, G.; Yager, K. G.; Doerk, G. S.; Black, C. T.

2016-01-01

Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. Here we expand on traditional DSA chemical patterning. A blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This is in contrast to the typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist. PMID:27480327

Selective directed self-assembly of coexisting morphologies using block copolymer blends

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stein, A.; Wright, G.; Yager, K. G.

Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. We expand on traditional DSA chemical patterning. Moreover, a blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This contrastsmore » with typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist.« less

Selective directed self-assembly of coexisting morphologies using block copolymer blends

DOE PAGES

Stein, A.; Wright, G.; Yager, K. G.; ...

2016-08-02

Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. We expand on traditional DSA chemical patterning. Moreover, a blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This contrastsmore » with typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist.« less

Electronic structure of BaO/W cathode surfaces

NASA Technical Reports Server (NTRS)

Muller, Wolfgang

1989-01-01

The local electronic structure of the emissive layer of barium dispenser thermionic cathodes is investigated theoretically using the relativistic scattered-wave approach. The interaction of Ba and O with W, Os, and W-Os alloy surfaces is studied with atomic clusters modeling different absorption environments representative of B- and M-type cathodes. Ba is found to be strongly oxidized, while O and the metal substrate are in a reduced chemical state. The presence of O enhances the surface dipole and Ba binding energy relative to Ba on W. Model results for W-Os alloy substrates show only relatively small changes in Ba and O for identical geometries, but very large charge redistributions inside the substrate, which are attributed to the electronegativity difference between Os and W. If Os is present in the surface layer, the charge transfer from Ba to the substrate and the Ba binding energy increase relative to W. Explanations are offered for the improved electron emission from alloy surfaces and the different emission enhancement for different alloy substrates.

Substrate effects on photoluminescence and low temperature phase transition of methylammonium lead iodide hybrid perovskite thin films

NASA Astrophysics Data System (ADS)

Shojaee, S. A.; Harriman, T. A.; Han, G. S.; Lee, J.-K.; Lucca, D. A.

2017-07-01

We examine the effects of substrates on the low temperature photoluminescence (PL) spectra and phase transition in methylammonium lead iodide hybrid perovskite (CH3NH3PbI3) thin films. Structural characterization at room temperature with X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy indicated that while the chemical structure of films deposited on glass and quartz was similar, the glass substrate induced strain in the perovskite films and suppressed the grain growth. The luminescence response and phase transition of the perovskite thin films were studied by PL spectroscopy. The induced strain was found to affect both the room temperature and low temperature PL spectra of the hybrid perovskite films. In addition, it was found that the effects of the glass substrate inhibited a tetragonal to orthorhombic phase transition such that it occurred at lower temperatures.

Two-dimensional silica opens new perspectives

NASA Astrophysics Data System (ADS)

Büchner, Christin; Heyde, Markus

2017-12-01

In recent years, silica films have emerged as a novel class of two-dimensional (2D) materials. Several groups succeeded in epitaxial growth of ultrathin SiO2 layers using different growth methods and various substrates. The structures consist of tetrahedral [SiO4] building blocks in two mirror symmetrical planes, connected via oxygen bridges. This arrangement is called a silica bilayer as it is the thinnest 2D arrangement with the stoichiometry SiO2 known today. With all bonds saturated within the nano-sheet, the interaction with the substrate is based on van der Waals forces. Complex ring networks are observed, including hexagonal honeycomb lattices, point defects and domain boundaries, as well as amorphous domains. The network structures are highly tuneable through variation of the substrate, deposition parameters, cooling procedure, introducing dopants or intercalating small species. The amorphous networks and structural defects were resolved with atomic resolution microscopy and modeled with density functional theory and molecular dynamics. Such data contribute to our understanding of the formation and characteristic motifs of glassy systems. Growth studies and doping with other chemical elements reveal ways to tune ring sizes and defects as well as chemical reactivities. The pristine films have been utilized as molecular sieves and for confining molecules in nanocatalysis. Post growth hydroxylation can be used to tweak the reactivity as well. The electronic properties of silica bilayers are favourable for using silica as insulators in 2D material stacks. Due to the fully saturated atomic structure, the bilayer interacts weakly with the substrate and can be described as quasi-freestanding. Recently, a mm-scale film transfer under structure retention has been demonstrated. The chemical and mechanical stability of silica bilayers is very promising for technological applications in 2D heterostacks. Due to the impact of this bilayer system for glass science, catalysis and the field of 2D materials, a large number of theoretical and experimental studies on silica bilayers have been reported in the last years. This review aims to provide an overview on the insights gained on this material and to point out opportunities for further discovery in various fields.

Nanoparticle layer deposition for highly controlled multilayer formation based on high- coverage monolayers of nanoparticles

PubMed Central

Liu, Yue; Williams, Mackenzie G.; Miller, Timothy J.; Teplyakov, Andrew V.

2015-01-01

This paper establishes a strategy for chemical deposition of functionalized nanoparticles onto solid substrates in a layer-by-layer process based on self-limiting surface chemical reactions leading to complete monolayer formation within the multilayer system without any additional intermediate layers – nanoparticle layer deposition (NPLD). This approach is fundamentally different from previously established traditional layer-by-layer deposition techniques and is conceptually more similar to well-known atomic and molecular – layer deposition processes. The NPLD approach uses efficient chemical functionalization of the solid substrate material and complementary functionalization of nanoparticles to produce a nearly 100% coverage of these nanoparticles with the use of “click chemistry”. Following this initial deposition, a second complete monolayer of nanoparticles is deposited using a copper-catalyzed “click reaction” with the azide-terminated silica nanoparticles of a different size. This layer-by-layer growth is demonstrated to produce stable covalently-bound multilayers of nearly perfect structure over macroscopic solid substrates. The formation of stable covalent bonds is confirmed spectroscopically and the stability of the multilayers produced is tested by sonication in a variety of common solvents. The 1-, 2- and 3-layer structures are interrogated by electron microscopy and atomic force microscopy and the thickness of the multilayers formed is fully consistent with that expected for highly efficient monolayer formation with each cycle of growth. This approach can be extended to include a variety of materials deposited in a predesigned sequence on different substrates with a highly conformal filling. PMID:26726273

Patterned growth of carbon nanotubes on Si substrates without predeposition of metal catalysts

NASA Astrophysics Data System (ADS)

Chen, Y.; Yu, J.

2005-07-01

Aligned carbon nanotubes (CNTs) can be readily synthesized on quartz or silicon-oxide-coated Si substrates using a chemical vapor deposition method, but it is difficult to grow them on pure Si substrates without predeposition of metal catalysts. We report that aligned CNTs were grown by pyrolysis of iron phthalocyanine at 1000°C on the templates created on Si substrates with simple mechanical scratching. Scanning electron microscopy and x-ray energy spectroscopy analysis revealed that the trenches and patterns created on the surface of Si substrates were preferred nucleation sites for nanotube growth due to a high surface energy, metastable surface structure, and possible capillarity effect. A two-step pyrolysis process maintained Fe as an active catalyst.

Surface-texture evolution of different chemical-vapor-deposited zinc sulfide flats polished with various magnetorheological fluids

DOE PAGES

Salzman, S.; Romanofsky, H. J.; Jacobs, S. D.; ...

2015-08-19

The macro-structure of chemical-vapor-deposited (CVD) zinc sulfide (ZnS) substrates is characterizedby cone-like structures that start growing at the early stages of deposition. As deposition progresses,these cones grow larger and reach centimeter size in height and millimeter size in width. It is challengingto polish out these features from the top layer, particularly for the magnetorheological finishing (MRF)process. A conventional MR fluid tends to leave submillimeter surface artifacts on the finished surface,which is a direct result of the cone-like structure. Here we describe the MRF process of polishing four CVD ZnS substrates, manufactured by four differentvendors, with conventional MR fluid at pHmore » 10 and zirconia-coated-CI (carbonyl iron) MR fluids at pH 4, 5,and 6. We report on the surface–texture evolution of the substrates as they were MRF polished with thedifferent fluids. We show that performances of the zirconia-coated-CI MR fluid at pH 4 are significantlyhigher than that of the same fluid at pH levels of 5 and 6 and moderately higher than that of a conventionalMR fluid at pH 10. An improvement in surface–texture variability from part to part was also observedwith the pH 4 MR fluid.« less

Luminescence studies of HgCdTe- and InAsSb-based quantum-well structures

NASA Astrophysics Data System (ADS)

Izhnin, I. I.; Izhnin, A. I.; Fitsych, O. I.; Voitsekhovskii, A. V.; Gorn, D. I.; Semakova, A. A.; Bazhenov, N. L.; Mynbaev, K. D.; Zegrya, G. G.

2018-04-01

Results of photoluminescence studies of single-quantum-well HgCdTe-based structures and electroluminescence studies of multiple-quantum-well InAsSb-based structures are reported. HgCdTe structures were grown with molecular beam epitaxy on GaAs substrates. InAsSb-based structures were grown with metal-organic chemical vapor deposition on InAs substrates. The common feature of luminescence spectra of all the structures was the presence of peaks with the energy much larger than that of calculated optical transitions between the first quantization levels for electrons and heavy holes. Possibility of observation of optical transitions between the quantization levels of electrons and first and/or second heavy and light hole levels is discussed in the paper in relation to the specifics of the electronic structure of the materials under consideration.

Fabrication of novel plasmonics-active substrates

NASA Astrophysics Data System (ADS)

Dhawan, Anuj; Gerhold, Michael; Du, Yan; Misra, Veena; Vo-Dinh, Tuan

2009-02-01

This paper describes methodologies for fabricating of highly efficient plasmonics-active SERS substrates - having metallic nanowire structures with pointed geometries and sub-5 nm gap between the metallic nanowires enabling concentration of high EM fields in these regions - on a wafer-scale by a reproducible process that is compatible with large-scale development of these substrates. Excitation of surface plasmons in these nanowire structures leads to substantial enhancement in the Raman scattering signal obtained from molecules lying in the vicinity of the nanostructure surface. The methodologies employed included metallic coating of silicon nanowires fabricated by employing deep UV lithography as well as controlled growth of silicon germanium on silicon nanostructures to form diamond-shaped nanowire structures followed by metallic coating. These SERS substrates were employed for detecting chemical and biological molecules of interest. In order to characterize the SERS substrates developed in this work, we obtained SERS signals from molecules such as p-mercaptobenzoic acid (pMBA) and cresyl fast violet (CFV) attached to or adsorbed on the metal-coated SERS substrates. It was observed that both gold-coated triangular shaped nanowire substrates as well as gold-coated diamond shaped nanowire substrates provided very high SERS signals for the nanowires having sub-15 nm gaps and that the SERS signal depends on the closest spacing between the metal-coated silicon and silicon germanium nanowires. SERS substrates developed by the different processes were also employed for detection of biological molecules such as DPA (Dipicolinic Acid), an excellent marker for spores of bacteria such as Anthrax.

Substrate transport and anion permeation proceed through distinct pathways in glutamate transporters

PubMed Central

Cheng, Mary Hongying; Torres-Salazar, Delany; Gonzalez-Suarez, Aneysis D; Amara, Susan G; Bahar, Ivet

2017-01-01

Advances in structure-function analyses and computational biology have enabled a deeper understanding of how excitatory amino acid transporters (EAATs) mediate chloride permeation and substrate transport. However, the mechanism of structural coupling between these functions remains to be established. Using a combination of molecular modeling, substituted cysteine accessibility, electrophysiology and glutamate uptake assays, we identified a chloride-channeling conformer, iChS, transiently accessible as EAAT1 reconfigures from substrate/ion-loaded into a substrate-releasing conformer. Opening of the anion permeation path in this iChS is controlled by the elevator-like movement of the substrate-binding core, along with its wall that simultaneously lines the anion permeation path (global); and repacking of a cluster of hydrophobic residues near the extracellular vestibule (local). Moreover, our results demonstrate that stabilization of iChS by chemical modifications favors anion channeling at the expense of substrate transport, suggesting a mutually exclusive regulation mediated by the movement of the flexible wall lining the two regions. DOI: http://dx.doi.org/10.7554/eLife.25850.001 PMID:28569666

Cys-X scanning for expansion of active-site residues and modulation of catalytic functions in a glutathione transferase.

PubMed

Norrgård, Malena A; Hellman, Ulf; Mannervik, Bengt

2011-05-13

We propose Cys-X scanning as a semisynthetic approach to engineer the functional properties of recombinant proteins. As in the case of Ala scanning, key residues in the primary structure are identified, and one of them is replaced by Cys via site-directed mutagenesis. The thiol of the residue introduced is subsequently modified by alternative chemical reagents to yield diverse Cys-X mutants of the protein. This chemical approach is orthogonal to Ala or Cys scanning and allows the expansion of the repertoire of amino acid side chains far beyond those present in natural proteins. In its present application, we have introduced Cys-X residues in human glutathione transferase (GST) M2-2, replacing Met-212 in the substrate-binding site. To achieve selectivity of the modifications, the Cys residues in the wild-type enzyme were replaced by Ala. A suite of simple substitutions resulted in a set of homologous Met derivatives ranging from normethionine to S-heptyl-cysteine. The chemical modifications were validated by HPLC and mass spectrometry. The derivatized mutant enzymes were assayed with alternative GST substrates representing diverse chemical reactions: aromatic substitution, epoxide opening, transnitrosylation, and addition to an ortho-quinone. The Cys substitutions had different effects on the alternative substrates and differentially enhanced or suppressed catalytic activities depending on both the Cys-X substitution and the substrate assayed. As a consequence, the enzyme specificity profile could be changed among the alternative substrates. The procedure lends itself to large-scale production of Cys-X modified protein variants.

A Two-Dimensional 'Zigzag' Silica Polymorph on a Metal Support.

PubMed

Kuhness, David; Yang, Hyun Jin; Klemm, Hagen W; Prieto, Mauricio; Peschel, Gina; Fuhrich, Alexander; Menzel, Dietrich; Schmidt, Thomas; Yu, Xin; Shaikhutdinov, Shamil; Lewandowski, Adrian; Heyde, Markus; Kelemen, Anna; Włodarczyk, Radosław; Usvyat, Denis; Schütz, Martin; Sauer, Joachim; Freund, Hans-Joachim

2018-05-16

We present a new polymorph of the two-dimensional (2D) silica film with a characteristic 'zigzag' line structure and a rectangular unit cell which forms on a Ru(0001) metal substrate. This new silica polymorph may allow for important insights into growth modes and transformations of 2D silica films as a model system for the study of glass transitions. Based on scanning tunneling microscopy, low energy electron diffraction, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy measurements on the one hand, and density functional theory calculations on the other, a structural model for the 'zigzag' polymorph is proposed. In comparison to established monolayer and bilayer silica, this 'zigzag' structure system has intermediate characteristics in terms of coupling to the substrate and stoichiometry. The silica 'zigzag' phase is transformed upon reoxidation at higher annealing temperature into a SiO 2 silica bilayer film which is chemically decoupled from the substrate.

Development of pyrethroid-like fluorescent substrates for glutathione S-transferase

PubMed Central

Huang, Huazhang; Yao, Hongwei; Liu, Jun-Yan; Samra, Aman I.; Kamita, Shizuo G.; Cornel, Anthony J.; Hammock, Bruce D.

2012-01-01

The availability of highly sensitive substrates is critical for the development of precise and rapid assays for detecting changes in glutathione S-transferase (GST) activity that are associated with GST-mediated metabolism of insecticides. In this study, six pyrethroid-like compounds were synthesized and characterized as substrates for insect and mammalian GSTs. All of the substrates were esters composed of the same alcohol moiety, 7-hydroxy-4-methylcoumarin, and acid moieties that structurally mimic some commonly used pyrethroid insecticides including cypermethrin and cyhalothrin. CpGSTD1, a recombinant Delta class GST from the mosquito Culex pipiens, metabolized our pyrethroid-like substrates with both chemical and geometric (i.e., the cis-isomers were metabolized at 2- to 5-fold higher rates than the corresponding trans-isomers) preference. A GST preparation from mouse liver also metabolized most of our pyrethroid-like substrates with both chemical and geometric preference but at 10- to 170-fold lower rates. CpGSTD1 and mouse GSTs metabolized CDNB, a general GST substrate, at more than 200-fold higher rates than our novel pyrethroid-like substrates. There was a 10-fold difference in the specificity constant (kcat/KM ratio) of CpGSTD1 for CDNB and those of CpGSTD1 for cis-DCVC and cis-TFMCVC suggesting that cis-DCVC and cis-TFMCVC may be useful for the detection of GST-based metabolism of pyrethroids in mosquitoes. PMID:23000005

Surface wave chemical detector using optical radiation

DOEpatents

Thundat, Thomas G.; Warmack, Robert J.

2007-07-17

A surface wave chemical detector comprising at least one surface wave substrate, each of said substrates having a surface wave and at least one measurable surface wave parameter; means for exposing said surface wave substrate to an unknown sample of at least one chemical to be analyzed, said substrate adsorbing said at least one chemical to be sensed if present in said sample; a source of radiation for radiating said surface wave substrate with different wavelengths of said radiation, said surface wave parameter being changed by said adsorbing; and means for recording signals representative of said surface wave parameter of each of said surface wave substrates responsive to said radiation of said different wavelengths, measurable changes of said parameter due to adsorbing said chemical defining a unique signature of a detected chemical.

The Effects of ph on Structural and Optical Characterization of Iron Oxide Thin Films

NASA Astrophysics Data System (ADS)

Tezel, Fatma Meydaneri; Özdemir, Osman; Kariper, I. Afşin

In this study, the iron oxide thin films have been produced by chemical bath deposition (CBD) method as a function of pH onto amorphous glass substrates. The surface images of the films were investigated with scanning electron microscope (SEM). The crystal structures, orientation of crystallization, crystallite sizes, and dislocation density i.e. structural properties of the thin films were analyzed with X-ray diffraction (XRD). The optical band gap (Eg), optical transmission (T%), reflectivity (R%), absorption coefficient (α), refraction index (n), extinction coefficient (k) and dielectric constant (ɛ) of the thin films were investigated depending on pH, deposition time, solution temperature, substrate temperature, thickness of the films by UV-VIS spectrometer.

Atomic Chain Electronics

NASA Technical Reports Server (NTRS)

Yamada, Toshishige; Saini, Subhash (Technical Monitor)

1998-01-01

Adatom chains, precise structures artificially created on an atomically regulated surface, are the smallest possible candidates for future nanoelectronics. Since all the devices are created by combining adatom chains precisely prepared with atomic precision, device characteristics are predictable, and free from deviations due to accidental structural defects. In this atomic dimension, however, an analogy to the current semiconductor devices may not work. For example, Si structures are not always semiconducting. Adatom states do not always localize at the substrate surface when adatoms form chemical bonds to the substrate atoms. Transport properties are often determined for the entire system of the chain and electrodes, and not for chains only. These fundamental issues are discussed, which will be useful for future device considerations.

Resonant x-ray diffraction revealing chemical disorder in sputtered L10 FeNi on Si(0 0 1)

NASA Astrophysics Data System (ADS)

Frisk, Andreas; Lindgren, Bengt; Pappas, Spiridon D.; Johansson, Erik; Andersson, Gabriella

2016-10-01

In the search for new rare earth free permanent magnetic materials, FeNi with a L10 structure is a possible candidate. We have synthesized the phase in the thin film form by sputtering onto HF-etched Si(0 0 1) substrates. Monatomic layers of Fe and Ni were alternately deposited on a Cu buffer layer, all of which grew epitaxially on the Si substrates. A good crystal structure and epitaxial relationship was confirmed by in-house x-ray diffraction (XRD). The chemical order, which to some part is the origin of an uniaxial magnetic anisotropy, was measured by resonant XRD. The 0 0 1 superlattice reflection was split in two symmetrically spaced peaks due to a composition modulation of the Fe and Ni layers. Furthermore the influence of roughness induced chemical anti-phase domains on the RXRD pattern is exemplified. A smaller than expected magnetic uniaxial anisotropy energy was obtained, which is partly due to the composition modulations, but the major reason is concluded to be the Cu buffer surface roughness.

Resonant x-ray diffraction revealing chemical disorder in sputtered L10 FeNi on Si(0 0 1).

PubMed

Frisk, Andreas; Lindgren, Bengt; Pappas, Spiridon D; Johansson, Erik; Andersson, Gabriella

2016-10-12

In the search for new rare earth free permanent magnetic materials, FeNi with a L10 structure is a possible candidate. We have synthesized the phase in the thin film form by sputtering onto HF-etched Si(0 0 1) substrates. Monatomic layers of Fe and Ni were alternately deposited on a Cu buffer layer, all of which grew epitaxially on the Si substrates. A good crystal structure and epitaxial relationship was confirmed by in-house x-ray diffraction (XRD). The chemical order, which to some part is the origin of an uniaxial magnetic anisotropy, was measured by resonant XRD. The 0 0 1 superlattice reflection was split in two symmetrically spaced peaks due to a composition modulation of the Fe and Ni layers. Furthermore the influence of roughness induced chemical anti-phase domains on the RXRD pattern is exemplified. A smaller than expected magnetic uniaxial anisotropy energy was obtained, which is partly due to the composition modulations, but the major reason is concluded to be the Cu buffer surface roughness.

Computational study of sheath structure in oxygen containing plasmas at medium pressures

NASA Astrophysics Data System (ADS)

Hrach, Rudolf; Novak, Stanislav; Ibehej, Tomas; Hrachova, Vera

2016-09-01

Plasma mixtures containing active species are used in many plasma-assisted material treatment technologies. The analysis of such systems is rather difficult, as both physical and chemical processes affect plasma properties. A combination of experimental and computational approaches is the best suited, especially at higher pressures and/or in chemically active plasmas. The first part of our study of argon-oxygen mixtures was based on experimental results obtained in the positive column of DC glow discharge. The plasma was analysed by the macroscopic kinetic approach which is based on the set of chemical reactions in the discharge. The result of this model is a time evolution of the number densities of each species. In the second part of contribution the detailed analysis of processes taking place during the interaction of oxygen containing plasma with immersed substrates was performed, the results of the first model being the input parameters. The used method was the particle simulation technique applied to multicomponent plasma. The sheath structure and fluxes of charged particles to substrates were analysed in the dependence on plasma pressure, plasma composition and surface geometry.

NMR Crystallography of a Carbanionic Intermediate in Tryptophan Synthase: Chemical Structure, Tautomerization, and Reaction Specificity.

PubMed

Caulkins, Bethany G; Young, Robert P; Kudla, Ryan A; Yang, Chen; Bittbauer, Thomas J; Bastin, Baback; Hilario, Eduardo; Fan, Li; Marsella, Michael J; Dunn, Michael F; Mueller, Leonard J

2016-11-23

Carbanionic intermediates play a central role in the catalytic transformations of amino acids performed by pyridoxal-5'-phosphate (PLP)-dependent enzymes. Here, we make use of NMR crystallography-the synergistic combination of solid-state nuclear magnetic resonance, X-ray crystallography, and computational chemistry-to interrogate a carbanionic/quinonoid intermediate analogue in the β-subunit active site of the PLP-requiring enzyme tryptophan synthase. The solid-state NMR chemical shifts of the PLP pyridine ring nitrogen and additional sites, coupled with first-principles computational models, allow a detailed model of protonation states for ionizable groups on the cofactor, substrates, and nearby catalytic residues to be established. Most significantly, we find that a deprotonated pyridine nitrogen on PLP precludes formation of a true quinonoid species and that there is an equilibrium between the phenolic and protonated Schiff base tautomeric forms of this intermediate. Natural bond orbital analysis indicates that the latter builds up negative charge at the substrate C α and positive charge at C4' of the cofactor, consistent with its role as the catalytic tautomer. These findings support the hypothesis that the specificity for β-elimination/replacement versus transamination is dictated in part by the protonation states of ionizable groups on PLP and the reacting substrates and underscore the essential role that NMR crystallography can play in characterizing both chemical structure and dynamics within functioning enzyme active sites.

NMR Crystallography of a Carbanionic Intermediate in Tryptophan Synthase: Chemical Structure, Tautomerization, and Reaction Specificity

PubMed Central

2016-01-01

Carbanionic intermediates play a central role in the catalytic transformations of amino acids performed by pyridoxal-5′-phosphate (PLP)-dependent enzymes. Here, we make use of NMR crystallography—the synergistic combination of solid-state nuclear magnetic resonance, X-ray crystallography, and computational chemistry—to interrogate a carbanionic/quinonoid intermediate analogue in the β-subunit active site of the PLP-requiring enzyme tryptophan synthase. The solid-state NMR chemical shifts of the PLP pyridine ring nitrogen and additional sites, coupled with first-principles computational models, allow a detailed model of protonation states for ionizable groups on the cofactor, substrates, and nearby catalytic residues to be established. Most significantly, we find that a deprotonated pyridine nitrogen on PLP precludes formation of a true quinonoid species and that there is an equilibrium between the phenolic and protonated Schiff base tautomeric forms of this intermediate. Natural bond orbital analysis indicates that the latter builds up negative charge at the substrate Cα and positive charge at C4′ of the cofactor, consistent with its role as the catalytic tautomer. These findings support the hypothesis that the specificity for β-elimination/replacement versus transamination is dictated in part by the protonation states of ionizable groups on PLP and the reacting substrates and underscore the essential role that NMR crystallography can play in characterizing both chemical structure and dynamics within functioning enzyme active sites. PMID:27779384

Influence of hydrogen on the structure and stability of ultra-thin ZnO on metal substrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bieniek, Bjoern; Hofmann, Oliver T.; Institut für Festkörperphysik, TU Graz, 8010 Graz

2015-03-30

We investigate the atomic and electronic structure of ultra-thin ZnO films (1 to 4 layers) on the (111) surfaces of Ag, Cu, Pd, Pt, Ni, and Rh by means of density-functional theory. The ZnO monolayer is found to adopt an α-BN structure on the metal substrates with coincidence structures in good agreement with experiment. Thicker ZnO layers change into a wurtzite structure. The films exhibit a strong corrugation, which can be smoothed by hydrogen (H) adsorption. An H over-layer with 50% coverage is formed at chemical potentials that range from low to ultra-high vacuum H{sub 2} pressures. For the Agmore » substrate, both α-BN and wurtzite ZnO films are accessible in this pressure range, while for Cu, Pd, Pt, Rh, and Ni wurtzite films are favored. The surface structure and the density of states of these H passivated ZnO thin films agree well with those of the bulk ZnO(0001{sup ¯})-2×1-H surface.« less

Conformational Dynamics, Ligand Binding and Effects of Mutations in NirE an S-Adenosyl-L-Methionine Dependent Methyltransferase

NASA Astrophysics Data System (ADS)

Singh, Warispreet; Karabencheva-Christova, Tatyana G.; Black, Gary W.; Ainsley, Jon; Dover, Lynn; Christov, Christo Z.

2016-01-01

Heme d1, a vital tetrapyrrol involved in the denitrification processes is synthesized from its precursor molecule precorrin-2 in a chemical reaction catalysed by an S-adenosyl-L-methionine (SAM) dependent Methyltransferase (NirE). The NirE enzyme catalyses the transfer of a methyl group from the SAM to uroporphyrinogen III and serves as a novel potential drug target for the pharmaceutical industry. An important insight into the structure-activity relationships of NirE has been revealed by elucidating its crystal structure, but there is still no understanding about how conformational flexibility influences structure, cofactor and substrate binding by the enzyme as well as the structural effects of mutations of residues involved in binding and catalysis. In order to provide this missing but very important information we performed a comprehensive atomistic molecular dynamics study which revealed that i) the binding of the substrate contributes to the stabilization of the structure of the full complex; ii) conformational changes influence the orientation of the pyrrole rings in the substrate, iii) more open conformation of enzyme active site to accommodate the substrate as an outcome of conformational motions; and iv) the mutations of binding and active site residues lead to sensitive structural changes which influence binding and catalysis.

Transparent and conducting ZnO films grown by spray pyrolysis

NASA Astrophysics Data System (ADS)

Hadjeris, Lazhar; Herissi, Labidi; Badreddine Assouar, M.; Easwarakhanthan, Thomas; Bougdira, Jamal; Attaf, Nadhir; Salah Aida, M.

2009-03-01

ZnO films were prepared using the simple, flexible and cost-effective spray pyrolysis technique at different substrate temperatures and precursor molarity values. The films' structural, optical and electrical properties were investigated by x-ray diffraction, UV-VIS transmittance spectroscopy, profilometry and voltage-current-temperature (VIT) measurements. The films prepared at substrate temperatures above 400 °C appear better crystallized with (0 0 2) preferred orientation and exhibit higher visible transmittance (65-80%), higher electrical n-type semiconductor conductivity (10-50 (Ω cm)-1), lower activation energy (<0.35 eV) and smaller Urbach energy (80 meV). These results indicate that such sprayed ZnO films are chemically purer and have many fewer defects and less disorder owing to an almost complete chemical decomposition of the precursor droplets. ZnO films having desired optical and electrical properties for cheaper large-area solar cells may thus be tailored through the substrate temperature and the precursor molarity.

Analysis of synthetic diamond single crystals by X-ray topography and double-crystal diffractometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prokhorov, I. A., E-mail: igor.prokhorov@mail.ru; Ralchenko, V. G.; Bolshakov, A. P.

2013-12-15

Structural features of diamond single crystals synthesized under high pressure and homoepitaxial films grown by chemical vapor deposition (CVD) have been analyzed by double-crystal X-ray diffractometry and topography. The conditions of a diffraction analysis of diamond crystals using Ge monochromators have been optimized. The main structural defects (dislocations, stacking faults, growth striations, second-phase inclusions, etc.) formed during crystal growth have been revealed. The nitrogen concentration in high-pressure/high-temperature (HPHT) diamond substrates is estimated based on X-ray diffraction data. The formation of dislocation bundles at the film-substrate interface in the epitaxial structures has been revealed by plane-wave topography; these dislocations are likelymore » due to the relaxation of elastic macroscopic stresses caused by the lattice mismatch between the substrate and film. The critical thicknesses of plastic relaxation onset in CVD diamond films are calculated. The experimental techniques for studying the real diamond structure in optimizing crystal-growth technology are proven to be highly efficient.« less

Visible light assisted photoelectrocatalytic degradation of sugarcane factory wastewater by sprayed CZTS thin films

NASA Astrophysics Data System (ADS)

Hunge, Y. M.; Mahadik, M. A.; Patil, V. L.; Pawar, A. R.; Gadakh, S. R.; Moholkar, A. V.; Patil, P. S.; Bhosale, C. H.

2017-12-01

Highly crystalline Cu2ZnSnS4 (CZTS) thin films have been deposited onto glass and FTO coated glass substrates by simple chemical spray-pyrolysis technique. It is an important material for solar energy conversion through the both photovoltaics and photocatalysis. The effect of substrate temperatures on the physico-chemical properties of the CZTS films is studied. The XRD study shows the formation of single phase CZTS with kesterite structure. FE-SEM analysis reveals nano flakes architecture with pin-hole and crake free surface with more adherent. The film deposited at optimized substrate temperature exhibits optical band gap energy of 1.90 eV, which lies in the visible region of the solar spectrum and useful for photocatalysis application. The photoelectrocatalytic activities of the large surface area (10 × 10 cm2) deposited CZTS thin film photocatalysts were evaluated for the degradation of sugarcane factory wastewater under visible light irradiation. The results show that the CZTS thin film photocatalyst exhibited about 90% degradation of sugar cane factory wastewater. The mineralization of sugarcane factory wastewater is studied by measuring chemical oxygen demand (COD) values.

Interfacial development of electrophoretically deposited graphene oxide films on Al alloys

DOE PAGES

Jin, Sumin; Dickerson, James H.; Pham, Viet Hung; ...

2015-07-28

Adhesion between film and substrate is critical for electronic device and coating applications. Interfacial development between electrophoretically deposited graphene oxide films on Al 1100 and Al 5052 alloys were investigated using FT-IR and XPS depth profiling techniques. Obtained results suggest metal ion permeation from the substrates into deposited graphene oxide films. The interface between the films and the substrates were primarily composed of Al-O-C bonds from oxygenated defects on graphene oxide plane rather than expected Al-C formation. Films heat treated at 150 °C had change in microstructure and peak shifts in XPS spectra suggesting change in chemical structure of bondsmore » between the films and the substrates.« less

Electrically pumped 1.3 microm room-temperature InAs/GaAs quantum dot lasers on Si substrates by metal-mediated wafer bonding and layer transfer.

PubMed

Tanabe, Katsuaki; Guimard, Denis; Bordel, Damien; Iwamoto, Satoshi; Arakawa, Yasuhiko

2010-05-10

An electrically pumped InAs/GaAs quantum dot laser on a Si substrate has been demonstrated. The double-hetero laser structure was grown on a GaAs substrate by metal-organic chemical vapor deposition and layer-transferred onto a Si substrate by GaAs/Si wafer bonding mediated by a 380-nm-thick Au-Ge-Ni alloy layer. This broad-area Fabry-Perot laser exhibits InAs quantum dot ground state lasing at 1.31 microm at room temperature with a threshold current density of 600 A/cm(2). (c) 2010 Optical Society of America.

Influence of substrate preparation on the shaping of the topography of the surface of nanoceramic oxide layers

NASA Astrophysics Data System (ADS)

Bara, Marek; Kubica, Marek

2014-02-01

The paper discusses the shaping mechanism and changes occurring in the structure and topography of the surface of nanoceramic oxide layers during their formation. The paper presents the influence of substrate preparation on the surface topography of oxide layers. The layers were produced via hard anodizing on the EN AW-5251 aluminum alloy. The layers obtained were subjected to microscope examinations, image and chemical composition analyses, and stereometric examinations. Heredity of substrate properties in the topography of the surface of nanoceramic oxide layers formed as a result of electrochemical oxidation has been shown.

Structures with Reconfigurable Circulatory Systems

DTIC Science & Technology

2008-05-16

chemical groups ( cinnamates , etc.) may be explored as they may result in faster kinetics which will facilitate transition between solid and liquid...Cysteine, an amino acid , is a critical substrate in biosynthesis of proteins, glutathione, taurine sulfate and the exceptionally metabolically active

Reduction of structural defects in thick 4H-SiC epitaxial layers grown on 4° off-axis substrates

NASA Astrophysics Data System (ADS)

Yazdanfar, M.; Ivanov, I. G.; Pedersen, H.; Kordina, O.; Janzén, E.

2013-06-01

By carefully controlling the surface chemistry of the chemical vapor deposition process for silicon carbide (SiC), 100 μm thick epitaxial layers with excellent morphology were grown on 4° off-axis SiC substrates at growth rates exceeding 100 μm/h. In order to reduce the formation of step bunching and structural defects, mainly triangular defects, the effect of varying parameters such as growth temperature, C/Si ratio, Cl/Si ratio, Si/H2 ratio, and in situ pre-growth surface etching time are studied. It was found that an in-situ pre growth etch at growth temperature and pressure using 0.6% HCl in hydrogen for 12 min reduced the structural defects by etching preferentially on surface damages of the substrate surface. By then applying a slightly lower growth temperature of 1575 °C, a C/Si ratio of 0.8, and a Cl/Si ratio of 5, 100 μm thick, step-bunch free epitaxial layer with a minimum triangular defect density and excellent morphology could be grown, thus enabling SiC power device structures to be grown on 4° off axis SiC substrates.

Influence of substrate bias voltage on structure and properties of the CrAlN films deposited by unbalanced magnetron sputtering

NASA Astrophysics Data System (ADS)

Lv, Yanhong; Ji, Li; Liu, Xiaohong; Li, Hongxuan; Zhou, Huidi; Chen, Jianmin

2012-02-01

The CrAlN films were deposited on silicon and stainless steel substrates by unbalanced magnetron sputtering system. The influence of substrate bias on deposition rate, composition, structure, morphology and properties of the CrAlN films was investigated. The results showed that, with the increase of the substrate bias voltage, the deposition rate decreased accompanied by a change of the preferred orientation of the CrAlN film from (2 2 0) to (2 0 0). The grain size and the average surface roughness of the CrAlN films declined as the bias voltage increases above -100 V. The morphology of the films changed from obviously columnar to dense glass-like structure with the increase of the bias voltage from -50 to -250 V. Meanwhile, the films deposited at moderate bias voltage had better mechanical and tribological properties, while the films deposited at higher bias voltage showed better corrosion resistance. It was found that the corrosion resistance improvement was not only attributed to the low pinhole density of the film, but also to chemical composition of films.

Metal-assisted etch combined with regularizing etch

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yim, Joanne; Miller, Jeff; Jura, Michael

In an aspect of the disclosure, a process for forming nanostructuring on a silicon-containing substrate is provided. The process comprises (a) performing metal-assisted chemical etching on the substrate, (b) performing a clean, including partial or total removal of the metal used to assist the chemical etch, and (c) performing an isotropic or substantially isotropic chemical etch subsequently to the metal-assisted chemical etch of step (a). In an alternative aspect of the disclosure, the process comprises (a) performing metal-assisted chemical etching on the substrate, (b) cleaning the substrate, including removal of some or all of the assisting metal, and (c) performingmore » a chemical etch which results in regularized openings in the silicon substrate.« less

Fabrication of ZnO nanorod using spray-pyrolysis and chemical bath deposition method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramadhani, Muhammad F., E-mail: brian@tf.itb.ac.id; Pasaribu, Maruli A. H., E-mail: brian@tf.itb.ac.id; Yuliarto, Brian, E-mail: brian@tf.itb.ac.id

2014-02-24

ZnO thin films with nanorod structure were deposited using Ultrasonic Spray Pyrolysis method for seed growth, and Chemical Bath Deposition (CBD) for nanorod growth. High purity Zn-hydrate and Urea are used to control Ph were dissolved in ethanol and aqua bidest in Ultrasonic Spray Pyrolysis process. Glass substrate was placed above the heater plate of reaction chamber, and subsequently sprayed with the range duration of 5, 10 and 20 minutes at the temperatures of 3500 C. As for the Chemical Bath Deposition, the glass substrate with ZnO seed on the surface was immerse to Zn-hydrate, HMTA (Hexa Methylene Tetra Amine)more » and deionized water solution for duration of 3, 5 and 7 hour and temperatures of 600 C, washed in distilled water, dried, and annealed at 3500 C for an hour. The characterization of samples was carried out to reveal the surface morphology using Scanning Electron Microscopy (SEM). From the data, the combination of 5 minutes of Ultrasonic Spray Pyrolysis process and 3 hour of CBD has showed the best structure of nanorod. Meanwhile the longer Spraying process and CBD yield the bigger nanorod structure that have been made, and it makes the films more dense which make the nanorod collide each other and as a result produce unsymetric nanorod structure.« less

Copper cladding on polymer surfaces by ionization-assisted deposition

NASA Astrophysics Data System (ADS)

Kohno, Tomoki; Tanaka, Kuniaki; Usui, Hiroaki

2018-03-01

Copper thin films were prepared on poly(ethylene terephthalate) (PET) and polyimide (PI) substrates by an ionization-assisted vapor deposition method. The films had a polycrystalline structure, and their crystallite size decreased with increasing ion acceleration voltage V a. Ion acceleration was effective in reducing the surface roughness of the films. Cross-sectional transmission electron microscopy revealed that the copper/polymer interface showed increased corrugation with increasing V a. The increase in V a also induced the chemical modification of polymer chains of the PET substrate, but the PI substrate underwent smaller modification after ion bombardment. Most importantly, the adhesion strength between the copper film and the PET substrate increased with increasing V a. It was concluded that ionization-assisted deposition is a promising technique for preparing metal clad layers on flexible polymer substrates.

Oxygen-implanted induced formation of oxide layer enhances blood compatibility on titanium for biomedical applications.

PubMed

Hung, Wei-Chiang; Chang, Fang-Mo; Yang, Tzu-Sen; Ou, Keng-Liang; Lin, Che-Tong; Peng, Pei-Wen

2016-11-01

Titanium dioxide (TiO2) layers were prepared on a Ti substrate by using oxygen plasma immersion ion implantation (oxygen PIII). The surface chemical states, structure, and morphology of the layers were studied using X-ray photoelectron spectroscopy, X-ray diffraction, Raman microscopy, atomic force microscopy and scanning electron microscope. The mechanical properties, such as the Young's modulus and hardness, of the layers were investigated using nanoindentation testing. The Ti(4+) chemical state was determined to be present on oxygen-PIII-treated surfaces, which consisted of nanocrystalline TiO2 with a rutile structure. Compared with Ti substrates, the oxygen-PIII-treated surfaces exhibited decreased Young's moduli and hardness. Parameters indicating the blood compatibility of the oxygen-PIII-treated surfaces, including the clotting time and platelet adhesion and activation, were studied in vitro. Clotting time assays indicated that the clotting time of oxygen-PIII-treated surfaces was longer than that of the Ti substrate, which was associated with decreased fibrinogen adsorption. In conclusion, the surface characteristics and the blood compatibility of Ti implants can be modified and improved using oxygen PIII. Copyright © 2016 Elsevier B.V. All rights reserved.

Cotranslocational processing of the protein substrate calmodulin by an AAA+ unfoldase occurs via unfolding and refolding intermediates.

PubMed

Augustyniak, Rafal; Kay, Lewis E

2018-05-22

Protein remodeling by AAA+ enzymes is central for maintaining proteostasis in a living cell. However, a detailed structural description of how this is accomplished at the level of the substrate molecules that are acted upon is lacking. Here, we combine chemical cross-linking and methyl transverse relaxation-optimized NMR spectroscopy to study, at atomic resolution, the stepwise unfolding and subsequent refolding of the two-domain substrate calmodulin by the VAT AAA+ unfoldase from Thermoplasma acidophilum By engineering intermolecular disulphide bridges between the substrate and VAT we trap the substrate at different stages of translocation, allowing structural studies throughout the translocation process. Our results show that VAT initiates substrate translocation by pulling on intrinsically unstructured N or C termini of substrate molecules without showing specificity for a particular amino acid sequence. Although the B1 domain of protein G is shown to unfold cooperatively, translocation of calmodulin leads to the formation of intermediates, and these differ on an individual domain level in a manner that depends on whether pulling is from the N or C terminus. The approach presented generates an atomic resolution picture of substrate unfolding and subsequent refolding by unfoldases that can be quite different from results obtained via in vitro denaturation experiments.

Strain induced chemical potential difference between monolayer graphene sheets.

PubMed

Zhang, Yupeng; Luo, Chengzhi; Li, Weiping; Pan, Chunxu

2013-04-07

Monolayer graphene sheets were deposited on a transparent and flexible polydimethylsiloxane (PDMS) substrate, and a tensile strain was loaded by stretching the substrate in one direction. It was found that an electric potential difference between stretched and static monolayer graphene sheets reached 8 mV when the strain was 5%. Theoretical calculations for the band structure and total energy revealed an alternative way to experimentally tune the band gap of monolayer graphene, and induce the generation of electricity.

Superconductors

DOEpatents

Newkirk, Lawrence R.; Valencia, Flavio A.

1977-02-01

The structural quality of niobium germanide as a high-transition-temperature superconducting material is substantially improved by the presence of about 5 at. % oxygen. Niobium germanide having this oxygen content may readily be prepared as a bulk coating bonded to a metallic substrate by chemical vapor deposition techniques.

Yeast enolase: mechanism of activation by metal ions.

PubMed

Brewer, J M

1981-01-01

Yeast enolase as prepared by current procedures is inherently chemically homogeneous, though deamidation and partial denaturation can produce electrophoretically distinct forms. A true isozyme of the enzyme exists but does not survive the purification procedure. The chemical sequence for both has been established. The enzyme behaves in solution like a compact, nearly spherical molecule of moderate hydration. Strong intramolecular forces maintain the structure of the individual subunits. The enzyme as isolated is dimeric. If dissociated in the presence of magnesium ions and substrate, then the subunits are active, but if the dissociation occurs in the absence of metal ions, they are inactive until they have reassociated and undergone a first order "annealing" process. Magnesium (II) enhances association. The interaction between the subunits is hydrophobic in character. The enzyme can bind up to 2 mol of most metal ions in "conformational" sites which then allows up to 2 mol of substrate or some substrate analogue to bind. This is not sufficient for catalysis, but conformational metal ions do more than just allow substrate binding. A change in the environment of the metal ions occurs on substrate or substrate analogue binding. There is an absolute correlation between the occurrence of a structural change undergone by the 3-amino analogue of phosphoenolpyruvate and whether the metal ions produce any level of enzymatic activity. For catalysis, two more moles of metal ions, called "catalytic", must bind. There is evidence that the enzymatic reaction involves a carbanion mechanism. It is likely that two more moles of metal ion can bind which inhibit the reaction. The requirement for 2 mol of metal ion per subunit which contribute in different ways to catalysis is exhibited by a number of other enzymes.

Electromagnetic modelling of Raman enhancement from nanoscale substrates: a route to estimation of the magnitude of the chemical enhancement mechanism in SERS.

PubMed

Brown, Richard J C; Wang, Jian; Tantra, Ratna; Yardley, Rachel E; Milton, Martin J T

2006-01-01

Despite widespread use for more than two decades, the SERS phenomenon has defied accurate physical and chemical explanation. The relative contributions from electronic and chemical mechanisms are difficult to quantify and are often not reproduced under nominally similar experimental conditions. This work has used electromagnetic modelling to predict the Raman enhancement expected from three configurations: metal nanoparticles, structured metal surfaces, and sharp metal tips interacting with metal surfaces. In each case, parameters such as artefact size, artefact separation and incident radiation wavelength have been varied and the resulting electromagnetic field modelled. This has yielded an electromagnetic description of these configurations with predictions of the maximum expected Raman enhancement, and hence a prediction of the optimum substrate configuration for the SERS process. When combined with experimental observations of the dependence of Raman enhancement with changing ionic strength, the modelling results have allowed a novel estimate of the size of the chemical enhancement mechanism to be produced.

Enzyme That Makes You Cry-Crystal Structure of Lachrymatory Factor Synthase from Allium cepa.

PubMed

Silvaroli, Josie A; Pleshinger, Matthew J; Banerjee, Surajit; Kiser, Philip D; Golczak, Marcin

2017-09-15

The biochemical pathway that gives onions their savor is part of the chemical warfare against microbes and animals. This defense mechanism involves formation of a volatile lachrymatory factor (LF) ((Z)-propanethial S-oxide) that causes familiar eye irritation associated with onion chopping. LF is produced in a reaction catalyzed by lachrymatory factor synthase (LFS). The principles by which LFS facilitates conversion of a sulfenic acid substrate into LF have been difficult to experimentally examine owing to the inherent substrate reactivity and lability of LF. To shed light on the mechanism of LF production in the onion, we solved crystal structures of LFS in an apo-form and in complex with a substrate analogue, crotyl alcohol. The enzyme closely resembles the helix-grip fold characteristic for plant representatives of the START (star-related lipid transfer) domain-containing protein superfamily. By comparing the structures of LFS to that of the abscisic acid receptor, PYL10, a representative of the START protein superfamily, we elucidated structural adaptations underlying the catalytic activity of LFS. We also delineated the architecture of the active site, and based on the orientation of the ligand, we propose a mechanism of catalysis that involves sequential proton transfer accompanied by formation of a carbanion intermediate. These findings reconcile chemical and biochemical information regarding thioaldehyde S-oxide formation and close a long-lasting gap in understanding of the mechanism responsible for LF production in the onion.

Enzyme That Makes You Cry–Crystal Structure of Lachrymatory Factor Synthase from Allium cepa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silvaroli, Josie A.; Pleshinger, Matthew J.; Banerjee, Surajit

The biochemical pathway that gives onions their savor is part of the chemical warfare against microbes and animals. This defense mechanism involves formation of a volatile lachrymatory factor (LF) ((Z)-propanethial S-oxide) that causes familiar eye irritation associated with onion chopping. LF is produced in a reaction catalyzed by lachrymatory factor synthase (LFS). The principles by which LFS facilitates conversion of a sulfenic acid substrate into LF have been difficult to experimentally examine owing to the inherent substrate reactivity and lability of LF. To shed light on the mechanism of LF production in the onion, we solved crystal structures of LFSmore » in an apo-form and in complex with a substrate analogue, crotyl alcohol. The enzyme closely resembles the helix-grip fold characteristic for plant representatives of the START (star-related lipid transfer) domain-containing protein superfamily. By comparing the structures of LFS to that of the abscisic acid receptor, PYL10, a representative of the START protein superfamily, we elucidated structural adaptations underlying the catalytic activity of LFS. We also delineated the architecture of the active site, and based on the orientation of the ligand, we propose a mechanism of catalysis that involves sequential proton transfer accompanied by formation of a carbanion intermediate. These findings reconcile chemical and biochemical information regarding thioaldehyde S-oxide formation and close a long-lasting gap in understanding of the mechanism responsible for LF production in the onion.« less

All MBE grown InAs/GaAs quantum dot lasers on on-axis Si (001).

PubMed

Kwoen, Jinkwan; Jang, Bongyong; Lee, Joohang; Kageyama, Takeo; Watanabe, Katsuyuki; Arakawa, Yasuhiko

2018-04-30

Directly grown III-V quantum dot (QD) laser on on-axis Si (001) is a good candidate for achieving monolithically integrated Si photonics light source. Nowadays, laser structures containing high quality InAs / GaAs QD are generally grown by molecular beam epitaxy (MBE). However, the buffer layer between the on-axis Si (001) substrate and the laser structure are usually grown by metal-organic chemical vapor deposition (MOCVD). In this paper, we demonstrate all MBE grown high-quality InAs/GaAs QD lasers on on-axis Si (001) substrates without using patterning and intermediate layers of foreign material.

Interaction of a single acetophenone molecule with group III-IV elements mediated by Si(001)

NASA Astrophysics Data System (ADS)

Racis, A.; Jurczyszyn, L.; Radny, M. W.

2018-03-01

A theoretical study of an influence of the acetophenone molecule adsorbed on the Si(001) on the local chemical reactivity of silicon surface is presented. The obtained results indicate that the interaction of the molecule with silicon substrate breaks the intra-dimer π bonds in four surface silicon dimers interacting directly with adsorbed molecule. This leads to the formation of two pairs of unpaired dangling bonds at two opposite sides of the molecule. It is demonstrated that these dangling bonds increase considerably the local chemical reactivity of the silicon substrate in the vicinity of the adsorbed molecule. Consequently, it is shown that such molecule bonded with Si(001) can stabilize the position of In and Pb adatoms diffusing on silicon substrate at two sides and initiate the one-dimensional aggregation of the metallic adatoms on the Si(001) substrate anchored at both sides of the adsorbed molecule. This type of aggregation leads to the growth of chain-like atomic structures in opposite directions, pinned to adsorbed molecule and oriented perpendicular to the rows of surface silicon dimers.

On the Electrodeposition of Ca-P Coatings on Nitinol Alloy: A Comparison Between Different Surface Modification Methods

NASA Astrophysics Data System (ADS)

Etminanfar, M. R.; Khalil-Allafi, J.

2016-02-01

In this study, a combination of surface modification process and the electrochemical deposition of Ca-P coatings was used for the modification of the Nitinol shape memory alloy. DSC, SEM, GIB-XRD, FT-Raman, XPS, and FTIR measurements were performed for the characterization of the samples. Results indicated that chemical etching and boiling of the samples in distilled water formed TiO film on the surface. After the chemical modification, subsequent aging of the sample, at 470 °C for 30 min, converted the oxide film to a stable structure of titanium dioxide. In that case, the treated substrate indicated a superelastic behavior. At the same electrochemical condition, the treated substrate revealed more stable and uniform Ca-P coatings in comparison with the abraded Nitinol substrate. This difference was attributed to the presence of hydroxyl groups on the titanium dioxide surface. Also, after soaking the sample in SBF, the needle-like coating on the treated substrate was completely covered with the hydroxyapatite phase which shows a good bioactivity of the coating.

Thin film composition with biological substance and method of making

DOEpatents

Campbell, Allison A.; Song, Lin

1999-01-01

The invention provides a thin-film composition comprising an underlying substrate of a first material including a plurality of attachment sites; a plurality of functional groups chemically attached to the attachment sites of the underlying substrate; and a thin film of a second material deposited onto the attachment sites of the underlying substrate, and a biologically active substance deposited with the thin-film. Preferably the functional groups are attached to a self assembling monolayer attached to the underlying substrate. Preferred functional groups attached to the underlying substrate are chosen from the group consisting of carboxylates, sulfonates, phosphates, optionally substituted, linear or cyclo, alkyl, alkene, alkyne, aryl, alkylaryl, amine, hydroxyl, thiol, silyl, phosphoryl, cyano, metallocenyl, carbonyl, and polyphosphate. Preferred materials for the underlying substrate are selected from the group consisting of a metal, a metal alloy, a plastic, a polymer, a proteic film, a membrane, a glass or a ceramic. The second material is selected from the group consisting of inorganic crystalline structures, inorganic amorphus structures, organic crystalline structures, and organic amorphus structures. Preferred second materials are phosphates, especially calcium phosphates and most particularly calcium apatite. The biologically active molecule is a protein, peptide, DNA segment, RNA segment, nucleotide, polynucleotide, nucleoside, antibiotic, antimicrobal, radioisotope, chelated radioisotope, chelated metal, metal salt, anti-inflamatory, steriod, nonsteriod anti-inflammatory, analgesic, antihistamine, receptor binding agent, or chemotherapeutic agent, or other biologically active material. Preferably the biologically active molecule is an osteogenic factor the compositions listed above.

Key advances in the chemical modification of nanocelluloses.

PubMed

Habibi, Youssef

2014-03-07

Nanocelluloses, including nanocrystalline cellulose, nanofibrillated cellulose and bacterial cellulose nanofibers, have become fascinating building blocks for the design of new biomaterials. Derived from the must abundant and renewable biopolymer, they are drawing a tremendous level of attention, which certainly will continue to grow in the future driven by the sustainability trend. This growing interest is related to their unsurpassed quintessential physical and chemical properties. Yet, owing to their hydrophilic nature, their utilization is restricted to applications involving hydrophilic or polar media, which limits their exploitation. With the presence of a large number of chemical functionalities within their structure, these building blocks provide a unique platform for significant surface modification through various chemistries. These chemical modifications are prerequisite, sometimes unavoidable, to adapt the interfacial properties of nanocellulose substrates or adjust their hydrophilic-hydrophobic balance. Therefore, various chemistries have been developed aiming to surface-modify these nano-sized substrates in order to confer to them specific properties, extending therefore their use to highly sophisticated applications. This review collocates current knowledge in the research and development of nanocelluloses and emphasizes more particularly on the chemical modification routes developed so far for their functionalization.

Proteopedia: A Collaborative, Virtual 3D Web-Resource for Protein and Biomolecule Structure and Function

ERIC Educational Resources Information Center

Hodis, Eran; Prilusky, Jaime, Sussman, Joel L.

2010-01-01

Protein structures are hard to represent on paper. They are large, complex, and three-dimensional (3D)--four-dimensional if conformational changes count! Unlike most of their substrates, which can easily be drawn out in full chemical formula, drawing every atom in a protein would usually be a mess. Simplifications like showing only the surface of…

Microscopic Electronic and Mechanical Properties of Ultra-Thin Layered Materials

DTIC Science & Technology

2016-07-25

Graphene single layers grown by chemical vapor deposition on single crystal Cu substrates are subject to nonuniform physisorption strains that...the observed highly nonuniform strains. 4. Connecting dopant bond type with electronic structure in N-doped graphene (reference [4]) Robust methods

Impact of cleaning methods on the structural properties and morphology of SrTiO3 surface

NASA Astrophysics Data System (ADS)

Arnay, Iciar; Rubio-Zuazo, Juan; Castro, German R.

2018-01-01

SrTiO3 is a widely used substrate for the epitaxial growth of complex systems. Nevertheless, in order to get good quality interface and avoid the formation of defects in the adsorbed layer it is essential to prepare the surface of the substrate prior to the deposition. Thermal and chemical treatments are mostly used to eliminate superficial contamination and improve the surface quality. However, there is a lack of information regarding the impact of these treatments on the formation of structural defects at the SrTiO3 surface. In this work we present a detailed characterization of the SrTiO3 surface for the different cleaning methods paying special attention to the formation of oxygen vacancies, large surface mosaicity and roughness. We prove that thermal treatment induces large surface roughness and that chemical etching produces important structural defects at the surface. Our results show that mechanical polishing provided the best compromise in terms of large surface domains, low roughness, absence of oxygen vacancies and absence of atomic structure modification, although with the presence of low level of contaminants at the SrTiO3 surface.

Determination of a refractive index and an extinction coefficient of standard production of CVD-graphene.

PubMed

Ochoa-Martínez, Efraín; Gabás, Mercedes; Barrutia, Laura; Pesquera, Amaia; Centeno, Alba; Palanco, Santiago; Zurutuza, Amaia; Algora, Carlos

2015-01-28

The refractive index and extinction coefficient of chemical vapour deposition grown graphene are determined by ellipsometry analysis. Graphene films were grown on copper substrates and transferred as both monolayers and bilayers onto SiO2/Si substrates by using standard manufacturing procedures. The chemical nature and thickness of residual debris formed after the transfer process were elucidated using photoelectron spectroscopy. The real layered structure so deduced has been used instead of the nominal one as the input in the ellipsometry analysis of monolayer and bilayer graphene, transferred onto both native and thermal silicon oxide. The effect of these contamination layers on the optical properties of the stacked structure is noticeable both in the visible and the ultraviolet spectral regions, thus masking the graphene optical response. Finally, the use of heat treatment under a nitrogen atmosphere of the graphene-based stacked structures, as a method to reduce the water content of the sample, and its effect on the optical response of both graphene and the residual debris layer are presented. The Lorentz-Drude model proposed for the optical response of graphene fits fairly well the experimental ellipsometric data for all the analysed graphene-based stacked structures.

Rich variety of substrates for surface enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Nguyen, Bich Ha; Hieu Nguyen, Van; Nhung Tran, Hong

2016-09-01

The efficiency of the application of surface enhanced Raman spectroscopy (SERS) technique to each specified purpose significantly depends on the choice of the SERS substrate with an appropriate structure as well as on its performance. Until the present time a rich variety of SERS substrates was fabricated. They can be classified according to their structures. The present work is a review of main types of SERS substrates for using in the trace analysis application. They can be classified into 4 groups: (1) Substrates using gold nanoparticles (AuNPs) with spherical shape such as colloidal AuNPs, AuNPs fabricated by pulsed laser deposition, by sputtering or by capillary force assembly (CFA), substrates fabricated by electrospinning technique, substrates using metallic nanoparticle arrays fabricated by electron beam lithography combined with CFA method, substrates using silver nanoparticle (AgNP) arrays grain by chemical seeded method, substrates with tunable surface plasmon resonance, substrates based on precies subnanometer plasmonic junctions within AuNP assemblies, substrates fabricated by simultaneously immobilizing both AuNPs and AgNPs on the same glass sides etc. (2) Substrates using nanostructures with non-spherical shapes such as gold nanowire (NW), or highly anisotropic nickel NW together with large area, free-standing carpets, substrates with obviously angular, quasi-vertically aligned cuboid-shaped TiO2 NW arrays decorated with AgNPs, substrates using gold nanoprism monolayer films, substrates using silver nanocube dimmers or monodisperse close-packed gold nanotriangle monolayers. (3) Substrates using multiparticle complex nanostructure such as nanoparticle cluster arrays, gold nanoflowers and nanodendrites. (4) Flexible substrate such as paper-based swab with gold nanorods, adhesive polymer tapes fabricated by inkjet printing method and flexible and adhesive SERS tapes fabricated by decorating AuNPs via the conventional drop-dry method.

Neurotransmitter and psychostimulant recognition by the dopamine transporter

PubMed Central

Wang, Kevin H.; Penmatsa, Aravind; Gouaux, Eric

2015-01-01

Na+/Cl−-coupled biogenic amine transporters are the primary targets of therapeutic and abused drugs, ranging from antidepressants to the psychostimulants cocaine and amphetamines, and to their cognate substrates. Here we determine x-ray crystal structures of the Drosophila melanogaster dopamine transporter (dDAT) bound to its substrate dopamine (DA), a substrate analogue 3,4-dichlorophenethylamine, the psychostimulants D-amphetamine, methamphetamine, or to cocaine and cocaine analogues. All ligands bind to the central binding site, located approximately halfway across the membrane bilayer, in close proximity to bound sodium and chloride ions. The central binding site recognizes three chemically distinct classes of ligands via conformational changes that accommodate varying sizes and shapes, thus illustrating molecular principles that distinguish substrates from inhibitors in biogenic amine transporters. PMID:25970245

276 nm Substrate-Free Flip-Chip AlGaN Light-Emitting Diodes

NASA Astrophysics Data System (ADS)

Hwang, Seongmo; Morgan, Daniel; Kesler, Amanda; Lachab, Mohamed; Zhang, Bin; Heidari, Ahmad; Nazir, Haseeb; Ahmad, Iftikhar; Dion, Joe; Fareed, Qhalid; Adivarahan, Vinod; Islam, Monirul; Khan, Asif

2011-03-01

Lateral-conduction, substrate-free flip-chip (SFFC) light-emitting diodes (LEDs) with peak emission at 276 nm are demonstrated for the first time. The AlGaN multiple quantum well LED structures were grown by metal-organic chemical vapor deposition (MOCVD) on thick-AlN laterally overgrown on sapphire substrates. To fabricate the SFFC LEDs, a newly-developed laser-assisted ablation process was employed to separate the substrate from the LED chips. The chips had physical dimensions of 1100×900 µm2, and were comprised of four devices each with a 100×100 µm2 junction area. Electrical and optical characterization of the devices revealed no noticeable degradation to their performance due to the laser-lift-off process.

Lattice distortion of square iron nitride monolayers induced by changing symmetry of substrate

NASA Astrophysics Data System (ADS)

Hattori, Takuma; Iimori, Takushi; Miyamachi, Toshio; Komori, Fumio

2018-04-01

Rectangular iron nitride monatomic layers are fabricated on the threefold symmetric Cu(111) substrate by taking advantage of the stability of the square nitride film. Two different ordered structures are observed on the Cu(111) substrate by scanning tunneling microscopy after annealing at 510 K and 580 K. Their chemical composition and lattice symmetry are investigated by x-ray photoelectron spectroscopy and low energy electron diffraction. The monolayer film prepared at 580 K is a distorted Fe2N monolayer analogous to a ferromagnetic square Fe2N monolayer with a clock reconstruction on the Cu(001) substrate. The lattice deformation of the square Fe2N monolayer is induced by using Cu(111) with threefold symmetry.

Multicomponent patterned ultrathin carbon nanomembranes by laser ablation

NASA Astrophysics Data System (ADS)

Frese, Natalie; Scherr, Julian; Beyer, André; Terfort, Andreas; Gölzhäuser, Armin; Hampp, Norbert; Rhinow, Daniel

2018-01-01

Carbon nanomembranes (CNMs) are a class of two-dimensional materials, which are obtained by electron beam-induced crosslinking of aromatic self-assembled monolayers (SAMs) on solid substrates. CNMs made from a single type of precursor molecule are uniform with homogeneous chemical and physical properties. We have developed a method for the fabrication of internally patterned CNMs resembling a key feature of biological membranes. Direct laser patterning is used to obtain multicomponent patterned SAMs on gold, which are subsequently crosslinked by electron irradiation. We demonstrate that the structure of internally patterned CNMs is preserved upon transfer to different substrates. The method enables rapid fabrication of patterned 2D materials with local variations in chemical and physical properties on the micrometer to centimeter scale.

Composite materials with metal oxide attached to lead chalcogenide nanocrystal quantum dots with linkers

DOEpatents

Fuke, Nobuhiro; Koposov, Alexey Y; Sykora, Milan; Hoch, Laura

2014-12-16

Composite materials useful for devices such as photoelectrochemical solar cells include a substrate, a metal oxide film on the substrate, nanocrystalline quantum dots (NQDs) of lead sulfide, lead selenide, and lead telluride, and linkers that attach the NQDs to the metal oxide film. Suitable linkers preserve the 1s absorption peak of the NQDs. A suitable linker has a general structure A-B-C where A is a chemical group adapted for binding to a MO.sub.x and C is a chemical group adapted for binding to a NQD and B is a divalent, rigid, or semi-rigid organic spacer moiety. Other linkers that preserve the 1s absorption peak may also be used.

Novel Aldo-Keto Reductases for the Biocatalytic Conversion of 3-Hydroxybutanal to 1,3-Butanediol: Structural and Biochemical Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Taeho; Flick, Robert; Brunzelle, Joseph

The nonnatural alcohol 1,3-butanediol (1,3-BDO) is a valuable building block for the synthesis of various polymers. One of the potential pathways for the biosynthesis of 1,3-BDO includes the biotransformation of acetaldehyde to 1,3-BDO via 3-hydroxybutanal (3-HB) using aldolases and aldo-keto reductases (AKRs). This pathway requires an AKR selective for 3-HB, but inactive toward acetaldehyde, so it can be used for one-pot synthesis. In this work, we screened more than 20 purified uncharacterized AKRs for 3-HB reduction and identified 10 enzymes with significant activity and nine proteins with detectable activity. PA1127 fromPseudomonas aeruginosashowed the highest activity and was selected for comparativemore » studies with STM2406 fromSalmonella entericaserovar Typhimurium, for which we have determined the crystal structure. Both AKRs used NADPH as a cofactor, reduced a broad range of aldehydes, and showed low activities toward acetaldehyde. The crystal structures of STM2406 in complex with cacodylate or NADPH revealed the active site with bound molecules of a substrate mimic or cofactor. Site-directed mutagenesis of STM2406 and PA1127 identified the key residues important for the activity against 3-HB and aromatic aldehydes, which include the residues of the substrate-binding pocket and C-terminal loop. Our results revealed that the replacement of the STM2406 Asn65 by Met enhanced the activity and the affinity of this protein toward 3-HB, resulting in a 7-fold increase ink cat/K m. Our work provides further insights into the molecular mechanisms of the substrate selectivity of AKRs and for the rational design of these enzymes toward new substrates. IMPORTANCEIn this study, we identified several aldo-keto reductases with significant activity in reducing 3-hydroxybutanal to 1,3-butanediol (1,3-BDO), an important commodity chemical. Biochemical and structural studies of these enzymes revealed the key catalytic and substrate-binding residues, including the two structural determinants necessary for high activity in the biosynthesis of 1,3-BDO. This work expands our understanding of the molecular mechanisms of the substrate selectivity of aldo-keto reductases and demonstrates the potential for protein engineering of these enzymes for applications in the biocatalytic production of 1,3-BDO and other valuable chemicals.« less

X-ray structures of LeuT in substrate-free outward-open and apo inward-open states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krishnamurthy, Harini; Gouaux, Eric

2012-08-09

Neurotransmitter sodium symporters are integral membrane proteins that remove chemical transmitters from the synapse and terminate neurotransmission mediated by serotonin, dopamine, noradrenaline, glycine and GABA ({gamma}-aminobutyric acid). Crystal structures of the bacterial homologue, LeuT, in substrate-bound outward-occluded and competitive inhibitor-bound outward-facing states have advanced our mechanistic understanding of neurotransmitter sodium symporters but have left fundamental questions unanswered. Here we report crystal structures of LeuT mutants in complexes with conformation-specific antibody fragments in the outward-open and inward-open states. In the absence of substrate but in the presence of sodium the transporter is outward-open, illustrating how the binding of substrate closes themore » extracellular gate through local conformational changes: hinge-bending movements of the extracellular halves of transmembrane domains 1, 2 and 6, together with translation of extracellular loop 4. The inward-open conformation, by contrast, involves large-scale conformational changes, including a reorientation of transmembrane domains 1, 2, 5, 6 and 7, a marked hinge bending of transmembrane domain 1a and occlusion of the extracellular vestibule by extracellular loop 4. These changes close the extracellular gate, open an intracellular vestibule, and largely disrupt the two sodium sites, thus providing a mechanism by which ions and substrate are released to the cytoplasm. The new structures establish a structural framework for the mechanism of neurotransmitter sodium symporters and their modulation by therapeutic and illicit substances.« less

Effects of soft X-ray radiation damage on paraffin-embedded rat tissues supported on ultralene: a chemical perspective.

PubMed

Bedolla, Diana E; Mantuano, Andrea; Pickler, Arissa; Mota, Carla Lemos; Braz, Delson; Salata, Camila; Almeida, Carlos Eduardo; Birarda, Giovanni; Vaccari, Lisa; Barroso, Regina Cély; Gianoncelli, Alessandra

2018-05-01

Radiation damage is an important aspect to be considered when analysing biological samples with X-ray techniques as it can induce chemical and structural changes in the specimens. This work aims to provide new insights into the soft X-ray induced radiation damage of the complete sample, including not only the biological tissue itself but also the substrate and embedding medium, and the tissue fixation procedure. Sample preparation and handling involves an unavoidable interaction with the sample matrix and could play an important role in the radiation-damage mechanism. To understand the influence of sample preparation and handling on radiation damage, the effects of soft X-ray exposure at different doses on ultralene, paraffin and on paraffin-embedded rat tissues were studied using Fourier-transform infrared (FTIR) microspectroscopy and X-ray microscopy. Tissues were preserved with three different commonly used fixatives: formalin, glutaraldehyde and Karnovsky. FTIR results showed that ultralene and paraffin undergo a dose-dependent degradation of their vibrational profiles, consistent with radiation-induced oxidative damage. In addition, formalin fixative has been shown to improve the preservation of the secondary structure of proteins in tissues compared with both glutaraldehyde and Karnovsky fixation. However, conclusive considerations cannot be drawn on the optimal fixation protocol because of the interference introduced by both substrate and embedding medium in the spectral regions specific to tissue lipids, nucleic acids and carbohydrates. Notably, despite the detected alterations affecting the chemical architecture of the sample as a whole, composed of tissue, substrate and embedding medium, the structural morphology of the tissues at the micrometre scale is essentially preserved even at the highest exposure dose.

Controlled Interphases in Glass Fiber and Particulate Reinforced Polymers: Structure of Silane Coupling Agents in Solutions and On Substrates

DTIC Science & Technology

1993-01-01

to dissolve into water. Table 3. Typical industrially used silane coupling agents Organofunctional Chemical Formula Group Cationic styryl CH2...can also react with the surface as some unreacted silanol groups remain in the oligomers. The notion of physisorbed and chemisorbed silanes is used ...silanes use many silanol groups for covalent bonding with the substrate surface whereas the loosely chemisorbed silanes use only a few silanols to bond to

Vertically aligned carbon nanofibers as sacrificial templates for nanofluidic structures

NASA Astrophysics Data System (ADS)

Melechko, A. V.; McKnight, T. E.; Guillorn, M. A.; Merkulov, V. I.; Ilic, B.; Doktycz, M. J.; Lowndes, D. H.; Simpson, M. L.

2003-02-01

We report a method to fabricate nanoscale pipes ("nanopipes") suitable for fluidic transport. Vertically aligned carbon nanofibers grown by plasma-enhanced chemical vapor deposition are used as sacrificial templates for nanopipes with internal diameters as small as 30 nm and lengths up to several micrometers that are oriented perpendicular to the substrate. This method provides a high level of control over the nanopipe location, number, length, and diameter, permitting them to be deterministically positioned on a substrate and arranged into arrays.

Nanoparticle Over Mirror plasmonic structures prepared with use of Au colloid produced by laser ablation in water

NASA Astrophysics Data System (ADS)

Sawczak, Mirosław; Zyskowski, Marcin; Karczewski, Jakub; Atanasov, Petar A.; Nedyalkov, Nikolay N.; Nikov, Rumen G.; Stankova, Nadya A.; Śliwiński, Gerard

2016-01-01

Recently, an intensive research is carried out on plasmonic structures due to their potential application in many areas such as sensing, light harvesting and energy conversion and storage. In particular, a growing interest is observed in the Nanoparticle Over Mirror (NOM) structures for which the lithography and surface chemical functionalization represent the most popular production routes1. However, the application of those techniques is limited by the low efficacy, process complexity and chemical contamination of nanoparticles (NP). In this work, we report the contamination-free and low cost fabrication method of NOMs based on wet coating and ultrasonic-assisted nanocolloid drying process. The glass plates covered with magnetron sputtered 100 nm thick Au film and subsequently with Al2O3 layers (6 - 36 nm) by means of pulsed laser deposition are used as substrates. Au NPs are produced in the form of colloidal suspension by means of laser ablation in water using the 1064 nm, 6 ns Nd:YAG laser. The NOM synthesis is finalized by imposing of the Au NP suspension onto the as prepared Au-Al2O3/glass substrates and dried. To avoid NP agglomeration, the wet coated substrates are sonicated using 20W, 20 kHz ultrasound generator. SEM inspection of the obtained NOM structures confirms the positive sonication effect, i.e. the presence of agglomerate-free, homogenous layers. These consist of NPs (36 nm average diameter) which are characterized by the resonance absorption band at 528 nm. For NOM structures the UV-vis spectra reveal increased infrared activity and peak shift in agreement with theoretical modeling2. The NOM structure characterization is completed by analysis of the SEM and profilometry measurement results.

Ridge InGaAs/InP multi-quantum-well selective growth in nanoscale trenches on Si (001) substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, S.; Zhou, X.; Li, M.

Metal organic chemical vapor deposition of InGaAs/InP multi-quantum-well in nanoscale V-grooved trenches on Si (001) substrate was studied using the aspect ratio trapping method. A high quality GaAs/InP buffer layer with two convex (111) B facets was selectively grown to promote the highly uniform, single-crystal ridge InP/InGaAs multi-quantum-well structure growth. Material quality was confirmed by transmission electron microscopy and room temperature micro-photoluminescence measurements. This approach shows great promise for the fabrication of photonics devices and nanolasers on Si substrate.

Influence of Soil Properties on Soldierless Termite Distribution.

PubMed

Bourguignon, Thomas; Drouet, Thomas; Šobotník, Jan; Hanus, Robert; Roisin, Yves

2015-01-01

In tropical rainforests, termites constitute an important part of the soil fauna biomass, and as for other soil arthropods, variations in soil composition create opportunities for niche partitioning. The aim of this study was twofold: first, we tested whether soil-feeding termite species differ in the foraging substrate; second, we investigated whether soil-feeding termites select their foraging sites to enhance nutrients intake. To do so, we collected termites and analysed the composition and structure of their feeding substrates. Although Anoplotermes-group members are all considered soil-feeders, our results show that some species specifically feed on abandoned termite nests and very rotten wood, and that this substrate selection is correlated with previous stable isotope analyses, suggesting that one component of niche differentiation among species is substrate selection. Our results show that the composition and structure of bare soils on which different termite species foraged do not differ, suggesting that there is no species specialization for a particular type of bare soil. Finally, the bare soil on which termites forage does not differ from random soil samples. Overall, our results suggest that few species of the Anoplotermes-group are specialized toward substrates rich in organic matter, but that the vast majority forage on soil independently of its structural and chemical composition, being ecologically equivalent for this factor.

Selective oxidation of aliphatic C-H bonds in alkylphenols by a chemomimetic biocatalytic system.

PubMed

Du, Lei; Dong, Sheng; Zhang, Xingwang; Jiang, Chengying; Chen, Jingfei; Yao, Lishan; Wang, Xiao; Wan, Xiaobo; Liu, Xi; Wang, Xinquan; Huang, Shaohua; Cui, Qiu; Feng, Yingang; Liu, Shuang-Jiang; Li, Shengying

2017-06-27

Selective oxidation of aliphatic C-H bonds in alkylphenols serves significant roles not only in generation of functionalized intermediates that can be used to synthesize diverse downstream chemical products, but also in biological degradation of these environmentally hazardous compounds. Chemo-, regio-, and stereoselectivity; controllability; and environmental impact represent the major challenges for chemical oxidation of alkylphenols. Here, we report the development of a unique chemomimetic biocatalytic system originated from the Gram-positive bacterium Corynebacterium glutamicum The system consisting of CreHI (for installation of a phosphate directing/anchoring group), CreJEF/CreG/CreC (for oxidation of alkylphenols), and CreD (for directing/anchoring group offloading) is able to selectively oxidize the aliphatic C-H bonds of p - and m -alkylated phenols in a controllable manner. Moreover, the crystal structures of the central P450 biocatalyst CreJ in complex with two representative substrates provide significant structural insights into its substrate flexibility and reaction selectivity.

Selective oxidation of aliphatic C–H bonds in alkylphenols by a chemomimetic biocatalytic system

PubMed Central

Du, Lei; Dong, Sheng; Zhang, Xingwang; Jiang, Chengying; Chen, Jingfei; Yao, Lishan; Wang, Xiao; Wan, Xiaobo; Liu, Xi; Wang, Xinquan; Huang, Shaohua; Cui, Qiu; Liu, Shuang-Jiang; Li, Shengying

2017-01-01

Selective oxidation of aliphatic C–H bonds in alkylphenols serves significant roles not only in generation of functionalized intermediates that can be used to synthesize diverse downstream chemical products, but also in biological degradation of these environmentally hazardous compounds. Chemo-, regio-, and stereoselectivity; controllability; and environmental impact represent the major challenges for chemical oxidation of alkylphenols. Here, we report the development of a unique chemomimetic biocatalytic system originated from the Gram-positive bacterium Corynebacterium glutamicum. The system consisting of CreHI (for installation of a phosphate directing/anchoring group), CreJEF/CreG/CreC (for oxidation of alkylphenols), and CreD (for directing/anchoring group offloading) is able to selectively oxidize the aliphatic C–H bonds of p- and m-alkylated phenols in a controllable manner. Moreover, the crystal structures of the central P450 biocatalyst CreJ in complex with two representative substrates provide significant structural insights into its substrate flexibility and reaction selectivity. PMID:28607077

Chemical strain engineering of magnetism in PrVO3 thin films

NASA Astrophysics Data System (ADS)

Prellier, Wilfrid; Copie, Olivier; Varignon, Julien; Rotella, Helene; Steciuk, Gwladys; Boullay, Philippe; Pautrat, Alain; David, Adrian; Mercey, Bernard; Ghosez, Philippe

Transition metal oxides having a perovskite structure present a wide range of functional properties ranging from insulator-to-metal, ferroelectricity, colossal magnetoresistance, high-temperature superconductivity and multiferroicity. Such systems are generally characterized by strong electronic correlations, complex phase diagrams and competing ground states. In addition, small perturbation induced by external stimuli (electric or magnetic field, temperature, strain, pressure..) may change structure, and ultimately modify the physical properties. Here, we synthetize an orthorhombic perovskite praseodymium vanadate (PrVO3), which is grown on strontium titanate substrate. We show that the control of the content of oxygen vacancies, the so-called chemical strain, can indeed result in unexpected properties. We further demonstrate that the Néel temperature can be tuned using the same substrate in agreement with first-principles calculations, and demonstrate that monitoring the concentration of oxygen vacancies through the oxygen partial pressure or the growth temperature can produce a substantial macroscopic tensile strain of a few percents.

Effects of bias voltage on diamond like carbon coatings deposited using titanium isopropoxide (TIPOT) and acetylene/argon mixtures onto various substrate materials.

PubMed

Said, R; Ghumman, C A A; Teodoro, M N D; Ahmed, W; Abuazza, A; Gracio, J

2010-04-01

RF-PECVD was used to prepare amorphous of carbon (DLC) onto stainless steel 316 and glass substrates. The substrates were negatively biased at between 100 V to 400 V. Thin films of DLC have been deposited using C2H2 and titanium isopropoxide (TIPOT). Argon was used to generate the plasma in the PECVD system chamber. DEKTAK 8 surface stylus profilometer was used to measure the film thickness and the deposition rate was calculated. Micro Raman spectroscopy was employed to determine the chemical structure and bonding present in the films. Composition analysis of the samples was carried out using VGTOF SIMS (IX23LS) instrument. In addition, X-ray photoelectron spectroscopy (XPS) was used to analyze the composition and chemical state of the films. The wettability of the films was examined using the optical contact angle meter (CAM200) system. Two types of liquids with different polarities were used to study changes in the surface energy. The as-grown films were in the thickness range of 200-400 nm. Raman spectroscopy results showed that the I(D)/I(G) ratio decreased when the bias voltage on the stainless steel substrates was increased. This indicates an increase in the graphitic nature of the film deposited. In contrast, on the glass substrates the I(D)/I(G) ratio increased when the bias voltage was increased indicates a greater degree of diamond like character. Chemical composition determined using XPS showed the presence of carbon and oxygen in both samples on glass and stainless steel substrates. Both coatings the contact angle of the films decreased except for 400 V which showed a slight increase. The oxygen is thought to play an important role on the polar component of a-C.

Chemical lift-off and direct wafer bonding of GaN/InGaN P-I-N structures grown on ZnO

NASA Astrophysics Data System (ADS)

Pantzas, K.; Rogers, D. J.; Bove, P.; Sandana, V. E.; Teherani, F. H.; El Gmili, Y.; Molinari, M.; Patriarche, G.; Largeau, L.; Mauguin, O.; Suresh, S.; Voss, P. L.; Razeghi, M.; Ougazzaden, A.

2016-02-01

p-GaN/i-InGaN/n-GaN (PIN) structures were grown epitaxially on ZnO-buffered c-sapphire substrates by metal organic vapor phase epitaxy using the industry standard ammonia precursor for nitrogen. Scanning electron microscopy revealed continuous layers with a smooth interface between GaN and ZnO and no evidence of ZnO back-etching. Energy Dispersive X-ray Spectroscopy revealed a peak indium content of just under 5 at% in the active layers. The PIN structure was lifted off the sapphire by selectively etching away the ZnO buffer in an acid and then direct bonded onto a glass substrate. Detailed high resolution transmission electron microscoy and grazing incidence X-ray diffraction studies revealed that the structural quality of the PIN structures was preserved during the transfer process.

Effects of sea lamprey substrate modification and carcass nutrients on macroinvertebrate assemblages in a small Atlantic coastal stream

USGS Publications Warehouse

Weaver, Daniel M.; Coghlan, Stephen M.; Zydlewski, Joseph D.

2018-01-01

Aquatic macroinvertebrates respond to patch dynamics arising from interactions of physical and chemical disturbances across space and time. Anadromous fish, such as sea lamprey, Petromyzon marinus, migrate from the ocean and alter physical and chemical properties of recipient spawning streams. Sea lamprey disturb stream benthos physically through nest construction and spawning, and enrich food webs through nutrient deposition from decomposing carcasses. Sea lamprey spawning nests support greater macroinvertebrate abundance than adjacent reference areas, but concurrent effects of stream bed modification and nutrient supplementation have not been examined sequentially. We added carcasses and cleared substrate experimentally to mimic the physical disturbance and nutrient enrichment associated with lamprey spawning, and characterized effects on macroinvertebrate assemblage structure. We found that areas receiving cleared substrate and carcass nutrients were colonized largely by Simuliidae compared to upstream and downstream control areas that were colonized largely by Hydropsychidae, Philopotamidae, and Chironomidae. Environmental factors such as stream flow likely shape assemblages by physically constraining macroinvertebrate establishment and feeding. Our results indicate potential changes in macroinvertebrate assemblages from the physical and chemical changes to streams brought by spawning populations of sea lamprey.

A new class of HIV-1 protease inhibitor: the crystallographic structure, inhibition and chemical synthesis of an aminimide peptide isostere.

PubMed

Rutenber, E E; McPhee, F; Kaplan, A P; Gallion, S L; Hogan, J C; Craik, C S; Stroud, R M

1996-09-01

The essential role of HIV-1 protease (HIV-1 PR) in the viral life cycle makes it an attractive target for the development of substrate-based inhibitors that may find efficacy as anti-AIDS drugs. However, resistance has arisen to potent peptidomimetic drugs necessitating the further development of novel chemical backbones for diversity based chemistry focused on probing the active site for inhibitor interactions and binding modes that evade protease resistance. AQ148 is a potent inhibitor of HIV-1 PR and represents a new class of transition state analogues incorporating an aminimide peptide isostere. A 3-D crystallographic structure of AQ148, a tetrapeptide isostere, has been determined in complex with its target HIV-1 PR to a resolution of 2.5 A and used to evaluate the specific structural determinants of AQ148 potency and to correlate structure-activity relationships within the class of related compounds. AQ148 is a competitive inhibitor of HIV-1 PR with a Ki value of 137 nM. Twenty-nine derivatives have been synthesized and chemical modifications have been made at the P1, P2, P1', and P2' sites. The atomic resolution structure of AQ148 bound to HIV-1 PR reveals both an inhibitor binding mode that closely resembles that of other peptidomimetic inhibitors and specific protein/inhibitor interactions that correlate with structure-activity relationships. The structure provides the basis for the design, synthesis and evaluation of the next generation of hydroxyethyl aminimide inhibitors. The aminimide peptide isostere is a scaffold with favorable biological properties well suited to both the combinatorial methods of peptidomimesis and the rational design of potent and specific substrate-based analogues.

Targeting Cullin–RING E3 ubiquitin ligases for drug discovery: structure, assembly and small-molecule modulation

PubMed Central

Bulatov, Emil; Ciulli, Alessio

2015-01-01

In the last decade, the ubiquitin–proteasome system has emerged as a valid target for the development of novel therapeutics. E3 ubiquitin ligases are particularly attractive targets because they confer substrate specificity on the ubiquitin system. CRLs [Cullin–RING (really interesting new gene) E3 ubiquitin ligases] draw particular attention, being the largest family of E3s. The CRLs assemble into functional multisubunit complexes using a repertoire of substrate receptors, adaptors, Cullin scaffolds and RING-box proteins. Drug discovery targeting CRLs is growing in importance due to mounting evidence pointing to significant roles of these enzymes in diverse biological processes and human diseases, including cancer, where CRLs and their substrates often function as tumour suppressors or oncogenes. In the present review, we provide an account of the assembly and structure of CRL complexes, and outline the current state of the field in terms of available knowledge of small-molecule inhibitors and modulators of CRL activity. A comprehensive overview of the reported crystal structures of CRL subunits, components and full-size complexes, alone or with bound small molecules and substrate peptides, is included. This information is providing increasing opportunities to aid the rational structure-based design of chemical probes and potential small-molecule therapeutics targeting CRLs. PMID:25886174

Effect of substrate temperature and gas flow ratio on the nanocomposite TiAlBN coating

NASA Astrophysics Data System (ADS)

Rosli, Z. M.; Kwan, W. L.; Juoi, J. M.

2016-07-01

Nanocomposite TiAlBN (nc-TiAlBN) coatings were successfully deposited via RF magnetron sputtering by varying the nitrogen-to-total gas flow ratio (RN), and substrate temperature (TS). All coatings were deposited on AISI 316 substrates using single Ti-Al-BN hot-pressed disc as a target. The grain size, phases, and chemical composition of the coatings were evaluated using glancing angle X-ray diffraction analysis (GAXRD) and X-ray photoelectron spectroscopy (XPS). Results showed that the grains size of the deposited nc-TiAlBN coatings were in the range of 3.5 to 5.7 nm and reached a nitride saturation state as early as 15 % RN. As the nitrogen concentration decreases, boron concentration increased from 9 at.% to 16.17 at.%. and thus, increase the TiB2 phase within the coatings. The TS, however, showed no significant effect either on the crystallographic structure, grain size, or in the chemical composition of the deposited nc-TiAlBN coating.

Substrate Binding Drives Active-Site Closing of Human Blood Group B Galactosyltransferase as Revealed by Hot-Spot Labeling and NMR Spectroscopy Experiments.

PubMed

Weissbach, Sophie; Flügge, Friedemann; Peters, Thomas

2018-05-04

Crystallography has shown that human blood group A (GTA) and B (GTB) glycosyltransferases undergo transitions between "open", "semiclosed", and "closed" conformations upon substrate binding. However, the timescales of the corresponding conformational reorientations are unknown. Crystal structures show that the Trp and Met residues are located at "conformational hot spots" of the enzymes. Therefore, we utilized 15 N side-chain labeling of Trp residues and 13 C-methyl labeling of Met residues to study substrate-induced conformational transitions of GTB. Chemical-shift perturbations (CSPs) of Met and Trp residues in direct contact with substrate ligands reflect binding kinetics, whereas the CSPs of Met and Trp residues at remote sites reflect conformational changes of the enzyme upon substrate binding. Acceptor binding is fast on the chemical-shift timescale with rather small CSPs in the range of less than approximately 20 Hz. Donor binding matches the intermediate exchange regime to yield an estimate for exchange rate constants of approximately 200-300 Hz. Donor or acceptor binding to GTB saturated with acceptor or donor substrate, respectively, is slow (<10 Hz), as are coupled protein motions, reflecting mutual allosteric control of donor and acceptor binding. Remote CSPs suggest that substrate binding drives the enzyme into the closed state required for catalysis. These findings should contribute to better understanding of the mechanism of glycosyl transfer of GTA and GTB. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Properties of the carbon-palladium nanocomposites studied by Raman spectroscopy method

NASA Astrophysics Data System (ADS)

Belka, Radosław; Suchańska, Małgorzata

2013-10-01

In this paper, the results for thin carbon-palladium (C-Pd) nanocomposites obtained by PVD (Physical Vapour Deposition) and PVD/CVD (Chemical Vapour Deposition) method, carried out using Raman spectroscopy method are presented. Studies reveal the dominance of fullerene-like structure for PVD samples and graphite-like structures for CVD samples. The type of substrate and metal content have great impact on spectra shapes.

Molecular modeling studies of substrate binding by penicillin acylase.

PubMed

Chilov, G G; Stroganov, O V; Svedas, V K

2008-01-01

Molecular modeling has revealed intimate details of the mechanism of binding of natural substrate, penicillin G (PG), in the penicillin acylase active center and solved questions raised by analysis of available X-ray structures, mimicking Michaelis complex, which substantially differ in the binding pattern of the PG leaving group. Three MD trajectories were launched, starting from PDB complexes of the inactive mutant enzyme with PG (1FXV) and native penicillin acylase with sluggishly hydrolyzed substrate analog penicillin G sulfoxide (1GM9), or from the complex obtained by PG docking. All trajectories converged to a similar PG binding mode, which represented the near-to-attack conformation, consistent with chemical criteria of how reactive Michaelis complex should look. Simulated dynamic structure of the enzyme-substrate complex differed significantly from 1FXV, resembling rather 1GM9; however, additional contacts with residues bG385, bS386, and bN388 have been found, which were missing in X-ray structures. Combination of molecular docking and molecular dynamics also clarified the nature of extremely effective phenol binding in the hydrophobic pocket of penicillin acylase, which lacked proper explanation from crystallographic experiments. Alternative binding modes of phenol were probed, and corresponding trajectories converged to a single binding pattern characterized by a hydrogen bond between the phenol hydroxyl and the main chain oxygen of bS67, which was not evident from the crystal structure. Observation of the trajectory, in which phenol moved from its steady bound to pre-dissociation state, mapped the consequence of molecular events governing the conformational transitions in a coil region a143-a146 coupled to substrate binding and release of the reaction products. The current investigation provided information on dynamics of the conformational transitions accompanying substrate binding and significance of poorly structured and flexible regions in maintaining catalytic framework.

Rebar graphene from functionalized boron nitride nanotubes.

PubMed

Li, Yilun; Peng, Zhiwei; Larios, Eduardo; Wang, Gunuk; Lin, Jian; Yan, Zheng; Ruiz-Zepeda, Francisco; José-Yacamán, Miguel; Tour, James M

2015-01-27

The synthesis of rebar graphene on Cu substrates is described using functionalized boron nitride nanotubes (BNNTs) that were annealed or subjected to chemical vapor deposition (CVD) growth of graphene. Characterization shows that the BNNTs partially unzip and form a reinforcing bar (rebar) network within the graphene layer that enhances the mechanical strength through covalent bonds. The rebar graphene is transferrable to other substrates without polymer assistance. The optical transmittance and conductivity of the hybrid rebar graphene film was tested, and a field effect transistor was fabricated to explore its electrical properties. This method of synthesizing 2D hybrid graphene/BN structures should enable the hybridization of various 1D nanotube and 2D layered structures with enhanced mechanical properties.

Study of InGaAs-based modulation doped field effect transistor structures using variable-angle spectroscopic ellipsometry

NASA Technical Reports Server (NTRS)

Alterovitz, S. A.; Sieg, R. M.; Yao, H. D.; Snyder, P. G.; Woollam, J. A.; Pamulapati, J.; Bhattacharya, P. K.; Sekula-Moise, P. A.

1991-01-01

Variable-angle spectroscopic ellipsometry was used to estimate the thicknesses of all layers within the optical penetration depth of InGaAs-based modulation doped field effect transistor structures. Strained and unstrained InGaAs channels were made by molecular beam epitaxy (MBE) on InP substrates and by metal-organic chemical vapor deposition on GaAs substrates. In most cases, ellipsometrically determined thicknesses were within 10% of the growth-calibration results. The MBE-made InGaAs strained layers showed large strain effects, indicating a probable shift in the critical points of their dielectric function toward the InP lattice-matched concentration.

Study the effect of nitrogen flow rate on tribological properties of tantalum nitride based coatings

NASA Astrophysics Data System (ADS)

Chauhan, Dharmesh B.; Chauhan, Kamlesh V.; Sonera, Akshay L.; Makwana, Nishant S.; Dave, Divyeshkumar P.; Rawal, Sushant K.

2018-05-01

Tantalum Nitride (TaN) based coatings are well-known for their high temperature stability and chemical inertness. We have studied the effect of nitrogen flow rate variation on the structural and tribological properties of TaN based coating deposited by RF magnetron sputtering process. The nitrogen flow rate was varied from 5 to 30 sccm. X-ray diffractometer (XRD) and Atomic Force Microscopy (AFM) were used to determine structure and surface topography of coating. Pin on disc tribometer was used to determine tribological properties of coating. TaN coated brass and mild steel substrates shows higher wear resistance compared to uncoated substrates of brass and mild steel.

When lithography meets self-assembly: a review of recent advances in the directed assembly of complex metal nanostructures on planar and textured surfaces

NASA Astrophysics Data System (ADS)

Hughes, Robert A.; Menumerov, Eredzhep; Neretina, Svetlana

2017-07-01

One of the foremost challenges in nanofabrication is the establishment of a processing science that integrates wafer-based materials, techniques, and devices with the extraordinary physicochemical properties accessible when materials are reduced to nanoscale dimensions. Such a merger would allow for exacting controls on nanostructure positioning, promote cooperative phenomenon between adjacent nanostructures and/or substrate materials, and allow for electrical contact to individual or groups of nanostructures. With neither self-assembly nor top-down lithographic processes being able to adequately meet this challenge, advancements have often relied on a hybrid strategy that utilizes lithographically-defined features to direct the assembly of nanostructures into organized patterns. While these so-called directed assembly techniques have proven viable, much of this effort has focused on the assembly of periodic arrays of spherical or near-spherical nanostructures comprised of a single element. Work directed toward the fabrication of more complex nanostructures, while still at a nascent stage, has nevertheless demonstrated the possibility of forming arrays of nanocubes, nanorods, nanoprisms, nanoshells, nanocages, nanoframes, core-shell structures, Janus structures, and various alloys on the substrate surface. In this topical review, we describe the progress made in the directed assembly of periodic arrays of these complex metal nanostructures on planar and textured substrates. The review is divided into three broad strategies reliant on: (i) the deterministic positioning of colloidal structures, (ii) the reorganization of deposited metal films at elevated temperatures, and (iii) liquid-phase chemistry practiced directly on the substrate surface. These strategies collectively utilize a broad range of techniques including capillary assembly, microcontact printing, chemical surface modulation, templated dewetting, nanoimprint lithography, and dip-pen nanolithography and employ a wide scope of chemical processes including redox reactions, alloying, dealloying, phase separation, galvanic replacement, preferential etching, template-mediated reactions, and facet-selective capping agents. Taken together, they highlight the diverse toolset available when fabricating organized surfaces of substrate-supported nanostructures.

Method for producing a hybridization of detector array and integrated circuit for readout

NASA Technical Reports Server (NTRS)

Fossum, Eric R. (Inventor); Grunthaner, Frank J. (Inventor)

1993-01-01

A process is explained for fabricating a detector array in a layer of semiconductor material on one substrate and an integrated readout circuit in a layer of semiconductor material on a separate substrate in order to select semiconductor material for optimum performance of each structure, such as GaAs for the detector array and Si for the integrated readout circuit. The detector array layer is lifted off its substrate, laminated on the metallized surface on the integrated surface, etched with reticulating channels to the surface of the integrated circuit, and provided with interconnections between the detector array pixels and the integrated readout circuit through the channels. The adhesive material for the lamination is selected to be chemically stable to provide electrical and thermal insulation and to provide stress release between the two structures fabricated in semiconductor materials that may have different coefficients of thermal expansion.

Field-assisted organization, substrate effects and magnetic behavior of Ag 30Co 70 core-shell nanoparticles

NASA Astrophysics Data System (ADS)

Crisan, A. D.; Angelakeris, M.; Simeonidis, K.; Tsiaoussis, I.; Crisan, O.

2010-11-01

In core-shell systems with non-magnetic core and magnetic shell, the electron transport and magnetic properties are expected to show enhanced behavior due to the particular morpho-structural features of the conductive and magnetic regions. This may lead to novel advanced GMR materials and spin valves. This is the case of core-shell Ag-Co colloidal nanoscale particles that organize into regular arrays. An insight on the structure and morphology of the newly synthesized Ag-Co nanoparticles deposited on different substrates will be presented. The influence of the substrate on different morphologies and organization dynamics is discussed. It is shown that the magnetic behavior of the Ag-Co nanoparticles is highly influenced by the corona-like morphology of Co shell, chemical environment of the magnetic atoms and by the fact that they exhibit strongly reduced coordination due to the surface states.

Covalent modification of graphene and graphite using diazonium chemistry: tunable grafting and nanomanipulation.

PubMed

Greenwood, John; Phan, Thanh Hai; Fujita, Yasuhiko; Li, Zhi; Ivasenko, Oleksandr; Vanderlinden, Willem; Van Gorp, Hans; Frederickx, Wout; Lu, Gang; Tahara, Kazukuni; Tobe, Yoshito; Uji-I, Hiroshi; Mertens, Stijn F L; De Feyter, Steven

2015-05-26

We shine light on the covalent modification of graphite and graphene substrates using diazonium chemistry under ambient conditions. We report on the nature of the chemical modification of these graphitic substrates, the relation between molecular structure and film morphology, and the impact of the covalent modification on the properties of the substrates, as revealed by local microscopy and spectroscopy techniques and electrochemistry. By careful selection of the reagents and optimizing reaction conditions, a high density of covalently grafted molecules is obtained, a result that is demonstrated in an unprecedented way by scanning tunneling microscopy (STM) under ambient conditions. With nanomanipulation, i.e., nanoshaving using STM, surface structuring and functionalization at the nanoscale is achieved. This manipulation leads to the removal of the covalently anchored molecules, regenerating pristine sp(2) hybridized graphene or graphite patches, as proven by space-resolved Raman microscopy and molecular self-assembly studies.

Influence of microstructure and chemical composition of sputter deposited TiO2 thin films on in vitro bioactivity.

PubMed

Lilja, Mirjam; Genvad, Axel; Astrand, Maria; Strømme, Maria; Enqvist, Håkan

2011-12-01

Functionalisation of biomedical implants via surface modifications for tailored tissue response is a growing field of research. Crystalline TiO(2) has been proven to be a bone bioactive, non-resorbable material. In contact with body fluids a hydroxyapaptite (HA) layer forms on its surface facilitating the bone contact. Thus, the path of improving biomedical implants via deposition of crystalline TiO(2) on the surface is interesting to follow. In this study we have evaluated the influence of microstructure and chemical composition of sputter deposited titanium oxide thin films on the in vitro bioactivity. We find that both substrate bias, topography and the flow ratio of the gases used during sputtering affect the HA layer formed on the films after immersion in simulated body fluid at 37°C. A random distribution of anatase and rutile crystals, formed at negative substrate bias and low Ar to O(2) gas flow ratios, are shown to favor the growth of flat HA crystal structures whereas higher flow ratios and positive substrate bias induced growth of more spherical HA structures. These findings should provide valuable information when optimizing the bioactivity of titanium oxide coatings as well as for tailoring process parameters for sputtered-based production of bioactive titanium oxide implant surfaces.

Lattice Matched Iii-V IV Semiconductor Heterostructures: Metalorganic Chemical Vapor Deposition and Remote Plasma Enhanced Chemical Vapor Deposition.

NASA Astrophysics Data System (ADS)

Choi, Sungwoo

1992-01-01

This thesis describes the growth and characterization of wide gap III-V compound semiconductors such as aluminum gallium arsenide (Al_{rm x} Ga_{rm 1-x}As), gallium nitride (GaN), and gallium phosphide (GaP), deposited by the metalorganic chemical vapor deposition (MOCVD) and remote plasma enhanced chemical vapor deposition (Remote PECVD). In the first part of the thesis, the optimization of GaAs and Al_{rm x}Ga _{rm 1-x}As hetero -epitaxial layers on Ge substrates is described in the context of the application in the construction of cascade solar cells. The emphasis on this study is on the trade-offs in the choice of the temperature related to increasing interdiffusion/autodoping and increasing perfection of the epilayer with increasing temperature. The structural, chemical, optical, and electrical properties of the heterostructures are characterized by x-ray rocking curve measurement, scanning electron microscopy (SEM), electron beam induced current (EBIC), cross-sectional transmission electron microscopy (X-TEM), Raman spectroscopy, secondary ion mass spectrometry (SIMS), and steady-state and time-resolved photoluminescence (PL). Based on the results of this work the optimum growth temperature is 720^circC. The second part of the thesis describes the growth of GaN and GaP layers on silicon and sapphire substrates and the homoepitaxy of GaP by remote PECVD. I have designed and built an ultra high vacuum (UHV) deposition system which includes: the gas supply system, the pumping system, the deposition chamber, the load-lock chamber, and the waste disposal system. The work on the deposition of GaN on Si and sapphire focuses onto the understanding of the growth kinetics. In addition, Auger electron spectroscopy (AES) for surface analysis, x-ray diffraction methods and microscopic analyses using SEM and TEM for structural characterization, infrared (IR) and ultraviolet (UV) absorption measurements for optical characterization, and electrical characterization results on the GaN films are presented. In the deposition GaP thin films by remote PECVD, trimethylgallium and in-situ generated phosphine precursors are employed as source gases which permits homo- and heteroepitaxial growth as substrate temperature of 590-620^ circC. Also, the growth kinetics of gallium phosphide is discussed. As in the case of GaN, the surface, structural, chemical, optical, and electrical properties are characterized and the results are discussed.

Mechanically enhanced nested-network hydrogels as a coating material for biomedical devices.

PubMed

Wang, Zhengmu; Zhang, Hongbin; Chu, Axel J; Jackson, John; Lin, Karen; Lim, Chinten James; Lange, Dirk; Chiao, Mu

2018-04-01

Well-organized composite formations such as hierarchical nested-network (NN) structure in bone tissue and reticular connective tissue present remarkable mechanical strength and play a crucial role in achieving physical and biological functions for living organisms. Inspired by these delicate microstructures in nature, an analogous scaffold of double network hydrogel was fabricated by creating a poly(2-hydroxyethyl methacrylate) (pHEMA) network in the porous structure of alginate hydrogels. The resulting hydrogel possessed hierarchical NN structure and showed significantly improved mechanical strength but still maintained high elasticity comparable to soft tissues due to a mutual strengthening effect between the two networks. The tough hydrogel is also self-lubricated, exhibiting a surface friction coefficient comparable with polydimethylsiloxane (PDMS) substrates lubricated by a commercial aqueous lubricant (K-Y Jelly) and other low surface friction hydrogels. Additional properties of this hydrogel include high hydrophilicity, good biocompatibility, tunable cell adhesion and bacterial resistance after incorporation of silver nanoparticles. Firm bonding of the hydrogel on silicone substrates could be achieved through facile chemical modification, thus enabling the use of this hydrogel as a versatile coating material for biomedical applications. In this study, we developed a tough hydrogel by crosslinking HEMA monomers in alginate hydrogels and forming a well-organized structure of hierarchical nested network (NN). Different from most reported stretchable alginate-based hydrogels, the NN hydrogel shows higher compressive strength but retains comparable softness to alginate counterparts. This work further demonstrated the good integration of the tough hydrogel with silicone substrates through chemical modification and micropillar structures. Other properties including surface friction, biocompatibility and bacterial resistance were investigated and the hydrogel shows a great promise as a versatile coating material for biomedical applications. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Ion-implanted Si-nanostructures buried in a SiO{sub 2} substrate studied with soft-x-ray spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, R.; Rubensson, J.E.; Eisebitt, S.

1997-04-01

In recent years silicon nanostructures have gained great interest because of their optical luminescence, which immediately suggests several applications, e.g., in optoelectronic devices. Nanostructures are also investigated because of the fundamental physics involved in the underlying luminescence mechanism, especially attention has been drawn to the influence of the reduced dimensions on the electronic structure. The forming of stable and well-defined nanostructured materials is one goal of cluster physics. For silicon nanostructures this goal has so far not been reached, but various indirect methods have been established, all having the problem of producing less well defined and/or unstable nanostructures. Ion implantationmore » and subsequent annealing is a promising new technique to overcome some of these difficulties. In this experiment the authors investigate the electronic structure of ion-implanted silicon nanoparticles buried in a stabilizing SiO{sub 2} substrate. Soft X-ray emission (SXE) spectroscopy features the appropriate information depth to investigate such buried structures. SXE spectra to a good approximation map the local partial density of occupied states (LPDOS) in broad band materials like Si. The use of monochromatized synchrotron radiation (MSR) allows for selective excitation of silicon atoms in different chemical environments. Thus, the emission from Si atom sites in the buried structure can be separated from contributions from the SiO{sub 2} substrate. In this preliminary study strong size dependent effects are found, and the electronic structure of the ion-implanted nanoparticles is shown to be qualitatively different from porous silicon. The results can be interpreted in terms of quantum confinement and chemical shifts due to neighboring oxygen atoms at the interface to SiO{sub 2}.« less

Peptide interfaces with graphene: an emerging intersection of analytical chemistry, theory, and materials.

PubMed

Russell, Shane R; Claridge, Shelley A

2016-04-01

Because noncovalent interface functionalization is frequently required in graphene-based devices, biomolecular self-assembly has begun to emerge as a route for controlling substrate electronic structure or binding specificity for soluble analytes. The remarkable diversity of structures that arise in biological self-assembly hints at the possibility of equally diverse and well-controlled surface chemistry at graphene interfaces. However, predicting and analyzing adsorbed monolayer structures at such interfaces raises substantial experimental and theoretical challenges. In contrast with the relatively well-developed monolayer chemistry and characterization methods applied at coinage metal surfaces, monolayers on graphene are both less robust and more structurally complex, levying more stringent requirements on characterization techniques. Theory presents opportunities to understand early binding events that lay the groundwork for full monolayer structure. However, predicting interactions between complex biomolecules, solvent, and substrate is necessitating a suite of new force fields and algorithms to assess likely binding configurations, solvent effects, and modulations to substrate electronic properties. This article briefly discusses emerging analytical and theoretical methods used to develop a rigorous chemical understanding of the self-assembly of peptide-graphene interfaces and prospects for future advances in the field.

Characterization of Plasma Synthesized Vertical Carbon Nanofibers for Nanoelectronics Applications

NASA Technical Reports Server (NTRS)

Lee, Jaesung; Feng, Philip X.-L.; Kaul, Anupama B.

2013-01-01

We report on the material characterization of carbon nanofibers (CNFs) which are assembled into a three-dimensional (3D) configuration for making new nanoelectromechanical systems (NEMS). High-resolution scanning electron microscopy (SEM) and x-ray electron dispersive spectroscopy (XEDS) are employed to decipher the morphology and chemical compositions of the CNFs at various locations along individual CNFs grown on silicon (Si) and refractory nitride (NbTiN) substrates, respectively. The measured characteristics suggest interesting properties of the CNF bodies and their capping catalyst nanoparticles, and growth mechanisms on the two substrates. Laser irradiation on the CNFs seems to cause thermal oxidation and melting of catalyst nanoparticles. The structural morphology and chemical compositions of the CNFs revealed in this study should aid in the applications of the CNFs to nanoelectronics and NEMS.

Substrate-Specific Development of Thermophilic Bacterial Consortia by Using Chemically Pretreated Switchgrass.

PubMed

Eichorst, Stephanie A; Joshua, Chijioke; Sathitsuksanoh, Noppadon; Singh, Seema; Simmons, Blake A; Singer, Steven W

2014-12-01

Microbial communities that deconstruct plant biomass have broad relevance in biofuel production and global carbon cycling. Biomass pretreatments reduce plant biomass recalcitrance for increased efficiency of enzymatic hydrolysis. We exploited these chemical pretreatments to study how thermophilic bacterial consortia adapt to deconstruct switchgrass (SG) biomass of various compositions. Microbial communities were adapted to untreated, ammonium fiber expansion (AFEX)-pretreated, and ionic-liquid (IL)-pretreated SG under aerobic, thermophilic conditions using green waste compost as the inoculum to study biomass deconstruction by microbial consortia. After microbial cultivation, gravimetric analysis of the residual biomass demonstrated that both AFEX and IL pretreatment enhanced the deconstruction of the SG biomass approximately 2-fold. Two-dimensional nuclear magnetic resonance (2D-NMR) experiments and acetyl bromide-reactive-lignin analysis indicated that polysaccharide hydrolysis was the dominant process occurring during microbial biomass deconstruction, and lignin remaining in the residual biomass was largely unmodified. Small-subunit (SSU) rRNA gene amplicon libraries revealed that although the dominant taxa across these chemical pretreatments were consistently represented by members of the Firmicutes, the Bacteroidetes, and Deinococcus-Thermus, the abundance of selected operational taxonomic units (OTUs) varied, suggesting adaptations to the different substrates. Combining the observations of differences in the community structure and the chemical and physical structure of the biomass, we hypothesize specific roles for individual community members in biomass deconstruction. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Fabrication of long-term stable superoleophobic surface based on copper oxide/cobalt oxide with micro-nanoscale hierarchical roughness

NASA Astrophysics Data System (ADS)

Barthwal, Sumit; Lim, Si-Hyung

2015-02-01

We have demonstrated a simple and cost-effective technique for the large-area fabrication of a superoleophobic surface using copper as a substrate. The whole process included three simple steps: First, the copper substrate was oxidized under hot alkaline conditions to fabricate flower-like copper oxide microspheres by heating at a particular temperature for an interval of time. Second, the copper-oxide-covered copper substrate was further heated in a solution of cobalt nitrate and ammonium nitrate in the presence of an ammonia solution to fabricate cobalt oxide nanostructures. We applied this second step to increase the surface roughness because it is an important criterion for improved superoleophobicity. Finally, to reduce the surface energy of the fabricated structures, the surfaces were chemically modified with perfluorooctyltrichlorosilane. Contact-angle measurements indicate that the micro-nano binary (MNB) hierarchical structures fabricated on the copper substrate became super-repellent toward a broad range of liquids with surface tension in the range of 21.5-72 mN/m. In an attempt to significantly improve the superoleophobic property of the surface, we also examined and compared the role of nanostructures in MNB hierarchical structures with only micro-fabricated surfaces. The fabricated MNB hierarchical structures also displays thermal stability and excellent long-term stability after exposure in air for more than 9 months. Our method might provide a general route toward the preparation of novel hierarchical films on metal substrates for various industrial applications.

Anisotropic wetting of microstructured surfaces as a function of surface chemistry.

PubMed

Neuhaus, Sonja; Spencer, Nicholas D; Padeste, Celestino

2012-01-01

In order to study the influence of surface chemistry on the wetting of structured surfaces, microstructures consisting of grooves or squares were produced via hot embossing of poly(ethylene-alt-tetrafluoroethylene) ETFE substrates. The structured substrates were modified with polymer brushes, thereby changing their surface functionality and wettability. Water droplets were most strongly pinned to the structure when the surface was moderately hydrophilic, as in the case of poly(4-vinylpyridine) (P4VP) or poly(vinyl(N-methyl-2-pyridone) (PVMP) brush-modified substrates. As a result, the droplet shape was determined by the features of the microstructure. The water contact angles (CA) were considerably higher than on flat surfaces and differed, in the most extreme case, by 37° when measured on grooved substrates, parallel and perpendicular to the grooves. On hydrophobic substrates (pristine ETFE), the same effects were observed but were much less pronounced. On very hydrophilic sampes (those modified with poly(N-methyl-vinylpyridinium) (QP4VP)), the microstructure had no influence on the drop shape. These findings are explained by significant differences in apparent and real contact angles at the relatively smooth edges of the embossed structures. Finally, the highly anisotropic grooved microstructure was combined with a gradient in polymer brush composition and wettability. In the case of a parallel alignment of the gradient direction to the grooves, the directed spreading of water droplets could be observed. © 2011 American Chemical Society

Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals.

PubMed

Liu, Yuanyue; Merinov, Boris V; Goddard, William A

2016-04-05

It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion-substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems.

Role of the α clamp in the protein translocation mechanism of anthrax toxin

PubMed Central

Brown, Michael J.; Thoren, Katie L.; Krantz, Bryan A.

2015-01-01

Membrane-embedded molecular machines are utilized to move water-soluble proteins across these barriers. Anthrax toxin forms one such machine through the self-assembly of its three component proteins—protective antigen (PA), lethal factor (LF), and edema factor (EF). Upon endocytosis into host cells, acidification of the endosome induces PA to form a membrane-inserted channel, which unfolds LF and EF and translocates them into the host cytosol. Translocation is driven by the proton motive force, comprised of the chemical potential, the proton-gradient (ΔpH), and the membrane potential (ΔΨ). A crystal structure of the lethal toxin core complex revealed an “α clamp” structure that binds to substrate helices nonspecifically. Here we test the hypothesis that through the recognition of unfolding helical structure the α clamp can accelerate the rate of translocation. We produced a synthetic PA mutant in which an α helix was crosslinked into the α clamp to block its function. This synthetic construct impairs translocation by raising a yet uncharacterized translocation barrier shown to be much less force dependent than the known unfolding barrier. We also report that the α clamp more stably binds substrates that can form helices than those, such as polyproline, that cannot. Hence the α clamp recognizes substrates by a general shape-complementarity mechanism. Substrates that are incapable of forming compact secondary structure (due to the introduction of a polyproline track) are severely deficient for translocation. Therefore, the α clamp and its recognition of helical structure in the translocating substrate play key roles in the molecular mechanism of protein translocation. PMID:26344833

Initial stages of growth and the influence of temperature during chemical vapor deposition of sp{sup 2}-BN films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chubarov, Mikhail; Pedersen, Henrik; Högberg, Hans

2015-11-15

Knowledge of the structural evolution of thin films, starting by the initial stages of growth, is important to control the quality and properties of the film. The authors present a study on the initial stages of growth and the temperature influence on the structural evolution of sp{sup 2} hybridized boron nitride (BN) thin films during chemical vapor deposition (CVD) with triethyl boron and ammonia as precursors. Nucleation of hexagonal BN (h-BN) occurs at 1200 °C on α-Al{sub 2}O{sub 3} with an AlN buffer layer (AlN/α-Al{sub 2}O{sub 3}). At 1500 °C, h-BN grows with a layer-by-layer growth mode on AlN/α-Al{sub 2}O{sub 3} upmore » to ∼4 nm after which the film structure changes to rhombohedral BN (r-BN). Then, r-BN growth proceeds with a mixed layer-by-layer and island growth mode. h-BN does not grow on 6H-SiC substrates; instead, r-BN nucleates and grows directly with a mixed layer-by-layer and island growth mode. These differences may be caused by differences in substrate surface temperature due to different thermal conductivities of the substrate materials. These results add to the understanding of the growth process of sp{sup 2}-BN employing CVD.« less

Fabrication of self-healing super-hydrophobic surfaces on aluminium alloy substrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yang; Wei Liu, Xiao; Zhang, Hai Feng, E-mail: wy3121685@163.com

We present a method to fabricate a super-hydrophobic surface with a self-healing ability on an aluminium alloy substrate. The coatings are obtained by combining a two-step process (first, the substrate is immersed in a solution of HCl, HF and H{sub 2}O, and then in boiling water) and succeeding surface fluorination with a solution of poly(vinylidene-fluoride-co-hexafluoropropylene) and a fluoroalkyl silane. The morphological features and chemical composition were studied by scanning electron micrometry and energy-dispersive X-ray spectroscopy. The prepared super-hydrophobic aluminium surfaces showed hierarchical structures forming pores, petals and particles with a contact angle of 161° and a sliding angle of 3°.

Self-powered p-NiO/n-ZnO heterojunction ultraviolet photodetectors fabricated on plastic substrates

PubMed Central

Hasan, Md Rezaul; Xie, Ting; Barron, Sara C.; Liu, Guannan; Nguyen, Nhan V.; Motayed, Abhishek; Rao, Mulpuri V.; Debnath, Ratan

2016-01-01

A self-powered ultraviolet (UV) photodetector (PD) based on p-NiO and n-ZnO was fabricated using low-temperature sputtering technique on indium doped tin oxide (ITO) coated plastic polyethylene terephthalate (PET) substrates. The p-n heterojunction showed very fast temporal photoresponse with excellent quantum efficiency of over 63% under UV illumination at an applied reverse bias of 1.2 V. The engineered ultrathin Ti/Au top metal contacts and UV transparent PET/ITO substrates allowed the PDs to be illuminated through either front or back side. Morphology, structural, chemical and optical properties of sputtered NiO and ZnO films were also investigated. PMID:26900532

Molecules for organic electronics studied one by one.

PubMed

Meyer, Jörg; Wadewitz, Anja; Lokamani; Toher, Cormac; Gresser, Roland; Leo, Karl; Riede, Moritz; Moresco, Francesca; Cuniberti, Gianaurelio

2011-08-28

The electronic and geometrical structure of single difluoro-bora-1,3,5,7-tetraphenyl-aza-dipyrromethene (aza-BODIPY) molecules adsorbed on the Au(111) surface is investigated by low temperature scanning tunneling microscopy and spectroscopy in conjunction with ab initio density functional theory simulations of the density of states and of the interaction with the substrate. Our DFT calculations indicate that the aza-bodipy molecule forms a chemical bond with the Au(111) substrate, with distortion of the molecular geometry and significant charge transfer between the molecule and the substrate. Nevertheless, most likely due to the low corrugation of the Au(111) surface, diffusion of the molecule is observed for applied bias in excess of 1 V.

Fabrication of large tungsten structures by chemical vapor deposition

NASA Technical Reports Server (NTRS)

Kahle, V. E.; Lewis, W. J.; Stubbs, V. R.

1971-01-01

Process is accomplished by reducing tungsten hexafluoride with hydrogen. Metallic tungsten of essentially 100 percent purity and density is produced and built up as dense deposit on heated mandrel assembly. Process variations are building up, sealing or bonding refractory metals at temperatures below transition temperatures of base metal substrates.

A naturally occurring diatom frustule as a SERS substrate for the detection and quantification of chemicals

NASA Astrophysics Data System (ADS)

Chamuah, Nabadweep; Chetia, Lakhi; Zahan, Nashrat; Dutta, Sibasish; Ahmed, Gazi A.; Nath, Pabitra

2017-05-01

Naturally occurring photonic crystal structures play an important role in different fields of application. Herein, we exploit the periodic pore pattern of a diatom frustule and demonstrate surface-enhanced Raman scattering (SERS) using its structure as a template for the SERS substrate. Gold nanoparticles (AuNPs) were initially allowed to self-assemble on the surface and inside the pores of the diatoms. The enhancement in the localized surface plasmon resonance (LSPR) field magnitude for the assembled AuNPs on the diatom frustule were studied using simulation software. For the proposed SERS substrate, an average field enhancement of the order of 108 magnitude was observed. We demonstrate the operation of the designed substrate for the detection and quantification of Raman signals from two Raman active samples, namely malachite green (MG) and fluoride concentrations in drinking water. Using the proposed SERS substrate, an MG concentration as low as 1 nM with a relative standard deviation (RSD) of 7.57% and a fluoride concentration of 100 nM with an RSD of 17.26% could be measured with the Raman spectrometer. We envision that the proposed technique could emerge as an inexpensive alternative fabrication method of SERS substrates which can produce an enhanced LSPR field magnitude and scatter intense Raman signals from Raman active samples.

Precise micropatterning of silver nanoparticles on plastic substrates

NASA Astrophysics Data System (ADS)

Ammosova, Lena; Jiang, Yu; Suvanto, Mika; Pakkanen, Tapani A.

2017-04-01

Conventional fabrication methods to obtain metal patterns on polymer substrates are restricted by high operating temperature and complex preparation steps. The present study demonstrates a simple yet versatile method for preparation of silver nanoparticle micropatterns on polymer substrates with various surface geometry. With the microworking robot technique, we were able not only to directly structure the surface, but also precisely deposit silver nanoparticle ink on the desired surface location with the minimum usage of ink material. The prepared silver nanoparticle ink, containing silver cations and polyethylene glycol (PEG) as a reducing agent, yields silver nanoparticle micropatterns on plastic substrates at low sintering temperature without any contamination. The influence of the ink behaviour was studied, such as substrate wettability, ink volume, and sintering temperature. The ultraviolet visible (UV-vis), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) measurements revealed the formation of micropatterns with uniformly distributed silver nanoparticles. The prepared patterns are expected to have a broad range of applications in optics, medicine, and sensor devices owing to the unique properties of silver. Furthermore, the deposition of a chemical compound, which is different from the substrate material, not only adds a fourth dimension to the prestructured three-dimensional (3D) surfaces, but also opens new application areas to the conventional surface structures.

Effect of charged impurities and morphology on oxidation reactivity of graphene

NASA Astrophysics Data System (ADS)

Yamamoto, Mahito; Cullen, William; Einstein, Theodore; Fuhrer, Michael

2012-02-01

Chemical reactivity of single layer graphene supported on a substrate is observed to be enhanced over thicker graphene. Possible mechanisms for the enhancement are Fermi level fluctuations due to ionized impurities on the substrate, and structural deformation of graphene induced by coupling to the substrate geometry. Here, we study the substrate-dependent oxidation reactivity of graphene, employing various substrates such as SiO2, mica, SiO2 nanoparticle thin film, and hexagonal boron nitride, which exhibit different charged impurity concentrations and surface roughness. Graphene is prepared on each substrate via mechanical exfoliation and oxidized in Ar/O2 mixture at temperatures from 400-600 ^oC. After oxidation, the Raman spectrum of graphene is measured, and the Raman D to G peak ratio is used to quantify the density of point defects introduced by oxidation. We will discuss the correlations among the defect density in oxidized graphene, substrate charge inhomogeneity, substrate corrugations, and graphene layer thickness. This work has been supported by the University of Maryland NSF-MRSEC under Grant No. DMR 05-20471 with supplemental funding from NRI, and NSF-DMR 08-04976.

Characterization of remote O2-plasma-enhanced CVD SiO2/GaN(0001) structure using photoemission measurements

NASA Astrophysics Data System (ADS)

Truyen, Nguyen Xuan; Ohta, Akio; Makihara, Katsunori; Ikeda, Mitsuhisa; Miyazaki, Seiichi

2018-01-01

The control of chemical composition and bonding features at a SiO2/GaN interface is a key to realizing high-performance GaN power devices. In this study, an ∼5.2-nm-thick SiO2 film has been deposited on an epitaxial GaN(0001) surface by remote O2-plasma-enhanced chemical vapor deposition (O2-RPCVD) using SiH4 and Ar/O2 mixture gases at a substrate temperature of 500 °C. The depth profile of chemical structures and electronic defects of the O2-RPCVD SiO2/GaN structures has been evaluated from a combination of SiO2 thinning examined by X-ray photoelectron spectroscopy (XPS) and the total photoelectron yield spectroscopy (PYS) measurements. As a highlight, we found that O2-RPCVD is effective for fabricating an abrupt SiO2/GaN interface.

Adsorption of human serum albumin: Dependence on molecular architecture of the oppositely charged surface

NASA Astrophysics Data System (ADS)

Sukhishvili, Svetlana A.; Granick, Steve

1999-05-01

We contrast the adsorption of human serum albumin (HSA) onto two solid substrates previously primed with the same polyelectrolyte of net opposite charge to form one of two alternative structures: randomly adsorbed polymer and the "brush" configuration. These structures were formed either by the adsorption of quaternized poly-4-vinylpyridine (QPVP) or by end-grafting QPVP chains of the same chemical makeup and the same molecular weight to surfaces onto which QPVP segments did not adsorb. The adsorption of HSA was quantified by using Fourier transform infrared spectroscopy in attenuated total reflection (FTIR-ATR). The two substrates showed striking differences with regard to HSA adsorption. First, the brush substrate induced lesser perturbations in the secondary structure of the adsorbed HSA, reflecting easier conformational adjustment for longer free segments of polyelectrolyte upon binding with the protein. Second, the penetration of HSA into the brush substrate was kinetically retarded relative to the randomly adsorbed polymer, probably due to both pore size restriction and electrostatic sticking between charged groups of HSA and QPVP molecules. Third, release of HSA from the adsorbed layer, as the ionic strength was increased from a low level up to the high level of 1 M NaCl, was largely inhibited for the brush substrate, but occurred easily and rapidly for the substrate with statistically adsorbed QPVP chains. Finally, even after addition of a strong polymeric adsorption competitor (sodium polystyrene sulfonate), HSA remained trapped within a brush substrate though it desorbed slowly from the preadsorbed QPVP layer. This method to produce irreversible trapping of the protein within a brush substrate without major conformational change may find application in biosensor design.

Superconducting structure with layers of niobium nitride and aluminum nitride

DOEpatents

Murduck, James M.; Lepetre, Yves J.; Schuller, Ivan K.; Ketterson, John B.

1989-01-01

A superconducting structure is formed by depositing alternate layers of aluminum nitride and niobium nitride on a substrate. Deposition methods include dc magnetron reactive sputtering, rf magnetron reactive sputtering, thin-film diffusion, chemical vapor deposition, and ion-beam deposition. Structures have been built with layers of niobium nitride and aluminum nitride having thicknesses in a range of 20 to 350 Angstroms. Best results have been achieved with films of niobium nitride deposited to a thickness of approximately 70 Angstroms and aluminum nitride deposited to a thickness of approximately 20 Angstroms. Such films of niobium nitride separated by a single layer of aluminum nitride are useful in forming Josephson junctions. Structures of 30 or more alternating layers of niobium nitride and aluminum nitride are useful when deposited on fixed substrates or flexible strips to form bulk superconductors for carrying electric current. They are also adaptable as voltage-controlled microwave energy sources.

Preparation of composite micro/nano structure on the silicon surface by reactive ion etching: Enhanced anti-reflective and hydrophobic properties

NASA Astrophysics Data System (ADS)

Zeng, Yu; Fan, Xiaoli; Chen, Jiajia; He, Siyu; Yi, Zao; Ye, Xin; Yi, Yougen

2018-05-01

A silicon substrate with micro-pyramid structure (black silicon) is prepared by wet chemical etching and then subjected to reactive ion etching (RIE) in the mixed gas condition of SF6, CHF3 and He. We systematically study the impacts of flow rates of SF6, CHF3 and He, the etching pressure and the etching time on the surface morphology and reflectivity through various characterizations. Meanwhile, we explore and obtain the optimal combination of parameters for the preparation of composite structure that match the RIE process based on the basis of micro-pyramid silicon substrate. The composite sample prepared under the optimum parameters exhibits excellent anti-reflective performance, hydrophobic, self-cleaning and anti-corrosive properties. Based on the above characteristics, the composite micro/nano structure can be applied to solar cells, photodetectors, LEDs, outdoor devices and other important fields.

Superconducting structure with layers of niobium nitride and aluminum nitride

DOEpatents

Murduck, J.M.; Lepetre, Y.J.; Schuller, I.K.; Ketterson, J.B.

1989-07-04

A superconducting structure is formed by depositing alternate layers of aluminum nitride and niobium nitride on a substrate. Deposition methods include dc magnetron reactive sputtering, rf magnetron reactive sputtering, thin-film diffusion, chemical vapor deposition, and ion-beam deposition. Structures have been built with layers of niobium nitride and aluminum nitride having thicknesses in a range of 20 to 350 Angstroms. Best results have been achieved with films of niobium nitride deposited to a thickness of approximately 70 Angstroms and aluminum nitride deposited to a thickness of approximately 20 Angstroms. Such films of niobium nitride separated by a single layer of aluminum nitride are useful in forming Josephson junctions. Structures of 30 or more alternating layers of niobium nitride and aluminum nitride are useful when deposited on fixed substrates or flexible strips to form bulk superconductors for carrying electric current. They are also adaptable as voltage-controlled microwave energy sources. 8 figs.

Structural and optical properties of nano-structured CdS thin films prepared by chemical bath deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bai, Rekha, E-mail: rekha.mittal07@gmail.com; Kumar, Dinesh; Chaudhary, Sujeet

2016-05-06

Cadmium sulfide (CdS) thin films have been deposited on conducting glass substrates by chemical bath deposition (CBD) technique. The effect of precursor concentration on the structural, morphological, compositional, and optical properties of the CdS films has been studied. Crystal structure of these CdS films is characterized by X-ray diffraction (XRD) and it reveals polycrystalline structure with mixture of cubic and wurtzite phases with grain size decreasing as precursor concentration is increased. Optical studies reveal that the CdS thin films have high transmittance in visible spectral region reaching 90% and the films possess direct optical band gap that decreases from 2.46more » to 2.39 eV with decreasing bath concentration. Our study suggests that growth is nucleation controlled.« less

Microbial trace fossils in Antarctica and the search for evidence of early life on Mars

NASA Technical Reports Server (NTRS)

Friedmann, E. Imre; Friedmann, Roseli O.

1989-01-01

It is possible to hypothesize that, if microbial life evolved on early Mars, fossil remnants of these organisms may be preserved on the surface. However, the cooling and drying of Mars probably resembled a cold desert and such an environment is not suitable for the process of fossilization. The frigid Ross Desert of Antarctica is probably the closest terrestrial analog to conditions that may have prevailed on the surface of the cooling and drying Mars. In this desert, cryptoendolithic microbial communities live in the airspaces of porous rocks, the last habitable niche in a hostile outside environment. The organisms produce characteristic chemical and physical changes in the rock substrate. Environmental changes (deterioration of conditions) may result in the death of the community. Although no cellular structures are fossilized, the conspicuous changes in the rock substrate are preserved as trace fossils. Likewise, microbial trace fossils (without cellular structures) may also be preserved on Mars: Discontinuities in structure or chemistry of the rock that are independent of physical or chemical gradients may be of biological origin. Ross Desert trace fossils can be used as a model for planning search strategies and for instrument design to find evidence of past Martian life.

Interface architecture determined electrocatalytic activity of Pt on vertically oriented TiO(2) nanotubes.

PubMed

Rettew, Robert E; Allam, Nageh K; Alamgir, Faisal M

2011-02-01

The surface atomic structure and chemical state of Pt is consequential in a variety of surface-intensive devices. Herein we present the direct interrelationship between the growth scheme of Pt films, the resulting atomic and electronic structure of Pt species, and the consequent activity for methanol electro-oxidation in Pt/TiO(2) nanotube hybrid electrodes. X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) measurements were performed to relate the observed electrocatalytic activity to the oxidation state and the atomic structure of the deposited Pt species. The atomic structure as well as the oxidation state of the deposited Pt was found to depend on the pretreatment of the TiO(2) nanotube surfaces with electrodeposited Cu. Pt growth through Cu replacement increases Pt dispersion, and a separation of surface Pt atoms beyond a threshold distance from the TiO(2) substrate renders them metallic, rather than cationic. The increased dispersion and the metallic character of Pt results in strongly enhanced electrocatalytic activity toward methanol oxidation. This study points to a general phenomenon whereby the growth scheme and the substrate-to-surface-Pt distance dictates the chemical state of the surface Pt atoms, and thereby, the performance of Pt-based surface-intensive devices.

Uniting Superhydrophobic, Superoleophobic and Lubricant Infused Slippery Behavior on Copper Oxide Nano-structured Substrates

PubMed Central

Ujjain, Sanjeev Kumar; Roy, Pritam Kumar; Kumar, Sumana; Singha, Subhash; Khare, Krishnacharya

2016-01-01

Alloys, specifically steel, are considered as the workhorse of our society and are inimitable engineering materials in the field of infrastructure, industry and possesses significant applications in our daily life. However, creating a robust synthetic metallic surface that repels various liquids has remained extremely challenging. The wettability of a solid surface is known to be governed by its geometric nano-/micro structure and the chemical composition. Here, we are demonstrating a facile and economical way to generate copper oxide micro-nano structures with spherical (0D), needle (1D) and hierarchical cauliflower (3D) morphologies on galvanized steel substrates using a simple chemical bath deposition method. These nano/micro textured steel surfaces, on subsequent coating of a low surface energy material display excellent superhydrophobic, superoleophobic and slippery behavior. Polydimethylsiloxane coated textured surfaces illustrate superhydrophobicity with water contact angle about 160°(2) and critical sliding angle ~2°. When functionalized with low-surface energy perfluoroalkylsilane, these surfaces display high repellency for low surface tension oils as well as hydrocarbons. Among them, the hierarchical cauliflower morphology exhibits re-entrant structure thereby showing the best superoleophobicity with contact angle 149° for dodecane. Once infused with a lubricant like silicone oil, they show excellent slippery behavior with low contact angle hysteresis (~ 2°) for water drops. PMID:27752098

Uniting Superhydrophobic, Superoleophobic and Lubricant Infused Slippery Behavior on Copper Oxide Nano-structured Substrates

NASA Astrophysics Data System (ADS)

Ujjain, Sanjeev Kumar; Roy, Pritam Kumar; Kumar, Sumana; Singha, Subhash; Khare, Krishnacharya

2016-10-01

Alloys, specifically steel, are considered as the workhorse of our society and are inimitable engineering materials in the field of infrastructure, industry and possesses significant applications in our daily life. However, creating a robust synthetic metallic surface that repels various liquids has remained extremely challenging. The wettability of a solid surface is known to be governed by its geometric nano-/micro structure and the chemical composition. Here, we are demonstrating a facile and economical way to generate copper oxide micro-nano structures with spherical (0D), needle (1D) and hierarchical cauliflower (3D) morphologies on galvanized steel substrates using a simple chemical bath deposition method. These nano/micro textured steel surfaces, on subsequent coating of a low surface energy material display excellent superhydrophobic, superoleophobic and slippery behavior. Polydimethylsiloxane coated textured surfaces illustrate superhydrophobicity with water contact angle about 160°(2) and critical sliding angle ~2°. When functionalized with low-surface energy perfluoroalkylsilane, these surfaces display high repellency for low surface tension oils as well as hydrocarbons. Among them, the hierarchical cauliflower morphology exhibits re-entrant structure thereby showing the best superoleophobicity with contact angle 149° for dodecane. Once infused with a lubricant like silicone oil, they show excellent slippery behavior with low contact angle hysteresis (~ 2°) for water drops.

Apparatus for thermally evolving chemical analytes from a removable substrate

DOEpatents

Linker, Kevin L.; Hannum, David W.

2003-06-03

Method and apparatus suited to convenient field use for heating a porous metallic substrate swiped on the surface of an article possibly bearing residue of contraband or other target chemical substances. The preferred embodiment of the device includes means for holding the swiped substrate between electrodes bearing opposite electrical charges, thereby completing an electrical circuit in which current can flow through the porous metallic substrate. Resistance causes the substrate to heat, thus driving adherent target chemicals, if present, into a space from which they are carried via gas flow into a detector such as a portable IMS for analysis.

Nano- and microcrystalline diamond deposition on pretreated WC-Co substrates: structural properties and adhesion

NASA Astrophysics Data System (ADS)

Fraga, M. A.; Contin, A.; Rodríguez, L. A. A.; Vieira, J.; Campos, R. A.; Corat, E. J.; Trava Airoldi, V. J.

2016-02-01

Many developments have been made to improve the quality and adherence of CVD diamond films onto WC-Co hard metal tools by the removing the cobalt from the substrate surface through substrate pretreatments. Here we compare the efficiency of three chemical pretreatments of WC-Co substrates for this purpose. First, the work was focused on a detailed study of the composition and structure of as-polished and pretreated substrate surfaces to characterize the effects of the substrate preparation. Considering this objective, a set of WC-9% Co substrates, before and after pretreatment, was analyzed by FEG-SEM, EDS and x-ray diffraction (XRD). The second stage of the work was devoted to the evaluation of the influence of seeding process, using 4 nm diamond nanoparticles, on the morphology and roughness of the pretreated substrates. The last and most important stage was to deposit diamond coatings with different crystallite sizes (nano and micro) by hot-filament CVD to understand fully the mechanism of growth and adhesion of CVD diamond films on pretreated WC-Co substrates. The transition from nano to microcrystalline diamond was achieved by controlling the CH4/H2 gas ratio. The nano and microcrystalline samples were grown under same time at different substrate temperatures 600 °C and 800 °C, respectively. The different substrate temperatures allowed the analysis of the cobalt diffusion from the bulk to the substrate surface during CVD film growth. Furthermore, it was possible to evaluate how the coating adhesion is affected by the diffusion. The diamond coatings were characterized by Raman spectroscopy, XRD, EDS, FEG-SEM, atomic force microscope and 1500 N Rockwell indentation to evaluate the adhesion.

Electronic, structural and chemical effects of charge-transfer at organic/inorganic interfaces

NASA Astrophysics Data System (ADS)

Otero, R.; Vázquez de Parga, A. L.; Gallego, J. M.

2017-07-01

During the last decade, interest on the growth and self-assembly of organic molecular species on solid surfaces spread over the scientific community, largely motivated by the promise of cheap, flexible and tunable organic electronic and optoelectronic devices. These efforts lead to important advances in our understanding of the nature and strength of the non-bonding intermolecular interactions that control the assembly of the organic building blocks on solid surfaces, which have been recently reviewed in a number of excellent papers. To a large extent, such studies were possible because of a smart choice of model substrate-adsorbate systems where the molecule-substrate interactions were purposefully kept low, so that most of the observed supramolecular structures could be understood simply by considering intermolecular interactions, keeping the role of the surface always relatively small (although not completely negligible). On the other hand, the systems which are more relevant for the development of organic electronic devices include molecular species which are electron donors, acceptors or blends of donors and acceptors. Adsorption of such organic species on solid surfaces is bound to be accompanied by charge-transfer processes between the substrate and the adsorbates, and the physical and chemical properties of the molecules cannot be expected any longer to be the same as in solution phase. In recent years, a number of groups around the world have started tackling the problem of the adsorption, self- assembly and electronic and chemical properties of organic species which interact rather strongly with the surface, and for which charge-transfer must be considered. The picture that is emerging shows that charge transfer can lead to a plethora of new phenomena, from the development of delocalized band-like electron states at molecular overlayers, to the existence of new substrate-mediated intermolecular interactions or the strong modification of the chemical reactivity of the adsorbates. The aim of this review is to start drawing general conclusions and developing new concepts which will help the scientific community to proceed more efficiently towards the understanding of organic/inorganic interfaces in the strong interaction limit, where charge-transfer effects must be taken into consideration.

Comprehensive structural and substrate specificity classification of the Saccharomyces cerevisiae methyltransferome.

PubMed

Wlodarski, Tomasz; Kutner, Jan; Towpik, Joanna; Knizewski, Lukasz; Rychlewski, Leszek; Kudlicki, Andrzej; Rowicka, Maga; Dziembowski, Andrzej; Ginalski, Krzysztof

2011-01-01

Methylation is one of the most common chemical modifications of biologically active molecules and it occurs in all life forms. Its functional role is very diverse and involves many essential cellular processes, such as signal transduction, transcriptional control, biosynthesis, and metabolism. Here, we provide further insight into the enzymatic methylation in S. cerevisiae by conducting a comprehensive structural and functional survey of all the methyltransferases encoded in its genome. Using distant homology detection and fold recognition, we found that the S. cerevisiae methyltransferome comprises 86 MTases (53 well-known and 33 putative with unknown substrate specificity). Structural classification of their catalytic domains shows that these enzymes may adopt nine different folds, the most common being the Rossmann-like. We also analyzed the domain architecture of these proteins and identified several new domain contexts. Interestingly, we found that the majority of MTase genes are periodically expressed during yeast metabolic cycle. This finding, together with calculated isoelectric point, fold assignment and cellular localization, was used to develop a novel approach for predicting substrate specificity. Using this approach, we predicted the general substrates for 24 of 33 putative MTases and confirmed these predictions experimentally in both cases tested. Finally, we show that, in S. cerevisiae, methylation is carried out by 34 RNA MTases, 32 protein MTases, eight small molecule MTases, three lipid MTases, and nine MTases with still unknown substrate specificity.

Au coated PS nanopillars as a highly ordered and reproducible SERS substrate

NASA Astrophysics Data System (ADS)

Kim, Yong-Tae; Schilling, Joerg; Schweizer, Stefan L.; Sauer, Guido; Wehrspohn, Ralf B.

2017-07-01

Noble metal nanostructures with nanometer gap size provide strong surface-enhanced Raman scattering (SERS) which can be used to detect trace amounts of chemical and biological molecules. Although several approaches were reported to obtain active SERS substrates, it still remains a challenge to fabricate SERS substrates with high sensitivity and reproducibility using low-cost techniques. In this article, we report on the fabrication of Au sputtered PS nanopillars based on a template synthetic method as highly ordered and reproducible SERS substrates. The SERS substrates are fabricated by anodic aluminum oxide (AAO) template-assisted infiltration of polystyrene (PS) resulting in hemispherical structures, and a following Au sputtering process. The optimum gap size between adjacent PS nanopillars and thickness of the Au layers for high SERS sensitivity are investigated. Using the Au sputtered PS nanopillars as an active SERS substrate, the Raman signal of 4-methylbenzenethiol (4-MBT) with a concentration down to 10-9 M is identified with good signal reproducibility, showing great potential as promising tool for SERS-based detection.

Shape-engineering substrate-based plasmonic nanomaterials

NASA Astrophysics Data System (ADS)

Gilroy, Kyle D.

The advancement of next generation technologies is reliant on our ability to engineer matter at the nanoscale. Since the morphological features of nanomaterials dictate their chemical and physical properties, a significant effort has been put forth to develop syntheses aimed at fine tuning their size, shape and composition. This massive effort has resulted in a maturing colloidal chemistry containing an extensive collection of morphologies with compositions nearly spanning the entire transition of the periodic table. While colloidal nanoparticles have opened the door to promising applications in fields such as cancer theranostics, drug delivery, catalysis and sensing; the synthetic protocols for the placement of nanomaterials on surfaces, a requisite for chip-based devices, are ill-developed. This dissertation serves to address this limitation by highlighting a series of syntheses related to the design of substrate-based nanoparticles whose size, shape and composition are controllably engineered to a desired endpoint. The experimental methods are based on a template-mediated approach which sees chemical modifications made to prepositioned thermally assembled metal nanostructures which are well bonded to a sapphire substrate. The first series of investigations will highlight synthetic routes utilizing galvanic replacement reactions, where the prepositioned templates are chemically transformed into hollow nanoshells. Detailed studies are provided highlighting discoveries related to (i) hollowing, (ii) defect transfer, (iii) strain induction, (iv) interdiffusion, (v) crystal structure and (vi) the localized surface plasmon resonance (LSPR). The second series of investigations, based on heterogeneous nucleation, have Au templates serve as nucleation sites for metal atoms arriving in either the solution- or vapor phase. The solution-phase heterogeneous nucleation of Ag on Au reveals that chemical kinetics (injection rate & precursor concentration) can be used to control the nature of how Ag atoms grow on the Au template. It was discovered that (i) slow kinetics leads to an anisotropic growth mode (heterodimeric structures), (ii) fast kinetics causes a very uniform deposition (Au-Ag coreshell morphology, or Au Ag) and (iii) medium kinetics produces structures with an intermediate morphology (truncated octahedron). In the second case, where the nucleation event is carried out at high temperatures, the Ag vapor is sourced from a sublimating foil onto adjacent Au templates. This process drives the composition and morphology from a Au Wulff-shape to a homogeneous Au-Ag nanoprism. By tracking over time the (i) morphological features, (ii) LSPR and (iii) composition; insights into the fundamental atomic scale growth mechanisms are elucidated. Overall, substrate-based template-mediated syntheses have proven to be an effective route for directing growth pathways toward a desired endpoint giving rise to an impressive new group of complex substrate-based nanostructures with asymmetric, core-shell and hollowed morphologies. While this dissertation is focused heavily on the development of synthetic procedures aimed at generating substrate-based plasmonic nanomaterials, the last chapter will serve to highlight a series of on-going studies aimed at defining these nanomaterials as highly effective heterogeneous catalysts. Several examples are shown including (i) nanoparticle films synthesize via sputter deposition, (ii) mechanically induced nanotexturing of bulk copper foils, (iii) ultra-small AuPd nanoparticles synthesized via pulse laser, (iv) substrate-based AuCu nanoprisms and (v) the Wulff in a Cage Morphology.

Morphological evolution of thin polymer film on chemically patterned substrates

NASA Astrophysics Data System (ADS)

Singh, Satya Pal

2018-05-01

In this paper work, pattern formation in ultra thin polymer film, adsorbed on chemically patterned substrates, is reported under strong confinement. The observations indicate for the strong influence of the surface attraction over evolution of spindoal waves, leading to the flattening of the film. But, the film appears to be torn apart in strip or nano fiber like structures, because of coalescences of the monomers at the free ends of the chains. The beads at the free ends of the chain are relatively more mobile. The chain diffusion towards attractive part of the chemically patterned surfaces is clearly seen. Prewetting or crystallization like phenomena seems to appear resulting into formation of strips with coexistence of molten phase drops at the top of the ruptured film. The investigation mimics spindoal dewetting because of the fact that the rupturing occurs in case of strong attractive surface. The investigation is of technical importance as it highlights the formation of nano scale strips and fibers though in a quasi equilibrium case.

A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes

NASA Astrophysics Data System (ADS)

Yang, Jinhui; Cooper, Jason K.; Toma, Francesca M.; Walczak, Karl A.; Favaro, Marco; Beeman, Jeffrey W.; Hess, Lucas H.; Wang, Cheng; Zhu, Chenhui; Gul, Sheraz; Yano, Junko; Kisielowski, Christian; Schwartzberg, Adam; Sharp, Ian D.

2017-03-01

Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. Here, we demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co3O4/Co(OH)2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. These films comprise compact and continuous nanocrystalline Co3O4 spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH)2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p+n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.

Recent progress in the development of solid catalysts for biomass conversion into high value-added chemicals

PubMed Central

Hara, Michikazu; Nakajima, Kiyotaka; Kamata, Keigo

2015-01-01

In recent decades, the substitution of non-renewable fossil resources by renewable biomass as a sustainable feedstock has been extensively investigated for the manufacture of high value-added products such as biofuels, commodity chemicals, and new bio-based materials such as bioplastics. Numerous solid catalyst systems for the effective conversion of biomass feedstocks into value-added chemicals and fuels have been developed. Solid catalysts are classified into four main groups with respect to their structures and substrate activation properties: (a) micro- and mesoporous materials, (b) metal oxides, (c) supported metal catalysts, and (d) sulfonated polymers. This review article focuses on the activation of substrates and/or reagents on the basis of groups (a)–(d), and the corresponding reaction mechanisms. In addition, recent progress in chemocatalytic processes for the production of five industrially important products (5-hydroxymethylfurfural, lactic acid, glyceraldehyde, 1,3-dihydroxyacetone, and furan-2,5-dicarboxylic acid) as bio-based plastic monomers and their intermediates is comprehensively summarized. PMID:27877800

Recent progress in the development of solid catalysts for biomass conversion into high value-added chemicals.

PubMed

Hara, Michikazu; Nakajima, Kiyotaka; Kamata, Keigo

2015-06-01

In recent decades, the substitution of non-renewable fossil resources by renewable biomass as a sustainable feedstock has been extensively investigated for the manufacture of high value-added products such as biofuels, commodity chemicals, and new bio-based materials such as bioplastics. Numerous solid catalyst systems for the effective conversion of biomass feedstocks into value-added chemicals and fuels have been developed. Solid catalysts are classified into four main groups with respect to their structures and substrate activation properties: (a) micro- and mesoporous materials, (b) metal oxides, (c) supported metal catalysts, and (d) sulfonated polymers. This review article focuses on the activation of substrates and/or reagents on the basis of groups (a)-(d), and the corresponding reaction mechanisms. In addition, recent progress in chemocatalytic processes for the production of five industrially important products (5-hydroxymethylfurfural, lactic acid, glyceraldehyde, 1,3-dihydroxyacetone, and furan-2,5-dicarboxylic acid) as bio-based plastic monomers and their intermediates is comprehensively summarized.

Recent progress in the development of solid catalysts for biomass conversion into high value-added chemicals

NASA Astrophysics Data System (ADS)

Hara, Michikazu; Nakajima, Kiyotaka; Kamata, Keigo

2015-06-01

In recent decades, the substitution of non-renewable fossil resources by renewable biomass as a sustainable feedstock has been extensively investigated for the manufacture of high value-added products such as biofuels, commodity chemicals, and new bio-based materials such as bioplastics. Numerous solid catalyst systems for the effective conversion of biomass feedstocks into value-added chemicals and fuels have been developed. Solid catalysts are classified into four main groups with respect to their structures and substrate activation properties: (a) micro- and mesoporous materials, (b) metal oxides, (c) supported metal catalysts, and (d) sulfonated polymers. This review article focuses on the activation of substrates and/or reagents on the basis of groups (a)-(d), and the corresponding reaction mechanisms. In addition, recent progress in chemocatalytic processes for the production of five industrially important products (5-hydroxymethylfurfural, lactic acid, glyceraldehyde, 1,3-dihydroxyacetone, and furan-2,5-dicarboxylic acid) as bio-based plastic monomers and their intermediates is comprehensively summarized.

X-ray characterization of Ge dots epitaxially grown on nanostructured Si islands on silicon-on-insulator substrates.

PubMed

Zaumseil, Peter; Kozlowski, Grzegorz; Yamamoto, Yuji; Schubert, Markus Andreas; Schroeder, Thomas

2013-08-01

On the way to integrate lattice mismatched semiconductors on Si(001), the Ge/Si heterosystem was used as a case study for the concept of compliant substrate effects that offer the vision to be able to integrate defect-free alternative semiconductor structures on Si. Ge nanoclusters were selectively grown by chemical vapour deposition on Si nano-islands on silicon-on-insulator (SOI) substrates. The strain states of Ge clusters and Si islands were measured by grazing-incidence diffraction using a laboratory-based X-ray diffraction technique. A tensile strain of up to 0.5% was detected in the Si islands after direct Ge deposition. Using a thin (∼10 nm) SiGe buffer layer between Si and Ge the tensile strain increases to 1.8%. Transmission electron microscopy studies confirm the absence of a regular grid of misfit dislocations in such structures. This clear experimental evidence for the compliance of Si nano-islands on SOI substrates opens a new integration concept that is not only limited to Ge but also extendable to semiconductors like III-V and II-VI materials.

High Ms Fe16N2 thin film with Ag under layer on GaAs substrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allard Jr, Lawrence Frederick

2016-01-01

(001) textured Fe16N2 thin film with Ag under layer is successfully grown on GaAs substrate using a facing target sputtering (FTS) system. After post annealing, chemically ordered Fe16N2 phase is formed and detected by X-ray diffraction (XRD). High saturation magnetization (Ms) is measured by a vibrating sample magnetometer (VSM). In comparison with Fe16N2 with Ag under layer on MgO substrate and Fe16N2 with Fe under layer on GaAs substrate, the current layer structure shows a higher Ms value, with a magnetically softer feature in contrast to the above cases. In addition, X-ray photoelectron spectroscopy (XPS) is performed to characterize themore » binding energy of N atoms. To verify the role of strain that the FeN layer experiences in the above three structures, Grazing Incidence X-ray Diffraction (GIXRD) is conducted to reveal a large in-plane lattice constant due to the in-plane biaxial tensile strain. INTRODUCTION« less

Microscopic aspects of wetting using classical density functional theory

NASA Astrophysics Data System (ADS)

Yatsyshin, P.; Durán-Olivencia, M.-A.; Kalliadasis, S.

2018-07-01

Wetting is a rather efficient mechanism for nucleation of a phase (typically liquid) on the interface between two other phases (typically solid and gas). In many experimentally accessible cases of wetting, the interplay between the substrate structure, and the fluid–fluid and fluid–substrate intermolecular interactions brings about an entire ‘zoo’ of possible fluid configurations, such as liquid films with a thickness of a few nanometers, liquid nanodrops and liquid bridges. These fluid configurations are often associated with phase transitions occurring at the solid–gas interface and at lengths of just several molecular diameters away from the substrate. In this special issue article, we demonstrate how a fully microscopic classical density-functional framework can be applied to the efficient, rational and systematic exploration of the rich phase space of wetting phenomena. We consider a number of model prototype systems such as wetting on a planar wall, a chemically patterned wall and a wedge. Through density-functional computations we demonstrate that for these simply structured substrates the behaviour of the solid–gas interface is already highly complex and non-trivial.

Apparatus and Process for Controlled Nanomanufacturing Using Catalyst Retaining Structures

NASA Technical Reports Server (NTRS)

Nguyen, Cattien (Inventor)

2013-01-01

An apparatus and method for the controlled fabrication of nanostructures using catalyst retaining structures is disclosed. The apparatus includes one or more modified force microscopes having a nanotube attached to the tip portion of the microscopes. An electric current is passed from the nanotube to a catalyst layer of a substrate, thereby causing a localized chemical reaction to occur in a resist layer adjacent the catalyst layer. The region of the resist layer where the chemical reaction occurred is etched, thereby exposing a catalyst particle or particles in the catalyst layer surrounded by a wall of unetched resist material. Subsequent chemical vapor deposition causes growth of a nanostructure to occur upward through the wall of unetched resist material having controlled characteristics of height and diameter and, for parallel systems, number density.

Fiber optic detector and method for using same for detecting chemical species

DOEpatents

Baylor, Lewis C.; Buchanan, Bruce R.

1995-01-01

An optical sensing device for uranyl and other substances, a method for making an optical sensing device and a method for chemically binding uranyl and other indicators to glass, quartz, cellulose and similar substrates. The indicator, such as arsenazo III, is immobilized on the substrate using a chemical binding process. The immobilized arsenazo III causes uranyl from a fluid sample to bind irreversibly to the substrate at its active sites, thus causing absorption of a portion of light transmitted through the substrate. Determination of the amount of light absorbed, using conventional means, yields the concentration of uranyl present in the sample fluid. The binding of uranyl on the substrate can be reversed by subsequent exposure of the substrate to a solution of 2,6-pyridinedicarboxylic acid. The chemical binding process is suitable for similarly binding other indicators, such as bromocresol green.

Carbon Nanotubes/Nanofibers by Plasma Enhanced Chemical Vapour Deposition

NASA Technical Reports Server (NTRS)

Teo, K. B. K.; Hash, D. B.; Bell, M. S.; Chhowalla, M.; Cruden, B. A.; Amaratunga, G. A. J.; Meyyappan, M.; Milne, W. I.

2005-01-01

Plasma enhanced chemical vapour deposition (PECVD) has been recently used for the production of vertically aligned carbon nanotubedfibers (CN) directly on substrates. These structures are potentially important technologically as electron field emitters (e.g. microguns, microwave amplifiers, displays), nanoelectrodes for sensors, filter media, superhydrophobic surfaces and thermal interface materials for microelectronics. A parametric study on the growth of CN grown by glow discharge dc-PECVD is presented. In this technique, a substrate containing thin film Ni catalyst is exposed to C2H2 and NH3 gases at 700 C. Without plasma, this process is essentially thermal CVD which produces curly spaghetti-like CN as seen in Fig. 1 (a). With the plasma generated by biasing the substrate at -6OOV, we observed that the CN align vertically during growth as shown in Fig. l(b), and that the magnitude of the applied substrate bias affects the degree of alignment. The thickness of the thin film Ni catalyst was found to determine the average diameter and inversely the length of the CN. The yield and density of the CN were controlled by the use of different diffusion barrier materials under the Ni catalyst. Patterned CN growth [Fig. l(c)], with la variation in CN diameter of 4.1% and 6.3% respectively, is achieved by lithographically defining the Ni thin film prior to growth. The shape of the structures could be varied from very straight nanotube-like to conical tip-like nanofibers by increasing the ratio of C2H2 in the gas flow. Due to the plasma decomposition of C2H2, amorphous carbon (a-C) is an undesirable byproduct which could coat the substrate during CN growth. Using a combination of depth profiled Auger electron spectroscopy to study the substrate and in-situ mass spectroscopy to examine gas phase neutrals and ions, the optimal conditions for a-C free growth of CN is determined.

Terminal Olefin Profiles and Phylogenetic Analyses of Olefin Synthases of Diverse Cyanobacterial Species.

PubMed

Zhu, Tao; Scalvenzi, Thibault; Sassoon, Nathalie; Lu, Xuefeng; Gugger, Muriel

2018-07-01

Cyanobacteria can synthesize alkanes and alkenes, which are considered to be infrastructure-compatible biofuels. In terms of physiological function, cyanobacterial hydrocarbons are thought to be essential for membrane flexibility for cell division, size, and growth. The genetic basis for the biosynthesis of terminal olefins (1-alkenes) is a modular type I polyketide synthase (PKS) termed olefin synthase (Ols). The modular architectures of Ols and structural characteristics of alkenes have been investigated only in a few species of the small percentage (approximately 10%) of cyanobacteria that harbor putative Ols pathways. In this study, investigations of the domains, modular architectures, and phylogenies of Ols in 28 cyanobacterial strains suggested distinctive pathway evolution. Structural feature analyses revealed 1-alkenes with three carbon chain lengths (C 15 , C 17 , and C 19 ). In addition, the total cellular fatty acid profile revealed the diversity of the carbon chain lengths, while the fatty acid feeding assay indicated substrate carbon chain length specificity of cyanobacterial Ols enzymes. Finally, in silico analyses suggested that the N terminus of the modular Ols enzyme exhibited characteristics typical of a fatty acyl-adenylate ligase (FAAL), suggesting a mechanism of fatty acid activation via the formation of acyl-adenylates. Our results shed new light on the diversity of cyanobacterial terminal olefins and a mechanism for substrate activation in the biosynthesis of these olefins. IMPORTANCE Cyanobacterial terminal olefins are hydrocarbons with promising applications as advanced biofuels. Despite the basic understanding of the genetic basis of olefin biosynthesis, the structural diversity and phylogeny of the key modular olefin synthase (Ols) have been poorly explored. An overview of the chemical structural traits of terminal olefins in cyanobacteria is provided in this study. In addition, we demonstrated by in vivo fatty acid feeding assays that cyanobacterial Ols enzymes might exhibit substrate carbon chain length specificity. Furthermore, by performing bioinformatic analyses, we observed that the substrate activation domain of Ols exhibited features typical of a fatty acyl-adenylate ligase (FAAL), which activates fatty acids by converting them to fatty acyl-adenylates. Our results provide further insight into the chemical structures of terminal olefins and further elucidate the mechanism of substrate activation for terminal olefin biosynthesis in cyanobacteria. Copyright © 2018 American Society for Microbiology.

Ordered to isotropic morphology transition in pattern-directed dewetting of polymer thin films on substrates with different feature heights.

PubMed

Roy, Sudeshna; Mukherjee, Rabibrata

2012-10-24

Controlled dewetting of a thin polymer film on a topographically patterned substrate is an interesting approach for aligning isotropic dewetted structures. In this article, we investigate the influence of substrate feature height (H(S)) on the dewetting pathway and final pattern morphology by studying the dewetting of polystyrene (PS) thin films on grating substrates with identical periodicity (λ(P) = 1.5 μm), but H(S) varying between 10 nm and 120 nm. We identify four distinct categories of final dewetted morphology, with different extent of ordering: (1) array of aligned droplets (H(S) ≈ 120 nm); (2) aligned undulating ribbons (H(S) ≈ 70-100 nm); (3) multilength scale structures with coexisting large droplets uncorrelated to the substrate and smaller droplets/ribbons aligned along the stripes (H(S) ≈ 40-60 nm); and (4) large droplets completely uncorrelated to the substrate (H(S) < 25 nm). The distinct morphologies across the categories are attributed to two major factors: (a) whether the as-cast film is continuous (H(S)≤ 80 nm) or discontinuous (H(S)≥ 100 nm) and (b) in case of a continuous film, whether the film ruptures along each substrate stripe (H(S)≥ 70 nm) or with nucleation of random holes that are not correlated to the substrate features (H(S)≤ 60 nm). While the ranges of H(S) values indicated in the parentheses are valid for PS films with an equivalent thickness (h(E)) ≈ 50.3 nm on a flat substrate, a change in h(E) merely alters the cut-off values of H(S), as the final dewetted morphologies and transition across categories remain generically unaltered. We finally show that the structures obtained by dewetting on different H(S) substrates exhibits different levels of hydrophobicity because of combined spatial variation of chemical and topographic contrast along the surface. Thus, the work reported in this article can find potential application in fabricating surfaces with controlled wettability.

A strategy for design and fabrication of low cost microchannel for future reproductivity of bio/chemical lab-on-chip application

NASA Astrophysics Data System (ADS)

Humayun, Q.; Hashim, U.; Ruzaidi, C. M.; Noriman, N. Z.

2017-03-01

The fabrication and characterization of sensitive and selective fluids delivery system for the application of nano laboratory on a single chip is a challenging task till to date. This paper is one of the initial attempt to resolve this challenging task by using a simple, cost effective and reproductive technique for pattering a microchannel structures on SU-8 resist. The objective of the research is to design, fabricate and characterize polydimethylsiloxane (PDMS) microchannel. The proposed device mask was designed initially by using AutoCAD software and then the designed was transferred to transparency sheet and to commercial chrome mask for better photo masking process. The standard photolithography process coupled with wet chemical etching process was used for the fabrication of proposed microchannel. This is a low cost fabrication technique for the formation of microchannel structure at resist. The fabrication process start from microchannel formation and then the structure was transformed to PDMS substrate, the microchannel structure was cured from mold and then the cured mold was bonded with the glass substrate by plasma oxidation bonding process. The surface morphology was characterized by high power microscope (HPM) and the structure was characterized by Hawk 3 D surface nanoprofiler. The next part of the research will be focus onto device testing and validation by using real biological samples by the implementation of a simple manual injection technique.

Interfacial Engineering of Nanoporous Architectures in Ga2O3 Film toward Self-Aligned Tubular Nanostructure with an Enhanced Photocatalytic Activity on Water Splitting.

PubMed

Shrestha, Nabeen K; Bui, Hoa Thi; Lee, Taegweon; Noh, Yong-Young

2018-04-17

The present work demonstrates the formation of self-aligned nanoporous architecture of gallium oxide by anodization of gallium metal film controlled at -15 °C in aqueous electrolyte consisting of phosphoric acid. SEM examination of the anodized film reveals that by adding ethylene glycol to the electrolyte and optimizing the ratio of phosphoric acid and water, chemical etching at the oxide/electrolyte interfaces can be controlled, leading to the formation of aligned nanotubular oxide structures with closed bottom. XPS analysis confirms the chemical composition of the oxide film as Ga 2 O 3 . Further, XRD and SAED examination reveals that the as-synthesized nanotubular structure is amorphous, and can be crystallized to β-Ga 2 O 3 phase by annealing the film at 600 °C. The nanotubular structured film, when used as photoanode for photoelectrochemical splitting of water, achieved a higher photocurrent of about two folds than that of the nanoporous film, demonstrating the rewarding effect of the nanotubular structure. In addition, the work also demonstrates the formation of highly organized nonporous Ga 2 O 3 structure on a nonconducting glass substrate coated with thin film of Ga-metal, highlighting that the current approach can be extended for the formation of self-organized nanoporous Ga 2 O 3 thin film even on nonconducting flexible substrates.

Analysis of the tertiary structure of the ribonuclease P ribozyme-substrate complex by site-specific photoaffinity crosslinking.

PubMed Central

Harris, M E; Kazantsev, A V; Chen, J L; Pace, N R

1997-01-01

Bacterial ribonuclease P (RNase P), an endonuclease involved in tRNA maturation, is a ribonucleoprotein containing a catalytic RNA. The secondary structure of this ribozyme is well-established, and a low-resolution model of the three-dimensional structure of the ribozyme-substrate complex has been proposed based on site-specific crosslinking and phylogenetic comparative data [Harris ME et al., 1994 EMBO J 13:3953-3963]. However, several substructures of that model were poorly constrained by the available data. In the present analysis, additional constraints between elements within the Escherichia coli RNase P RNA-pre-tRNA complex were determined by intra- and intermolecular crosslinking experiments. Circularly permuted RNase P RNAs were used to position an azidophenacyl photoactive crosslinking agent specifically at strategic sites within the ribozyme-substrate complex. Crosslink sites were mapped by primer extension and confirmed by analysis of the mobility of the crosslinked RNA lariats on denaturing acrylamide gels relative to circular and linear RNA standards. Crosslinked species generally retained significant catalytic activity, indicating that the results reflect the native ribozyme structure. The crosslinking results support the general configuration of the structure model and predicate new positions and orientations for helices that were previously poorly constrained by the data set. The expanded library of crosslinking constraints was used, together with secondary and tertiary structure identified by phylogenetic sequence comparisons, to refine significantly the model of RNase P RNA with bound substrate pre-tRNA. The crosslinking results and data from chemical-modification and mutational studies are discussed in the context of the current structural perspective on this ribozyme. PMID:9174092

Chemically synthesis and characterization of MnS thin films by SILAR method

NASA Astrophysics Data System (ADS)

Yıldırım, M. Ali; Yıldırım, Sümeyra Tuna; Cavanmirza, İlke; Ateş, Aytunç

2016-03-01

MnS thin films were synthesized on glass substrates using SILAR method. The film thickness effect on structural, morphological, optical and electrical properties of the films was investigated. The X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) studies showed that all the films exhibited polycrystalline nature with β-MnS structure and were covered well on glass substrates. The bandgap and resistivity values of the films decreased from 3.39 eV to 2.92 eV and from 11.84 × 106 to 2.21 × 105 Ω-cm as the film thickness increased from 180 to 350 nm, respectively. The refractive index (n) and dielectric constants (ɛo, ɛ∞) values were calculated.

Rebar Graphene from Functionalized Boron Nitride Nanotubes

PubMed Central

2015-01-01

The synthesis of rebar graphene on Cu substrates is described using functionalized boron nitride nanotubes (BNNTs) that were annealed or subjected to chemical vapor deposition (CVD) growth of graphene. Characterization shows that the BNNTs partially unzip and form a reinforcing bar (rebar) network within the graphene layer that enhances the mechanical strength through covalent bonds. The rebar graphene is transferrable to other substrates without polymer assistance. The optical transmittance and conductivity of the hybrid rebar graphene film was tested, and a field effect transistor was fabricated to explore its electrical properties. This method of synthesizing 2D hybrid graphene/BN structures should enable the hybridization of various 1D nanotube and 2D layered structures with enhanced mechanical properties. PMID:25486451

Attachment dynamics of Photosystem I on nano-tailored surfaces for photovoltaic applications

NASA Astrophysics Data System (ADS)

Mukherjee, Dibyendu; Bruce, Barry D.; Khomami, Bamin

2010-03-01

Photosystem I (PSI), a biological photodiode, is a supra-molecular protein complex that charge separates upon exposure to light. Effective use of photo-electrochemical activities of PSI for hybrid photovoltaic (PV) device fabrications requires optimal encapsulation of these proteins onto organic/ inorganic substrates. Our results indicate that various experimental parameters alter the surface attachment dynamics of PSI deposited from colloidal aqueous buffer suspensions onto OH-terminated alkanethiolate/Au SAM substrates, thereby resulting in complex structural arrangements which affect the electron transfer and capture pathway of PSI. We present surface topographical, specific adsorption and polarization fluorescence characterizations of PSI/Au SAM substrates to elucidate the protein-surface interaction kinetics as well as the directional attachment dynamics of PSI. Our final goal is to enable site-specific homogeneous attachment of directionally aligned PSI onto chemically tailored nano-patterned substrates.

Novel electrochemical nickel metallization in silicon impedance engineering for mixed-signal system-on-chip crosstalk isolation

NASA Astrophysics Data System (ADS)

Zhang, Xi

One of the major challenges for single chip radio frequency integrated circuits (RFIC's) built on Si is the RE crosstalk through the Si substrate. Noise from switching transient in digital circuits can be transmitted through Si substrate and degrades the performance of analog circuit elements. A highly conductive moat or Faraday cage type structure of through-the-wafer thickness in the Si substrate was demonstrated to be effective in shielding electromagnetic interference thereby reducing RE cross-talk in high performance mixed signal integrated circuits. Such a structure incorporated into the p- Si substrate was realized by electroless Ni metallization over selected regions with ultra-high-aspect-ratio macropores that was etched electrochemically in p- Si substrates. The metallization process was conducted by immersing the macroporous Si sample in an alkaline aqueous solution containing Ni2+ without a reducing agent. It was found that working at slightly elevated temperature, Ni 2+ was rapidly reduced and deposited in the macropores. During the wet chemical process, conformal metallization on the pore wall was achieved. The entire porous Si skeleton was gradually replaced by Ni along the extended duration of immersion. In a p-/p+ epi Si substrate used for high performance digital CMOS, the suppression of crosstalk by the arrayed metallic Ni via structure fabricated from the front p side was significant that the crosstalk went down to the noise floor of the conventional measurement instruments. The process and mechanism of forming such a Ni structure over the original Si were studied. Theoretical computation relevant to the process was carried out to show a good consistency with the experiments.

Patterning of supported gold monolayers via chemical lift-off lithography

PubMed Central

Slaughter, Liane S; Cheung, Kevin M; Kaappa, Sami; Cao, Huan H; Yang, Qing; Young, Thomas D; Serino, Andrew C; Malola, Sami; Olson, Jana M; Link, Stephan

2017-01-01

The supported monolayer of Au that accompanies alkanethiolate molecules removed by polymer stamps during chemical lift-off lithography is a scarcely studied hybrid material. We show that these Au–alkanethiolate layers on poly(dimethylsiloxane) (PDMS) are transparent, functional, hybrid interfaces that can be patterned over nanometer, micrometer, and millimeter length scales. Unlike other ultrathin Au films and nanoparticles, lifted-off Au–alkanethiolate thin films lack a measurable optical signature. We therefore devised fabrication, characterization, and simulation strategies by which to interrogate the nanoscale structure, chemical functionality, stoichiometry, and spectral signature of the supported Au–thiolate layers. The patterning of these layers laterally encodes their functionality, as demonstrated by a fluorescence-based approach that relies on dye-labeled complementary DNA hybridization. Supported thin Au films can be patterned via features on PDMS stamps (controlled contact), using patterned Au substrates prior to lift-off (e.g., selective wet etching), or by patterning alkanethiols on Au substrates to be reactive in selected regions but not others (controlled reactivity). In all cases, the regions containing Au–alkanethiolate layers have a sub-nanometer apparent height, which was found to be consistent with molecular dynamics simulations that predicted the removal of no more than 1.5 Au atoms per thiol, thus presenting a monolayer-like structure. PMID:29259879

Spatial and temporal distribution of benthic macroinvertebrates in a Southeastern Brazilian river.

PubMed

Silveira, M P; Buss, D F; Nessimian, J L; Baptista, D F

2006-05-01

Benthic macroinvertebrate assemblages are structured according to physical and chemical parameters that define microhabitats, including food supply, shelter to escape predators, and other biological parameters that influence reproductive success. The aim of this study is to investigate spatial and temporal distribution of macroinvertebrate assemblages at the Macaé river basin, in Rio de Janeiro state, Southeastern Brazil. According to the "Habitat Assessment Field Data Sheet--High Gradient Streams" (Barbour et al., 1999), the five sampling sites are considered as a reference condition. Despite the differences in hydrological parameters (mean width, depth and discharge) among sites, the physicochemical parameters and functional feeding groups' general structure were similar, except for the less impacted area, which showed more shredders. According to the Detrended Correspondence Analysis based on substrates, there is a clear distinction between pool and riffle assemblages. In fact, the riffle litter substrate had higher taxa in terms of richness and abundance, but the pool litter substrate had the greatest number of exclusive taxa. A Cluster Analysis based on sampling sites data showed that temporal variation was the main factor in structuring macroinvertebrate assemblages in the studied habitats.

Structural and elastoplastic properties of β -Ga2O3 films grown on hybrid SiC/Si substrates

NASA Astrophysics Data System (ADS)

Osipov, A. V.; Grashchenko, A. S.; Kukushkin, S. A.; Nikolaev, V. I.; Osipova, E. V.; Pechnikov, A. I.; Soshnikov, I. P.

2018-04-01

Structural and mechanical properties of gallium oxide films grown on (001), (011) and (111) silicon substrates with a buffer layer of silicon carbide are studied. The buffer layer was fabricated by the atom substitution method, i.e., one silicon atom per unit cell in the substrate was substituted by a carbon atom by chemical reaction with carbon monoxide. The surface and bulk structure properties of gallium oxide films have been studied by atomic-force microscopy and scanning electron microscopy. The nanoindentation method was used to investigate the elastoplastic characteristics of gallium oxide, and also to determine the elastic recovery parameter of the films under study. The ultimate tensile strength, hardness, elastic stiffness constants, elastic compliance constants, Young's modulus, linear compressibility, shear modulus, Poisson's ratio and other characteristics of gallium oxide have been calculated by quantum chemistry methods based on the PBESOL functional. It is shown that all these properties of gallium oxide are essentially anisotropic. The calculated values are compared with experimental data. We conclude that a change in the silicon orientation leads to a significant reorientation of gallium oxide.

Oxide mediated liquid-solid growth of high aspect ratio aligned gold silicide nanowires on Si(110) substrates.

PubMed

Bhatta, Umananda M; Rath, Ashutosh; Dash, Jatis K; Ghatak, Jay; Yi-Feng, Lai; Liu, Chuan-Pu; Satyam, P V

2009-11-18

Silicon nanowires grown using the vapor-liquid-solid method are promising candidates for nanoelectronics applications. The nanowires grow from an Au-Si catalyst during silicon chemical vapor deposition. In this paper, the effect of temperature, oxide at the interface and substrate orientation on the nucleation and growth kinetics during formation of nanogold silicide structures is explained using an oxide mediated liquid-solid growth mechanism. Using real time in situ high temperature transmission electron microscopy (with 40 ms time resolution), we show the formation of high aspect ratio ( approximately 15.0) aligned gold silicide nanorods in the presence of native oxide at the interface during in situ annealing of gold thin films on Si(110) substrates. Steps observed in the growth rate and real time electron diffraction show the existence of liquid Au-Si nano-alloy structures on the surface besides the un-reacted gold nanostructures. These results might enable us to engineer the growth of nanowires and similar structures with an Au-Si alloy as a catalyst.

Influence of substrate rocks on Fe Mn crust composition

NASA Astrophysics Data System (ADS)

Hein, James R.; Morgan, Charles L.

1999-05-01

Principal Component and other statistical analyses of chemical and mineralogical data of Fe-Mn oxyhydroxide crusts and their underlying rock substrates in the central Pacific indicate that substrate rocks do not influence crust composition. Two ridges near Johnston Atoll were dredged repetitively and up to seven substrate rock types were recovered from small areas of similar water depths. Crusts were analyzed mineralogically and chemically for 24 elements, and substrates were analyzed mineralogically and chemically for the 10 major oxides. Compositions of crusts on phosphatized substrates are distinctly different from crusts on substrates containing no phosphorite. However, that relationship only indicates that the episodes of phosphatization that mineralized the substrate rocks also mineralized the crusts that grew on them. A two-fold increase in copper contents in crusts that grew on phosphatized clastic substrate rocks, relative to crusts on other substrate rock types, is also associated with phosphatization and must have resulted from chemical reorganization during diagenesis. Phosphatized crusts show increases in Sr, Zn, Ca, Ba, Cu, Ce, V, and Mo contents and decreases in Fe, Si, and As contents relative to non-phosphatized crusts. Our statistical results support previous studies which show that crust compositions reflect predominantly direct precipitation from seawater (hydrogenetic), and to lesser extents reflect detrital input and diagenetic replacement of parts of the older crust generation by carbonate fluorapatite.

Influence of substrate rocks on Fe-Mn crust composition

USGS Publications Warehouse

Hein, J.R.; Morgan, C.L.

1999-01-01

Principal Component and other statistical analyses of chemical and mineralogical data of Fe-Mn oxyhydroxide crusts and their underlying rock substrates in the central Pacific indicate that substrate rocks do not influence crust composition. Two ridges near Johnston Atoll were dredged repetitively and up to seven substrate rock types were recovered from small areas of similar water depths. Crusts were analyzed mineralogically and chemically for 24 elements, and substrates were analyzed mineralogically and chemically for the 10 major oxides. Compositions of crusts on phosphatized substrates are distinctly different from crusts on substrates containing no phosphorite. However, that relationship only indicates that the episodes of phosphatization that mineralized the substrate rocks also mineralized the crusts that grew on them. A two-fold increase in copper contents in crusts that grew on phosphatized clastic substrate rocks, relative to crusts on other substrate rock types, is also associated with phosphatization and must have resulted from chemical reorganization during diagenesis. Phosphatized crusts show increases in Sr, Zn, Ca, Ba, Cu, Ce, V, and Mo contents and decreases in Fe, Si, and As contents relative to non-phosphatized crusts. Our statistical results support previous studies which show that crust compositions reflect predominantly direct precipitation from seawater (hydrogenetic), and to lesser extents reflect detrital input and diagenetic replacement of parts of the older crust generation by carbonate fluorapatite.

Indistinguishability and identifiability of kinetic models for the MurC reaction in peptidoglycan biosynthesis.

PubMed

Hattersley, J G; Pérez-Velázquez, J; Chappell, M J; Bearup, D; Roper, D; Dowson, C; Bugg, T; Evans, N D

2011-11-01

An important question in Systems Biology is the design of experiments that enable discrimination between two (or more) competing chemical pathway models or biological mechanisms. In this paper analysis is performed between two different models describing the kinetic mechanism of a three-substrate three-product reaction, namely the MurC reaction in the cytoplasmic phase of peptidoglycan biosynthesis. One model involves ordered substrate binding and ordered release of the three products; the competing model also assumes ordered substrate binding, but with fast release of the three products. The two versions are shown to be distinguishable; however, if standard quasi-steady-state assumptions are made distinguishability cannot be determined. Once model structure uniqueness is ensured the experimenter must determine if it is possible to successfully recover rate constant values given the experiment observations, a process known as structural identifiability. Structural identifiability analysis is carried out for both models to determine which of the unknown reaction parameters can be determined uniquely, or otherwise, from the ideal system outputs. This structural analysis forms an integrated step towards the modelling of the full pathway of the cytoplasmic phase of peptidoglycan biosynthesis. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Retuning Rieske-type Oxygenases to Expand Substrate Range

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohammadi, Mahmood; Viger, Jean-François; Kumar, Pravindra

2012-09-17

Rieske-type oxygenases are promising biocatalysts for the destruction of persistent pollutants or for the synthesis of fine chemicals. In this work, we explored pathways through which Rieske-type oxygenases evolve to expand their substrate range. BphAE{sub p4}, a variant biphenyl dioxygenase generated from Burkholderia xenovorans LB400 BphAE{sub LB400} by the double substitution T335A/F336M, and BphAE{sub RR41}, obtained by changing Asn{sup 338}, Ile{sup 341}, and Leu{sup 409} of BphAE{sub p4} to Gln{sup 338}, Val{sup 341}, and Phe{sup 409}, metabolize dibenzofuran two and three times faster than BphAE{sub LB400}, respectively. Steady-state kinetic measurements of single- and multiple-substitution mutants of BphAE{sub LB400} showed thatmore » the single T335A and the double N338Q/L409F substitutions contribute significantly to enhanced catalytic activity toward dibenzofuran. Analysis of crystal structures showed that the T335A substitution relieves constraints on a segment lining the catalytic cavity, allowing a significant displacement in response to dibenzofuran binding. The combined N338Q/L409F substitutions alter substrate-induced conformational changes of protein groups involved in subunit assembly and in the chemical steps of the reaction. This suggests a responsive induced fit mechanism that retunes the alignment of protein atoms involved in the chemical steps of the reaction. These enzymes can thus expand their substrate range through mutations that alter the constraints or plasticity of the catalytic cavity to accommodate new substrates or that alter the induced fit mechanism required to achieve proper alignment of reaction-critical atoms or groups.« less

Evolutionarily Conserved Linkage between Enzyme Fold, Flexibility, and Catalysis

PubMed Central

Ramanathan, Arvind; Agarwal, Pratul K.

2011-01-01

Proteins are intrinsically flexible molecules. The role of internal motions in a protein's designated function is widely debated. The role of protein structure in enzyme catalysis is well established, and conservation of structural features provides vital clues to their role in function. Recently, it has been proposed that the protein function may involve multiple conformations: the observed deviations are not random thermodynamic fluctuations; rather, flexibility may be closely linked to protein function, including enzyme catalysis. We hypothesize that the argument of conservation of important structural features can also be extended to identification of protein flexibility in interconnection with enzyme function. Three classes of enzymes (prolyl-peptidyl isomerase, oxidoreductase, and nuclease) that catalyze diverse chemical reactions have been examined using detailed computational modeling. For each class, the identification and characterization of the internal protein motions coupled to the chemical step in enzyme mechanisms in multiple species show identical enzyme conformational fluctuations. In addition to the active-site residues, motions of protein surface loop regions (>10 Å away) are observed to be identical across species, and networks of conserved interactions/residues connect these highly flexible surface regions to the active-site residues that make direct contact with substrates. More interestingly, examination of reaction-coupled motions in non-homologous enzyme systems (with no structural or sequence similarity) that catalyze the same biochemical reaction shows motions that induce remarkably similar changes in the enzyme–substrate interactions during catalysis. The results indicate that the reaction-coupled flexibility is a conserved aspect of the enzyme molecular architecture. Protein motions in distal areas of homologous and non-homologous enzyme systems mediate similar changes in the active-site enzyme–substrate interactions, thereby impacting the mechanism of catalyzed chemistry. These results have implications for understanding the mechanism of allostery, and for protein engineering and drug design. PMID:22087074

Evolutionarily conserved linkage between enzyme fold, flexibility, and catalysis.

PubMed

Ramanathan, Arvind; Agarwal, Pratul K

2011-11-01

Proteins are intrinsically flexible molecules. The role of internal motions in a protein's designated function is widely debated. The role of protein structure in enzyme catalysis is well established, and conservation of structural features provides vital clues to their role in function. Recently, it has been proposed that the protein function may involve multiple conformations: the observed deviations are not random thermodynamic fluctuations; rather, flexibility may be closely linked to protein function, including enzyme catalysis. We hypothesize that the argument of conservation of important structural features can also be extended to identification of protein flexibility in interconnection with enzyme function. Three classes of enzymes (prolyl-peptidyl isomerase, oxidoreductase, and nuclease) that catalyze diverse chemical reactions have been examined using detailed computational modeling. For each class, the identification and characterization of the internal protein motions coupled to the chemical step in enzyme mechanisms in multiple species show identical enzyme conformational fluctuations. In addition to the active-site residues, motions of protein surface loop regions (>10 Å away) are observed to be identical across species, and networks of conserved interactions/residues connect these highly flexible surface regions to the active-site residues that make direct contact with substrates. More interestingly, examination of reaction-coupled motions in non-homologous enzyme systems (with no structural or sequence similarity) that catalyze the same biochemical reaction shows motions that induce remarkably similar changes in the enzyme-substrate interactions during catalysis. The results indicate that the reaction-coupled flexibility is a conserved aspect of the enzyme molecular architecture. Protein motions in distal areas of homologous and non-homologous enzyme systems mediate similar changes in the active-site enzyme-substrate interactions, thereby impacting the mechanism of catalyzed chemistry. These results have implications for understanding the mechanism of allostery, and for protein engineering and drug design.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramanathan, Arvind; Agarwal, Pratul K

Proteins are intrinsically flexible molecules. The role of internal motions in a protein's designated function is widely debated. The role of protein structure in enzyme catalysis is well established, and conservation of structural features provides vital clues to their role in function. Recently, it has been proposed that the protein function may involve multiple conformations: the observed deviations are not random thermodynamic fluctuations; rather, flexibility may be closely linked to protein function, including enzyme catalysis. We hypothesize that the argument of conservation of important structural features can also be extended to identification of protein flexibility in interconnection with enzyme function.more » Three classes of enzymes (prolyl-peptidyl isomerase, oxidoreductase, and nuclease) that catalyze diverse chemical reactions have been examined using detailed computational modeling. For each class, the identification and characterization of the internal protein motions coupled to the chemical step in enzyme mechanisms in multiple species show identical enzyme conformational fluctuations. In addition to the active-site residues, motions of protein surface loop regions (>10 away) are observed to be identical across species, and networks of conserved interactions/residues connect these highly flexible surface regions to the active-site residues that make direct contact with substrates. More interestingly, examination of reaction-coupled motions in non-homologous enzyme systems (with no structural or sequence similarity) that catalyze the same biochemical reaction shows motions that induce remarkably similar changes in the enzyme substrate interactions during catalysis. The results indicate that the reaction-coupled flexibility is a conserved aspect of the enzyme molecular architecture. Protein motions in distal areas of homologous and non-homologous enzyme systems mediate similar changes in the active-site enzyme substrate interactions, thereby impacting the mechanism of catalyzed chemistry. These results have implications for understanding the mechanism of allostery, and for protein engineering and drug design.« less

In-Silico Analysis of Binding Site Features and Substrate Selectivity in Plant Flavonoid-3-O Glycosyltransferases (F3GT) through Molecular Modeling, Docking and Dynamics Simulation Studies

PubMed Central

Sharma, Ranu; Panigrahi, Priyabrata; Suresh, C.G.

2014-01-01

Flavonoids are a class of plant secondary metabolites that act as storage molecules, chemical messengers, as well as participate in homeostasis and defense processes. They possess pharmaceutical properties important for cancer treatment such as antioxidant and anti-tumor activities. The drug-related properties of flavonoids can be improved by glycosylation. The enzymes glycosyltransferases (GTs) glycosylate acceptor molecules in a regiospecific manner with the help of nucleotide sugar donor molecules. Several plant GTs have been characterized and their amino acid sequences determined. However, three-dimensional structures of only a few are reported. Here, phylogenetic analysis using amino acid sequences have identified a group of GTs with the same regiospecific activity. The structures of these closely related GTs were modeled using homologous GT structures. Their substrate binding sites were elaborated by docking flavonoid acceptor and UDP-sugar donor molecules in the modeled structures. Eight regions near the acceptor binding site in the N- and C- terminal domain of GTs have been identified that bind and specifically glycosylate the 3-OH group of acceptor flavonoids. Similarly, a conserved motif in the C-terminal domain is known to bind a sugar donor substrate. In certain GTs, the substitution of a specific glutamine by histidine in this domain changes the preference of sugar from glucose to galactose as a result of changed pattern of interactions. The molecular modeling, docking, and molecular dynamics simulation studies have revealed the chemical and topological features of the binding site and thus provided insights into the basis of acceptor and donor recognition by GTs. PMID:24667893

Substrate temperature effect on the structural anisotropy in amorphous Tb-Fe films

NASA Astrophysics Data System (ADS)

Harris, V. G.; Hellman, F.; Elam, W. T.; Koon, N. C.

1993-05-01

Using extended x-ray absorption fine structures (EXAFS) measurements we have investigated the atomic environment around the Fe atom in a series of amorphous Tb0.26Fe0.74 films having different magnetic anisotropy energies owing to different deposition temperatures. The polarization properties of synchrotron radiation allowed the separate study of structure parallel and perpendicular to the sample plane. An anisotropy between these two structures was observed. Modeling results indicate this anisotropy is due to anisotropic pair correlations where the Fe-Fe pairs are statistically preferred in-plane and the Fe-Tb pairs out-of-plane. The amplitude of this anisotropy scales with both the substrate temperature and the magnetic anisotropy energy. A ≊1% in-plane compression of the Fe-Fe distance was measured between the in-plane and out-of-plane structure of the sample grown at 77 K. This sample had no detectable local chemical anisotropy suggesting that intrinsic stress plays an important role in determining its magnetic anisotropy.

Natural Populations of Shipworm Larvae Are Attracted to Wood by Waterborne Chemical Cues

PubMed Central

Toth, Gunilla B.; Larsson, Ann I.; Jonsson, Per R.; Appelqvist, Christin

2015-01-01

The life cycle of many sessile marine invertebrates includes a dispersive planktonic larval stage whose ability to find a suitable habitat in which to settle and transform into benthic adults is crucial to maximize fitness. To facilitate this process, invertebrate larvae commonly respond to habitat-related chemical cues to guide the search for an appropriate environment. Furthermore, small-scale hydrodynamic conditions affect dispersal of chemical cues, as well as swimming behavior of invertebrate larvae and encounter with potential habitats. Shipworms within the family Teredinidae are dependent on terrestrially derived wood in order to complete their life cycle, but very little is known about the cues and processes that promote settlement. We investigated the potential for remote detection of settling substrate via waterborne chemical cues in teredinid larvae through a combination of empirical field and laboratory flume experiments. Natural populations of teredinid larvae were significantly more abundant close to wooden structures enclosed in plankton net compared to empty control nets, clearly showing that shipworm larvae can sense and respond to chemical cues associated with suitable settling substrate in the field. However, the flume experiments, using ecologically relevant flow velocities, showed that the boundary layer around experimental wooden panels was thin and that the mean flow velocity exceeded larval swimming velocity approximately 5 mm (≈ 25 larval body lengths) from the panel surface. Therefore, we conclude that the scope for remote detection of waterborne cues is limited and that the likely explanation for the higher abundance of shipworm larvae associated with the wooden panels in the field is a response to a cue during or after attachment on, or very near, the substrate. Waterborne cues probably guide the larva in its decision to remain attached and settle, or to detach and continue swimming and drifting until the next encounter with a solid substrate. PMID:25970270

Tungsten-encapsulated gadolinium nanoislands with enhanced magnetocaloric response

DOE PAGES

Logan, Jonathan M.; Rosenmann, Daniel; Sangpo, Tenzin; ...

2017-07-03

Here, we report a method for growing chemically pure, oxide-free, air-stable Gd nanoislands with enhanced magnetic properties. These nanoislands are grown by solid-state dewetting and are fully encapsulated in tungsten such that they remain stable in ambient environments. They display good crystalline properties with hexagonally close-packed crystal structure and strong preferential orientation. We show that the choice of substrate strongly affects their shape, crystal orientation, and magnetic properties. The temperature-dependent magnetic coercivity and remanence of the Gd islands can vary by as much as a factor of three depending on the substrate used. The magneto- caloric properties of Gd islandsmore » grown on a sapphire substrate exceed those of high-quality Gd thin films.« less

Effect of growth parameters on crystallinity and properties of ZnO films grown by plasma assisted MOCVD

NASA Astrophysics Data System (ADS)

Losurdo, M.; Giangregorio, M. M.; Sacchetti, A.; Capezzuto, P.; Bruno, G.; Malandrino, G.; Fragalà, I. L.

2007-07-01

Thin films of ZnO have been grown by plasma assisted metal-organic chemical vapour deposition (PA-MOCVD) using a 13.56 MHz O 2 plasma and the Zn(TTA)•tmed (HTTA=2-thenoyltrifluoroacetone, TMED=N,N,N',N'-tetramethylethylendiamine) precursor. The effects of growth parameters such as the plasma activation, the substrate, the surface temperature, and the ratio of fluxes of precursors on the structure, morphology, and optical and electrical properties of ZnO thin films have been studied. Under a very low plasma power of 20 W, c-axis oriented hexagonal ZnO thin films are grown on hexagonal sapphire (0001), cubic Si(001) and amorphous quartz substrates. The substrate temperature mainly controls grain size.

The structural basis of secondary active transport mechanisms.

PubMed

Forrest, Lucy R; Krämer, Reinhard; Ziegler, Christine

2011-02-01

Secondary active transporters couple the free energy of the electrochemical potential of one solute to the transmembrane movement of another. As a basic mechanistic explanation for their transport function the model of alternating access was put forward more than 40 years ago, and has been supported by numerous kinetic, biochemical and biophysical studies. According to this model, the transporter exposes its substrate binding site(s) to one side of the membrane or the other during transport catalysis, requiring a substantial conformational change of the carrier protein. In the light of recent structural data for a number of secondary transport proteins, we analyze the model of alternating access in more detail, and correlate it with specific structural and chemical properties of the transporters, such as their assignment to different functional states in the catalytic cycle of the respective transporter, the definition of substrate binding sites, the type of movement of the central part of the carrier harboring the substrate binding site, as well as the impact of symmetry on fold-specific conformational changes. Besides mediating the transmembrane movement of solutes, the mechanism of secondary carriers inherently involves a mechanistic coupling of substrate flux to the electrochemical potential of co-substrate ions or solutes. Mainly because of limitations in resolution of available transporter structures, this important aspect of secondary transport cannot yet be substantiated by structural data to the same extent as the conformational change aspect. We summarize the concepts of coupling in secondary transport and discuss them in the context of the available evidence for ion binding to specific sites and the impact of the ions on the conformational state of the carrier protein, which together lead to mechanistic models for coupling. Copyright © 2010 Elsevier B.V. All rights reserved.

Direct dry transfer of CVD graphene to an optical substrate by in situ photo-polymerization

NASA Astrophysics Data System (ADS)

Kessler, Felipe; Muñoz, Pablo A. R.; Phelan, Ciaran; Romani, Eric C.; Larrudé, Dunieskys R. G.; Freire, Fernando L.; Thoroh de Souza, Eunézio A.; de Matos, Christiano J. S.; Fechine, Guilhermino J. M.

2018-05-01

Here, we report on a method that allows graphene produced by chemical vapor deposition (CVD) to be directly transferred to an optically transparent photo resin, by in situ photo-polymerization of the latter, with high efficiency and low contamination. Two photocurable resins, A and B, with different viscosities but essentially the same chemical structure, were used. Raman spectroscopy and surface energy results show that large continuous areas of graphene were transferred with minimal defects to the lower viscosity resin (B), due to the better contact between the resin and graphene. As a proof-of-principle optical experiment, graphene on the polymeric substrate was subjected to high-intensity femtosecond infrared pulses and third-harmonic generation was observed with no noticeable degradation of the sample. A sheet third-order susceptibility χ (3) = 0.71 ×10-28m3V-2 was obtained, matching that of graphene on a glass substrate. These results indicate the suitability of the proposed transfer method, and of the photo resin, for the production of nonlinear photonic components and devices.

The Barrier Properties of PET Coated DLC Film Deposited by Microwave Surface-Wave PECVD

NASA Astrophysics Data System (ADS)

Yin, Lianhua; Chen, Qiang

2017-12-01

In this paper we report the investigation of diamond-like carbon (DLC) deposited by microwave surface-wave plasma enhanced chemical vapor deposition (PECVD) on the polyethylene terephthalate (PET) web for the purpose of the barrier property improvement. In order to characterize the properties of DLC coatings, we used several substrates, silicon wafer, glass, and PET web and KBr tablet. The deposition rate was obtained by surface profiler based on the DLC deposited on glass substrates; Fourier transform infrared spectroscope (FTIR) was carried out on KBr tablets to investigate chemical composition and bonding structure; the morphology of the DLC coating was analyzed by atomic force microscope (AFM) on Si substrates. For the barrier properties of PET webs, we measured the oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) after coated with DLC films. We addressed the film barrier property related to process parameters, such as microwave power and pulse parameter in this work. The results show that the DLC coatings can greatly improve the barrier properties of PET webs.

Scalable high-mobility MoS2 thin films fabricated by an atmospheric pressure chemical vapor deposition process at ambient temperature

NASA Astrophysics Data System (ADS)

Huang, Chung-Che; Al-Saab, Feras; Wang, Yudong; Ou, Jun-Yu; Walker, John C.; Wang, Shuncai; Gholipour, Behrad; Simpson, Robert E.; Hewak, Daniel W.

2014-10-01

Nano-scale MoS2 thin films are successfully deposited on a variety of substrates by atmospheric pressure chemical vapor deposition (APCVD) at ambient temperature, followed by a two-step annealing process. These annealed MoS2 thin films are characterized with scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), micro-Raman, X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-VIS-NIR spectrometry, photoluminescence (PL) and Hall Effect measurement. Key optical and electronic properties of APCVD grown MoS2 thin films are determined. This APCVD process is scalable and can be easily incorporated with conventional lithography as the deposition is taking place at room temperature. We also find that the substrate material plays a significant role in the crystalline structure formation during the annealing process and single crystalline MoS2 thin films can be achieved by using both c-plane ZnO and c-plane sapphire substrates. These APCVD grown nano-scale MoS2 thin films show great promise for nanoelectronic and optoelectronic applications.

Homology modelling of Drosophila cytochrome P450 enzymes associated with insecticide resistance.

PubMed

Jones, Robert T; Bakker, Saskia E; Stone, Deborah; Shuttleworth, Sally N; Boundy, Sam; McCart, Caroline; Daborn, Phillip J; ffrench-Constant, Richard H; van den Elsen, Jean M H

2010-10-01

Overexpression of the cytochrome P450 gene Cyp6g1 confers resistance against DDT and a broad range of other insecticides in Drosophila melanogaster Meig. In the absence of crystal structures of CYP6G1 or complexes with its substrates, structural studies rely on homology modelling and ligand docking to understand P450-substrate interactions. Homology models are presented for CYP6G1, a P450 associated with resistance to DDT and neonicotinoids, and two other enzymes associated with insecticide resistance in D. melanogaster, CYP12D1 and CYP6A2. The models are based on a template of the X-ray structure of the phylogenetically related human CYP3A4, which is known for its broad substrate specificity. The model of CYP6G1 has a much smaller active site cavity than the template. The cavity is also 'V'-shaped and is lined with hydrophobic residues, showing high shape and chemical complementarity with the molecular characteristics of DDT. Comparison of the DDT-CYP6G1 complex and a non-resistant CYP6A2 homology model implies that tight-fit recognition of this insecticide is important in CYP6G1. The active site can accommodate differently shaped substrates ranging from imidacloprid to malathion but not the pyrethroids permethrin and cyfluthrin. The CYP6G1, CYP12D1 and CYP6A2 homology models can provide a structural insight into insecticide resistance in flies overexpressing P450 enzymes with broad substrate specificities.

Electrochemically deposited gallium oxide nanostructures on silicon substrates

PubMed Central

2014-01-01

We report a synthesis of β-Ga2O3 nanostructures on Si substrate by electrochemical deposition using a mixture of Ga2O3, HCl, NH4OH, and H2O. The presence of Ga3+ ions contributed to the deposition of Ga2O3 nanostructures on the Si surface with the assistance of applied potentials. The morphologies of the grown structures strongly depended on the molarity of Ga2O3 and pH level of electrolyte. β-Ga2O3 nanodot-like structures were grown on Si substrate at a condition with low molarity of Ga2O3. However, Ga2O3 nanodot structures covered with nanorods on top of their surfaces were obtained at higher molarity, and the densities of nanorods seem to increase with the decrease of pH level. High concentration of Ga3+ and OH- ions may promote the reaction of each other to produce Ga2O3 nanorods in the electrolyte. Such similar nature of Ga2O3 nanorods was also obtained by using hydrothermal process. The grown structures seem to be interesting for application in electronic and optoelectronic devices as well as to be used as a seed structure for subsequent chemical synthesis of GaN by thermal transformation method. PMID:24629107

An in vivo study of the biocompatibility of classic and novel device materials on the central nervous system

NASA Astrophysics Data System (ADS)

Jaboro, Claudine

2007-12-01

Investigation of novel biomaterials is an essential part of the development of electrical stimulation and chemical drug delivery for biomedical applications. In evaluating biocompatibility, the material's surface and the tissue should both be analyzed to determine their interaction during neural exposure. This includes a material investigation of bulk sapphire substrate, platinum (Pt) deposited on sapphire substrate using magnetron sputtering and aluminum nitride (AlN) which was deposited on sapphire substrate using plasma source molecular beam epitaxy (PSMBE). Zinc titania coverslip glass and borosilicate glass were used as control materials. The materials were implanted for periods of 10, 28 and 90 days on the cortical surface of the brain in a rat animal model. The chronic implants were analyzed both pre- and post- implantation for device structure/tissue interactions down to the atomic level. The characterization techniques used to explore structural and chemical changes on or within the material included optical microscopy, atomic force microscopy (AFM) and x-ray photoelectron spectroscopy (XPS). Magnetic Resonance Imaging (MRI) and histology were used to determine the effects of the implants in vivo. Biocompatibility is the ability of a material or device to be exposed to the dynamic environment of the body and elicit little or no adverse effects. The data suggests that the biocompatibility of a material may be directly associated with structure and topology. The sapphire, zinc titania coverslip glass and platinum all had signs of bio-incompatibility. The aluminum nitride and borosilicate glass materials were both biocompatible based on our studies. The borosilicate glass elicited no response from the tissue while the aluminum nitride had a positive affect on the tissue encouraging the attachment of proteins and tissue without glial scars instigation. The material characterization, MR imaging and histological data show that surface features such as roughness in addition to chemical stability may have a direct effect on the neurocompatibility of the chronic implants.

Aluminum concentration and substrate temperature in chemical sprayed ZnO:Al thin solid films

NASA Astrophysics Data System (ADS)

Lozada, Erick Velázquez; Castañeda, L.; Aguilar, E. Austria

2018-02-01

The continuous interest in the synthesis and properties study of materials has permitted the development of semiconductor oxides. Zinc oxide (ZnO) with hexagonal wurzite structure is a wide band gap n-type semiconductor and interesting material over a wide range. Chemically sprayed aluminium-doped zinc oxide thin films (ZnO:Al) were deposited on soda-lime glass substrates starting from zinc pentanedionate and aluminium pentanedionate. The influence of both the dopant concentration in the starting solution and the substrate temperature on the composition, morphology, and transport properties of the ZnO:Al thin films were studied. The structure of all the ZnO:Al thin films was polycrystalline, and variation in the preferential growth with the aluminium content in the solution was observed: from an initial (002) growth in films with low Al content, switching to a predominance of (101) planes for heavily dopant regime. The crystallite size was found to decrease with doping concentration and range from 33 to 20 nm. First-order Raman scattering from ZnO:Al, all having the wurtzite structure. The assignments of the E2 mode in ZnO:Al differ from previous investigations. The film composition and the dopant concentration were determined by Auger Electron Spectroscopy (AES); these results showed that the films are almost stoichiometric ZnO. The optimum deposition conditions leading to conductive and transparent ZnO:Al thin films were also found. In this way a resistivity of 0.03 Ω-cm with a (002) preferential growth, were obtained in optimized ZnO:Al thin films.

High catalytic activity of Au/CeOx/TiO2(110) controlled by the nature of the mixed-metal oxide at the nanometer level.

PubMed

Park, Joon B; Graciani, Jesus; Evans, Jaime; Stacchiola, Dario; Ma, Shuguo; Liu, Ping; Nambu, Akira; Sanz, Javier Fernández; Hrbek, Jan; Rodriguez, José A

2009-03-31

Mixed-metal oxides play a very important role in many areas of chemistry, physics, materials science, and geochemistry. Recently, there has been a strong interest in understanding phenomena associated with the deposition of oxide nanoparticles on the surface of a second (host) oxide. Here, scanning tunneling microscopy, photoemission, and density-functional calculations are used to study the behavior of ceria nanoparticles deposited on a TiO(2)(110) surface. The titania substrate imposes nontypical coordination modes on the ceria nanoparticles. In the CeO(x)/TiO(2)(110) systems, the Ce cations adopt an structural geometry and an oxidation state (+3) that are quite different from those seen in bulk ceria or for ceria nanoparticles deposited on metal substrates. The increase in the stability of the Ce(3+) oxidation state leads to an enhancement in the chemical and catalytic activity of the ceria nanoparticles. The codeposition of ceria and gold nanoparticles on a TiO(2)(110) substrate generates catalysts with an extremely high activity for the production of hydrogen through the water-gas shift reaction (H(2)O + CO --> H(2) + CO(2)) or for the oxidation of carbon monoxide (2CO + O(2) --> 2CO(2)). The enhanced stability of the Ce(3+) state is an example of structural promotion in catalysis described here on the atomic level. The exploration of mixed-metal oxides at the nanometer level may open avenues for optimizing catalysts through stabilization of unconventional surface structures with special chemical activity.

Limiting Size of Monolayer Graphene Flakes Grown on Silicon Carbide or via Chemical Vapor Deposition on Different Substrates

NASA Astrophysics Data System (ADS)

Alekseev, N. I.

2018-05-01

The maximum size of homogeneous monolayer graphene flakes that form during the high-temperature evaporation of silicon from a surface of SiC or during graphene synthesis via chemical vapor deposition is estimated, based on the theoretical calculations developed in this work. Conditions conducive to the fragmentation of a monolayer graphene sheet to form discrete fragments or terrace-type structures in which excess energy due to dangling bonds at the edges is compensated for by the lack of internal stress are indentified and described. The results from calculations for the sizes of graphene structures are compared with experimental findings for the most successful graphene syntheses reported in the literature.

Snapshots of C-S Cleavage in Egt2 Reveals Substrate Specificity and Reaction Mechanism.

PubMed

Irani, Seema; Naowarojna, Nathchar; Tang, Yang; Kathuria, Karan R; Wang, Shu; Dhembi, Anxhela; Lee, Norman; Yan, Wupeng; Lyu, Huijue; Costello, Catherine E; Liu, Pinghua; Zhang, Yan Jessie

2018-05-17

Sulfur incorporation in the biosynthesis of ergothioneine, a histidine thiol derivative, differs from other well-characterized transsulfurations. A combination of a mononuclear non-heme iron enzyme-catalyzed oxidative C-S bond formation and a subsequent pyridoxal 5'-phosphate (PLP)-mediated C-S lyase reaction leads to the net transfer of a sulfur atom from a cysteine to a histidine. In this study, we structurally and mechanistically characterized a PLP-dependent C-S lyase Egt2, which mediates the sulfoxide C-S bond cleavage in ergothioneine biosynthesis. A cation-π interaction between substrate and enzyme accounts for Egt2's preference of sulfoxide over thioether as a substrate. Using mutagenesis and structural biology, we captured three distinct states of the Egt2 C-S lyase reaction cycle, including a labile sulfenic intermediate captured in Egt2 crystals. Chemical trapping and high-resolution mass spectrometry were used to confirm the involvement of the sulfenic acid intermediate in Egt2 catalysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

Multi-junction solar cell device

DOEpatents

Friedman, Daniel J.; Geisz, John F.

2007-12-18

A multi-junction solar cell device (10) is provided. The multi-junction solar cell device (10) comprises either two or three active solar cells connected in series in a monolithic structure. The multi-junction device (10) comprises a bottom active cell (20) having a single-crystal silicon substrate base and an emitter layer (23). The multi-junction device (10) further comprises one or two subsequent active cells each having a base layer (32) and an emitter layer (23) with interconnecting tunnel junctions between each active cell. At least one layer that forms each of the top and middle active cells is composed of a single-crystal III-V semiconductor alloy that is substantially lattice-matched to the silicon substrate (22). The polarity of the active p-n junction cells is either p-on-n or n-on-p. The present invention further includes a method for substantially lattice matching single-crystal III-V semiconductor layers with the silicon substrate (22) by including boron and/or nitrogen in the chemical structure of these layers.

Structural basis for catalysis at the membrane-water interface.

PubMed

Dufrisne, Meagan Belcher; Petrou, Vasileios I; Clarke, Oliver B; Mancia, Filippo

2017-11-01

The membrane-water interface forms a uniquely heterogeneous and geometrically constrained environment for enzymatic catalysis. Integral membrane enzymes sample three environments - the uniformly hydrophobic interior of the membrane, the aqueous extramembrane region, and the fuzzy, amphipathic interfacial region formed by the tightly packed headgroups of the components of the lipid bilayer. Depending on the nature of the substrates and the location of the site of chemical modification, catalysis may occur in each of these environments. The availability of structural information for alpha-helical enzyme families from each of these classes, as well as several beta-barrel enzymes from the bacterial outer membrane, has allowed us to review here the different ways in which each enzyme fold has adapted to the nature of the substrates, products, and the unique environment of the membrane. Our focus here is on enzymes that process lipidic substrates. This article is part of a Special Issue entitled: Bacterial Lipids edited by Russell E. Bishop. Copyright © 2016 Elsevier B.V. All rights reserved.

Ferrocene pixels by laser-induced forward transfer: towards flexible microelectrode printing

NASA Astrophysics Data System (ADS)

Mitu, B.; Matei, A.; Filipescu, M.; Palla Papavlu, A.; Bercea, A.; Lippert, T.; Dinescu, M.

2017-03-01

The aim of this work is to demonstrate the potential of laser-induced forward transfer (LIFT) as a printing technology, alternative to standard microfabrication techniques, in the area of flexible micro-electrode fabrication. First, ferrocene thin films are deposited onto fused silica and fused silica substrates previously coated with a photodegradable polymer film (triazene polymer) by matrix assisted pulsed laser evaporation (MAPLE). The morphology and chemical structure of the ferrocene thin films deposited by MAPLE has been investigated by atomic force microscopy and Fourier transformed infrared spectroscopy, and no structural damage occurs as a result of the laser deposition. Second, LIFT is applied to print for the first time ferrocene pixels and lines onto flexible polydimethylsiloxane (PDMS) substrates. The ferrocene pixels and lines are flawlessly transferred onto the PDMS substrates in air at room temperature, without the need of additional conventional photolithography processes. We believe that these results are very promising for a variety of applications ranging from flexible electronics to lab-on-a-chip devices, MEMS, and medical implants.

Ferroelectric domain structure of anisotropically strained NaNbO3 epitaxial thin films

NASA Astrophysics Data System (ADS)

Schwarzkopf, J.; Braun, D.; Schmidbauer, M.; Duk, A.; Wördenweber, R.

2014-05-01

NaNbO3 thin films have been grown under anisotropic biaxial strain on several oxide substrates by liquid-delivery spin metalorganic chemical vapor deposition. Compressive lattice strain of different magnitude, induced by the deposition of NaNbO3 films with varying film thickness on NdGaO3 single crystalline substrates, leads to modifications of film orientation and phase symmetry, which are similar to the phase transitions in Pb-containing oxides near the morphotropic phase boundary. Piezoresponse force microscopy measurements exhibit large out-of-plane polarization components, but no distinctive domain structure, while C-V measurements indicate relaxor properties in these films. When tensile strain is provoked by the epitaxial growth on DyScO3, TbScO3, and GdScO3 single crystalline substrates, NaNbO3 films behave rather like a normal ferroelectric. The application of these rare-earth scandate substrates yields well-ordered ferroelectric stripe domains of the type a1/a2 with coherent domain walls aligned along the [001] substrate direction as long as the films are fully strained. With increasing plastic lattice relaxation, initially, a 2D domain pattern with still exclusively in-plane electric polarization, and finally, domains with in-plane and out-of-plane polar components evolve.

A self-assembled synthesis of carbon nanotubes for interconnects.

PubMed

Chen, Zexiang; Cao, Guichuan; Lin, Zulun; Koehler, Irmgard; Bachmann, Peter K

2006-02-28

We report a novel approach to grow highly oriented, freestanding and structured carbon nanotubes (CNTs) between two substrates, using microwave plasma chemical vapour deposition. Sandwiched, multi-layered catalyst structures are employed to generate such structures. The as-grown CNTs adhere well to both the substrate and the top contact, and provide a low-resistance electric contact between the two. High-resolution scanning electron microscope (SEM) images show that the CNTs grow perpendicular to these surfaces. This presents a simple way to grow CNTs in different, predetermined directions in a single growth step. The overall resistance of a CNT bundle and two CNT-terminal contacts is measured to be about 14.7 k Ω. The corresponding conductance is close to the quantum limit conductance G(0). This illustrates that our new approach is promising for the direct assembly of CNT-based interconnects in integrated circuits (ICs) or other micro-electronic devices.

Hydride vapor phase epitaxy of high structural perfection thick AlN layers on off-axis 6H-SiC

NASA Astrophysics Data System (ADS)

Volkova, Anna; Ivantsov, Vladimir; Leung, Larry

2011-01-01

The employment of more than 10 μm thick AlN epilayers on SiC substrates for AlGaN/GaN high-electron-mobility transistors (HEMTs) substantially raises their performance in high-power energy-efficient amplifiers for 4G wireless mobile stations. In this paper, structural properties and surface morphology of thick AlN epilayers deposited by hydride vapor phase epitaxy (HVPE) on off-axis conductive 6H-SiC substrates are reported. The epilayers were examined in detail by high-resolution X-ray diffraction (XRD), atomic force microscopy (AFM), Nomarski differential interference contrast (DIC), scanning electron microscopy (SEM), and selective wet chemical etching. At optimal substrate preparation and growth conditions, a full width at half-maximum (FWHM) of the XRD rocking curve (RC) for the symmetric (00.2) reflex was very close to that of the substrate (less than 40 arcsec) suggesting low screw dislocation density in the epilayer (˜10 6 cm -2) and small in-plane tilt misorientation. Reciprocal space mapping around asymmetric reflexes and measured lattice parameters indicated a fully relaxed state of the epilayers. The unit-cell-high stepped areas of the epilayers with 0.5 nm root mean square (RMS) roughness over 1×1 μm 2 scan were alternated with step-bunching instabilities up to 350 nm in height. Low warp of the substrates makes them suitable for precise epitaxy of HEMT structures.

Influence of substrate misorientation on the photoluminescence and structural properties of InGaAs/GaAsP multiple quantum wells

NASA Astrophysics Data System (ADS)

Dong, Hailiang; Sun, Jing; Ma, Shufang; Liang, Jian; Lu, Taiping; Liu, Xuguang; Xu, Bingshe

2016-03-01

InGaAs/GaAsP multiple quantum wells (MQWs) were grown by metal-organic chemical vapor deposition on vicinal GaAs (001) substrates with different miscut angles of 0°, 2° and 15° towards [110]. The crystal structures of InGaAs/GaAsP were characterized by high-resolution X-ray diffraction and Raman spectroscopy. The surface morphologies of InGaAs/GaAsP MQWs were observed by atomic force microscopy. The mechanisms for step flow, step bunching and pyramid growth on 0°, 2° and 15° misoriented substrates were discussed. The results provide a comprehensive phenomenological understanding of the self-ordering mechanism of vicinal GaAs substrates, which could be harnessed for designing the quantum optical properties of low-dimensional systems. From low-temperature photoluminescence, it was observed that the luminescence from the MQWs grown on a vicinal surface exhibits a red-shift with respect to the 0° case. An extra emission was observed from the 2° and 15° off samples, indicating the characteristics of quantum wire and pyramidal self-controlled quantum-dot systems, respectively. Its absence from the PL spectrum on 0° surfaces indicates that indium segregation is modified on the surfaces. The relationship between InGaAs/GaAsP MQWs grown on vicinal substrates and their optical and structural properties was explained, which provides a technological basis for obtaining different self-controlled nanostructures.

Chemical probing of the human sirtuin 5 active site reveals its substrate acyl specificity and peptide-based inhibitors.

PubMed

Roessler, Claudia; Nowak, Theresa; Pannek, Martin; Gertz, Melanie; Nguyen, Giang T T; Scharfe, Michael; Born, Ilona; Sippl, Wolfgang; Steegborn, Clemens; Schutkowski, Mike

2014-09-26

Sirtuins are NAD(+)-dependent deacetylases acting as sensors in metabolic pathways and stress response. In mammals there are seven isoforms. The mitochondrial sirtuin 5 is a weak deacetylase but a very efficient demalonylase and desuccinylase; however, its substrate acyl specificity has not been systematically analyzed. Herein, we investigated a carbamoyl phosphate synthetase 1 derived peptide substrate and modified the lysine side chain systematically to determine the acyl specificity of Sirt5. From that point we designed six potent peptide-based inhibitors that interact with the NAD(+) binding pocket. To characterize the interaction details causing the different substrate and inhibition properties we report several X-ray crystal structures of Sirt5 complexed with these peptides. Our results reveal the Sirt5 acyl selectivity and its molecular basis and enable the design of inhibitors for Sirt5. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Growth of gallium nitride and indium nitride nanowires on conductive and flexible carbon cloth substrates.

PubMed

Yang, Yi; Ling, Yichuan; Wang, Gongming; Lu, Xihong; Tong, Yexiang; Li, Yat

2013-03-07

We report a general strategy for synthesis of gallium nitride (GaN) and indium nitride (InN) nanowires on conductive and flexible carbon cloth substrates. GaN and InN nanowires were prepared via a nanocluster-mediated growth method using a home built chemical vapor deposition (CVD) system with Ga and In metals as group III precursors and ammonia as a group V precursor. Electron microscopy studies reveal that the group III-nitride nanowires are single crystalline wurtzite structures. The morphology, density and growth mechanism of these nanowires are determined by the growth temperature. Importantly, a photoelectrode fabricated by contacting the GaN nanowires through a carbon cloth substrate shows pronounced photoactivity for photoelectrochemical water oxidation. The ability to synthesize group III-nitride nanowires on conductive and flexible substrates should open up new opportunities for nanoscale photonic, electronic and electrochemical devices.

Substrate tunnels in enzymes: structure-function relationships and computational methodology.

PubMed

Kingsley, Laura J; Lill, Markus A

2015-04-01

In enzymes, the active site is the location where incoming substrates are chemically converted to products. In some enzymes, this site is deeply buried within the core of the protein, and, in order to access the active site, substrates must pass through the body of the protein via a tunnel. In many systems, these tunnels act as filters and have been found to influence both substrate specificity and catalytic mechanism. Identifying and understanding how these tunnels exert such control has been of growing interest over the past several years because of implications in fields such as protein engineering and drug design. This growing interest has spurred the development of several computational methods to identify and analyze tunnels and how ligands migrate through these tunnels. The goal of this review is to outline how tunnels influence substrate specificity and catalytic efficiency in enzymes with buried active sites and to provide a brief summary of the computational tools used to identify and evaluate these tunnels. © 2015 Wiley Periodicals, Inc.

Fabrication of non-hexagonal close packed colloidal array on a substrate by transfer

NASA Astrophysics Data System (ADS)

Banik, Meneka; Mukherjee, Rabibrata

Self-organized colloidal arrays find application in fabrication of solar cells with advanced light management strategies. We report a simple spincoating based approach for fabricating two dimensional colloidal crystals with hexagonal and non-hexagonal close packed assembly on flat and nanopatterned substrates. The non-HCP arrays were fabricated by spin coating the particles onto soft lithographically fabricated substrates. The substrate patterns impose directionality to the particles by confining them within the grooves. We have developed a technique by which the HCP and non-HCP arrays can be transferred to any surface. For this purpose the colloidal arrays were fabricated on a UV degradable PMMA layer, resulting in transfer of the particles on UV exposure. This allows the colloidal structures to be transported across substrates irrespective of their surface energy, wettability or morphology. Since the particles are transferred without exposing it to any kind of chemical or thermal environment, it can be utilized for placing particles on top of thin film solar cells for improving their absorption efficiency.

Substrate Tunnels in Enzymes: Structure-Function Relationships and Computational Methodology

PubMed Central

Kingsley, Laura J.; Lill, Markus A.

2015-01-01

In enzymes, the active site is the location where incoming substrates are chemically converted to products. In some enzymes, this site is deeply buried within the core of the protein and in order to access the active site, substrates must pass through the body of the protein via a tunnel. In many systems, these tunnels act as filters and have been found to influence both substrate specificity and catalytic mechanism. Identifying and understanding how these tunnels exert such control has been of growing interest over the past several years due to implications in fields such as protein engineering and drug design. This growing interest has spurred the development of several computational methods to identify and analyze tunnels and how ligands migrate through these tunnels. The goal of this review is to outline how tunnels influence substrate specificity and catalytic efficiency in enzymes with tunnels and to provide a brief summary of the computational tools used to identify and evaluate these tunnels. PMID:25663659

Nanoscale infrared absorption spectroscopy of individual nanoparticles enabled by scattering-type near-field microscopy.

PubMed

Stiegler, Johannes M; Abate, Yohannes; Cvitkovic, Antonija; Romanyuk, Yaroslav E; Huber, Andreas J; Leone, Stephen R; Hillenbrand, Rainer

2011-08-23

Infrared absorption spectroscopy is a powerful and widely used tool for analyzing the chemical composition and structure of materials. Because of the diffraction limit, however, it cannot be applied for studying individual nanostructures. Here we demonstrate that the phase contrast in substrate-enhanced scattering-type scanning near-field optical microscopy (s-SNOM) provides a map of the infrared absorption spectrum of individual nanoparticles with nanometer-scale spatial resolution. We succeeded in the chemical identification of silicon nitride nanoislands with heights well below 10 nm, by infrared near-field fingerprint spectroscopy of the Si-N stretching bond. Employing a novel theoretical model, we show that the near-field phase spectra of small particles correlate well with their far-field absorption spectra. On the other hand, the spectral near-field contrast does not scale with the volume of the particles. We find a nearly linear scaling law, which we can attribute to the near-field coupling between the near-field probe and the substrate. Our results provide fundamental insights into the spectral near-field contrast of nanoparticles and clearly demonstrate the capability of s-SNOM for nanoscale chemical mapping based on local infrared absorption. © 2011 American Chemical Society

In Vitro Screening of Environmental Chemicals Identifies Zearalenone as a Novel Substrate of the Placental BCRP/ABCG2 Transporter

PubMed Central

Xiao, Jingcheng; Wang, Qi; Bircsak, Kristin M.; Wen, Xia; Aleksunes, Lauren M.

2015-01-01

The BCRP (ABCG2) transporter is responsible for the efflux of chemicals from the placenta to the maternal circulation. Inhibition of BCRP activity could enhance exposure of offspring to environmental chemicals leading to altered reproductive, endocrine, and metabolic development. The purpose of this study was to characterize environmental chemicals as potential substrates and inhibitors of the human placental BCRP transporter. The interaction of BCRP with a panel of environmental chemicals was assessed using the ATPase and inverted plasma membrane vesicle assays as well as a cell-based fluorescent substrate competition assay. Human HEK cells transfected with wild-type BCRP or the Q141K genetic variant, as well as BeWo placental cells that endogenously express BCRP were used to further test inhibitor and substrate interactions. To varying degrees, the eleven chemicals inhibited BCRP activity in activated ATPase membranes and inverted membrane vesicles. Further, genistein, zearalenone, and tributyltin increased the retention of the fluorescent BCRP substrate, Hoechst 33342, between 50–100% in BeWo cells. Additional experiments characterized the mycotoxin and environmental estrogen, zearalenone, as a novel substrate and inhibitor of BCRP in WT-BCRP and BeWo cells. Interestingly, the BCRP genetic variant Q141K exhibited reduced efflux of zearalenone compared to the wild-type protein. Taken together, screening assays and direct quantification experiments identified zearalenone as a novel human BCRP substrate. Additional in vivo studies are needed to directly determine whether placental BCRP prevents fetal exposure to zearalenone. PMID:26052432

Review of SERS Substrates for Chemical Sensing

PubMed Central

Mosier-Boss, Pamela A.

2017-01-01

The SERS effect was initially discovered in the 1970s. Early research focused on understanding the phenomenon and increasing enhancement to achieve single molecule detection. From the mid-1980s to early 1990s, research started to move away from obtaining a fundamental understanding of the phenomenon to the exploration of analytical applications. At the same time, significant developments occurred in the field of photonics that led to the advent of inexpensive, robust, compact, field-deployable Raman systems. The 1990s also saw rapid development in nanoscience. This convergence of technologies (photonics and nanoscience) has led to accelerated development of SERS substrates to detect a wide range of chemical and biological analytes. It would be a monumental task to discuss all the different kinds of SERS substrates that have been explored. Likewise, it would be impossible to discuss the use of SERS for both chemical and biological detection. Instead, a review of the most common metallic (Ag, Cu, and Au) SERS substrates for chemical detection only is discussed, as well as SERS substrates that are commercially available. Other issues with SERS for chemical detection have been selectivity, reversibility, and reusability of the substrates. How these issues have been addressed is also discussed in this review. PMID:28594385

Semiconductor Laser Diode Arrays by MOCVD (Metalorganic Chemical Vapor Deposition)

DTIC Science & Technology

1987-09-01

laser diode arrays are intended to be used as an optical pump for solid state yttrium aluminum garnet (YAG) lasers. In particular, linear uniform...corresponds to about . , 8080A. Such thin layer structures, while difficult to grow by such conventional growth methods as liquid phase epitaxy ( LPE ...lower yet than for DH lasers grown by LPE . , - Conventional self-aligned stripe laser This structure is formed by growing (on an n-type GaAs substrate

Atomic structures of Ruddlesden-Popper faults in LaCoO3/SrRuO3 multilayer thin films induced by epitaxial strain

NASA Astrophysics Data System (ADS)

Wang, Wei; Zhang, Hui; Shen, Xi; Guan, Xiangxiang; Yao, Yuan; Wang, Yanguo; Sun, Jirong; Yu, Richeng

2018-05-01

In this paper, scanning transmission electron microscopy is used to study the microstructures of the defects in LaCoO3/SrRuO3 multilayer films grown on the SrTiO3 substrates, and these films have different thickness of SrRuO3 (SRO) layers. Several types of Ruddlesden-Popper (R.P.) faults at an atomic level are found, and these chemical composition fluctuations in the growth process are induced by strain fields originating from the film-film and film-substrate lattice mismatches. Furthermore, we propose four types of structural models based on the atomic arrangements of the R.P. planar faults, which severely affect the functional properties of the films.

Spontaneous grafting of diazonium salts: chemical mechanism on metallic surfaces.

PubMed

Mesnage, Alice; Lefèvre, Xavier; Jégou, Pascale; Deniau, Guy; Palacin, Serge

2012-08-14

The spontaneous reaction of diazonium salts on various substrates has been widely employed since it consists of a simple immersion of the substrate in the diazonium salt solution. As electrochemical processes involving the same diazonium salts, the spontaneous grafting is assumed to give covalently poly(phenylene)-like bonded films. Resistance to solvents and to ultrasonication is commonly accepted as indirect proof of the existence of a covalent bond. However, the most relevant attempts to demonstrate a metal-C interface bond have been obtained by an XPS investigation of spontaneously grafted films on copper. Similarly, our experiments give evidence of such a bond in spontaneously grafted films on nickel substrates in acetonitrile. In the case of gold substrates, the formation of a spontaneous film was unexpected but reported in the literature in parallel to our observations. Even if no interfacial bond was observed, formation of the films was explained by grafting of aryl cations or radicals on the surface arising from dediazoniation, the film growing later by azo coupling, radical addition, or cationic addition on the grafted phenyl layer. Nevertheless, none of these mechanisms fits our experimental results showing the presence of an Au-N bond. In this work, we present a fine spectroscopic analysis of the coatings obtained on gold and nickel substrates that allow us to propose a chemical structure of such films, in particular, their interface with the substrates. After testing the most probable mechanisms, we have concluded in favor of the involvement of two complementary mechanisms which are the direct reaction of diazonium salts with the gold surface that accounts for the observed Au-N interfacial bonds as well as the formation of aryl cations able to graft on the substrate through Au-C linkages.

Antimony sulfide thin films prepared by laser assisted chemical bath deposition

NASA Astrophysics Data System (ADS)

Shaji, S.; Garcia, L. V.; Loredo, S. L.; Krishnan, B.; Aguilar Martinez, J. A.; Das Roy, T. K.; Avellaneda, D. A.

2017-01-01

Antimony sulfide (Sb2S3) thin films were prepared by laser assisted chemical bath deposition (LACBD) technique. These thin films were deposited on glass substrates from a chemical bath containing antimony chloride, acetone and sodium thiosulfate under various conditions of normal chemical bath deposition (CBD) as well as in-situ irradiation of the chemical bath using a continuous laser of 532 nm wavelength. Structure, composition, morphology, optical and electrical properties of the Sb2S3 thin films produced by normal CBD and LACBD were analyzed by X-Ray diffraction (XRD), Raman Spectroscopy, Atomic force microscopy (AFM), X-Ray photoelectron spectroscopy (XPS), UV-vis spectroscopy and Photoconductivity. The results showed that LACBD is an effective synthesis technique to obtain Sb2S3 thin films for optoelectronic applications.

Detecting Below-Ground Processes, Diversity, and Ecosystem Function in a Savanna Ecosystem Using Spectroscopy Across Different Vegetation Layers

NASA Astrophysics Data System (ADS)

Cavender-Bares, J.; Schweiger, A. K.; Madritch, M. D.; Gamon, J. A.; Hobbie, S. E.; Montgomery, R.; Townsend, P. A.

2017-12-01

Above-and below-ground plant traits are important for substrate input to the rhizosphere. The substrate composition of the rhizosphere, in turn, affects the diversity of soil organisms, influences soil biochemistry, and water content, and resource availability for plant growth. This has substantial consequences for ecosystem functions, such as above-ground productivity and stability. Above-ground plant chemical and structural traits can be linked to the characteristics of other plant organs, including roots. Airborne imaging spectroscopy has been successfully used to model and predict chemical and structural traits of the above-ground vegetation. However, remotely sensed images capture, almost exclusively, signals from the top of the canopy, providing limited direct information about understory vegetation. Here, we use a data set collected in a savanna ecosystem consisting of spectral measurements gathered at the leaf, the whole plant, and vegetation canopy level to test for hypothesized linkages between above- and below-ground processes that influence root biomass, soil biochemistry, and the diversity of the soil community. In this environment, consisting of herbaceous vegetation intermixed with shrubs and trees growing at variable densities, we investigate the contribution of different vegetation strata to soil characteristics and test the ability of imaging spectroscopy to detect these in plant communities with contrasting vertical structure.

Light beam shaping and homogenization (LSBH) by irregular microlens structure for medical applications

NASA Astrophysics Data System (ADS)

Semchishen, Vladimir A.; Mrochen, Michael; Seminogov, Vladimir N.; Panchenko, Vladislav Y.; Seiler, Theo

1998-04-01

Purpose: The increasing interest in a homogeneous Gaussian light beam profile for applications in ophthalmology e.g. photorefractive keratectomy (PRK) requests simple optical systems with low energy losses. Therefore, we developed the Light Shaping Beam Homogenizer (LSBH) working from UV up to mid-IR. Method: The irregular microlenses structure on a quartz surface was fabricated by using photolithography, chemical etching and chemical polishing processes. This created a three dimensional structure on the quartz substrate characterized in case of a Gaussian beam by random law distribution of individual irregularities tilts. The LSBH was realized for the 193 nm and the 2.94 micrometer wavelengths. Simulation results obtained by 3-D analysis for an arbitrary incident light beam were compared to experimental results. Results: The correlation to a numerical Gaussian fit is better than 94% with high uniformity for an incident beam with an intensity modulation of nearly 100%. In the far field the cross section of the beam shows always rotation symmetry. Transmittance and damage threshold of the LSBH are only dependent on the substrate characteristics. Conclusions: considering our experimental and simulation results it is possible to control the angular distribution of the beam intensity after LSBH with higher efficiency compared to diffraction or holographic optical elements.

Design and isolation of ribozyme-substrate pairs using RNase P-based ribozymes containing altered substrate binding sites.

PubMed Central

Mobley, E M; Pan, T

1999-01-01

Substrate recognition and cleavage by the bacterial RNase P RNA requires two domains, a specificity domain, or S-domain, and a catalytic domain, or C-domain. The S-domain binds the T stem-loop region in a pre-tRNA substrate to confer specificity for tRNA substrates. In this work, the entire S-domain of the Bacillus subtilis RNase P RNA is replaced with an artificial substrate binding module. New RNA substrates are isolated by in vitro selection using two libraries containing random regions of 60 nt. At the end of the selection, the cleavage rates of the substrate library are approximately 0.7 min(-1)in 10 mM MgCl(2)at 37 degrees C, approximately 4-fold better than the cleavage of a pre-tRNA substrate by the wild-type RNase P RNA under the same conditions. The contribution of the S-domain replacement to the catalytic efficiency is from 6- to 22 000-fold. Chemical and nuclease mapping of two ribozyme-product complexes shows that this contribution correlates with direct interactions between the S-domain replacement and the selected substrate. These results demonstrate the feasibility of design and isolation of RNase P-based, matching ribozyme-substrate pairs without prior knowledge of the sequence or structure of the interactive modules in the ribozyme or substrate. PMID:10518624

Preparation of dilute magnetic semiconductor films by metalorganic chemical vapor deposition

NASA Technical Reports Server (NTRS)

Nouhi, Akbar (Inventor); Stirn, Richard J. (Inventor)

1988-01-01

A method for preparation of a dilute magnetic semiconductor (DMS) film is provided, in which a Group II metal source, a Group VI metal source and a transition metal magnetic ion source are pyrolyzed in the reactor of a metalorganic chemical vapor deposition (MOCVD) system by contact with a heated substrate. As an example, the preparation of films of Cd(sub 1-x)Mn(sub x)Te, in which 0 is less than or equal to x less than or equal to 0.7, on suitable substrates (e.g., GaAs) is described. As a source of manganese, tricarbonyl (methylcyclopentadienyl) manganese (TCPMn) is employed. To prevent TCPMn condensation during its introduction into the reactor, the gas lines, valves and reactor tubes are heated. A thin-film solar cell of n-i-p structure, in which the i-type layer comprises a DMS, is also described; the i-type layer is suitably prepared by MOCVD.

Preparation of dilute magnetic semiconductor films by metalorganic chemical vapor deposition

NASA Technical Reports Server (NTRS)

Nouhi, Akbar (Inventor); Stirn, Richard J. (Inventor)

1990-01-01

A method for preparation of a dilute magnetic semiconductor (DMS) film is provided, wherein a Group II metal source, a Group VI metal source and a transition metal magnetic ion source are pyrolyzed in the reactor of a metalorganic chemical vapor deposition (MOCVD) system by contact with a heated substrate. As an example, the preparation of films of Cd.sub.1-x Mn.sub.x Te, wherein 0.ltoreq..times..ltoreq.0.7, on suitable substrates (e.g., GaAs) is described. As a source of manganese, tricarbonyl (methylcyclopentadienyl) maganese (TCPMn) is employed. To prevent TCPMn condensation during the introduction thereof int the reactor, the gas lines, valves and reactor tubes are heated. A thin-film solar cell of n-i-p structure, wherein the i-type layer comprises a DMS, is also described; the i-type layer is suitably prepared by MOCVD.

VO2 Thermochromic Films on Quartz Glass Substrate Grown by RF-Plasma-Assisted Oxide Molecular Beam Epitaxy

PubMed Central

Zhang, Dong; Sun, Hong-Jun; Wang, Min-Huan; Miao, Li-Hua; Liu, Hong-Zhu; Zhang, Yu-Zhi; Bian, Ji-Ming

2017-01-01

Vanadium dioxide (VO2) thermochromic thin films with various thicknesses were grown on quartz glass substrates by radio frequency (RF)-plasma assisted oxide molecular beam epitaxy (O-MBE). The crystal structure, morphology and chemical stoichiometry were investigated systemically by X-ray diffraction (XRD), atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) analyses. An excellent reversible metal-to-insulator transition (MIT) characteristics accompanied by an abrupt change in both electrical resistivity and optical infrared (IR) transmittance was observed from the optimized sample. Remarkably, the transition temperature (TMIT) deduced from the resistivity-temperature curve was reasonably consistent with that obtained from the temperature-dependent IR transmittance. Based on Raman measurement and XPS analyses, the observations were interpreted in terms of residual stresses and chemical stoichiometry. This achievement will be of great benefit for practical application of VO2-based smart windows. PMID:28772673

Low Al-composition p-GaN/Mg-doped Al0.25Ga0.75N/n+-GaN polarization-induced backward tunneling junction grown by metal-organic chemical vapor deposition on sapphire substrate

PubMed Central

Zhang, Kexiong; Liang, Hongwei; Liu, Yang; Shen, Rensheng; Guo, Wenping; Wang, Dongsheng; Xia, Xiaochuan; Tao, Pengcheng; Yang, Chao; Luo, Yingmin; Du, Guotong

2014-01-01

Low Al-composition p-GaN/Mg-doped Al0.25Ga0.75N/n+-GaN polarization-induced backward tunneling junction (PIBTJ) was grown by metal-organic chemical vapor deposition on sapphire substrate. A self-consistent solution of Poisson-Schrödinger equations combined with polarization-induced theory was used to model PIBTJ structure, energy band diagrams and free carrier concentrations distribution. The PIBTJ displays reliable and reproducible backward tunneling with a current density of 3 A/cm2 at the reverse bias of −1 V. The absence of negative differential resistance behavior of PIBTJ at forward bias can mainly be attributed to the hole compensation centers, including C, H and O impurities, accumulated at the p-GaN/Mg-doped AlGaN heterointerface. PMID:25205042

Doping-stabilized two-dimensional black phosphorus.

PubMed

Xuan, Xiaoyu; Zhang, Zhuhua; Guo, Wanlin

2018-05-03

Two-dimensional (2D) black phosphorus (BP) has attracted broad interests but remains to be synthesized. One of the issues lies in its large number of 2D allotropes with highly degenerate energies, especially 2D blue phosphorus. Here, we show that both nitrogen and hole-carrier doping can lift the energy degeneracy and locate 2D BP in a deep global energy minimum, while arsenic doping favours the formation of 2D blue phosphorus, attributed to a delicate interplay between s-p overlapping and repulsion of lone pairs. Chemically inert substrates, e.g. graphene and hexagonal boron nitride, can be synergic with carrier doping to stabilize the BP further over other 2D allotropes, while frequently used metal substrates severely reduce the stability of 2D BP. These results not only offer new insight into the structural stability of 2D phosphorus but also suggest a promising pathway towards the chemical synthesis of 2D BP.

Facile fabrication of homogeneous 3D silver nanostructures on gold-supported polyaniline membranes as promising SERS substrates.

PubMed

Xu, Ping; Mack, Nathan H; Jeon, Sea-Ho; Doorn, Stephen K; Han, Xijiang; Wang, Hsing-Lin

2010-06-01

We report a facile synthesis of large-area homogeneous three-dimensional (3D) Ag nanostructures on Au-supported polyaniline (PANI) membranes through a direct chemical reduction of metal ions by PANI. The citric acid absorbed on the Au nuclei that are prefabricated on PANI membranes directs Ag nanoaprticles (AgNPs) to self-assemble into 3D Ag nanosheet structures. The fabricated hybrid metal nanostructures display uniform surface-enhanced Raman scattering (SERS) responses throughout the whole surface area, with an average enhancement factor of 10(6)-10(7). The nanocavities formed by the stereotypical stacking of these Ag nanosheets and the junctions and gaps between two neighboring AgNPs are believed to be responsible for the strong SERS response upon plasmon absorption. These homogeneous metal nanostructure decorated PANI membranes can be used as highly efficient SERS substrates for sensitive detection of chemical and biological analytes.

Click chemistry modification of natural keratin fibers for sustained shrink-resist performance.

PubMed

Yu, Dan; Cai, Jackie Y; Church, Jeffrey S; Wang, Lijing

2015-01-01

This paper introduces a novel chemical treatment for achieving sustained shrink-resist performance on natural keratin fibers. The new treatment involves the controlled reduction of keratin in the cuticle region of the fiber, and the application of a water soluble diacrylate, namely glycerol 1,3-diglycerolate diacrylate (GDA), on the reduced keratin substrate. The acrylate groups of the GDA react with cysteine residues in the reduced keratin through thiol-ene click reactions at room temperature, leading to GDA grafting and the formation of GDA crosslinks in the keratin structure. The modified substrates were characterized by infrared spectroscopy and scanning electron microscopy, and assessed for its shrink-resistance and wet burst strength. This chemical modification has shown to alter the fiber surface morphology and hydrophilicity, resulting in substantially improved shrink-resistance with good fiber strength retention. Possible shrink-resistance mechanisms were also discussed. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

Low Al-composition p-GaN/Mg-doped Al0.25Ga0.75N/n+-GaN polarization-induced backward tunneling junction grown by metal-organic chemical vapor deposition on sapphire substrate.

PubMed

Zhang, Kexiong; Liang, Hongwei; Liu, Yang; Shen, Rensheng; Guo, Wenping; Wang, Dongsheng; Xia, Xiaochuan; Tao, Pengcheng; Yang, Chao; Luo, Yingmin; Du, Guotong

2014-09-10

Low Al-composition p-GaN/Mg-doped Al0.25Ga0.75N/n(+)-GaN polarization-induced backward tunneling junction (PIBTJ) was grown by metal-organic chemical vapor deposition on sapphire substrate. A self-consistent solution of Poisson-Schrödinger equations combined with polarization-induced theory was used to model PIBTJ structure, energy band diagrams and free carrier concentrations distribution. The PIBTJ displays reliable and reproducible backward tunneling with a current density of 3 A/cm(2) at the reverse bias of -1 V. The absence of negative differential resistance behavior of PIBTJ at forward bias can mainly be attributed to the hole compensation centers, including C, H and O impurities, accumulated at the p-GaN/Mg-doped AlGaN heterointerface.

Fabricating and Controlling Silicon Zigzag Nanowires by Diffusion-Controlled Metal-Assisted Chemical Etching Method.

PubMed

Chen, Yun; Zhang, Cheng; Li, Liyi; Tuan, Chia-Chi; Wu, Fan; Chen, Xin; Gao, Jian; Ding, Yong; Wong, Ching-Ping

2017-07-12

Silicon (Si) zigzag nanowires (NWs) have a great potential in many applications because of its high surface/volume ratio. However, fabricating Si zigzag NWs has been challenging. In this work, a diffusion-controlled metal-assisted chemical etching method is developed to fabricate Si zigzag NWs. By tailoring the composition of etchant to change its diffusivity, etching direction, and etching time, various zigzag NWs can be easily fabricated. In addition, it is also found that a critical length of NW (>1 μm) is needed to form zigzag nanowires. Also, the amplitude of zigzag increases as the location approaches the center of the substrate and the length of zigzag nanowire increases. It is also demonstrated that such zigzag NWs can help the silicon substrate for self-cleaning and antireflection. This method may provide a feasible and economical way to fabricate zigzag NWs and novel structures for broad applications.

Comparing the ice nucleation efficiencies of ice nucleating substrates to natural mineral dusts

NASA Astrophysics Data System (ADS)

Steinke, Isabelle; Funk, Roger; Höhler, Kristina; Haarig, Moritz; Hoffmann, Nadine; Hoose, Corinna; Kiselev, Alexei; Möhler, Ottmar; Leisner, Thomas

2014-05-01

Mineral dust particles in the atmosphere may act as efficient ice nuclei over a wide range of temperature and relative humidity conditions. The ice nucleation capability of dust particles mostly depends on the particle surface area and the associated physico-chemical surface properties. It has been observed that the surface-related ice nucleation efficiency of different dust particles and mineral species can vary by several orders of magnitude. However, the relation between aerosol surface properties and observed ice nucleation efficiency is still not completely understood due to the large variability of chemical compositions and morphological features. In order to gain a better understanding of small scale freezing processes, we investigated the freezing of several hundreds of small droplets (V=0.4 nl) deposited on materials with reasonably well defined surfaces such as crystalline silicon wafers, graphite and freshly cleaved mica sheets under atmospherically relevant conditions. These substrates are intended to serve as simple model structures compared to the surface of natural aerosol particles. To learn more about the impact of particle morphology on ice nucleation processes, we also investigated micro-structured silicon wafers with prescribed trenches. The ice nucleation efficiencies deduced from these experiments are expressed as ice nucleation active surface site density values. With this approach, the freezing properties of the above-described substrates could be compared to those of natural mineral dusts such as agricultural soil dusts, volcanic ash and fossil diatoms, which have been investigated in AIDA cloud chamber experiments. All tested ice nucleating substrates were consistently less efficient at nucleating ice than the natural mineral dusts. Crystalline silicon only had a negligible influence on the freezing of small droplets, leading to freezing near the homogeneous freezing temperature threshold. Applying surface structures to silicon led to a shift towards heterogeneous freezing. However, the measured ice nucleation active surface site densities were still smaller than those of mineral dusts.

Visualizing cellulase activity.

PubMed

Bubner, Patricia; Plank, Harald; Nidetzky, Bernd

2013-06-01

Commercial exploitation of lignocellulose for biotechnological production of fuels and commodity chemicals requires efficient-usually enzymatic-saccharification of the highly recalcitrant insoluble substrate. A key characteristic of cellulose conversion is that the actual hydrolysis of the polysaccharide chains is intrinsically entangled with physical disruption of substrate morphology and structure. This "substrate deconstruction" by cellulase activity is a slow, yet markedly dynamic process that occurs at different length scales from and above the nanometer range. Little is currently known about the role of progressive substrate deconstruction on hydrolysis efficiency. Application of advanced visualization techniques to the characterization of enzymatic degradation of different celluloses has provided important new insights, at the requisite nano-scale resolution and down to the level of single enzyme molecules, into cellulase activity on the cellulose surface. Using true in situ imaging, dynamic features of enzyme action and substrate deconstruction were portrayed at different morphological levels of the cellulose, thus providing new suggestions and interpretations of rate-determining factors. Here, we review the milestones achieved through visualization, the methods which significantly promoted the field, compare suitable (model) substrates, and identify limiting factors, challenges and future tasks. Copyright © 2013 Wiley Periodicals, Inc.

Structural evolution and electronic properties of n-type doped hydrogenated amorphous silicon thin films

NASA Astrophysics Data System (ADS)

He, Jian; Li, Wei; Xu, Rui; Qi, Kang-Cheng; Jiang, Ya-Dong

2011-12-01

The relationship between structure and electronic properties of n-type doped hydrogenated amorphous silicon (a-Si:H) thin films was investigated. Samples with different features were prepared by plasma enhanced chemical vapor deposition (PECVD) at various substrate temperatures. Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy were used to evaluate the structural evolution, meanwhile, electronic-spin resonance (ESR) and optical measurement were applied to explore the electronic properties of P-doped a-Si:H thin films. Results reveal that the changes in materials structure affect directly the electronic properties and the doping efficiency of dopant.

Expanding the Bioactive Chemical Space of Anthrabenzoxocinones through Engineering the Highly Promiscuous Biosynthetic Modification Steps.

PubMed

Mei, Xianyi; Yan, Xiaoli; Zhang, Hui; Yu, Mingjia; Shen, Guangqing; Zhou, Linjun; Deng, Zixin; Lei, Chun; Qu, Xudong

2018-01-19

Anthrabenzoxocinones (ABXs) including (-)-ABXs and (+)-ABXs are a group of bacterial FabF-specific inhibitors with potent antimicrobial activity of resistant strains. Optimization of their chemical structures is a promising method to develop potent antibiotics. Through biosynthetic investigation, we herein identified and characterized two highly promiscuous enzymes involved in the (-)-ABX structural modification. The promiscuous halogenase and methyltransferase can respectively introduce halogen-modifications into various positions of the ABX scaffolds and methylation to highly diverse substrates. Manipulation of their activity in both of the (-)-ABXs and (+)-ABXs biosyntheses led to the generation of 14 novel ABX analogues of both enantiomers. Bioactivity assessment revealed that a few of the analogues showed significantly improved antimicrobial activity, with the C3-hydroxyl and chlorine substitutions critical for their activity. This study enormously expands the bioactive chemical space of the ABX family and FabF-specific inhibitors. The disclosed broad-selective biosynthetic machineries and structure-activity relationship provide a solid basis for further generation of potent antimicrobial agents.

Divergent Synthesis of Heparan Sulfate Oligosaccharides

PubMed Central

2015-01-01

Heparan sulfates are implicated in a wide range of biological processes. A major challenge in deciphering their structure and activity relationship is the synthetic difficulties to access diverse heparan sulfate oligosaccharides with well-defined sulfation patterns. In order to expedite the synthesis, a divergent synthetic strategy was developed. By integrating chemical synthesis and two types of O-sulfo transferases, seven different hexasaccharides were obtained from a single hexasaccharide precursor. This approach combined the flexibility of chemical synthesis with the selectivity of enzyme-catalyzed sulfations, thus simplifying the overall synthetic operations. In an attempt to establish structure activity relationships of heparan sulfate binding with its receptor, the synthesized oligosaccharides were incorporated onto a glycan microarray, and their bindings with a growth factor FGF-2 were examined. The unique combination of chemical and enzymatic approaches expanded the capability of oligosaccharide synthesis. In addition, the well-defined heparan sulfate structures helped shine light on the fine substrate specificities of biosynthetic enzymes and confirm the potential sequence of enzymatic reactions in biosynthesis. PMID:26574650

Engineering an enantioselective amine oxidase for the synthesis of pharmaceutical building blocks and alkaloid natural products.

PubMed

Ghislieri, Diego; Green, Anthony P; Pontini, Marta; Willies, Simon C; Rowles, Ian; Frank, Annika; Grogan, Gideon; Turner, Nicholas J

2013-07-24

The development of cost-effective and sustainable catalytic methods for the production of enantiomerically pure chiral amines is a key challenge facing the pharmaceutical and fine chemical industries. This challenge is highlighted by the estimate that 40-45% of drug candidates contain a chiral amine, fueling a demand for broadly applicable synthetic methods that deliver target structures in high yield and enantiomeric excess. Herein we describe the development and application of a "toolbox" of monoamine oxidase variants from Aspergillus niger (MAO-N) which display remarkable substrate scope and tolerance for sterically demanding motifs, including a new variant, which exhibits high activity and enantioselectivity toward substrates containing the aminodiphenylmethane (benzhydrylamine) template. By combining rational structure-guided engineering with high-throughput screening, it has been possible to expand the substrate scope of MAO-N to accommodate amine substrates containing bulky aryl substituents. These engineered MAO-N biocatalysts have been applied in deracemization reactions for the efficient asymmetric synthesis of the generic active pharmaceutical ingredients Solifenacin and Levocetirizine as well as the natural products (R)-coniine, (R)-eleagnine, and (R)-leptaflorine. We also report a novel MAO-N mediated asymmetric oxidative Pictet-Spengler approach to the synthesis of (R)-harmicine.

X-ray characterization of Ge dots epitaxially grown on nanostructured Si islands on silicon-on-insulator substrates

PubMed Central

Zaumseil, Peter; Kozlowski, Grzegorz; Yamamoto, Yuji; Schubert, Markus Andreas; Schroeder, Thomas

2013-01-01

On the way to integrate lattice mismatched semiconductors on Si(001), the Ge/Si heterosystem was used as a case study for the concept of compliant substrate effects that offer the vision to be able to integrate defect-free alternative semiconductor structures on Si. Ge nanoclusters were selectively grown by chemical vapour deposition on Si nano-islands on silicon-on-insulator (SOI) substrates. The strain states of Ge clusters and Si islands were measured by grazing-incidence diffraction using a laboratory-based X-ray diffraction technique. A tensile strain of up to 0.5% was detected in the Si islands after direct Ge deposition. Using a thin (∼10 nm) SiGe buffer layer between Si and Ge the tensile strain increases to 1.8%. Transmission electron microscopy studies confirm the absence of a regular grid of misfit dislocations in such structures. This clear experimental evidence for the compliance of Si nano-islands on SOI substrates opens a new integration concept that is not only limited to Ge but also extendable to semiconductors like III–V and II–VI materials. PMID:24046490

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sandoval-Paz, M.G., E-mail: myrnasandoval@udec.cl; Rodríguez, C.A.; Porcile-Saavedra, P.F.

Copper (I) selenide thin films with orthorhombic and cubic structure were deposited on glass substrates by using the chemical bath deposition technique. The effects of the solution pH on the films growth and subsequently the structural, optical and electrical properties of the films were studied. Films with orthorhombic structure were obtained from baths wherein both metal complex and hydroxide coexist; while films with cubic structure were obtained from baths where the metal hydroxide there is no present. The structural modifications are accompanied by changes in bandgap energy, morphology and electrical resistivity of the films. - Graphical abstract: “Study of themore » crystallographic phase change on copper (I) selenide thin films prepared through chemical bath deposition by varying the pH of the solution” by M. G. Sandoval-Paz, C. A. Rodríguez, P. F. Porcile-Saavedra, C. Trejo-Cruz. Display Omitted - Highlights: • Copper (I) selenide thin films were obtained by chemical bath deposition. • Orthorhombic to cubic phase change was induced by varying the reaction solution pH. • Orthorhombic phase is obtained mainly from a hydroxides cluster mechanism. • Cubic phase is obtained mainly from an ion by ion mechanism. • Structural, optical and electrical properties are presented as a function of pH.« less

Physical and chemical differences between one-stage and two-stage hydrothermal pretreated hardwood substrates for use in cellulosic ethanol production

DOE PAGES

Guilliams, Andrew; Pattathil, Sivakumar; Willies, Deidre; ...

2016-02-03

Here, there are many different types of pretreatment carried out to prepare cellulosic substrates for fermentation. In this study, one- and two-stage hydrothermal pretreatment were carried out to determine their effects on subsequent fermentations. The two substrates were found to behave differently during fermentation. The two substrates were then characterized using physical and chemical parameters.

Improved Electrochromic Characteristics of a Honeycomb-Structured Film Composed of NiO.

PubMed

Yang, Hyeeun; Lee, Yulhee; Kim, Dong In; Seo, Hyeon Jin; Yu, Jung-Hoon; Nam, Sang-Hun; Boo, Jin-Hyo

2018-09-01

Color changes controlled by electronic energies have been studied for many years in order to fabricate energy-efficient smart windows. Reduction and oxidization of nickel oxide under the appropriate voltage can change the color of a window. For a superior nickel oxide (NiO) electrochromic device (ECD), it is important to control the chemical and physical characteristics of the surface. In this study, we applied polystyrene bead templates to nickel oxide films to fabricate a honeycomb-structured electrochromic (EC) layer. We synthesized uniform polystyrene beads using the chemical wet method and placed them on substrates to create honeycomb-structured NiO films. Then, the EC characteristics of the nickel oxide films with a honeycomb structure were evaluated with UV-Visible and cyclic voltammetry. FE-SEM and AFM were used to measure the morphologies of the nanostructures and the efficiencies of the redox reactions related to the specific surface area.

Enzyme Informatics

PubMed Central

Alderson, Rosanna G.; Ferrari, Luna De; Mavridis, Lazaros; McDonagh, James L.; Mitchell, John B. O.; Nath, Neetika

2012-01-01

Over the last 50 years, sequencing, structural biology and bioinformatics have completely revolutionised biomolecular science, with millions of sequences and tens of thousands of three dimensional structures becoming available. The bioinformatics of enzymes is well served by, mostly free, online databases. BRENDA describes the chemistry, substrate specificity, kinetics, preparation and biological sources of enzymes, while KEGG is valuable for understanding enzymes and metabolic pathways. EzCatDB, SFLD and MACiE are key repositories for data on the chemical mechanisms by which enzymes operate. At the current rate of genome sequencing and manual annotation, human curation will never finish the functional annotation of the ever-expanding list of known enzymes. Hence there is an increasing need for automated annotation, though it is not yet widespread for enzyme data. In contrast, functional ontologies such as the Gene Ontology already profit from automation. Despite our growing understanding of enzyme structure and dynamics, we are only beginning to be able to design novel enzymes. One can now begin to trace the functional evolution of enzymes using phylogenetics. The ability of enzymes to perform secondary functions, albeit relatively inefficiently, gives clues as to how enzyme function evolves. Substrate promiscuity in enzymes is one example of imperfect specificity in protein-ligand interactions. Similarly, most drugs bind to more than one protein target. This may sometimes result in helpful polypharmacology as a drug modulates plural targets, but also often leads to adverse side-effects. Many cheminformatics approaches can be used to model the interactions between druglike molecules and proteins in silico. We can even use quantum chemical techniques like DFT and QM/MM to compute the structural and energetic course of enzyme catalysed chemical reaction mechanisms, including a full description of bond making and breaking. PMID:23116471

Chemically Functionalized Carbon Nanotubes as Substrates for Neuronal Growth

PubMed Central

Hu, Hui; Ni, Yingchun; Montana, Vedrana; Haddon, Robert C.; Parpura, Vladimir

2009-01-01

We report the use of chemically modified carbon nanotubes as a substrate for cultured neurons. The morphological features of neurons that directly reflect their potential capability in synaptic transmission are characterized. The chemical properties of carbon nanotubes are systematically varied by attaching different functional groups that confer known characteristics to the substrate. By manipulating the charge carried by functionalized carbon nanotubes we are able to control the outgrowth and branching pattern of neuronal processes. PMID:21394241

Mechanisms of Enhanced Catalysis in Enzyme-DNA Nanostructures Revealed through Molecular Simulations and Experimental Analysis.

PubMed

Gao, Yingning; Roberts, Christopher C; Toop, Aaron; Chang, Chia-En A; Wheeldon, Ian

2016-08-03

Understanding and controlling the molecular interactions between enzyme substrates and DNA nanostructures has important implications in the advancement of enzyme-DNA technologies as solutions in biocatalysis. Such hybrid nanostructures can be used to create enzyme systems with enhanced catalysis by controlling the local chemical and physical environments and the spatial organization of enzymes. Here we have used molecular simulations with corresponding experiments to describe a mechanism of enhanced catalysis due to locally increased substrate concentrations. With a series of DNA nanostructures conjugated to horseradish peroxidase, we show that binding interactions between substrates and the DNA structures can increase local substrate concentrations. Increased local substrate concentrations in HRP(DNA) nanostructures resulted in 2.9- and 2.4-fold decreases in the apparent Michaelis constants of tetramethylbenzidine and 4-aminophenol, substrates of HRP with tunable binding interactions to DNA nanostructures with dissociation constants in the micromolar range. Molecular simulations and kinetic analysis also revealed that increased local substrate concentrations enhanced the rates of substrate association. Identification of the mechanism of increased local concentration of substrates in close proximity to enzymes and their active sites adds to our understanding of nanostructured biocatalysis from which we can develop guidelines for enhancing catalysis in rationally designed systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication and electrical properties of low temperature-processed thin-film-transistors with chemical-bath deposited ZnO layer.

PubMed

Ahn, Joo-Seob; Kwon, Ji-Hye; Yang, Heesun

2013-06-01

ZnO film was grown on ZnO quantum dot seed layer-coated substrate by a low-temperature chemical bath deposition, where sodium citrate serves as a complexing agent for Zn2+ ion. The ZnO film deposited under the optimal condition exhibited a highly uniform surface morphology with a thickness of approimately 30 nm. For the fabrication of thin-film-transistor with a bottom-gate structure, ZnO film was chemically deposited on the transparent substrate of a seed layer-coated SiN(x)/ITO (indium tin oxide)/glass. As-deposited ZnO channel was baked at low temperatures of 60-200 degrees C to investigate the effect of baking temperature on electrical performances. Compared to the device with 60 degrees C-baked ZnO channel, the TFT performances of one with 200 degrees C-baked channel were substantially improved, exhibiting an on-off current ratio of 3.6 x 10(6) and a saturated field-effect mobility of 0.27 cm2/V x s.

A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes

DOE PAGES

Yang, Jinhui; Cooper, Jason K.; Toma, Francesca M.; ...

2016-11-07

Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. We demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co 3 O 4 /Co(OH) 2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. Furthermore, these films comprise compact and continuous nanocrystalline Co 3 O 4more » spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH) 2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p + n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.« less

Influence of heat treatment temperature on the morphological and structural aspects of reticulated vitreous carbon used in polyaniline electrosynthesis

NASA Astrophysics Data System (ADS)

Gonçalves, E. S.; Dalmolin, C.; Biaggio, S. R.; Nascente, P. A. P.; Rezende, M. C.; Ferreira, N. G.

2007-08-01

Reticulated vitreous carbon (RVC) was obtained from different heat treatment temperature (HTT), in the range from 700 up to 2000 °C, and used as a substrate for polyaniline growth from electrosynthesis. The influence of HTT on RVC chemical surface was studied by X-ray photoelectron spectroscopy (XPS) and correlated to electrochemical parameters used in the electrosynthesis. XPS analyses have shown that RVC heteroatoms decrease as HTT increases. The results reveal the migration of chemical bonds from oxidized carbon forms towards carbon atoms as the unique final product. Cyclic voltammetry, electrochemical impedance spectroscopy, and stability test of polyaniline films were performed from oxidized and non-oxidized RVC substrates. Cyclic voltammetry in 0.5 mol L -1 H 2SO 4 revealed higher capacitance for the RVC treated at 1000 °C and oxidized in a hot H 2SO 4 solution. The charge accumulation after RVC chemical treatment has increased around ten times. The lowest electric resistivities and impedances were obtained for the RVC treated at 2000 °C, which also showed the highest polyaniline stability.

Engineering of III-Nitride Semiconductors on Low Temperature Co-fired Ceramics.

PubMed

Mánuel, J M; Jiménez, J J; Morales, F M; Lacroix, B; Santos, A J; García, R; Blanco, E; Domínguez, M; Ramírez, M; Beltrán, A M; Alexandrov, D; Tot, J; Dubreuil, R; Videkov, V; Andreev, S; Tzaneva, B; Bartsch, H; Breiling, J; Pezoldt, J; Fischer, M; Müller, J

2018-05-02

This work presents results in the field of advanced substrate solutions in order to achieve high crystalline quality group-III nitrides based heterostructures for high frequency and power devices or for sensor applications. With that objective, Low Temperature Co-fired Ceramics has been used, as a non-crystalline substrate. Structures like these have never been developed before, and for economic reasons will represent a groundbreaking material in these fields of Electronic. In this sense, the report presents the characterization through various techniques of three series of specimens where GaN was deposited on this ceramic composite, using different buffer layers, and a singular metal-organic chemical vapor deposition related technique for low temperature deposition. Other single crystalline ceramic-based templates were also utilized as substrate materials, for comparison purposes.

Nanogrids and Beehive-Like Nanostructures Formed by Plasma Etching the Self-Organized SiGe Islands

NASA Astrophysics Data System (ADS)

Chang, Yuan-Ming; Jian, Sheng-Rui; Juang, Jenh-Yih

2010-09-01

A lithography-free method for fabricating the nanogrids and quasi-beehive nanostructures on Si substrates is developed. It combines sequential treatments of thermal annealing with reactive ion etching (RIE) on SiGe thin films grown on (100)-Si substrates. The SiGe thin films deposited by ultrahigh vacuum chemical vapor deposition form self-assembled nanoislands via the strain-induced surface roughening (Asaro-Tiller-Grinfeld instability) during thermal annealing, which, in turn, serve as patterned sacrifice regions for subsequent RIE process carried out for fabricating nanogrids and beehive-like nanostructures on Si substrates. The scanning electron microscopy and atomic force microscopy observations confirmed that the resultant pattern of the obtained structures can be manipulated by tuning the treatment conditions, suggesting an interesting alternative route of producing self-organized nanostructures.

Decoupling thermal, chemical, and mechanical strain components in thin films

NASA Astrophysics Data System (ADS)

Silberstein, Meredith; Crumlin, Ethan; Shao-Horn, Yang; Boyce, Mary

2011-03-01

Many electrochemical systems have performance which is affected by internal strains due to thermal and/or chemical stimuli. The bi-material curvature method is a means to quantify these thermal and chemical strains and their coupling with mechanical stress. In this method, a thin layer of the material of interest is deposited on a substrate of intermediate thickness. The composite assumes a curvature that depends on the mismatch strains between the substrate and film. The Stoney formula provides an explicit expression for the film stress as a function of the elastic substrate properties, film and substrate thickness, and curvature. Here we study two distinct materials systems: Nafion used as the polymer electrolyte in low temperature fuel cells, and epitaxial perovskite thin films used as a catalyst for the oxygen reduction reaction in solid oxide fuel cells. The thermal, chemical, and mechanical strains are quantitatively determined as functions of temperature and atmospheric conditions by monitoring the curvature evolution with changes in these parameters. The extent of coupling of the thermal and chemical strains with mechanical stress is evaluated by conducting the experiment at multiple substrate thicknesses.

Fabrication of high temperature superconductors

DOEpatents

Balachandran, Uthamalingam; Dorris, Stephen E.; Ma, Beihai; Li, Meiya

2003-06-17

A method of forming a biaxially aligned superconductor on a non-biaxially aligned substrate substantially chemically inert to the biaxially aligned superconductor comprising is disclosed. A non-biaxially aligned substrate chemically inert to the superconductor is provided and a biaxially aligned superconductor material is deposited directly on the non-biaxially aligned substrate. A method forming a plume of superconductor material and contacting the plume and the non-biaxially aligned substrate at an angle greater than 0.degree. and less than 90.degree. to deposit a biaxially aligned superconductor on the non-biaxially aligned substrate is also disclosed. Various superconductors and substrates are illustrated.

Chemical synthesis and NMR characterization of structured polyunsaturated triacylglycerols.

PubMed

Fauconnot, Laëtitia; Robert, Fabien; Villard, Renaud; Dionisi, Fabiola

2006-02-01

The chemical synthesis of pure triacylglycerol (TAG) regioisomers, that contain long chain polyunsaturated fatty acids, such as arachidonic acid (AA) or docosahexaenoic acid (DHA), and saturated fatty acids, such as lauric acid (La) or palmitic acid (P), at defined positions, is described. A single step methodology using (benzotriazol-1-yloxy)-tripyrrolidinophosphonium hexafluorophosphate (PyBOP), an activator of carboxyl group commonly used in peptide synthesis and occasionally used in carboxylic acid esterification, has been developed for structured TAG synthesis. Identification of the fatty acyl chains for each TAG species was confirmed by atmospheric pressure chemical ionisation mass spectrometry (APCI-MS) and fatty acid positional distribution was determined by (1)H and (13)C NMR spectra. The generic described procedures can be applied to a large variety of substrates and was used for the production of specific triacylglycerols of defined molecular structures, with high regioisomeric purity. Combination of MS and NMR was shown to be an efficient tool for structural analysis of TAG. In particular, some NMR signals were demonstrated to be regioisomer specific, allowing rapid positional analysis of LC-PUFA containing TAG.

Marvels of enzyme catalysis at true atomic resolution: distortions, bond elongations, hidden flips, protonation states and atom identities.

PubMed

Neumann, Piotr; Tittmann, Kai

2014-12-01

Although general principles of enzyme catalysis are fairly well understood nowadays, many important details of how exactly the substrate is bound and processed in an enzyme remain often invisible and as such elusive. In fortunate cases, structural analysis of enzymes can be accomplished at true atomic resolution thus making possible to shed light on otherwise concealed fine-structural traits of bound substrates, intermediates, cofactors and protein groups. We highlight recent structural studies of enzymes using ultrahigh-resolution X-ray protein crystallography showcasing its enormous potential as a tool in the elucidation of enzymatic mechanisms and in unveiling fundamental principles of enzyme catalysis. We discuss the observation of seemingly hyper-reactive, physically distorted cofactors and intermediates with elongated scissile substrate bonds, the detection of 'hidden' conformational and chemical equilibria and the analysis of protonation states with surprising findings. In delicate cases, atomic resolution is required to unambiguously disclose the identity of atoms as demonstrated for the metal cluster in nitrogenase. In addition to the pivotal structural findings and the implications for our understanding of enzyme catalysis, we further provide a practical framework for resolution enhancement through optimized data acquisition and processing. Copyright © 2014 Elsevier Ltd. All rights reserved.

Solid-State Synthesized Nanostructured Au Dendritic Aggregates Towards Surface-Enhanced Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Gentile, A.; Ruffino, F.; D'Andrea, C.; Gucciardi, P. G.; Reitano, R.; Grimaldi, M. G.

2016-06-01

Micrometric Au structures, presenting a dendritic nano-structure, have been fabricated on a Si-based substrate. The fabrication method involves the deposition of a thin Au film on the substrate and a high-temperature annealing (1100°C) using fast heating and cooling ramps. The thermal process produces the growth, from the substrate, of Si micro-pillars whose top surfaces, covered by a crystalline Au layer, present a nanodendritic morphology. In addition to the micro-pillars, the sample surface presents a complex structural and chemical composition including Si3N4 regions due to the silicon-nitrogen intermixing during the heating stage. By studying the kinetic processes at the Au-Si interface during the thermal treatment, we describe the stages involved in the micro-pillars growth, in the dendritic morphology development, and in the Au atoms entrapment at the top of the dendritic surfaces. Finally, we present the analyses of the optical and surface enhanced Raman scattering properties of the Au dendritic aggregates. We show, in particular, that: (1) the Au dendrites aggregates act as effective scattering elements for the electromagnetic radiation in the infrared spectral region; and (2) the higher surface area due to the branched dendritic structure is responsible for the improvement in the sensitivity of the surface enhanced Raman scattering activity.

Frequent mechanical stress suppresses proliferation of mesenchymal stem cells from human bone marrow without loss of multipotency

NASA Astrophysics Data System (ADS)

Frank, Viktoria; Kaufmann, Stefan; Wright, Rebecca; Horn, Patrick; Yoshikawa, Hiroshi Y.; Wuchter, Patrick; Madsen, Jeppe; Lewis, Andrew L.; Armes, Steven P.; Ho, Anthony D.; Tanaka, Motomu

2016-04-01

Mounting evidence indicated that human mesenchymal stem cells (hMSCs) are responsive not only to biochemical but also to physical cues, such as substrate topography and stiffness. To simulate the dynamic structures of extracellular environments of the marrow in vivo, we designed a novel surrogate substrate for marrow derived hMSCs based on physically cross-linked hydrogels whose elasticity can be adopted dynamically by chemical stimuli. Under frequent mechanical stress, hMSCs grown on our hydrogel substrates maintain the expression of STRO-1 over 20 d, irrespective of the substrate elasticity. On exposure to the corresponding induction media, these cultured hMSCs can undergo adipogenesis and osteogenesis without requiring cell transfer onto other substrates. Moreover, we demonstrated that our surrogate substrate suppresses the proliferation of hMSCs by up to 90% without any loss of multiple lineage potential by changing the substrate elasticity every 2nd days. Such “dynamic in vitro niche” can be used not only for a better understanding of the role of dynamic mechanical stresses on the fate of hMSCs but also for the synchronized differentiation of adult stem cells to a specific lineage.

Adhesion and transfer of PTFE to metals studied by auger emission spectroscopy

NASA Technical Reports Server (NTRS)

Pepper, S. V.; Buckley, D. H.

1972-01-01

The adhesion and transfer of polytetrafluoroethylene (PTFE) to metals in ultrahigh vacuum has been studied using Auger emission spectroscopy. The transfer was effected both by compressive static contact and by sliding contact. The transfer observed after static contact was independent of the chemical constitution of the substrate. Electron induced desorption of the fluorine in the transferred PTFE showed that the fluorine had no chemical interaction with the metal substrate. The coefficient of friction on metals was independent of the chemical constitution of the substrate. However, sliding PTFE on soft metals such as aluminum, generated wear fragments that lodged in the PTFE and machined the substrate.

Adhesion and transfer of polytetrafluorethylene to metals studied by Auger emission spectroscopy

NASA Technical Reports Server (NTRS)

Pepper, S. V.; Buckley, D. H.

1972-01-01

The adhesion and transfer of polytetrafluoroethylene (PTFE) to metals in ultrahigh vacuum were studied. The transfer was effected both by compressive static contact and by sliding contact. The transfer observed after static contact was independent of the chemical constitution of the substrate. Electron-induced desorption of the fluorine in the transferred PTFE showed that the fluorine had no chemical interaction with the metal substrate. The coefficient of friction on metals was independent of the chemical constitution of the substrate. However, sliding PTFE on soft metals, such as aluminum, generated wear fragments that lodged in the PTFE and machined the substrate.

Electrospun polystyrene scaffolds as a synthetic substrate for xeno-free expansion and differentiation of human induced pluripotent stem cells.

PubMed

Leong, Meng Fatt; Lu, Hong Fang; Lim, Tze Chiun; Du, Chan; Ma, Nina K L; Wan, Andrew C A

2016-12-01

The use of human induced pluripotent stem cells (hiPSCs) for clinical tissue engineering applications requires expansion and differentiation of the cells using defined, xeno-free substrates. The screening and selection of suitable synthetic substrates however, is tedious, as their performance relies on the inherent material properties. In the present work, we demonstrate an alternative concept for xeno-free expansion and differentiation of hiPSCs using synthetic substrates, which hinges on the structure-function relationship between electrospun polystyrene scaffolds (ESPS) and pluripotent stem cell growth. ESPS of differential porosity was obtained by fusing the fibers at different temperatures. The more porous, loosely fused scaffolds were found to efficiently trap the cells, leading to a large number of three-dimensional (3D) aggregates which were shown to be pluripotent colonies. Immunostaining, PCR analyses, in vitro differentiation and in vivo teratoma formation studies demonstrated that these hiPSC aggregates could be cultured for up to 10 consecutive passages (P10) with maintenance of pluripotency. Flow cytometry showed that more than 80% of the cell population stained positive for the pluripotent marker OCT4 at P1, P5 and P10. P10 cells could be differentiated to neuronal-like cells and cultured within the ESPS for up to 18months. Our results suggest the usefulness of a generic class of synthetic substrates, exemplified by ESPS, for 'trapped aggregate culture' of hiPSCs. To realize the potential of human induced pluripotent stem cells (hiPSCs) in clinical medicine, robust, xeno-free substrates for expansion and differentiation of iPSCs are required. In the existing literature, synthetic materials have been reported that meet the requirement for non-xenogeneic substrates. However, the self-renewal and differentiation characteristics of hiPSCs are affected differently by the biocompatibility and physico-chemical properties of individual substrates. Although some rules based on chemical structure and substrate rigidity have been developed, most of these efforts are still empirical, and most synthetic substrates must still be rigorously screened for suitability. In this paper, we demonstrate an alternative concept for xeno-free expansion and differentiation of hiPSCs using synthetic substrates, which hinges on the structure-function relationship between electrospun polystyrene scaffolds (ESPS) and pluripotent stem cell growth. ESPS of differential porosity was obtained by fusing the fibers at different temperatures. The more porous, loosely fused scaffold was found to efficiently trap the cells, leading to a large number of three-dimensional (3D) aggregates. In the form of these trapped aggregates, we showed that hiPSCs could be cultured for up to 10 consecutive passages (P10) with maintenance of pluripotency, following which they could be differentiated to a chosen lineage. We believe that this novel, generic class of synthetic substrates that employs 'trapped aggregate culture' for expansion and differentiation of hiPSCs is an important conceptual advance, and would be of high interest to the readership of Acta Biomaterialia. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Development of GaAs/Si and GaAs/Si monolithic structures for future space solar cells

NASA Technical Reports Server (NTRS)

Spitzer, M. B.; Vernon, S. M.; Wolfson, R. G.; Tobin, S. P.

1984-01-01

The results of heteroepitaxial growth of GaAs and GaAlAs directly on Si are presented, and applications to new cell structures are suggested. The novel feature is the elimination of a Ge lattice transition region. This feature not only reduces the cost of substrate preparation, but also makes possible the fabrication of high efficiency monolithic cascade structures. All films to be discussed were grown by organometallic chemical vapor deposition at atmospheric pressure. This process yielded reproducible, large-area films of GaAs, grown directly on Si, that are tightly adherent and smooth, and are characterized by a defect density of 5 x 10(6) power/sq cm. Preliminary studies indicate that GaAlAs can also be grown in this way. A number of promising applications are suggested. Certainly these substrates are ideal for low-weight GaAs space solar ells. For very high efficiency, the absence of Ge makes the technology attractive for GaAlAs/Si monolithic cascades, in which the Si substrates would first be provided with a suitable p/n junction. An evaluation of a three bandgap cascade consisting of appropriately designed GaAlAs/GaAs/Si layers is also presented.

Insight Into the Radical Mechanism of Phycocyanobilin-Ferredoxin Oxidoreductase (Pcya) Revealed By X-Ray Crystallography And Biochemical Measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tu, S.-L.; Rockwell, N.; Lagarias, J.C.

2007-07-13

The X-ray crystal structure of the substrate-free form of phycocyanobilin (PCB)-ferredoxin oxidoreductase (PcyA; EC 1.3.7.5) from the cyanobacterium Nostoc sp. PCC7120 has been solved at 2.5 angstrom resolution. A comparative analysis of this structure with those recently reported for substrate-bound and substrate-free forms of PcyA from the cyanobacterium Synechocystis sp. PCC6803 (Hagiwara et al. (2006) Proc. Natl. Acad. Sci. U.S.A. 103, 27-32; Hagiwara et al. (2006) FEBS Lett. 580, 3823-3828) provides a compelling picture of substrate-induced changes in the PcyA enzyme and the chemical basis of PcyA's catalytic activity. On the basis of these structures and the biochemical analysis ofmore » site-directed mutants of Nostoc PcyA, including mutants reported in recent studies (Tu et al. (2006) J. Biol. Chem. 281, 3127-3136) as well as mutants described in this study, a revised mechanism for the PcyA-mediated four-electron reduction of biliverdin IX{alpha} to 3E/3Z-phycocyanobilin via enzyme-bound bilin radical intermediates is proposed. The mechanistic insight of these studies, along with homology modeling, have provided new insight into the catalytic mechanisms of other members of the ferredoxin-dependent bilin reductase family that are widespread in oxygenic photosynthetic organisms.« less

High quality thin films of thermoelectric misfit cobalt oxides prepared by a chemical solution method

PubMed Central

Rivas-Murias, Beatriz; Manuel Vila-Fungueiriño, José; Rivadulla, Francisco

2015-01-01

Misfit cobaltates ([Bi/Ba/Sr/Ca/CoO]nRS[CoO2]q) constitute the most promising family of thermoelectric oxides for high temperature energy harvesting. However, their complex structure and chemical composition makes extremely challenging their deposition by high-vacuum physical techniques. Therefore, many of them have not been prepared as thin films until now. Here we report the synthesis of high-quality epitaxial thin films of the most representative members of this family of compounds by a water-based chemical solution deposition method. The films show an exceptional crystalline quality, with an electrical conductivity and thermopower comparable to single crystals. These properties are linked to the epitaxial matching of the rock-salt layers of the structure to the substrate, producing clean interfaces free of amorphous phases. This is an important step forward for the integration of these materials with complementary n-type thermoelectric oxides in multilayer nanostructures. PMID:26153533

Strain and Structure Heterogeneity in MoS2 Atomic Layers Grown by Chemical Vapour Deposition

DTIC Science & Technology

2014-11-18

substrate and material. To better explain the experimental results and estimate the strain transferred to MoS2 layer under such tensile tests, a 3D... ACS Nano 7, 7126 7131 (2013). 29. He, K., Poole, C., Mak, K. F. & Shan, J. Experimental demonstration of continuous electronic structure tuning via...transition as it is thinned down from multi layer to monolayer, producing a significant enhancement of photoluminescence (PL) quantum yield as a result of the

Porous Shape Memory Polymers

PubMed Central

Hearon, Keith; Singhal, Pooja; Horn, John; Small, Ward; Olsovsky, Cory; Maitland, Kristen C.; Wilson, Thomas S.; Maitland, Duncan J.

2013-01-01

Porous shape memory polymers (SMPs) include foams, scaffolds, meshes, and other polymeric substrates that possess porous three-dimensional macrostructures. Porous SMPs exhibit active structural and volumetric transformations and have driven investigations in fields ranging from biomedical engineering to aerospace engineering to the clothing industry. The present review article examines recent developments in porous SMPs, with focus given to structural and chemical classification, methods of characterization, and applications. We conclude that the current body of literature presents porous SMPs as highly interesting smart materials with potential for industrial use. PMID:23646038

The analysis of ion-selective field-effect transistor operation in chemical sensors

NASA Astrophysics Data System (ADS)

Hotra, Zenon; Holyaka, Roman; Hladun, Michael; Humenuk, Iryna

2003-09-01

In this paper we present the research results of influence of substrate potential in ion-selective field-effect transistors (ISFET) on output signal of chemical sensors, e.g. PH-meters. It is shown that the instability of substrate-source p-n junction bias in well-known chemical sensors, which use grounded reference electrode - ISFET gate, affect on sensor characteristics in negative way. The analytical description and research results of 'substrate effect' on ISFET characteristics are considered.

Low-Temperature Process for Atomic Layer Chemical Vapor Deposition of an Al2O3 Passivation Layer for Organic Photovoltaic Cells.

PubMed

Kim, Hoonbae; Lee, Jihye; Sohn, Sunyoung; Jung, Donggeun

2016-05-01

Flexible organic photovoltaic (OPV) cells have drawn extensive attention due to their light weight, cost efficiency, portability, and so on. However, OPV cells degrade quickly due to organic damage by water vapor or oxygen penetration when the devices are driven in the atmosphere without a passivation layer. In order to prevent damage due to water vapor or oxygen permeation into the devices, passivation layers have been introduced through methods such as sputtering, plasma enhanced chemical vapor deposition, and atomic layer chemical vapor deposition (ALCVD). In this work, the structural and chemical properties of Al2O3 films, deposited via ALCVD at relatively low temperatures of 109 degrees C, 200 degrees C, and 300 degrees C, are analyzed. In our experiment, trimethylaluminum (TMA) and H2O were used as precursors for Al2O3 film deposition via ALCVD. All of the Al2O3 films showed very smooth, featureless surfaces without notable defects. However, we found that the plastic flexible substrate of an OPV device passivated with 300 degrees C deposition temperature was partially bended and melted, indicating that passivation layers for OPV cells on plastic flexible substrates need to be formed at temperatures lower than 300 degrees C. The OPV cells on plastic flexible substrates were passivated by the Al2O3 film deposited at the temperature of 109 degrees C. Thereafter, the photovoltaic properties of passivated OPV cells were investigated as a function of exposure time under the atmosphere.

Laser-assisted nanomaterial deposition, nanomanufacturing, in situ monitoring and associated apparatus

DOEpatents

Mao, Samuel S; Grigoropoulos, Costas P; Hwang, David J; Minor, Andrew M

2013-11-12

Laser-assisted apparatus and methods for performing nanoscale material processing, including nanodeposition of materials, can be controlled very precisely to yield both simple and complex structures with sizes less than 100 nm. Optical or thermal energy in the near field of a photon (laser) pulse is used to fabricate submicron and nanometer structures on a substrate. A wide variety of laser material processing techniques can be adapted for use including, subtractive (e.g., ablation, machining or chemical etching), additive (e.g., chemical vapor deposition, selective self-assembly), and modification (e.g., phase transformation, doping) processes. Additionally, the apparatus can be integrated into imaging instruments, such as SEM and TEM, to allow for real-time imaging of the material processing.

Growth of vertically aligned carbon nanofibers by low-pressure inductively coupled plasma-enhanced chemical vapor deposition

NASA Astrophysics Data System (ADS)

Caughman, J. B. O.; Baylor, L. R.; Guillorn, M. A.; Merkulov, V. I.; Lowndes, D. H.; Allard, L. F.

2003-08-01

Vertically aligned carbon nanofibers (VACNFs) have been grown using a low-pressure, plasma-enhanced, chemical vapor deposition process. The nanofibers are grown from a nickel catalyst that can be patterned to form arrays of individual, isolated VACNFs. The fibers are grown at pressures below 100 mTorr, using an inductively coupled plasma source with a radio-frequency bias on the sample substrate to allow for independent control of the ion energies. Plasma conditions are related to growth results by comparing optical emission from the plasma to the physical structure of the nanofibers. We find that the ratio of etching species in the plasma to depositing species is critical to the final shape of the carbon structures that are formed.

Structural and morphological study of chemically synthesized CdSe thin films

NASA Astrophysics Data System (ADS)

Agrawal, P.; Singh, Randhir; Sharma, Jeewan; Sachdeva, M.; Singh, Anupinder; Bhargava, A.

2018-05-01

Nanocrystalline CdSe thin films were prepared by Chemical Bath Deposition (CBD) method using potassium nitrilo-triacetic acid cadmium complex and sodium selenosulphite. The as deposited films were red in color, uniform and well adherent to the glass substrate. These films were strongly dependent on the deposition parameters such as bath composition, deposition temperature and time. Films were annealed at 350 °C for four hours. The morphological, structural and optical properties were studied using X-ray diffraction (XRD), UV-VIS spectrophotometer measurements, scanning electron microscopy and atomic force microscopy. The XRD analysis confirmed that films are predominantly in hexagonal phase. Scanning electron micrograph shows that the grains are uniformly spread all over the film and each grain contains many nanocrystals with spherical shapes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simoes, A.Z., E-mail: alezipo@yahoo.com; Riccardi, C.S.; Dos Santos, M.L.

Bismuth ferrite thin films were deposited on Pt/Ti/SiO{sub 2}/Si substrates by a soft chemical method and spin-coating technique. The effect of annealing atmosphere (air, N{sub 2} and O{sub 2}) on the structure and electrical properties of the films are reported. X-ray diffraction analysis reveals that the film annealed in air atmosphere is a single-phase perovskite structure. The films annealed in air showed better crystallinity and the presence of a single BFO phase leading to lower leakage current density and superior ferroelectric hysteresis loops at room temperature. In this way, we reveal that BFO film crystallized in air atmosphere by themore » soft chemical method can be useful for practical applications, including nonvolatile digital memories, spintronics and data-storage media.« less

A dual-band THz absorber based on graphene sheet and ribbons

NASA Astrophysics Data System (ADS)

Xing, Rui; Jian, Shuisheng

2018-03-01

A dual-band graphene absorber is proposed and investigated in this paper. The absorber consists of the gold substrate, the graphene sheet sandwiched by dielectric layers and the array of graphene ribbon placed on the top. The two absorption peaks of the dual-band are 99.8% at 4.95 THz and 99.6% at 9.2 THz, respectively. Due to the characteristic of tunable surface conductivity of graphene, the absorption can be controlled by adjusting the chemical potential of graphene. We also investigate the dependence of the absorption curve of the proposed absorber on the structure parameters. In addition, the structure of the absorber is very simple and it can be manufactured by chemical vapor deposition (CVD).

Chemical shift assignments of the partially deuterated Fyn SH2-SH3 domain.

PubMed

Kieken, Fabien; Loth, Karine; van Nuland, Nico; Tompa, Peter; Lenaerts, Tom

2018-04-01

Src Homology 2 and 3 (SH2 and SH3) are two key protein interaction modules involved in regulating the activity of many proteins such as tyrosine kinases and phosphatases by respective recognition of phosphotyrosine and proline-rich regions. In the Src family kinases, the inactive state of the protein is the direct result of the interaction of the SH2 and the SH3 domain with intra-molecular regions, leading to a closed structure incompetent with substrate modification. Here, we report the 1 H, 15 N and 13 C backbone- and side-chain chemical shift assignments of the partially deuterated Fyn SH3-SH2 domain and structural differences between tandem and single domains. The BMRB accession number is 27165.

Resolving the Chemically Discrete Structure of Synthetic Borophene Polymorphs.

PubMed

Campbell, Gavin P; Mannix, Andrew J; Emery, Jonathan D; Lee, Tien-Lin; Guisinger, Nathan P; Hersam, Mark C; Bedzyk, Michael J

2018-05-09

Atomically thin two-dimensional (2D) materials exhibit superlative properties dictated by their intralayer atomic structure, which is typically derived from a limited number of thermodynamically stable bulk layered crystals (e.g., graphene from graphite). The growth of entirely synthetic 2D crystals, those with no corresponding bulk allotrope, would circumvent this dependence upon bulk thermodynamics and substantially expand the phase space available for structure-property engineering of 2D materials. However, it remains unclear if synthetic 2D materials can exist as structurally and chemically distinct layers anchored by van der Waals (vdW) forces, as opposed to strongly bound adlayers. Here, we show that atomically thin sheets of boron (i.e., borophene) grown on the Ag(111) surface exhibit a vdW-like structure without a corresponding bulk allotrope. Using X-ray standing wave-excited X-ray photoelectron spectroscopy, the positions of boron in multiple chemical states are resolved with sub-angström spatial resolution, revealing that the borophene forms a single planar layer that is 2.4 Å above the unreconstructed Ag surface. Moreover, our results reveal that multiple borophene phases exhibit these characteristics, denoting a unique form of polymorphism consistent with recent predictions. This observation of synthetic borophene as chemically discrete from the growth substrate suggests that it is possible to engineer a much wider variety of 2D materials than those accessible through bulk layered crystal structures.

The initial stages of ZnO atomic layer deposition on atomically flat In0.53Ga0.47As substrates.

PubMed

Skopin, Evgeniy V; Rapenne, Laetitia; Roussel, Hervé; Deschanvres, Jean-Luc; Blanquet, Elisabeth; Ciatto, Gianluca; Fong, Dillon D; Richard, Marie-Ingrid; Renevier, Hubert

2018-06-21

InGaAs is one of the III-V active semiconductors used in modern high-electron-mobility transistors or high-speed electronics. ZnO is a good candidate material to be inserted as a tunneling insulator layer at the metal-semiconductor junction. A key consideration in many modern devices is the atomic structure of the hetero-interface, which often ultimately governs the electronic or chemical process of interest. Here, a complementary suite of in situ synchrotron X-ray techniques (fluorescence, reflectivity and absorption) as well as modeling is used to investigate both structural and chemical evolution during the initial growth of ZnO by atomic layer deposition (ALD) on In0.53Ga0.47As substrates. Prior to steady-state growth behavior, we discover a transient regime characterized by two stages. First, substrate-inhibited ZnO growth takes place on InGaAs terraces. This leads eventually to the formation of a 1 nm-thick, two-dimensional (2D) amorphous layer. Second, the growth behavior and its modeling suggest the occurrence of dense island formation, with an aspect ratio and surface roughness that depends sensitively on the growth condition. Finally, ZnO ALD on In0.53Ga0.47As is characterized by 2D steady-state growth with a linear growth rate of 0.21 nm cy-1, as expected for layer-by-layer ZnO ALD.

Substrate-Based Noble-Metal Nanomaterials: Shape Engineering and Applications

NASA Astrophysics Data System (ADS)

Hajfathalian, Maryam

Nanostructures have potential for use in state-of-the-art applications such as sensing, imaging, therapeutics, drug delivery, and electronics. The ability to fabricate and engineer these nanoscale materials is essential for the continued development of such devices. Because the morphological features of nanomaterials play a key role in determining chemical and physical properties, there is great interest in developing and improving methods capable of controlling their size, shape, and composition. While noble nanoparticles have opened the door to promising applications in fields such as imaging, cancer targeting, photothermal treatment, drug delivery, catalysis and sensing, the synthetic processes required to form these nanoparticles on surfaces are not well-developed. Herein is a detailed account on efforts for adapting established solution-based seed-mediated synthetic protocols to structure in a substrate-based platform. These syntheses start by (i) defining heteroepitaxially oriented nanostructured seeds at site-specific locations using lithographic or directed-assembly techniques, and then (ii) transforming the seeds using either a solution or vapor phase processing route to activate kinetically- or thermodynamically-driven growth modes, to arrive at nanocrystals with complex and useful geometries. The first series of investigations highlight synthesis-routes based on heterogeneous nucleation, where templates serve as nucleation sites for metal atoms arriving in the vapor phase. In the first research direction, the vapor-phase heterogeneous nucleation of Ag on Au was carried out at high temperatures, where the Ag vapor was sourced from a sublimating foil onto adjacent Au templates. This process transformed both the composition and morphology of the initial Au Wulff-shaped nanocrystals to a homogeneous AuAg nanoprism. In the second case, the vapor-phase heterogeneous nucleation of Cu atoms on Au nanocrystal templates was investigated by placing a Cu foil next to Au templates and heating, which caused the Cu atoms from the foil to sublimate from the foil and heterogeneously nucleation on the surface of the immobilized Au seeds. This process caused the composition and morphology of the Au Wulff-shape to transform into a homogeneous AuCu nanotriangle. Lastly, we characterized the morphological features and composition, optical properties, and also the catalytic and photocatalytic performance toward hydrogenation of 4-nitrophenolate. The second series of investigations highlight synthetic routes utilizing competencies of substrate-based techniques with colloidal chemistry. We have demonstrated two substrate-based syntheses yielding bimetallic nanostructures where shape control was achieved through (i) facet-selective capping agents and (ii) additive and subtractive process. In the first case a citrate-based cubic structure has been synthesized in the presence or absence of ascorbic acid and the role of each has been considered in shape control. Reactions were carried out in which Ag+ ions were reduced onto substrate-immobilized Ag, Au, Pd, and Pt seeds. It was discovered that for syntheses lacking ascorbic acid, citrate acts as both the capping and the reducing agent, resulting in a robust nanocube growth mode; however, when ascorbic acid was included in these syntheses, then the growth mode reverted to one that advances the octahedral geometry. The conclusion of these results was that citrate, or one of its oxidation products, selectively caps (100) facets, but where this capability was compromised by ascorbic acid. In the second case, galvanic replacement reactions have been carried out on immobilized cubic and Wulff structures to create the substrate-based nanoshells and nanocages, where the prepositioned templates were chemically transformed into hollow structures. In this novel research, Wulff-shaped templates of Au, Pt, or Pd, formed through the dewetting of ultrathin films, were first transformed into core?shell structures through the reduction of Ag+ ions onto their surface and then further transformed through the galvanic replacement of Ag with Au. Detailed studies were provided highlighting discoveries related to (i) alloying, (ii) dealloying, (iii) hollowing, (iv) crystal structure and (vi) the localized surface plasmon resonance (LSPR). Overall, a series of synthetic strategies based on physical and chemical vapor deposition were devised and validated to achieve novel substrate- based nanomaterials with different shapes and compositions for a variety of applications such as sensing, plasmonics, catalysis, and photocatalysis. The novel research in this dissertation also takes advantage of competencies of substrate-based techniques with colloidal chemistry and, brings this rich and exciting chemistry and its associated functionalities to the substrate surface.

Mannanase hydrolysis of spruce galactoglucomannan focusing on the influence of acetylation on enzymatic mannan degradation.

PubMed

Arnling Bååth, Jenny; Martínez-Abad, Antonio; Berglund, Jennie; Larsbrink, Johan; Vilaplana, Francisco; Olsson, Lisbeth

2018-01-01

Galactoglucomannan (GGM) is the most abundant hemicellulose in softwood, and consists of a backbone of mannose and glucose units, decorated with galactose and acetyl moieties. GGM can be hydrolyzed into fermentable sugars, or used as a polymer in films, gels, and food additives. Endo -β-mannanases, which can be found in the glycoside hydrolase families 5 and 26, specifically cleave the mannan backbone of GGM into shorter oligosaccharides. Information on the activity and specificity of different mannanases on complex and acetylated substrates is still lacking. The aim of this work was to evaluate and compare the modes of action of two mannanases from Cellvibrio japonicus ( Cj Man5A and Cj Man26A) on a variety of mannan substrates, naturally and chemically acetylated to varying degrees, including naturally acetylated spruce GGM. Both enzymes were evaluated in terms of cleavage patterns and their ability to accommodate acetyl substitutions. Cj Man5A and Cj Man26A demonstrated different substrate preferences on mannan substrates with distinct backbone and decoration structures. Cj Man5A action resulted in higher amounts of mannotriose and mannotetraose than that of Cj Man26A, which mainly generated mannose and mannobiose as end products. Mass spectrometric analysis of products from the enzymatic hydrolysis of spruce GGM revealed that an acetylated hexotriose was the shortest acetylated oligosaccharide produced by Cj Man5A, whereas Cj Man26A generated acetylated hexobiose as well as diacetylated oligosaccharides. A low degree of native acetylation did not significantly inhibit the enzymatic action. However, a high degree of chemical acetylation resulted in decreased hydrolyzability of mannan substrates, where reduced substrate solubility seemed to reduce enzyme activity. Our findings demonstrate that the two mannanases from C. japonicus have different cleavage patterns on linear and decorated mannan polysaccharides, including the abundant and industrially important resource spruce GGM. Cj Man26A released higher amounts of fermentable sugars suitable for biofuel production, while Cj Man5A, producing higher amounts of oligosaccharides, could be a good candidate for the production of oligomeric platform chemicals and food additives. Furthermore, chemical acetylation of mannan polymers was found to be a potential strategy for limiting the biodegradation of mannan-containing materials.

Impacts of supplementing chemical fertilizers with organic fertilizers manufactured using pig manure as a substrate on the spread of tetracycline resistance genes in soil.

PubMed

Kang, Yijun; Hao, Yangyang; Shen, Min; Zhao, Qingxin; Li, Qing; Hu, Jian

2016-08-01

Using pig manure (PM) compost as a partial substitute for the conventional chemical fertilizers (CFs) is considered an effective approach in sustainable agricultural systems. This study aimed to analyze the impacts of supplementing CF with organic fertilizers (OFs) manufactured using pig manure as a substrate on the spread of tetracycline resistance genes (TRGs) as well as the community structures and diversities of tetracycline-resistant bacteria (TRB) in bulk and cucumber rhizosphere soils. In this study, three organic fertilizers manufactured using the PM as a substrate, namely fresh PM, common OF, and bio-organic fertilizer (BF), were supplemented with a CF. Composted manures combined with a CF did not significantly increase TRB compared with the CF alone, but PM treatment resulted in the long-term survival of TRB in soil. The use of CF+PM also increased the risk of spreading TRGs in soil. As beneficial microorganisms in BF may function as reservoirs for the spread of antibiotic resistance genes, care should be taken when adding them to the OF matrix. The PM treatment significantly altered the community structures and increased the species diversity of TRB, especially in the rhizosphere soil. BF treatment caused insignificant changes in the community structure of TRB compared with CF treatment, yet it reduced the species diversities of TRB in soil. Thus, the partial use of fresh PM as a substitute for CF could increase the risk of spread of TRGs. Apart from plant growth promotion, BF was a promising fertilizer owing to its potential ability to control TRGs. Copyright © 2016 Elsevier Inc. All rights reserved.

Computational Approach for Epitaxial Polymorph Stabilization through Substrate Selection.

PubMed

Ding, Hong; Dwaraknath, Shyam S; Garten, Lauren; Ndione, Paul; Ginley, David; Persson, Kristin A

2016-05-25

With the ultimate goal of finding new polymorphs through targeted synthesis conditions and techniques, we outline a computational framework to select optimal substrates for epitaxial growth using first principle calculations of formation energies, elastic strain energy, and topological information. To demonstrate the approach, we study the stabilization of metastable VO2 compounds which provides a rich chemical and structural polymorph space. We find that common polymorph statistics, lattice matching, and energy above hull considerations recommends homostructural growth on TiO2 substrates, where the VO2 brookite phase would be preferentially grown on the a-c TiO2 brookite plane while the columbite and anatase structures favor the a-b plane on the respective TiO2 phases. Overall, we find that a model which incorporates a geometric unit cell area matching between the substrate and the target film as well as the resulting strain energy density of the film provide qualitative agreement with experimental observations for the heterostructural growth of known VO2 polymorphs: rutile, A and B phases. The minimal interfacial geometry matching and estimated strain energy criteria provide several suggestions for substrates and substrate-film orientations for the heterostructural growth of the hitherto hypothetical anatase, brookite, and columbite polymorphs. These criteria serve as a preliminary guidance for the experimental efforts stabilizing new materials and/or polymorphs through epitaxy. The current screening algorithm is being integrated within the Materials Project online framework and data and hence publicly available.

Computational Approach for Epitaxial Polymorph Stabilization through Substrate Selection

DOE PAGES

Ding, Hong; Dwaraknath, Shyam S.; Garten, Lauren; ...

2016-05-04

With the ultimate goal of finding new polymorphs through targeted synthesis conditions and techniques, we outline a computational framework to select optimal substrates for epitaxial growth using first principle calculations of formation energies, elastic strain energy, and topological information. To demonstrate the approach, we study the stabilization of metastable VO 2 compounds which provides a rich chemical and structural polymorph space. Here, we find that common polymorph statistics, lattice matching, and energy above hull considerations recommends homostructural growth on TiO 2 substrates, where the VO 2 brookite phase would be preferentially grown on the a-c TiO 2 brookite plane whilemore » the columbite and anatase structures favor the a-b plane on the respective TiO 2 phases. Overall, we find that a model which incorporates a geometric unit cell area matching between the substrate and the target film as well as the resulting strain energy density of the film provide qualitative agreement with experimental observations for the heterostructural growth of known VO 2 polymorphs: rutile, A and B phases. The minimal interfacial geometry matching and estimated strain energy criteria provide several suggestions for substrates and substrate-film orientations for the heterostructural growth of the hitherto hypothetical anatase, brookite, and columbite polymorphs. Our criteria serve as a preliminary guidance for the experimental efforts stabilizing new materials and/or polymorphs through epitaxy. The current screening algorithm is being integrated within the Materials Project online framework and data and hence publicly available.« less

Computational Approach for Epitaxial Polymorph Stabilization through Substrate Selection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Hong; Dwaraknath, Shyam S.; Garten, Lauren

With the ultimate goal of finding new polymorphs through targeted synthesis conditions and techniques, we outline a computational framework to select optimal substrates for epitaxial growth using first principle calculations of formation energies, elastic strain energy, and topological information. To demonstrate the approach, we study the stabilization of metastable VO 2 compounds which provides a rich chemical and structural polymorph space. Here, we find that common polymorph statistics, lattice matching, and energy above hull considerations recommends homostructural growth on TiO 2 substrates, where the VO 2 brookite phase would be preferentially grown on the a-c TiO 2 brookite plane whilemore » the columbite and anatase structures favor the a-b plane on the respective TiO 2 phases. Overall, we find that a model which incorporates a geometric unit cell area matching between the substrate and the target film as well as the resulting strain energy density of the film provide qualitative agreement with experimental observations for the heterostructural growth of known VO 2 polymorphs: rutile, A and B phases. The minimal interfacial geometry matching and estimated strain energy criteria provide several suggestions for substrates and substrate-film orientations for the heterostructural growth of the hitherto hypothetical anatase, brookite, and columbite polymorphs. Our criteria serve as a preliminary guidance for the experimental efforts stabilizing new materials and/or polymorphs through epitaxy. The current screening algorithm is being integrated within the Materials Project online framework and data and hence publicly available.« less

Composition dependences of crystal structure and electrical properties of epitaxial Pb(Zr,Ti)O3 films grown on Si and SrTiO3 substrates

NASA Astrophysics Data System (ADS)

Okamoto, Shoji; Okamoto, Satoshi; Yokoyama, Shintaro; Akiyama, Kensuke; Funakubo, Hiroshi

2016-10-01

{100}-oriented Pb(Zr x ,Ti1- x )O3 (PZT) thin films of approximately 2 µm thickness and Zr/(Zr + Ti) ratios of 0.39-0.65 were epitaxially grown on (100)cSrRuO3//(100)SrTiO3 (STO) and (100)cSrRuO3//(100)cLaNiO3//(100)CeO2//(100)YSZ//(100)Si (Si) substrates having different thermal expansion coefficients by pulsed metal-organic chemical vapor deposition (MOCVD). The effects of Zr/(Zr + Ti) ratio and type of substrate on the crystal structure and dielectric, ferroelectric and piezoelectric properties of the films were systematically investigated. The X-ray diffraction measurement showed that both films changed from having a tetragonal symmetry to rhombohedral symmetry through the coexisting region with increasing Zr/(Zr + Ti) ratio. This region showed the Zr/(Zr + Ti) ratios of 0.45-0.59 for the films on the STO substrates that were wider than the films on the Si substrates. Saturation polarization values were minimum at approximately Zr/(Zr + Ti) = 0.50 for the films on the STO substrates, and no obvious Zr/(Zr + Ti) ratio dependence was detected in the films on the Si substrates. On the other hand, the maximum field-induced strain values measured by scanning force microscopy at approximately Zr/(Zr + Ti) = 0.50 at 100 kV/cm were about 0.5 and 0.1% in the films on the Si and STO, respectively.

Direct visualization of critical hydrogen atoms in a pyridoxal 5'-phosphate enzyme.

PubMed

Dajnowicz, Steven; Johnston, Ryne C; Parks, Jerry M; Blakeley, Matthew P; Keen, David A; Weiss, Kevin L; Gerlits, Oksana; Kovalevsky, Andrey; Mueser, Timothy C

2017-10-16

Enzymes dependent on pyridoxal 5'-phosphate (PLP, the active form of vitamin B 6 ) perform a myriad of diverse chemical transformations. They promote various reactions by modulating the electronic states of PLP through weak interactions in the active site. Neutron crystallography has the unique ability of visualizing the nuclear positions of hydrogen atoms in macromolecules. Here we present a room-temperature neutron structure of a homodimeric PLP-dependent enzyme, aspartate aminotransferase, which was reacted in situ with α-methylaspartate. In one monomer, the PLP remained as an internal aldimine with a deprotonated Schiff base. In the second monomer, the external aldimine formed with the substrate analog. We observe a deuterium equidistant between the Schiff base and the C-terminal carboxylate of the substrate, a position indicative of a low-barrier hydrogen bond. Quantum chemical calculations and a low-pH room-temperature X-ray structure provide insight into the physical phenomena that control the electronic modulation in aspartate aminotransferase.Pyridoxal 5'-phosphate (PLP) is a ubiquitous co factor for diverse enzymes, among them aspartate aminotransferase. Here the authors use neutron crystallography, which allows the visualization of the positions of hydrogen atoms, and computation to characterize the catalytic mechanism of the enzyme.

Evaluation of Graphene/WO3 and Graphene/CeO x Structures as Electrodes for Supercapacitor Applications

NASA Astrophysics Data System (ADS)

Chaitoglou, Stefanos; Amade, Roger; Bertran, Enric

2017-12-01

The combination of graphene with transition metal oxides can result in very promising hybrid materials for use in energy storage applications thanks to its intriguing properties, i.e., highly tunable surface area, outstanding electrical conductivity, good chemical stability, and excellent mechanical behavior. In the present work, we evaluate the performance of graphene/metal oxide (WO3 and CeO x ) layered structures as potential electrodes in supercapacitor applications. Graphene layers were grown by chemical vapor deposition (CVD) on copper substrates. Single and layer-by-layer graphene stacks were fabricated combining graphene transfer techniques and metal oxides grown by magnetron sputtering. The electrochemical properties of the samples were analyzed and the results suggest an improvement in the performance of the device with the increase in the number of graphene layers. Furthermore, deposition of transition metal oxides within the stack of graphene layers further improves the areal capacitance of the device up to 4.55 mF/cm2, for the case of a three-layer stack. Such high values are interpreted as a result of the copper oxide grown between the copper substrate and the graphene layer. The electrodes present good stability for the first 850 cycles before degradation.

A study of the physical, chemical and biological properties of TiO2 coatings produced by micro-arc oxidation in a Ca-P-based electrolyte.

PubMed

dos Santos, Amanda; Araujo, Joyce R; Landi, Sandra M; Kuznetsov, Alexei; Granjeiro, José M; de Sena, Lidia Ágata; Achete, Carlos Alberto

2014-07-01

In this work, a porous and homogeneous titanium dioxide layer was grown on commercially pure titanium substrate using a micro-arc oxidation (MAO) process and Ca-P-based electrolyte. The structure and morphology of the TiO2 coatings were characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy, and profilometry. The chemical properties were studied using electron dispersive X-ray spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy. The wettability of the coating was evaluated using contact angle measurements. During the MAO process, Ca and P ions were incorporated into the oxide layer. The TiO2 coating was composed of a mixture of crystalline and amorphous structures. The crystalline part of the sample consisted of a major anatase phase and a minor rutile phase. A cross-sectional image of the coating-substrate interface reveals the presence of voids elongated along the interface. An osteoblast culture was performed to verify the cytocompatibility of the anodized surface. The results of the cytotoxicity tests show satisfactory cell viability of the titanium dioxide films produced in this study.

Effects of argon addition on a-CNx film deposition by hot carbon filament chemical vapor deposition

NASA Astrophysics Data System (ADS)

Watanabe, Yoshihisa; Aono, Masami; Yamazaki, Ayumi; Kitazawa, Nobuaki; Nakamura, Yoshikazu

2002-07-01

Using a carbon filament which supplies carbon and heat, amorphous carbon nitride (a-CNx) films were prepared on Si (100) substrates by hot filament chemical vapor deposition. Deposition was performed in a low-pressure atmosphere of pure nitrogen and a gas mixture of nitrogen and argon. Effects of argon additions to the nitrogen atmosphere on the film microstructure and interface composition between the film and substrate were studied by field-emission scanning electron microscopy (FESEM) and x-ray photoelectron spectroscopy (XPS). FESEM observations reveal that the film prepared in a pure nitrogen atmosphere has uniform nucleation and a densely packed columnar pieces structure. The film prepared in the nitrogen and argon gas mixture exhibits preferential nucleation and a tapered structure with macroscopic voids. Depth analyses using XPS reveal that the film prepared in pure nitrogen possesses a broad interface, which includes silicon carbide as well as a-CNx, whereas a sharp interface is discerned in the film prepared in the mixed nitrogen and argon gas. We observed that silicon carbide formation is suppressed by an argon addition to the nitrogen atmosphere during deposition. copyright 2002 American Vacuum Society.

Initial substrate moisture content and storage temperature affects chemical properties of bagged substrates containing controlled release fertilizer at two different temperatures

USDA-ARS?s Scientific Manuscript database

Bagged potting mixes can be stored for weeks or months before being used by consumers. Some bagged potting mixes are amended with controlled release fertilizers (CRF). The objective of this research was to observe how initial substrate moisture content and storage temperature affect the chemical p...

The role of chemical structure on the magnetic and electronic properties of Co{sub 2}FeAl{sub 0.5}Si{sub 0.5}/Si(111) interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuerbanjiang, Balati; Nedelkoski, Zlatko; Ghasemi, Arsham

2016-04-25

We show that Co{sub 2}FeAl{sub 0.5}Si{sub 0.5} film deposited on Si(111) has a single crystal structure and twin related epitaxial relationship with the substrate. Sub-nanometer electron energy loss spectroscopy shows that in a narrow interface region there is a mutual inter-diffusion dominated by Si and Co. Atomic resolution aberration-corrected scanning transmission electron microscopy reveals that the film has B2 ordering. The film lattice structure is unaltered even at the interface due to the substitutional nature of the intermixing. First-principles calculations performed using structural models based on the aberration corrected electron microscopy show that the increased Si incorporation in the filmmore » leads to a gradual decrease of the magnetic moment as well as significant spin-polarization reduction. These effects can have significant detrimental role on the spin injection from the Co{sub 2}FeAl{sub 0.5}Si{sub 0.5} film into the Si substrate, besides the structural integrity of this junction.« less

Surface- and Tip-Enhanced Raman Spectroscopy in Catalysis

PubMed Central

2016-01-01

Surface- and tip-enhanced Raman spectroscopy (SERS and TERS) techniques exhibit highly localized chemical sensitivity, making them ideal for studying chemical reactions, including processes at catalytic surfaces. Catalyst structures, adsorbates, and reaction intermediates can be observed in low quantities at hot spots where electromagnetic fields are the strongest, providing ample opportunities to elucidate reaction mechanisms. Moreover, under ideal measurement conditions, it can even be used to trigger chemical reactions. However, factors such as substrate instability and insufficient signal enhancement still limit the applicability of SERS and TERS in the field of catalysis. By the use of sophisticated colloidal synthesis methods and advanced techniques, such as shell-isolated nanoparticle-enhanced Raman spectroscopy, these challenges could be overcome. PMID:27075515

Modeling heat dissipation at the nanoscale: an embedding approach for chemical reaction dynamics on metal surfaces.

PubMed

Meyer, Jörg; Reuter, Karsten

2014-04-25

We present an embedding technique for metallic systems that makes it possible to model energy dissipation into substrate phonons during surface chemical reactions from first principles. The separation of chemical and elastic contributions to the interaction potential provides a quantitative description of both electronic and phononic band structure. Application to the dissociation of O2 at Pd(100) predicts translationally "hot" oxygen adsorbates as a consequence of the released adsorption energy (ca. 2.6 eV). This finding questions the instant thermalization of reaction enthalpies generally assumed in models of heterogeneous catalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel strategy for durable superhydrophobic coating on glass substrate via using silica chains to fix silica particles

NASA Astrophysics Data System (ADS)

Huang, Qi-Zhang; Fang, Yue-Yun; Liu, Peng-Yi; Zhu, Yan-Qing; Shi, Ji-Fu; Xu, Gang

2018-01-01

The practical application of superhydrophobic coatings on glass is usually restricted by their poor wear resistance due to the insufficient adhesion. A double-silica-layered structure was proposed to reinforce the coating adhesion on glass substrate. The wettability, surface morphologies, and chemical composition were investigated by water contact angle measurement, scanning electron microscopy (SEM), and fourier transformed infrared (FTIR) spectroscopy. The prepared superhydrophobic coating displays a good wear-resistance by emery paper and sand abrasion, which also has excellent thermal stability and UV resistance. This strategy shows a bright future for durable superhydrophobic coating on glass.

Insight into the role of substrate-binding residues in conferring substrate specificity for the multifunctional polysaccharide lyase Smlt1473.

PubMed

MacDonald, Logan C; Berger, Bryan W

2014-06-27

Anionic polysaccharides are of growing interest in the biotechnology industry due to their potential pharmaceutical applications in drug delivery and wound treatment. Chemical composition and polymer length strongly influence the physical and biological properties of the polysaccharide and thus its potential industrial and medical applications. One promising approach to determining monomer composition and controlling the degree of polymerization involves the use of polysaccharide lyases, which catalyze the depolymerization of anionic polysaccharides via a β-elimination mechanism. Utilization of these enzymes for the production of custom-made oligosaccharides requires a high degree of control over substrate specificity. Previously, we characterized a polysaccharide lyase (Smlt1473) from Stenotrophomonas maltophilia k279a, which exhibited significant activity against hyaluronan (HA), poly-β-d-glucuronic acid (poly-GlcUA), and poly-β-d-mannuronic acid (poly-ManA) in a pH-regulated manner. Here, we utilize a sequence structure guided approach based on a homology model of Smlt1473 to identify nine putative substrate-binding residues and examine their effect on substrate specificity via site-directed mutagenesis. Interestingly, single point mutations H221F and R312L resulted in increased activity and specificity toward poly-ManA and poly-GlcUA, respectively. Furthermore, a W171A mutant nearly eliminated HA activity, while increasing poly-ManA and poly-GlcUA activity by at least 35%. The effect of these mutations was analyzed by comparison with the high resolution structure of Sphingomonas sp. A1-III alginate lyase in complex with poly-ManA tetrasaccharide and by taking into account the structural differences between HA, poly-GlcUA, and poly-ManA. Overall, our results demonstrate that even minor changes in active site architecture have a significant effect on the substrate specificity of Smlt1473, whose structural plasticity could be applied to the design of highly active and specific polysaccharide lyases. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

Influence of metal electrodes on the response of humidity sensors coated with mesoporous silica

NASA Astrophysics Data System (ADS)

Bearzotti, Andrea

2008-01-01

Interesting effects of different metal electrodes on the behaviour of mesoporous based humidity sensors have been observed and studied by chemical characterization and electric measurements. The devices were prepared on passivated silicon slices utilizing an interdigitated structure as contacts. For comparison, the response of a device implemented on an alumina substrate has been reported. A block copolymer Pluronic F-127 has been used as the organic template and has been partially removed from the films by thermal calcination. A thin film mesoporous membrane has been deposited by dip-coating on the substrates in a sol-gel solution containing non-ionic block copolymers. Silica mesostructured films have been produced using an evaporation induced self-assembling process. The films were calcined at 150 °C to obtain the best performances in terms of stability, hysteresis and reproducibility of the response. The performance of the sensor has been found to be dependent on the film preparation method, the used electrodes and the substrate when exposed to different contents of relative humidity. Electrical characterization was performed under vacuum and dark conditions to investigate the properties of the materials in the absence of interfering chemicals, while the sensory properties were obtained in a controlled environment.

Nucleophile Promiscuity of Natural and Engineered Aldolases.

PubMed

Clapes, Pere; Hernández, Karel; Szekrenyi, Anna

2018-04-12

Asymmetric aldol addition reaction mediated by aldolases is recognized as a green and sustainable way for carbon-carbon bond formation. Research in this line has unveiled their unprecedented synthetic potentiality toward diverse new chemical structures, novel product families and even as a technology for industrial manufacturing processes. Despite that, aldolases have long been regarded as strictly selective catalysts, particularly for the nucleophilic substrate, limiting their broad applicability. In recent years, the advances in screening technologies and metagenomics uncovered novel C-C biocatalysts from superfamilies of widely known lyases. Moreover, protein engineering revealed the extraordinary malleability of different carboligases, offering a toolbox of biocatalysts active towards a large structural diversity of nucleophile substrates. In this paper, the nucleophile ambiguity of native and engineered aldolases is discussed with recent examples proving this novel concept. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Structure-Activity Study with Aryl Acylamidases

PubMed Central

Villarreal, David T.; Turco, Ronald F.; Konopka, Allan

1994-01-01

We examined the relationship between chemical structure and biodegradability of acylanilide herbicides by using a set of model compounds. Four bacterial isolates (one gram-negative and three gram-positive) that grew on acetanilide were used. These soil isolates cleaved the amide bond of acetanilide via an aryl acylamidase reaction, producing aniline and the organic acid acetate. A series of acetanilide analogs with alkyl substitutions on the nitrogen atom or the aromatic ring were tested for their ability to induce aryl acylamidase activity and act as substrates for the enzyme. The substrate range, in general, was limited to those analogs not disubstituted in the ortho position of the benzene ring or which did not contain an alkyl group on the nitrogen atom. These same N-substituted compounds did not induce enzyme activity either, whereas the ortho-substituted compounds could in some cases. PMID:16349428

RHEED and EELS study of Pd/Al bimetallic thin film growth on different α-Al 2O 3 substrates

NASA Astrophysics Data System (ADS)

Moroz, V.; Rajs, K.; Mašek, K.

2002-06-01

Pd/Al bimetallic thin films were grown by molecular beam epitaxy on single-crystalline α-Al 2O 3(0 0 0 1) and (1 1 2¯ 0) surfaces. Substrate and deposit crystallographic structures and evolution of deposit lattice parameter during the growth were studied by reflection high-energy electron diffraction. The electron energy loss spectroscopy was used as an auxiliary method for chemical analysis. The bimetallic films were prepared by successive deposition of both Pd and Al metals. The structure of Pd and Al deposits in early stages of the growth and its dependence on the preparation conditions were studied. Two phases of Pd clusters covered by Al overlayer have been found. The formation of Al overlayer strongly influenced the lattice parameter of Pd clusters.

The high-resolution structure of dihydrodipicolinate synthase from Escherichia coli bound to its first substrate, pyruvate

PubMed Central

Devenish, Sean R. A.; Gerrard, Juliet A.; Jameson, Geoffrey B.; Dobson, Renwick C. J.

2008-01-01

Dihydrodipicolinate synthase (DHDPS) mediates the key first reaction common to the biosynthesis of (S)-lysine and meso-diaminopimelate, molecules which play a crucial cross-linking role in bacterial cell walls. An effective inhibitor of DHDPS would represent a useful antibacterial agent; despite extensive effort, a suitable inhibitor has yet to be found. In an attempt to examine the specificity of the active site of DHDPS, the enzyme was cocrystallized with the substrate analogue oxaloacetate. The resulting crystals diffracted to 2.0 Å resolution, but solution of the protein structure revealed that pyruvate was bound in the active site rather than oxaloacetic acid. Kinetic analysis confirmed that the decarboxy­lation of oxaloacetate was not catalysed by DHDPS and was instead a slow spontaneous chemical process. PMID:19052357

Growth and characterization of textured well-faceted ZnO on planar Si(100), planar Si(111), and textured Si(100) substrates for solar cell applications.

PubMed

Tsai, Chin-Yi; Lai, Jyong-Di; Feng, Shih-Wei; Huang, Chien-Jung; Chen, Chien-Hsun; Yang, Fann-Wei; Wang, Hsiang-Chen; Tu, Li-Wei

2017-01-01

In this work, textured, well-faceted ZnO materials grown on planar Si(100), planar Si(111), and textured Si(100) substrates by low-pressure chemical vapor deposition (LPCVD) were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and cathode luminescence (CL) measurements. The results show that ZnO grown on planar Si(100), planar Si(111), and textured Si(100) substrates favor the growth of ZnO(110) ridge-like, ZnO(002) pyramid-like, and ZnO(101) pyramidal-tip structures, respectively. This could be attributed to the constraints of the lattice mismatch between the ZnO and Si unit cells. The average grain size of ZnO on the planar Si(100) substrate is slightly larger than that on the planar Si(111) substrate, while both of them are much larger than that on the textured Si(100) substrate. The average grain sizes (about 10-50 nm) of the ZnO grown on the different silicon substrates decreases with the increase of their strains. These results are shown to strongly correlate with the results from the SEM, AFM, and CL as well. The reflectance spectra of these three samples show that the antireflection function provided by theses samples mostly results from the nanometer-scaled texture of the ZnO films, while the micrometer-scaled texture of the Si substrate has a limited contribution. The results of this work provide important information for optimized growth of textured and well-faceted ZnO grown on wafer-based silicon solar cells and can be utilized for efficiency enhancement and optimization of device materials and structures, such as heterojunction with intrinsic thin layer (HIT) solar cells.

Structural insight into the substrate- and dioxygen-binding manner in the catalytic cycle of rieske nonheme iron oxygenase system, carbazole 1,9a-dioxygenase.

PubMed

Ashikawa, Yuji; Fujimoto, Zui; Usami, Yusuke; Inoue, Kengo; Noguchi, Haruko; Yamane, Hisakazu; Nojiri, Hideaki

2012-06-24

Dihydroxylation of tandemly linked aromatic carbons in a cis-configuration, catalyzed by multicomponent oxygenase systems known as Rieske nonheme iron oxygenase systems (ROs), often constitute the initial step of aerobic degradation pathways for various aromatic compounds. Because such RO reactions inherently govern whether downstream degradation processes occur, novel oxygenation mechanisms involving oxygenase components of ROs (RO-Os) is of great interest. Despite substantial progress in structural and physicochemical analyses, no consensus exists on the chemical steps in the catalytic cycles of ROs. Thus, determining whether conformational changes at the active site of RO-O occur by substrate and/or oxygen binding is important. Carbazole 1,9a-dioxygenase (CARDO), a RO member consists of catalytic terminal oxygenase (CARDO-O), ferredoxin (CARDO-F), and ferredoxin reductase. We have succeeded in determining the crystal structures of oxidized CARDO-O, oxidized CARDO-F, and both oxidized and reduced forms of the CARDO-O: CARDO-F binary complex. In the present study, we determined the crystal structures of the reduced carbazole (CAR)-bound, dioxygen-bound, and both CAR- and dioxygen-bound CARDO-O: CARDO-F binary complex structures at 1.95, 1.85, and 2.00 Å resolution. These structures revealed the conformational changes that occur in the catalytic cycle. Structural comparison between complex structures in each step of the catalytic mechanism provides several implications, such as the order of substrate and dioxygen bindings, the iron-dioxygen species likely being Fe(III)-(hydro)peroxo, and the creation of room for dioxygen binding and the promotion of dioxygen binding in desirable fashion by preceding substrate binding. The RO catalytic mechanism is proposed as follows: When the Rieske cluster is reduced, substrate binding induces several conformational changes (e.g., movements of the nonheme iron and the ligand residue) that create room for oxygen binding. Dioxygen bound in a side-on fashion onto nonheme iron is activated by reduction to the peroxo state [Fe(III)-(hydro)peroxo]. This state may react directly with the bound substrate, or O-O bond cleavage may occur to generate Fe(V)-oxo-hydroxo species prior to the reaction. After producing a cis-dihydrodiol, the product is released by reducing the nonheme iron. This proposed scheme describes the catalytic cycle of ROs and provides important information for a better understanding of the mechanism.

Investigation on nonlinear optical properties of MoS2 nanoflakes grown on silicon and quartz substrates

NASA Astrophysics Data System (ADS)

Bayesteh, Samaneh; Zahra Mortazavi, Seyedeh; Reyhani, Ali

2018-05-01

In this study, MoS2 nanoflakes were directly grown on different substrates—Si/SiO2 and quartz—by one-step thermal chemical vapor deposition using MoO3 and sulfide powders as precursors. Scanning electron microscopy and x-ray diffraction patterns demonstrated the formation of MoS2 structures on both substrates. Moreover, UV-visible and photoluminescence analysis confirmed the formation of MoS2 few-layer structures. According to Raman spectroscopy, by assessment of the line width and frequency shift differences between the and A 1g, it was inferred that the MoS2 grown on the silicon substrate was monolayer and that grown on the quartz substrate was multilayer. In addition, open-aperture and close-aperture Z-scan techniques were employed to study the nonlinear optical properties including nonlinear absorption and nonlinear refraction of the grown MoS2. All experiments were performed using a diode laser with a wavelength of 532 nm as the light source. It is noticeable that both samples demonstrate obvious self-defocusing behavior. The monolayer MoS2 grown on the silicon substrate displayed considerable two-photon absorption while, the multilayer MoS2 synthesized on the quartz exhibited saturable absorption. In general, few-layered MoS2 would be useful for the development of nanophotonic devices like optical limiters, optical switchers, etc.

Investigation of the Structural, Electrical, and Optical Properties of the Nano-Scale GZO Thin Films on Glass and Flexible Polyimide Substrates

PubMed Central

Wang, Fang-Hsing; Chen, Kun-Neng; Hsu, Chao-Ming; Liu, Min-Chu; Yang, Cheng-Fu

2016-01-01

In this study, Ga2O3-doped ZnO (GZO) thin films were deposited on glass and flexible polyimide (PI) substrates at room temperature (300 K), 373 K, and 473 K by the radio frequency (RF) magnetron sputtering method. After finding the deposition rate, all the GZO thin films with a nano-scale thickness of about 150 ± 10 nm were controlled by the deposition time. X-ray diffraction patterns indicated that the GZO thin films were not amorphous and all exhibited the (002) peak, and field emission scanning electron microscopy showed that only nano-scale particles were observed. The dependences of the structural, electrical, and optical properties of the GZO thin films on different deposition temperatures and substrates were investigated. X-ray photoemission spectroscopy (XPS) was used to measure the elemental composition at the chemical and electronic states of the GZO thin films deposited on different substrates, which could be used to clarify the mechanism of difference in electrical properties of the GZO thin films. In this study, the XPS binding energy spectra of Ga2p3/2 and Ga2p1/2 peaks, Zn2p3/2 and Zn2p1/2 peaks, the Ga3d peak, and O1s peaks for GZO thin films on glass and PI substrates were well compared. PMID:28335216

Short-term microbial effects of a large-scale mine-tailing storage facility collapse on the local natural environment

PubMed Central

Baldwin, Susan A.; Taylor, Jon; Gurr, David B.; Denesiuk, Daniel R.; Van Hamme, Jonathan D.; Fraser, Lauchlan H.

2018-01-01

We investigated the impacts of the Mount Polley tailings impoundment failure on chemical, physical, and microbial properties of substrates within the affected watershed, comprised of 70 hectares of riparian wetlands and 40 km of stream and lake shore. We established a biomonitoring network in October of 2014, two months following the disturbance, and evaluated riparian and wetland substrates for microbial community composition and function via 16S and full metagenome sequencing. A total of 234 samples were collected from substrates at 3 depths and 1,650,752 sequences were recorded in a geodatabase framework. These data revealed a wealth of information regarding watershed-scale distribution of microbial community members, as well as community composition, structure, and response to disturbance. Substrates associated with the impact zone were distinct chemically as indicated by elevated pH, nitrate, and sulphate. The microbial community exhibited elevated metabolic capacity for selenate and sulfate reduction and an abundance of chemolithoautotrophs in the Thiobacillus thiophilus/T. denitrificans/T. thioparus clade that may contribute to nitrate attenuation within the affected watershed. The most impacted area (a 6 km stream connecting two lakes) exhibited 30% lower microbial diversity relative to the remaining sites. The tailings impoundment failure at Mount Polley Mine has provided a unique opportunity to evaluate functional and compositional diversity soon after a major catastrophic disturbance to assess metabolic potential for ecosystem recovery. PMID:29694379

Application of lasers and pulsed power to coating removal

NASA Astrophysics Data System (ADS)

Young, Chris M.; Moeny, William M.; Curry, Randy D.; McDonald, Ken; Bosma, John T.

1995-03-01

Lasers and other pulsed power systems are uniquely suited for removal of coatings from a wide variety of substrates. Coatings which can be removed by these systems include paint, adhesives, epoxies, dips, rust, scale, and bird droppings. Suitable substrates include wood, metal, cloth, stone, ceramic, plastics, and even skin. These systems have the advantage over chemical stripping or mechanical abrasion in that the substrate is left virtually unharmed and in many cases the residue is reduced to a form that is more easily disposed of without toxic byproducts or expensive refurbishment. Furthermore, laser and other pulsed power based systems can be operated using only local containment without the need for special operator protective gear or complete enclosure of the substrate structure. Additional advantages are gained in these systems because they typically combine multiple removal mechanisms for greater effectiveness. For example, pulsed lasers create rapid heating of the coating. This rapid heating can result in chemical breakdown of the coating, thermomechanical stress induced dislocation, shock wave agitation, and physical ablation. This paper presents some of the latest research findings on coating removal using these systems. A comparative survey of the system technology, effectiveness, cost, and application is presented. Also presented is a survey of the commercial potential for the systems. Systems which are presented include lasers (CW, pulsed, Infrared, UV, etc.), flashlamps, electro-cathodic debonders, electron beams, and glow discharges.

Potentiodynamic Polarization Studies and Surface Chemical Composition of Bismuth Titanate (BixTiyOz) Films Produced through Radiofrequency Magnetron Sputtering

PubMed Central

Alfonso, José E.; Olaya, Jhon J.; Pinzón, Manuel J.; Marco, José F.

2013-01-01

The applications of Bismuth Titanate (BixTiyOz) materials have been focused on their electronic and optical properties, but with respect to the use of these compounds in applications like corrosion resistance, have been very few or nonexistent. For this reason, in the present investigation BixTiyOz thin films were deposited using RF magnetron sputtering onto silicon wafers, stainless steel 316L, and titanium alloy (Ti6Al4V) substrates, in order to carry out a study of the corrosion behavior of this compound. The structural properties of the coatings were studied through X-ray diffraction (XRD), the morphology was determined using Scanning Electron Microscopy (SEM), the corrosion resistance behavior of the coated and uncoated substrates was evaluated via the Potentiodynamic Polarization technique, and surface chemical composition was evaluated through X-ray photoelectron spectroscopy (XPS). The XRD results indicated that the films were amorphous. The SEM micrographs showed that the deposited films were homogeneous, but in some cases there were cracks. The potentiodynamic polarization technique showed that the corrosion current in the coated substrates decreased by an order of two magnitudes with respect to the uncoated substrates, but in both cases the corrosion mechanism was pitting due to the pores in the film. The XPS analysis shows that the deposited films contain both Bi3+ and Ti4+. PMID:28788338

Potentiodynamic Polarization Studies and Surface Chemical Composition of Bismuth Titanate (Bi x Ti y O z ) Films Produced through Radiofrequency Magnetron Sputtering.

PubMed

Alfonso, José E; Olaya, Jhon J; Pinzón, Manuel J; Marco, José F

2013-10-08

The applications of Bismuth Titanate (Bi x Ti y O z ) materials have been focused on their electronic and optical properties, but with respect to the use of these compounds in applications like corrosion resistance, have been very few or nonexistent. For this reason, in the present investigation Bi x Ti y O z thin films were deposited using RF magnetron sputtering onto silicon wafers, stainless steel 316L, and titanium alloy (Ti₆Al₄V) substrates, in order to carry out a study of the corrosion behavior of this compound. The structural properties of the coatings were studied through X-ray diffraction (XRD), the morphology was determined using Scanning Electron Microscopy (SEM), the corrosion resistance behavior of the coated and uncoated substrates was evaluated via the Potentiodynamic Polarization technique, and surface chemical composition was evaluated through X-ray photoelectron spectroscopy (XPS). The XRD results indicated that the films were amorphous. The SEM micrographs showed that the deposited films were homogeneous, but in some cases there were cracks. The potentiodynamic polarization technique showed that the corrosion current in the coated substrates decreased by an order of two magnitudes with respect to the uncoated substrates, but in both cases the corrosion mechanism was pitting due to the pores in the film. The XPS analysis shows that the deposited films contain both Bi 3+ and Ti 4+ .

Spherical silicon-shell photonic band gap structures fabricated by laser-assisted chemical vapor deposition

NASA Astrophysics Data System (ADS)

Wang, H.; Yang, Z. Y.; Lu, Y. F.

2007-02-01

Laser-assisted chemical vapor deposition was applied in fabricating three-dimensional (3D) spherical-shell photonic band gap (PBG) structures by depositing silicon shells covering silica particles, which had been self-assembled into 3D colloidal crystals. The colloidal crystals of self-assembled silica particles were formed on silicon substrates using the isothermal heating evaporation approach. A continuous wave Nd:YAG laser (1064nm wavelength) was used to deposit silicon shells by thermally decomposing disilane gas. Periodic silicon-shell/silica-particle PBG structures were obtained. By removing the silica particles enclosed in the silicon shells using hydrofluoric acid, hollow spherical silicon-shell arrays were produced. This technique is capable of fabricating structures with complete photonic band gaps, which is predicted by simulations with the plane wave method. The techniques developed in this study have the potential to flexibly engineer the positions of the PBGs by varying both the silica particle size and the silicon-shell thickness. Ellipsometry was used to investigate the specific photonic band gaps for both structures.

Fate of sessile droplet chemical agents in environmental substrates in the presence of physiochemical processes

NASA Astrophysics Data System (ADS)

Navaz, H. K.; Dang, A. L.; Atkinson, T.; Zand, A.; Nowakowski, A.; Kamensky, K.

2014-05-01

A general-purpose multi-phase and multi-component computer model capable of solving the complex problems encountered in the agent substrate interaction is developed. The model solves the transient and time-accurate mass and momentum governing equations in a three dimensional space. The provisions for considering all the inter-phase activities (solidification, evaporation, condensation, etc.) are included in the model. The chemical reactions among all phases are allowed and the products of the existing chemical reactions in all three phases are possible. The impact of chemical reaction products on the transport properties in porous media such as porosity, capillary pressure, and permeability is considered. Numerous validations for simulants, agents, and pesticides with laboratory and open air data are presented. Results for chemical reactions in the presence of pre-existing water in porous materials such as moisture, or separated agent and water droplets on porous substrates are presented. The model will greatly enhance the capabilities in predicting the level of threat after any chemical such as Toxic Industrial Chemicals (TICs) and Toxic Industrial Materials (TIMs) release on environmental substrates. The model's generality makes it suitable for both defense and pharmaceutical applications.

Atomic Covalent Functionalization of Graphene

PubMed Central

Johns, James E.; Hersam, Mark C.

2012-01-01

Conspectus Although graphene’s physical structure is a single atom thick, two-dimensional, hexagonal crystal of sp2 bonded carbon, this simple description belies the myriad interesting and complex physical properties attributed to this fascinating material. Because of its unusual electronic structure and superlative properties, graphene serves as a leading candidate for many next generation technologies including high frequency electronics, broadband photodetectors, biological and gas sensors, and transparent conductive coatings. Despite this promise, researchers could apply graphene more routinely in real-world technologies if they could chemically adjust graphene’s electronic properties. For example, the covalent modification of graphene to create a band gap comparable to silicon (~1 eV) would enable its use in digital electronics, and larger band gaps would provide new opportunities for graphene-based photonics. Towards this end, researchers have focused considerable effort on the chemical functionalization of graphene. Due to its high thermodynamic stability and chemical inertness, new methods and techniques are required to create covalent bonds without promoting undesirable side reactions or irreversible damage to the underlying carbon lattice. In this Account, we review and discuss recent theoretical and experimental work studying covalent modifications to graphene using gas phase atomic radicals. Atomic radicals have sufficient energy to overcome the kinetic and thermodynamic barriers associated with covalent reactions on the basal plane of graphene but lack the energy required to break the C-C sigma bonds that would destroy the carbon lattice. Furthermore, because they are atomic species, radicals substantially reduce the likelihood of unwanted side reactions that confound other covalent chemistries. Overall, these methods based on atomic radicals show promise for the homogeneous functionalization of graphene and the production of new classes of two-dimensional materials with fundamentally different electronic and physical properties. Specifically, we focus on recent studies of the addition of atomic hydrogen, fluorine, and oxygen to the basal plane of graphene. In each of these reactions a high energy, activating step initiates the process, breaking the local π structure and distorting the surrounding lattice. Scanning tunneling microscopy experiments reveal that substrate mediated interactions often dominate when the initial binding event occurs. We then compare these substrate effects with the results of theoretical studies that typically assume a vacuum environment. As the surface coverage increases, clusters often form around the initial distortion, and the stoichiometric composition of the saturated end product depends strongly on both the substrate and reactant species. In addition to these chemical and structural observations, we review how covalent modification can extend the range of physical properties that are achievable in two-dimensional materials. PMID:23030800

Surface-enhanced Raman scattering from AgNP-graphene-AgNP sandwiched nanostructures

NASA Astrophysics Data System (ADS)

Wu, Jian; Xu, Yijun; Xu, Pengyu; Pan, Zhenghui; Chen, Sheng; Shen, Qishen; Zhan, Li; Zhang, Yuegang; Ni, Weihai

2015-10-01

We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a ``hot surface'' for enhancing the Raman response of two-dimensional materials.We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a ``hot surface'' for enhancing the Raman response of two-dimensional materials. Electronic supplementary information (ESI) available: Additional SEM images, electric field enhancement profiles, Raman scattering spectra, and structure-dependent peak ratios. See DOI: 10.1039/c5nr04500b

Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) with Raman Imaging Applied to Lunar Meteorites.

PubMed

Smith, Joseph P; Smith, Frank C; Booksh, Karl S

2018-03-01

Lunar meteorites provide a more random sampling of the surface of the Moon than do the returned lunar samples, and they provide valuable information to help estimate the chemical composition of the lunar crust, the lunar mantle, and the bulk Moon. As of July 2014, ∼96 lunar meteorites had been documented and ten of these are unbrecciated mare basalts. Using Raman imaging with multivariate curve resolution-alternating least squares (MCR-ALS), we investigated portions of polished thin sections of paired, unbrecciated, mare-basalt lunar meteorites that had been collected from the LaPaz Icefield (LAP) of Antarctica-LAP 02205 and LAP 04841. Polarized light microscopy displays that both meteorites are heterogeneous and consist of polydispersed sized and shaped particles of varying chemical composition. For two distinct probed areas within each meteorite, the individual chemical species and associated chemical maps were elucidated using MCR-ALS applied to Raman hyperspectral images. For LAP 02205, spatially and spectrally resolved clinopyroxene, ilmenite, substrate-adhesive epoxy, and diamond polish were observed within the probed areas. Similarly, for LAP 04841, spatially resolved chemical images with corresponding resolved Raman spectra of clinopyroxene, troilite, a high-temperature polymorph of anorthite, substrate-adhesive epoxy, and diamond polish were generated. In both LAP 02205 and LAP 04841, substrate-adhesive epoxy and diamond polish were more readily observed within fractures/veinlet features. Spectrally diverse clinopyroxenes were resolved in LAP 04841. Factors that allow these resolved clinopyroxenes to be differentiated include crystal orientation, spatially distinct chemical zoning of pyroxene crystals, and/or chemical and molecular composition. The minerals identified using this analytical methodology-clinopyroxene, anorthite, ilmenite, and troilite-are consistent with the results of previous studies of the two meteorites using electron microprobe analysis. To our knowledge, this is the first report of MCR-ALS with Raman imaging used for the investigation of both lunar and other types of meteorites. We have demonstrated the use of multivariate analysis methods, namely MCR-ALS, with Raman imaging to investigate heterogeneous lunar meteorites. Our analytical methodology can be used to elucidate the chemical, molecular, and structural characteristics of phases in a host of complex, heterogeneous geological, geochemical, and extraterrestrial materials.

Plasmonic nanostructures for bioanalytical applications of SERS

NASA Astrophysics Data System (ADS)

Kahraman, Mehmet; Wachsmann-Hogiu, Sebastian

2016-03-01

Surface-enhanced Raman scattering (SERS) is a potential analytical technique for the detection and identification of chemicals and biological molecules and structures in the close vicinity of metallic nanostructures. We present a novel method to fabricate tunable plasmonic nanostructures and perform a comprehensive structural and optical characterization of the structures. Spherical latex particles are uniformly deposited on glass slides and used as templates to obtain nanovoid structures on polydimethylsiloxane surfaces. The diameter and depth of the nanovoids are controlled by the size of the latex particles. The nanovoids are coated with a thin Ag layer for fabrication of uniform plasmonic nanostructures. Structural characterization of the surfaces is performed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Optical properties of these plasmonic nanostructures are evaluated via UV/Vis spectroscopy, and SERS. The sample preparation step is the key point to obtain strong and reproducible SERS spectra from the biological structures. When the colloidal suspension is used as a SERS substrate for the protein detection, the electrostatic interaction of the proteins with the nanoparticles is described by the nature of their charge status, which influences the aggregation properties such as the size and shape of the aggregates, which is critical for the SERS experiment. However, when the solid SERS substrates are fabricated, SERS signal of the proteins that are background free and independent of the protein charge. Pros and cons of using plasmonic nano colloids and nanostructures as SERS substrate will be discussed for label-free detection of proteins using SERS.

Structural and optical properties of Sb65Se35-xGex thin films

NASA Astrophysics Data System (ADS)

Saleh, S. A.; Al-Hajry, A.; Ali, H. M.

2011-07-01

Sb65Se35-xGex (x=0-20 at.%) thin films, prepared by the electron beam evaporation technique on ultrasonically cleaned glass substrates at 300 K, were investigated. The amorphous structure of the thin films was confirmed by x-ray diffraction analysis. The structure was deduced from the Raman spectra measured for all germanium contents in the Sb-Se-Ge matrix. The absorption coefficient (α) of the films was determined by optical transmission measurements. The compositional dependence of the optical band gap is discussed in light of topological and chemical ordered network models.

Chemical vapor deposition growth

NASA Technical Reports Server (NTRS)

Ruth, R. P.; Manasevit, H. M.; Johnson, R. E.; Kenty, J. L.; Moudy, L. A.; Simpson, W. I.; Yang, J. J.

1976-01-01

A laboratory type CVD reactor system with a vertical deposition chamber and sample pedestal heated by an external RF coil has been extensively modified by installation of mass flow controllers, automatic process sequence timers, and special bellows-sealed air-operated valves for overall improved performance. Various film characterization procedures, including classical metallography, SEM analyses, X ray diffraction analyses, surface profilometry, and electrical measurements (resistivity, carrier concentration, mobility, spreading resistance profiles, and minority-carrier lifetime by the C-V-t method) area used to correlate Si sheet properties with CVD parameters and substrate properties. Evaluation procedures and measurements are given. Experimental solar cell structures were made both in epitaxial Si sheet (on sapphire substrates) and in polycrystalline material on alumina substrates, the former to provide an indication of what might be an upper limit on performance of the latter. Preliminary results are given, as obtained in cell structures not specially designed to allow for the unique properties of the sheet material, and fabricated in material known to be far from optimum for photovoltaic performance. Low power conversion efficiencies have been obtained in the epitaxial as well as the polycrystalline Si sheet.

Questing and the application for silicon based ternary compound within ultra-thin layer of SIS intermediate region

NASA Astrophysics Data System (ADS)

Chen, Shumin; Gao, Ming; Wan, Yazhou; Du, Huiwei; Li, Yong; Ma, Zhongquan

2016-12-01

A silicon based ternary compound was supposed to be solid synthesized with In, Si and O elements by magnetron sputtering of indium tin oxide target (ITO) onto crystal silicon substrate at 250 °C. To make clear the configuration of the intermediate region, a potential method to obtain the chemical bonding of Si with other existing elements was exploited by X-ray photoelectron spectroscopy (XPS) instrument combined with other assisted techniques. The phase composition and solid structure of the interfacial region between ITO and Si substrate were investigated by X-ray diffraction (XRD) and high resolution cross sectional transmission electron microscope (HR-TEM). A photovoltaic device with structure of Al/Ag/ITO/SiOx/p-Si/Al was assembled by depositing ITO films onto the p-Si substrate by using magnetron sputtering. The new matter has been assumed to be a buffer layer for semiconductor-insulator-semiconductor (SIS) photovoltaic device and plays critical role for the promotion of optoelectronic conversion performance from the view point of device physics.

Characterization of Gallium Indium Phosphide and Progress of Aluminum Gallium Indium Phosphide System Quantum-Well Laser Diode.

PubMed

Hamada, Hiroki

2017-07-28

Highly ordered gallium indium phosphide layers with the low bandgap have been successfully grown on the (100) GaAs substrates, the misorientation toward [01-1] direction, using the low-pressure metal organic chemical vapor deposition method. It is found that the optical properties of the layers are same as those of the disordered ones, essentially different from the ordered ones having two orientations towards [1-11] and [11-1] directions grown on (100) gallium arsenide substrates, which were previously reported. The bandgap at 300 K is 1.791 eV. The value is the smallest ever reported, to our knowledge. The high performance transverse stabilized AlGaInP laser diodes with strain compensated quantum well structure, which is developed in 1992, have been successfully obtained by controlling the misorientation angle and directions of GaAs substrates. The structure is applied to quantum dots laser diodes. This paper also describes the development history of the quantum well and the quantum dots laser diodes, and their future prospects.

Characterization of Gallium Indium Phosphide and Progress of Aluminum Gallium Indium Phosphide System Quantum-Well Laser Diode

PubMed Central

Hamada, Hiroki

2017-01-01

Highly ordered gallium indium phosphide layers with the low bandgap have been successfully grown on the (100) GaAs substrates, the misorientation toward [01−1] direction, using the low-pressure metal organic chemical vapor deposition method. It is found that the optical properties of the layers are same as those of the disordered ones, essentially different from the ordered ones having two orientations towards [1−11] and [11−1] directions grown on (100) gallium arsenide substrates, which were previously reported. The bandgap at 300 K is 1.791 eV. The value is the smallest ever reported, to our knowledge. The high performance transverse stabilized AlGaInP laser diodes with strain compensated quantum well structure, which is developed in 1992, have been successfully obtained by controlling the misorientation angle and directions of GaAs substrates. The structure is applied to quantum dots laser diodes. This paper also describes the development history of the quantum well and the quantum dots laser diodes, and their future prospects. PMID:28773227

IspE Inhibitors Identified by a Combination of In Silico and In Vitro High-Throughput Screening

PubMed Central

Tidten-Luksch, Naomi; Grimaldi, Raffaella; Torrie, Leah S.; Frearson, Julie A.; Hunter, William N.; Brenk, Ruth

2012-01-01

CDP-ME kinase (IspE) contributes to the non-mevalonate or deoxy-xylulose phosphate (DOXP) pathway for isoprenoid precursor biosynthesis found in many species of bacteria and apicomplexan parasites. IspE has been shown to be essential by genetic methods and since it is absent from humans it constitutes a promising target for antimicrobial drug development. Using in silico screening directed against the substrate binding site and in vitro high-throughput screening directed against both, the substrate and co-factor binding sites, non-substrate-like IspE inhibitors have been discovered and structure-activity relationships were derived. The best inhibitors in each series have high ligand efficiencies and favourable physico-chemical properties rendering them promising starting points for drug discovery. Putative binding modes of the ligands were suggested which are consistent with established structure-activity relationships. The applied screening methods were complementary in discovering hit compounds, and a comparison of both approaches highlights their strengths and weaknesses. It is noteworthy that compounds identified by virtual screening methods provided the controls for the biochemical screens. PMID:22563402

Electrical and optical properties of molybdenum doped zinc oxide films prepared by reactive RF magnetron sputtering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reddy, R. Subba; Sreedhar, A.; Uthanna, S., E-mail: uthanna@rediffmail.com

Molybdenum doped zinc oxide (MZO) films were deposited on to glass substrates held at temperatures in the range from 303 to 673 K by reactive RF magnetron sputtering method. The chemical composition, crystallographic structure and surface morphology, electrical and optical properties of the films were determined. The films contained the molybdenum of 2.7 at. % in ZnO. The films deposited at 303 K were of X-ray amorphous. The films formed at 473 K were of nanocrystalline in nature with wurtzite structure. The crystallite size of the films was increased with the increase of substrate temperature. The optical transmittance of the films was inmore » the visible range was 80–85%. The molybdenum (2.7 at %) doped zinc oxide films deposited at substrate temperature of 573 K were of nanocrystalline with electrical resistivity of 7.2×10{sup −3} Ωcm, optical transmittance of 85 %, optical band gap of 3.35 eV and figure of merit 30.6 Ω{sup −1}cm{sup −1}.« less

Cu-rGO subsurface layer creation on copper substrate and its resistance to oxidation

NASA Astrophysics Data System (ADS)

Pietrzak, Katarzyna; Strojny-Nędza, Agata; Olesińska, Wiesława; Bańkowska, Anna; Gładki, Andrzej

2017-11-01

On the basis of a specially designed experiment, this paper presents a model, which is an attempt to explain the mechanism of formatting and creating oxidation resistance of Cu-rGO subsurface layers. Practically zero chemical affinity of copper to carbon is a fundamental difficulty in creating composite structures of Cu-C, properties which are theoretically possible to estimate. In order to bind the thermally reduced graphene oxide with copper surface, the effect of structural rebuilding of the copper oxide, in the process of annealing in a nitrogen atmosphere, have been used. On intentionally oxidized and anoxic copper substrates the dispersed graphene oxide (GO) and thermally reduced graphene oxide (rGO) were loaded. Annealing processes after the binding effects of both graphene oxide forms to Cu substrates were tested. The methods for high-resolution electron microscopy were found subsurface rGO-Cu layer having a substantially greater resistance to oxidation than pure copper. The mechanism for the effective resistance to oxidation of the Cu-rGO has been presented in a hypothetical form.

Atomic scale study of strain relaxation in Sn islands on Sn-induced Si(111)-(2√3 ×2√3 ) surface

NASA Astrophysics Data System (ADS)

Wang, L. L.; Ma, X. C.; Ning, Y. X.; Ji, S. H.; Fu, Y. S.; Jia, J. F.; Kelly, K. F.; Xue, Q. K.

2009-04-01

Surface structure of the Sn islands 5 ML high, prepared on Si(111)-(2√3 ×2√3 )-Sn substrate, is investigated by low temperature scanning tunneling microscopy/spectroscopy. Due to the elastic strain relaxation in the islands, the in-plane unit cell structure distorts and the apparent height of the surface atoms varies regularly to form an overall modulated strip structure. The quantum well states are observed to depend on the relative position within this structure, which implies the change of the surface chemical potential induced by the elastic strain relaxation as well.

Nanocrystalline tin oxide nanofibers deposited by a novel focused electrospinning method. Application to the detection of TATP precursors.

PubMed

Santos, José Pedro; Fernández, Maria Jesús; Fontecha, José Luis; Matatagui, Daniel; Sayago, Isabel; Horrillo, Maria Carmen; Gracia, Isabel

2014-12-16

A new method of depositing tin dioxide nanofibers in order to develop chemical sensors is presented. It involves an electrospinning process with in-plane electrostatic focusing over micromechanized substrates. It is a fast and reproducible method. After an annealing process, which can be performed by the substrate heaters, it is observed that the fibers are intertwined forming porous networks that are randomly distributed on the substrate. The fiber diameters oscillate from 100 nm to 200 nm and fiber lengths reach several tens of microns. Each fiber has a polycrystalline structure with multiple nano-grains. The sensors have been tested for the detection of acetone and hydrogen peroxide (precursors of the explosive triacetone triperoxide, TATP) in air in the ppm range. High and fast responses to these gases have been obtained.

Electron field emission from phase pure nanotube films grown in a methane/hydrogen plasma

NASA Astrophysics Data System (ADS)

Küttel, Olivier M.; Groening, Oliver; Emmenegger, Christoph; Schlapbach, Louis

1998-10-01

Phase pure nanotube films were grown on silicon substrates by a microwave plasma under conditions which normally are used for the growth of chemical vapor deposited diamond films. However, instead of using any pretreatment leading to diamond nucleation we deposited metal clusters on the silicon substrate. The resulting films contain only nanotubes and also onion-like structures. However, no other carbon allotropes like graphite or amorphous clustered material could be found. The nanotubes adhere very well to the substrates and do not need any further purification step. Electron field emission was observed at fields above 1.5 V/μm and we observed an emission site density up to 104/cm2 at 3 V/μm. Alternatively, we have grown nanotube films by the hot filament technique, which allows to uniformly cover a two inch wafer.

Formation and properties of surface-anchored polymer assemblies with tunable physico-chemical characteristics

NASA Astrophysics Data System (ADS)

Wu, Tao

We describe two new methodologies leading to the formation of novel surface-anchored polymer assemblies on solid substrates. While the main goal is to understand the fundamentals pertaining to the preparation and properties of the surface-bound polymer assemblies (including neutral and chargeable polymers), several examples also are mentioned throughout the Thesis that point out to practical applications of such structures. The first method is based on generating assemblies comprising anchored polymers with a gradual variation of grafting densities on solid substrates. These structures are prepared by first covering the substrate with a molecular gradient of the polymerization initiator, followed by polymerization from these substrate-bound initiator centers ("grafting from"). We apply this technique to prepare grafting density gradients of poly(acryl amide) (PAAm) and poly(acrylic acid) (PAA) on silica-covered substrates. We show that using the grafting density gradient geometry, the characteristics of surface-anchored polymers in both the low grafting density ("mushroom") regime as well as the high grafting density ("brush") regime can be accessed conveniently on a single sample. We use a battery of experimental methods, including Fourier transform infrared spectroscopy (FTIR), Near-edge absorption fine structure spectroscopy (NEXAFS), contact angle, ellipsometry, to study the characteristics of the surface-bound polymer layers. We also probe the scaling laws of neutral polymer as a function of grafting density, and for weak polyelectrolyte, in addition to the grafting density, we study the affect of solution ionic strength and pH values. In the second novel method, which we coined as "mechanically assisted polymer assembly" (MAPA), we form surface anchored polymers by "grafting from" polymerization initiators deposited on elastic surfaces that have been previously extended uniaxially by a certain length increment, Deltax. Upon releasing the strain in the substrate after completion of polymerization, we show the grafting density of the polymers grafted to flexible substrates can be tuned as a function of Deltax.

DbPTM 3.0: an informative resource for investigating substrate site specificity and functional association of protein post-translational modifications.

PubMed

Lu, Cheng-Tsung; Huang, Kai-Yao; Su, Min-Gang; Lee, Tzong-Yi; Bretaña, Neil Arvin; Chang, Wen-Chi; Chen, Yi-Ju; Chen, Yu-Ju; Huang, Hsien-Da

2013-01-01

Protein modification is an extremely important post-translational regulation that adjusts the physical and chemical properties, conformation, stability and activity of a protein; thus altering protein function. Due to the high throughput of mass spectrometry (MS)-based methods in identifying site-specific post-translational modifications (PTMs), dbPTM (http://dbPTM.mbc.nctu.edu.tw/) is updated to integrate experimental PTMs obtained from public resources as well as manually curated MS/MS peptides associated with PTMs from research articles. Version 3.0 of dbPTM aims to be an informative resource for investigating the substrate specificity of PTM sites and functional association of PTMs between substrates and their interacting proteins. In order to investigate the substrate specificity for modification sites, a newly developed statistical method has been applied to identify the significant substrate motifs for each type of PTMs containing sufficient experimental data. According to the data statistics in dbPTM, >60% of PTM sites are located in the functional domains of proteins. It is known that most PTMs can create binding sites for specific protein-interaction domains that work together for cellular function. Thus, this update integrates protein-protein interaction and domain-domain interaction to determine the functional association of PTM sites located in protein-interacting domains. Additionally, the information of structural topologies on transmembrane (TM) proteins is integrated in dbPTM in order to delineate the structural correlation between the reported PTM sites and TM topologies. To facilitate the investigation of PTMs on TM proteins, the PTM substrate sites and the structural topology are graphically represented. Also, literature information related to PTMs, orthologous conservations and substrate motifs of PTMs are also provided in the resource. Finally, this version features an improved web interface to facilitate convenient access to the resource.

Nuclear spin hyperpolarization of the solvent using signal amplification by reversible exchange (SABRE).

PubMed

Moreno, Karlos X; Nasr, Khaled; Milne, Mark; Sherry, A Dean; Goux, Warren J

2015-08-01

Here we report the polarization of the solvent OH protons by SABRE using standard iridium-based catalysts under slightly acidic conditions. Solvent polarization was observed in the presence of a variety of structurally similar N-donor substrates while no solvent enhancement was observed in the absence of substrate or para-hydrogen (p-H2). Solvent polarization was sensitive to the polarizing field and catalyst:substrate ratio in a manner similar to that of substrate protons. SABRE experiments with pyridine-d5 suggest a mechanism where hyperpolarization is transferred from the free substrate to the solvent by chemical exchange while measured hyperpolarization decay times suggest a complimentary mechanism which occurs by direct coordination of the solvent to the catalytic complex. We found the solvent hyperpolarization to decay nearly 3 times more slowly than its characteristic spin-lattice relaxation time suggesting that the hyperpolarized state of the solvent may be sufficiently long lived (∼20s) to hyperpolarize biomolecules having exchangeable protons. This route may offer future opportunities for SABRE to impact metabolic imaging. Copyright © 2015 Elsevier Inc. All rights reserved.

Nuclear spin hyperpolarization of the solvent using signal amplification by reversible exchange (SABRE)

NASA Astrophysics Data System (ADS)

Moreno, Karlos X.; Nasr, Khaled; Milne, Mark; Sherry, A. Dean; Goux, Warren J.

2015-08-01

Here we report the polarization of the solvent OH protons by SABRE using standard iridium-based catalysts under slightly acidic conditions. Solvent polarization was observed in the presence of a variety of structurally similar N-donor substrates while no solvent enhancement was observed in the absence of substrate or para-hydrogen (p-H2). Solvent polarization was sensitive to the polarizing field and catalyst:substrate ratio in a manner similar to that of substrate protons. SABRE experiments with pyridine-d5 suggest a mechanism where hyperpolarization is transferred from the free substrate to the solvent by chemical exchange while measured hyperpolarization decay times suggest a complimentary mechanism which occurs by direct coordination of the solvent to the catalytic complex. We found the solvent hyperpolarization to decay nearly 3 times more slowly than its characteristic spin-lattice relaxation time suggesting that the hyperpolarized state of the solvent may be sufficiently long lived (∼20 s) to hyperpolarize biomolecules having exchangeable protons. This route may offer future opportunities for SABRE to impact metabolic imaging.

Chemical Microsensors For Detection Of Explosives And Chemical Warfare Agents

DOEpatents

Yang, Xiaoguang; Swanson, Basil I.

2001-11-13

An article of manufacture is provided including a substrate having an oxide surface layer and a layer of a cyclodextrin derivative chemically bonded to said substrate, said layer of a cyclodextrin derivative adapted for the inclusion of selected compounds, e.g., nitro-containing organic compounds, therewith. Such an article can be a chemical microsensor capable of detecting a resultant mass change from inclusion of the nitro-containing organic compound.

Chemical microsensors

DOEpatents

Li, DeQuan; Swanson, Basil I.

1995-01-01

An article of manufacture is provided including a substrate having an oxide surface layer and a selective thin film of a cyclodextrin derivative chemically bound upon said substrate, said film is adapted for the inclusion of a selected organic compound therewith. Such an article can be either a chemical sensor capable of detecting a resultant mass change from inclusion of the selected organic compound or a chemical separator capable of reversibly selectively separating a selected organic compound.

Preparation and surface characterization of plasma-treated and biomolecular-micropatterned polymer substrates

NASA Astrophysics Data System (ADS)

Langowski, Bryan Alfred

A micropatterning process creates distinct microscale domains on substrate surfaces that differ from the surfaces' original chemical/physical properties. Numerous micropatterning methods exist, each having relative advantages and disadvantages in terms of cost, ease, reproducibility, and versatility. Polymeric surfaces micropatterned with biomolecules have many applications, but are specifically utilized in tissue engineering as cell scaffolds that attempt to controlled tissue generation in vivo and ex vivo. As the physical and chemical cues presented by micropatterned substrates control resulting cellular behavior, characterization of these cues via surface-sensitive analytical techniques is essential in developing cell scaffolds that mimic complex in vivo physicochemical environments. The initial focus of this thesis is the chemical and physical characterization of plasma-treated, microcontact-printed (muCP) polymeric substrates used to direct nerve cell behavior. Unmodified and oxygen plasma-treated poly(methyl methacrylate) (PMMA) substrates were analyzed by surface sensitive techniques to monitor plasma-induced chemical and physical modifications. Additionally, protein-micropattern homogeneity and size were microscopically evaluated. Lastly, poly(dimethylsiloxane) (PDMS) stamps and contaminated PMMA substrates were characterized by spectroscopic and microscopic methods to identify a contamination source during microcontact printing. The final focus of this thesis is the development of microscale plasma-initiated patterning (muPIP) as a versatile, reproducible micropatterning method. Using muPIP, polymeric substrates were micropatterned with several biologically relevant inks. Polymeric substrates were characterized following muPIP by surface-sensitive techniques to identify the technique's underlying physical and chemical bases. In addition, neural stem cell response to muPIP-generated laminin micropatterns was microscopically and biologically evaluated. Finally, enhanced versatility of muPIP in generating microscale poly-L-lysine gradients was demonstrated.

Self-standing crystalline TiO2 nanotubes/CNTs heterojunction membrane: synthesis and characterization.

PubMed

Hesabi, Zohreh R; Allam, Nageh K; Dahmen, Klaus; Garmestani, Hamid; A El-Sayed, Mostafa

2011-04-01

In the present study, we report for the first time synthesis of TiO(2) nanotubes/CNTs heterojunction membrane. Chemical vapor deposition (CVD) of CNTs at 650 °C in a mixture of H(2)/He atmosphere led to in situ detachment of the anodically fabricated TiO(2) nanotube layers from the Ti substrate underneath. Morphological and structural evolution of TiO(2) nanotubes after CNTs deposition were investigated by field- emission scanning electron microscopy (FESEM), glancing angle X-ray diffraction (GAXRD), and X-ray photoelectron spectroscopy (XPS) analyses. © 2011 American Chemical Society

Identification of Enzyme Genes Using Chemical Structure Alignments of Substrate-Product Pairs.

PubMed

Moriya, Yuki; Yamada, Takuji; Okuda, Shujiro; Nakagawa, Zenichi; Kotera, Masaaki; Tokimatsu, Toshiaki; Kanehisa, Minoru; Goto, Susumu

2016-03-28

Although there are several databases that contain data on many metabolites and reactions in biochemical pathways, there is still a big gap in the numbers between experimentally identified enzymes and metabolites. It is supposed that many catalytic enzyme genes are still unknown. Although there are previous studies that estimate the number of candidate enzyme genes, these studies required some additional information aside from the structures of metabolites such as gene expression and order in the genome. In this study, we developed a novel method to identify a candidate enzyme gene of a reaction using the chemical structures of the substrate-product pair (reactant pair). The proposed method is based on a search for similar reactant pairs in a reference database and offers ortholog groups that possibly mediate the given reaction. We applied the proposed method to two experimentally validated reactions. As a result, we confirmed that the histidine transaminase was correctly identified. Although our method could not directly identify the asparagine oxo-acid transaminase, we successfully found the paralog gene most similar to the correct enzyme gene. We also applied our method to infer candidate enzyme genes in the mesaconate pathway. The advantage of our method lies in the prediction of possible genes for orphan enzyme reactions where any associated gene sequences are not determined yet. We believe that this approach will facilitate experimental identification of genes for orphan enzymes.

Interaction Between Graphene-Coated SiC Single Crystal and Liquid Copper

NASA Astrophysics Data System (ADS)

Homa, M.; Sobczak, N.; Sobczak, J. J.; Kudyba, A.; Bruzda, G.; Nowak, R.; Pietrzak, K.; Chmielewski, M.; Strupiński, W.

2018-04-01

The wettability of graphene-coated SiC single crystal (CGn/SiCsc) by liquid Cu (99.99%) was investigated by a sessile drop method in vacuum conditions at temperature of 1100 °C. The graphene layer was produced via a chemical vapor deposition routine using 4H-SiC single crystal cut out from 6″ wafer. A dispensed drop technique combined with a non-contact heating of a couple of materials was applied. The Cu drop was squeezed from a graphite capillary and deposited on the substrate directly in a vacuum chamber. The first Cu drop did not wet the CGn/SiCsc substrate and showed a lack of adhesion to the substrate: the falling Cu drop only touched the substrate forming a contact angle of θ 0 = 121° and then immediately rolled like a ball along the substrate surface. After settling near the edge of the substrate in about 0.15 s, the Cu drop formed an asymmetric shape with the right and left contact angles of different values (θ R = 86° and θ L = 70°, respectively), while in the next 30 min, θ R and θ L achieved the same final value of 52°. The second Cu drop was put down on the displacement path of the first drop, and immediately after the deposition, it also did not wet the substrate (θ = 123°). This drop kept symmetry and the primary position, but its wetting behavior was unusual: both θ R and θ L decreased in 17 min to the value of 23° and next, they increased to a final value of 65°. Visual observations revealed a presence of 2.5-mm-thick interfacial phase layer reactively formed under the second drop. Scanning electron microscopy (SEM) investigations revealed the presence of carbon-enriched precipitates on the top surface of the first Cu drop. These precipitates were identified by the Raman spectroscopy as double-layer graphene. The Raman spectrum taken from the substrate far from the drop revealed the presence of graphene, while that obtained from the first drop displacement path exhibited a decreased intensity of 2D peak. The results of SEM investigations and Raman spectroscopy studies suggest that the presence of graphene layer on the SiC substrate suppresses but does not completely prevent chemical interaction between liquid Cu drop and SiC. Both chemical degradation (etching) and mechanical degradation of the graphene layer during drop rolling due to high adhesion of the Cu drop to the SiC substrate are responsible for mass transfer through the 2nd drop/substrate interface that in turn results in significant changes of structure and chemistry of the drop and the interface.

Interaction Between Graphene-Coated SiC Single Crystal and Liquid Copper

NASA Astrophysics Data System (ADS)

Homa, M.; Sobczak, N.; Sobczak, J. J.; Kudyba, A.; Bruzda, G.; Nowak, R.; Pietrzak, K.; Chmielewski, M.; Strupiński, W.

2018-05-01

The wettability of graphene-coated SiC single crystal (CGn/SiCsc) by liquid Cu (99.99%) was investigated by a sessile drop method in vacuum conditions at temperature of 1100 °C. The graphene layer was produced via a chemical vapor deposition routine using 4H-SiC single crystal cut out from 6″ wafer. A dispensed drop technique combined with a non-contact heating of a couple of materials was applied. The Cu drop was squeezed from a graphite capillary and deposited on the substrate directly in a vacuum chamber. The first Cu drop did not wet the CGn/SiCsc substrate and showed a lack of adhesion to the substrate: the falling Cu drop only touched the substrate forming a contact angle of θ 0 = 121° and then immediately rolled like a ball along the substrate surface. After settling near the edge of the substrate in about 0.15 s, the Cu drop formed an asymmetric shape with the right and left contact angles of different values ( θ R = 86° and θ L = 70°, respectively), while in the next 30 min, θ R and θ L achieved the same final value of 52°. The second Cu drop was put down on the displacement path of the first drop, and immediately after the deposition, it also did not wet the substrate ( θ = 123°). This drop kept symmetry and the primary position, but its wetting behavior was unusual: both θ R and θ L decreased in 17 min to the value of 23° and next, they increased to a final value of 65°. Visual observations revealed a presence of 2.5-mm-thick interfacial phase layer reactively formed under the second drop. Scanning electron microscopy (SEM) investigations revealed the presence of carbon-enriched precipitates on the top surface of the first Cu drop. These precipitates were identified by the Raman spectroscopy as double-layer graphene. The Raman spectrum taken from the substrate far from the drop revealed the presence of graphene, while that obtained from the first drop displacement path exhibited a decreased intensity of 2D peak. The results of SEM investigations and Raman spectroscopy studies suggest that the presence of graphene layer on the SiC substrate suppresses but does not completely prevent chemical interaction between liquid Cu drop and SiC. Both chemical degradation (etching) and mechanical degradation of the graphene layer during drop rolling due to high adhesion of the Cu drop to the SiC substrate are responsible for mass transfer through the 2nd drop/substrate interface that in turn results in significant changes of structure and chemistry of the drop and the interface.

Design and fabrication of non silicon substrate based MEMS energy harvester for arbitrary surface applications

NASA Astrophysics Data System (ADS)

Balpande, Suresh S.; Pande, Rajesh S.

2016-04-01

Internet of Things (IoT) uses MEMS sensor nodes and actuators to sense and control objects through Internet. IOT deploys millions of chemical battery driven sensors at different locations which are not reliable many times because of frequent requirement of charging & battery replacement in case of underground laying, placement at harsh environmental conditions, huge count and difference between demand (24 % per year) and availability (energy density growing rate 8% per year). Energy harvester fabricated on silicon wafers have been widely used in manufacturing MEMS structures. These devices require complex fabrication processes, costly chemicals & clean room. In addition to this silicon wafer based devices are not suitable for curved surfaces like pipes, human bodies, organisms, or other arbitrary surface like clothes, structure surfaces which does not have flat and smooth surface always. Therefore, devices based on rigid silicon wafers are not suitable for these applications. Flexible structures are the key solution for this problems. Energy transduction mechanism generates power from free surrounding vibrations or impact. Sensor nodes application has been purposefully selected due to discrete power requirement at low duty cycle. Such nodes require an average power budget in the range of about 0.1 microwatt to 1 mW over a period of 3-5 seconds. Energy harvester is the best alternate source in contrast with battery for sensor node application. Novel design of Energy Harvester based on cheapest flexible non silicon substrate i.e. cellulose acetate substrate have been modeled, simulated and analyzed on COMSOL multiphysics and fabricated using sol-gel spin coating setup. Single cantilever based harvester generates 60-75 mV peak electric potential at 22Hz frequency and approximately 22 µW power at 1K-Ohm load. Cantilever array can be employed for generating higher voltage by replicating this structure. This work covers design, optimization, fabrication of harvester and schottky diodes based voltage multiplier.

Design and fabrication of non silicon substrate based MEMS energy harvester for arbitrary surface applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balpande, Suresh S., E-mail: balpandes@rknec.edu; Pande, Rajesh S.

Internet of Things (IoT) uses MEMS sensor nodes and actuators to sense and control objects through Internet. IOT deploys millions of chemical battery driven sensors at different locations which are not reliable many times because of frequent requirement of charging & battery replacement in case of underground laying, placement at harsh environmental conditions, huge count and difference between demand (24 % per year) and availability (energy density growing rate 8% per year). Energy harvester fabricated on silicon wafers have been widely used in manufacturing MEMS structures. These devices require complex fabrication processes, costly chemicals & clean room. In addition tomore » this silicon wafer based devices are not suitable for curved surfaces like pipes, human bodies, organisms, or other arbitrary surface like clothes, structure surfaces which does not have flat and smooth surface always. Therefore, devices based on rigid silicon wafers are not suitable for these applications. Flexible structures are the key solution for this problems. Energy transduction mechanism generates power from free surrounding vibrations or impact. Sensor nodes application has been purposefully selected due to discrete power requirement at low duty cycle. Such nodes require an average power budget in the range of about 0.1 microwatt to 1 mW over a period of 3-5 seconds. Energy harvester is the best alternate source in contrast with battery for sensor node application. Novel design of Energy Harvester based on cheapest flexible non silicon substrate i.e. cellulose acetate substrate have been modeled, simulated and analyzed on COMSOL multiphysics and fabricated using sol-gel spin coating setup. Single cantilever based harvester generates 60-75 mV peak electric potential at 22Hz frequency and approximately 22 µW power at 1K-Ohm load. Cantilever array can be employed for generating higher voltage by replicating this structure. This work covers design, optimization, fabrication of harvester and schottky diodes based voltage multiplier.« less

Sol-gel derived (La 0.8M 0.2)CrO 3 (M dbnd Ca, Sr) coating layer on stainless-steel substrate for use as a separator in intermediate-temperature solid oxide fuel cell

NASA Astrophysics Data System (ADS)

A Lee, E.; Lee, S.; Hwang, H. J.; Moon, J.-W.

A ceramic coating technique is applied to reduce the voltage drop caused by oxidation of the metallic separator (SUS444) in intermediate-temperature (IT) solid oxide fuel cell (SOFCs) systems. Precursor solutions for (La, Ca)CrO 3 (LCC) and (La, Sr)CrO 3 (LSC) coatings are prepared by adding nitric acid and ethylene glycol into an aqueous solution of lanthanum, strontium (or calcium) and chromium nitrates. Dried LCC and LSC gel films are heat-treated at 400-800 °C after dip-coating on the SUS444 substrate. XRD and Fourier-transform infrared (FT-IR) analysis is used to examine the crystallization behaviour and chemical structure of the precursor solution. The oxidation behaviour of the coated SUS444 substrate is compared with an uncoated SUS444 substrate. The oxidation of the SUS444 is inhibited by the LCC and LSC thin film layers.

Inducing morphological changes in lipid bilayer membranes with microfabricated substrates

NASA Astrophysics Data System (ADS)

Liu, Fangjie; Collins, Liam F.; Ashkar, Rana; Heberle, Frederick A.; Srijanto, Bernadeta R.; Collier, C. Patrick

2016-11-01

Lateral organization of lipids and proteins into distinct domains and anchoring to a cytoskeleton are two important strategies employed by biological membranes to carry out many cellular functions. However, these interactions are difficult to emulate with model systems. Here we use the physical architecture of substrates consisting of arrays of micropillars to systematically control the behavior of supported lipid bilayers - an important step in engineering model lipid membrane systems with well-defined functionalities. Competition between attractive interactions of supported lipid bilayers with the underlying substrate versus the energy cost associated with membrane bending at pillar edges can be systematically investigated as functions of pillar height and pitch, chemical functionalization of the microstructured substrate, and the type of unilamellar vesicles used for assembling the supported bilayer. Confocal fluorescent imaging and AFM measurements highlight correlations that exist between topological and mechanical properties of lipid bilayers and lateral lipid mobility in these confined environments. This study provides a baseline for future investigations into lipid domain reorganization on structured solid surfaces and scaffolds for cell growth.

Chemical Fabrication Used to Produce Thin-Film Materials for High Power-to- Weight-Ratio Space Photovoltaic Arrays

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Rybicki, George C.; Raffaelle, Ryne P.; Harris, Jerry D.; Hehemann, David G.; Junek, William; Gorse, Joseph; Thompson, Tracy L.; Hollingsworth, Jennifer A.; Buhro, William E.

2000-01-01

The key to achieving high specific power (watts per kilogram) space solar arrays is the development of a high-efficiency, thin-film solar cell that can be fabricated directly on a flexible, lightweight, space-qualified durable substrate such as Kapton (DuPont) or other polyimide or suitable polymer film. Cell efficiencies approaching 20 percent at AM0 (air mass zero) are required. Current thin-film cell fabrication approaches are limited by either (1) the ultimate efficiency that can be achieved with the device material and structure or (2) the requirement for high-temperature deposition processes that are incompatible with all presently known flexible polyimide or other polymer substrate materials. Cell fabrication processes must be developed that will produce high-efficiency cells at temperatures below 400 degrees Celsius, and preferably below 300 degress Celsius to minimize the problems associated with the difference between the coefficients of thermal expansion of the substrate and thin-film solar cell and/or the decomposition of the substrate.

Surface-enhanced Raman spectroscopy using silver-coated porous glass-ceramic substrates.

PubMed

Pan, Z; Zavalin, A; Ueda, A; Guo, M; Groza, M; Burger, A; Mu, R; Morgan, S H

2005-06-01

Surface-enhanced Raman scattering (SERS) has been studied using a silver-coated porous glass-ceramic material as a new type of substrate. The porous glass-ceramic is in the CaO-TiO2-P2O5 system prepared by controlled crystallization and subsequent chemical leaching of the dense glass-ceramic, leaving a solid skeleton with pores ranging in size from 50 nm to submicrometer. Silver was coated on the surface of the porous glass-ceramic by radio frequency (RF) sputtering or e-beam evaporation in vacuum. SERS spectra of excellent quality were obtained from several dyes and carboxylic acid molecules, including rhodamine 6G, crystal violet, isonicotinic acid, and benzoic acid, using this new substrate. This new substrate showed a good compatibility with these molecules. The porous glass ceramic with a nanometer-structured surface accommodated both test molecules and silver film. The absorbed molecules were therefore better interfaced with silver for surface-enhanced Raman scattering.

Graphene as a Buffer Layer for Silicon Carbide-on-Insulator Structures

PubMed Central

Astuti, Budi; Tanikawa, Masahiro; Rahman, Shaharin Fadzli Abd; Yasui, Kanji; Hashim, Abdul Manaf

2012-01-01

We report an innovative technique for growing the silicon carbide-on-insulator (SiCOI) structure by utilizing polycrystalline single layer graphene (SLG) as a buffer layer. The epitaxial growth was carried out using a hot-mesh chemical vapor deposition (HM-CVD) technique. Cubic SiC (3C-SiC) thin film in (111) domain was realized at relatively low substrate temperature of 750 °C. 3C-SiC energy bandgap of 2.2 eV was confirmed. The Si-O absorption band observed in the grown film can be caused by the out-diffusion of the oxygen atom from SiO2 substrate or oxygen doping during the cleaning process. Further experimental works by optimizing the cleaning process, growth parameters of the present growth method, or by using other growth methods, as well, are expected to realize a high quality SiCOI structure, thereby opening up the way for a breakthrough in the development of advanced ULSIs with multifunctionalities.

Structurally stable graphene oxide-based nanofiltration membranes with bioadhesive polydopamine coating

NASA Astrophysics Data System (ADS)

Wang, Chongbin; Li, Zhiyuan; Chen, Jianxin; Yin, Yongheng; Wu, Hong

2018-01-01

Graphene oxide (GO)-based membranes possess promising potential in liquid separation for its high flux. The state-of-art GO-based membranes need to be supported by a substrate to ensure that the ultra-thin GO layer can withstand transmembrane pressure in practical applications. The interfacial compatibility of this kind of composite membrane remains a great challenge due to the intrinsic difference in chemical/physical properties between the GO sheets and the substrate. In this paper, a structurally stable GO-based composite nanofiltration membrane was fabricated by coupling the mussel-inspired adhesive platform and filtration-assisted assembly of GO laminates. The water flux for the prepared GO-based nanofiltration membrane reached up to 85 L m-2 h-1 bar-1 with a high retention above 95% and 100% for Orange G and Congo Red, respectively. The membrane exhibited highly stable structure owing to the covalent and noncovalent interactions between GO separation layer and dopamine adhesive platform.

Effects of Piezoelectric Potential of ZnO on Resistive Switching Characteristics of Flexible ZnO/TiO2 Heterojunction Cells

NASA Astrophysics Data System (ADS)

Li, Hongxia; Zhou, You; Du, Gang; Huang, Yanwei; Ji, Zhenguo

2018-03-01

Flexible resistance random access memory (ReRAM) devices with a heterojunction structure of PET/ITO/ZnO/TiO2/Au were fabricated on polyethylene terephthalate/indium tin oxide (PET/ITO) substrates by different physical and chemical preparation methods. X-ray diffraction, scanning electron microscopy and atomic force microscopy were carried out to investigate the crystal structure, surface topography and cross-sectional structure of the prepared films. X-ray photoelectron spectroscopy was also used to identify the chemical state of Ti, O and Zn elements. Theoretical and experimental analyses were conducted to identify the effect of piezoelectric potential of ZnO on resistive switching characteristics of flexible ZnO/TiO2 heterojunction cells. The results showed a pathway to enhance the performance of ReRAM devices by engineering the interface barrier, which is also feasible for other electronics, optoelectronics and photovoltaic devices.

Structural and optical properties of PbS thin films grown by chemical bath deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seghaier, S.; Kamoun, N.; Guasch, C.

2007-09-19

Lead sulphide thin films are grown on glass substrates at various deposition times tD, in the range of 40-60 min per step of 2 min, using the chemical bath deposition technique. X-ray diffraction and atomic force microscopy are used to characterize the film structure. The surface composition is analysed by Auger electron spectroscopy. It appears that the as-prepared thin films are polycrystalline with cubic structure. Nanometric scale crystallites are uniformly distributed on the surface. They exhibit almost a stoechiometric composition with a [Pb]/[S] ratio equal to 1.10. Optical properties are studied in the range of 300-3300 nm by spectrophotometric measurements.more » Analysis of the optical absorption data of lead sulphide thin layers reveals a narrow optical direct band gap equal to 0.46 eV for the layer corresponding to a deposition time equal to 60 min.« less

Influence of synthesis parameters on CCVD growth of vertically aligned carbon nanotubes over aluminum substrate.

PubMed

Szabó, Anna; Kecsenovity, Egon; Pápa, Zsuzsanna; Gyulavári, Tamás; Németh, Krisztián; Horvath, Endre; Hernadi, Klara

2017-08-25

In the past two decades, important results have been achieved in the field of carbon nanotube (CNT) research, which revealed that carbon nanotubes have extremely good electrical and mechanical properties The range of applications widens more, if CNTs form a forest-like, vertically aligned structure (VACNT) Although, VACNT-conductive substrate structure could be very advantageous for various applications, to produce proper system without barrier films i.e. with good electrical contact is still a challenge. The aim of the current work is to develop a cheap and easy method for growing carbon nanotubes forests on conductive substrate with the CCVD (Catalytic Chemical Vapor Deposition) technique at 640 °C. The applied catalyst contained Fe and Co and was deposited via dip coating onto an aluminum substrate. In order to control the height of CNT forest several parameters were varied during the both catalyst layer fabrication (e.g. ink concentration, ink composition, dipping speed) and the CCVD synthesis (e.g. gas feeds, reaction time). As-prepared CNT forests were investigated with various methods such as scanning electron microscopy, Raman spectroscopy, and cyclic voltammetry. With such an easy process it was possible to tune both the height and the quality of carbon nanotube forests.

CVD growth of large-area and high-quality HfS2 nanoforest on diverse substrates

NASA Astrophysics Data System (ADS)

Zheng, Binjie; Wang, Zegao; Qi, Fei; Wang, Xinqiang; Yu, Bo; Zhang, Wanli; Chen, Yuanfu

2018-03-01

Two-dimensional layered transition metal dichalcogenides (TMDs) have attracted burgeoning attention due to their various properties and wide potential applications. As a new TMD, hafnium disulfide (HfS2) is theoretically predicted to have better electrical performance than widely studied MoS2. The experimental researches also confirmed the extraordinary feature in electronics and optoelectronics. However, the maximal device performance may not be achieved due to its own limitation of planar structure and challenge of transfer without contamination. Here, through the chemical vapor deposition (CVD) technique, inch-size HfS2 nanoforest has been directly grown on diverse objective substrates covering insulating, semiconducting and conducting substrates. This direct CVD growth without conventional transfer process avoids contamination and degradation in quality, suggesting its promising and wide applications in high-quality and multifarious devices. It is noted that all the HfS2 nanoforests grown on diverse substrates are constructed with vertically aligned few-layered HfS2 nanosheets with high crystalline quality and edge orientation. Moreover, due to its unique structure, the HfS2 nanoforest owns abundant exposed edge sites and large active surface area, which is essential to apply in high-performance catalyst, sensor, and energy storage or field emitter.

Surface-Embedded Stretchable Electrodes by Direct Printing and their Uses to Fabricate Ultrathin Vibration Sensors and Circuits for 3D Structures.

PubMed

Song, Jun Hyuk; Kim, Young-Tae; Cho, Sunghwan; Song, Woo-Jin; Moon, Sungmin; Park, Chan-Gyung; Park, Soojin; Myoung, Jae Min; Jeong, Unyong

2017-11-01

Printing is one of the easy and quick ways to make a stretchable wearable electronics. Conventional printing methods deposit conductive materials "on" or "inside" a rubber substrate. The conductors made by such printing methods cannot be used as device electrodes because of the large surface topology, poor stretchability, or weak adhesion between the substrate and the conducting material. Here, a method is presented by which conductive materials are printed in the way of being surface-embedded in the rubber substrate; hence, the conductors can be widely used as device electrodes and circuits. The printing process involves a direct printing of a metal precursor solution in a block-copolymer rubber substrate and chemical reduction of the precursor into metal nanoparticles. The electrical conductivity and sensitivity to the mechanical deformation can be controlled by adjusting the number of printing operations. The fabrication of highly sensitive vibration sensors is thus presented, which can detect weak pulses and sound waves. In addition, this work takes advantage of the viscoelasticity of the composite conductor to fabricate highly conductive stretchable circuits for complicated 3D structures. The printed electrodes are also used to fabricate a stretchable electrochemiluminescence display. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Competitive outcomes between wood-decaying fungi are altered in burnt wood.

PubMed

Edman, Mattias; Eriksson, Anna-Maria

2016-06-01

Fire is an important disturbance agent in boreal forests where it creates a wide variety of charred and other types of heat-modified dead wood substrates, yet how these substrates affect fungal community structure and development within wood is poorly understood. We allowed six species of wood-decaying basidiomycetes to compete in pairs in wood-discs that were experimentally burnt before fungal inoculation. The outcomes of interactions in burnt wood differed from those in unburnt control wood for two species:Antrodia sinuosanever lost on burnt wood and won over its competitor in 67% of the trials compared to 40% losses and 20% wins on unburnt wood. In contrast, Ischnoderma benzoinumwon all interactions on unburnt wood compared to 33% on burnt wood. However, the responses differed depending on the identity of the competing species, suggesting an interaction between competitor and substrate type. The observed shift in competitive balance between fungal species probably results from chemical changes in burnt wood, but the underlying mechanism needs further investigation. Nevertheless, the results indicate that forest fires indirectly structure fungal communities by modifying dead wood, and highlight the importance of fire-affected dead wood substrates in boreal forests. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Naturally occurring reverse tilt domains in a high-pretilt alignment nematic liquid crystal

NASA Astrophysics Data System (ADS)

Wang, Ruiting; Atherton, Timothy J.; Zhu, Minhua; Petschek, Rolfe G.; Rosenblatt, Charles

2007-08-01

A cell whose substrates were coated with the polyamic acid SE1211 (Nissan Chemical Industries) and baked at high temperatures was filled with a nematic liquid crystal in the isotropic phase. On cooling into the nematic phase, naturally occurring and temporally and thermally robust reverse tilt domains separated by thin filamentlike walls were observed. The properties of these structures are reported.

Preliminary results on complex ceramic layers deposition by atmospheric plasma spraying

NASA Astrophysics Data System (ADS)

Florea, Costel; Bejinariu, Costicǎ; Munteanu, Corneliu; Cimpoeşu, Nicanor

2017-04-01

In this article we obtain thin layers from complex ceramic powders using industrial equipment based on atmospheric plasma spraying. We analyze the influence of the substrate material roughness on the quality of the thin layers using scanning electron microscopy (SEM) and X-ray dispersive energy analyze (EDAX). Preliminary results present an important dependence between the surface state and the structural and chemical homogeneity.

Substrate effects on endothelial cell adherence rates.

PubMed

Scott, W J; Mann, P

1990-01-01

Endothelial cell attachment to a synthetic substrate was studied using an in vitro model system. Attachment rate was defined as the number of tritium-labeled endothelial cells attached to a synthetic substrate after 30 minutes. The surface of the synthetic substrate was chemically modified with either laminin or fibronectin. Labeled endothelial cells attached more rapidly to synthetic substrate, chemically modified with biomolecules, as compared with the untreated substrate controls. Unlabeled endothelial cells were grown to confluency on a second set of modified and untreated substrates. The cells were removed with 1% Triton, and the rate of re-endothelialization with tritium-labeled endothelial cells was determined. The rate was 11-13 times that of the same cells on untreated substrate. These data confirm that biomolecules increase the attachment rate of endothelial cells to synthetic substrate, and also suggest that endothelial cells may secrete a Triton-insoluble product (Sigma, St. Louis, MO) into subendothelial matrix that increases re-endothelialization.

Interwell coupling effect in Si/SiGe quantum wells grown by ultra high vacuum chemical vapor deposition

PubMed Central

Wang, Rui; Lu, Fen; Fan, Wei Jun; Liu, Chong Yang; Loh, Ter-Hoe; Nguyen, Hoai Son; Narayanan, Balasubramanian

2007-01-01

Si/Si0.66Ge0.34coupled quantum well (CQW) structures with different barrier thickness of 40, 4 and 2 nm were grown on Si substrates using an ultra high vacuum chemical vapor deposition (UHV-CVD) system. The samples were characterized using high resolution x-ray diffraction (HRXRD), cross-sectional transmission electron microscopy (XTEM) and photoluminescence (PL) spectroscopy. Blue shift in PL peak energy due to interwell coupling was observed in the CQWs following increase in the Si barrier thickness. The Si/SiGe heterostructure growth process and theoretical band structure model was validated by comparing the energy of the no-phonon peak calculated by the 6 + 2-bandk·pmethod with experimental PL data. Close agreement between theoretical calculations and experimental data was obtained.

Producing smart sensing films by means of organic field effect transistors.

PubMed

Manunza, Ileana; Orgiu, Emanuele; Caboni, Alessandra; Barbaro, Massimo; Bonfiglio, Annalisa

2006-01-01

We have fabricated the first example of totally flexible field effect device for chemical detection based on an organic field effect transistor (OFET) made by pentacene films grown on flexible plastic structures. The ion sensitivity is achieved by employing a thin Mylar foil as gate dielectric. A sensitivity of the device to the pH of the electrolyte solution has been observed A similar structure can be used also for detecting mechanical deformations on flexible surfaces. Thanks to the flexibility of the substrate and the low cost of the employed technology, these devices open the way for the production of flexible chemical and strain gauge sensors that can be employed in a variety of innovative applications such as wearable electronics, e-textiles, new man-machine interfaces.

Diameter Tuning of β-Ga2O3 Nanowires Using Chemical Vapor Deposition Technique.

PubMed

Kumar, Mukesh; Kumar, Vikram; Singh, R

2017-12-01

Diameter tuning of [Formula: see text]-Ga 2 O 3 nanowires using chemical vapor deposition technique have been investigated under various experimental conditions. Diameter of root grown [Formula: see text]-Ga 2 O 3 nanowires having monoclinic crystal structure is tuned by varying separation distance between metal source and substrate. Effect of gas flow rate and mixer ratio on the morphology and diameter of nanowires has been studied. Nanowire diameter depends on growth temperature, and it is independent of catalyst nanoparticle size at higher growth temperature (850-900 °C) as compared to lower growth temperature (800 °C). These nanowires show changes in structural strain value with change in diameter. Band-gap of nanowires increases with decrease in the diameter.

Chemical synthesis of oligoribonucleotides containing 2-aminopurine: substrates for the investigation of ribozyme function

NASA Technical Reports Server (NTRS)

Doudna, J. A.; Szostak, J. W.; Rich, A.; Usman, N.

1990-01-01

The chemical synthesis of a fully protected ribonucleoside phosphoramidite, containing 2-aminopurine as the base component, and its incorporation into short oligoribonucleotides as substrates for an engineered ribozyme from Tetrahymena is described.

A solid-state nuclear magnetic resonance study of post-plasma reactions in organosilicone microwave plasma-enhanced chemical vapor deposition (PECVD) coatings.

PubMed

Hall, Colin J; Ponnusamy, Thirunavukkarasu; Murphy, Peter J; Lindberg, Mats; Antzutkin, Oleg N; Griesser, Hans J

2014-06-11

Plasma-polymerized organosilicone coatings can be used to impart abrasion resistance and barrier properties to plastic substrates such as polycarbonate. Coating rates suitable for industrial-scale deposition, up to 100 nm/s, can be achieved through the use of microwave plasma-enhanced chemical vapor deposition (PECVD), with optimal process vapors such as tetramethyldisiloxane (TMDSO) and oxygen. However, it has been found that under certain deposition conditions, such coatings are subject to post-plasma changes; crazing or cracking can occur anytime from days to months after deposition. To understand the cause of the crazing and its dependence on processing plasma parameters, the effects of post-plasma reactions on the chemical bonding structure of coatings deposited with varying TMDSO-to-O2 ratios was studied with (29)Si and (13)C solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) using both single-pulse and cross-polarization techniques. The coatings showed complex chemical compositions significantly altered from the parent monomer. (29)Si MAS NMR spectra revealed four main groups of resonance lines, which correspond to four siloxane moieties (i.e., mono (M), di (D), tri (T), and quaternary (Q)) and how they are bound to oxygen. Quantitative measurements showed that the ratio of TMDSO to oxygen could shift the chemical structure of the coating from 39% to 55% in Q-type bonds and from 28% to 16% for D-type bonds. Post-plasma reactions were found to produce changes in relative intensities of (29)Si resonance lines. The NMR data were complemented by Fourier transform infrared (FTIR) spectroscopy. Together, these techniques have shown that the bonding environment of Si is drastically altered by varying the TMDSO-to-O2 ratio during PECVD, and that post-plasma reactions increase the cross-link density of the silicon-oxygen network. It appears that Si-H and Si-OH chemical groups are the most susceptible to post-plasma reactions. Coatings produced at a low TMDSO-to-oxygen ratio had little to no singly substituted moieties, displayed a highly cross-linked structure, and showed less post-plasma reactions. However, these chemically more stable coatings are less compatible mechanically with plastic substrates, because of their high stiffness.

Structural Basis for Dual Functionality of Isoflavonoid O-Methyltransferases in the Evolution of Plant Defense Responses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, C.; Deavours, B; Richard, S

2006-01-01

In leguminous plants such as pea (Pisum sativum), alfalfa (Medicago sativa), barrel medic (Medicago truncatula), and chickpea (Cicer arietinum), 4'-O-methylation of isoflavonoid natural products occurs early in the biosynthesis of defense chemicals known as phytoalexins. However, among these four species, only pea catalyzes 3-O-methylation that converts the pterocarpanoid isoflavonoid 6a-hydroxymaackiain to pisatin. In pea, pisatin is important for chemical resistance to the pathogenic fungus Nectria hematococca. While barrel medic does not biosynthesize 6a-hydroxymaackiain, when cell suspension cultures are fed 6a-hydroxymaackiain, they accumulate pisatin. In vitro, hydroxyisoflavanone 4'-O-methyltransferase (HI4'OMT) from barrel medic exhibits nearly identical steady state kinetic parameters for themore » 4'-O-methylation of the isoflavonoid intermediate 2,7,4'-trihydroxyisoflavanone and for the 3-O-methylation of the 6a-hydroxymaackiain isoflavonoid-derived pterocarpanoid intermediate found in pea. Protein x-ray crystal structures of HI4'OMT substrate complexes revealed identically bound conformations for the 2S,3R-stereoisomer of 2,7,4'-trihydroxyisoflavanone and the 6aR,11aR-stereoisomer of 6a-hydroxymaackiain. These results suggest how similar conformations intrinsic to seemingly distinct chemical substrates allowed leguminous plants to use homologous enzymes for two different biosynthetic reactions. The three-dimensional similarity of natural small molecules represents one explanation for how plants may rapidly recruit enzymes for new biosynthetic reactions in response to changing physiological and ecological pressures.« less

Structural Basis for Dual Functionality of Isoflavonoid O-Methyltransferases in the Evolution of Plant Defense Responses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, C.-J.; Deavours, B.E.; Richard, S.B.

2007-07-10

In leguminous plants such as pea (Pisum sativum), alfalfa (Medicago sativa), barrel medic (Medicago truncatula), and chickpea (Cicer arietinum), 4'-O-methylation of isoflavonoid natural products occurs early in the biosynthesis of defense chemicals known as phytoalexins. However, among these four species, only pea catalyzes 3-O-methylation that converts the pterocarpanoid isoflavonoid 6a-hydroxymaackiain to pisatin. In pea, pisatin is important for chemical resistance to the pathogenic fungus Nectria hematococca. While barrel medic does not biosynthesize 6a-hydroxymaackiain, when cell suspension cultures are fed 6a-hydroxymaackiain, they accumulate pisatin. In vitro, hydroxyisoflavanone 4'-O-methyltransferase (HI4'OMT) from barrel medic exhibits nearly identical steady state kinetic parameters for themore » 4'-O-methylation of the isoflavonoid intermediate 2,7,4'-trihydroxyisoflavanone and for the 3-O-methylation of the 6a-hydroxymaackiain isoflavonoid-derived pterocarpanoid intermediate found in pea. Protein x-ray crystal structures of HI4'OMT substrate complexes revealed identically bound conformations for the 2S,3R-stereoisomer of 2,7,4'-trihydroxyisoflavanone and the 6aR,11aR-stereoisomer of 6a-hydroxymaackiain. These results suggest how similar conformations intrinsic to seemingly distinct chemical substrates allowed leguminous plants to use homologous enzymes for two different biosynthetic reactions. The three-dimensional similarity of natural small molecules represents one explanation for how plants may rapidly recruit enzymes for new biosynthetic reactions in response to changing physiological and ecological pressures.« less

Comparative study between chemical and atmospheric pressure plasma jet cleaning on glass substrate

NASA Astrophysics Data System (ADS)

Elfa, Rizan Rizon; Ahmad, Mohd Khairul; Fhong, Soon Chin; Sahdan, Mohd Zainizan; Nayan, Nafarizal

2017-01-01

The atmospheric pressure plasma jet with low frequency and argon as working gas is presented in this paper to demonstrate its application for glass substrate clean and modification. The glass substrate clean by atmospheric pressure plasma jet is an efficient method to replace other substrate clean method. A comparative analysis is done in this paper between substrate cleaned by chemical and plasma treatment methods. Water contact angle reading is taken for a different method of substrate clean and period of treatment. Under the plasma treatment, the sample shows low surface adhesion due to having the surface property of super hydrophilic surface 7.26°. This comparative analysis is necessary in the industrial application for cost production due to sufficient time and method of substrate clean.

Engineering future light emitting diodes and photovoltaics with inexpensive materials: Integrating ZnO and Si into GaN-based devices

NASA Astrophysics Data System (ADS)

Bayram, C.; Shiu, K. T.; Zhu, Y.; Cheng, C. W.; Sadana, D. K.; Teherani, F. H.; Rogers, D. J.; Sandana, V. E.; Bove, P.; Zhang, Y.; Gautier, S.; Cho, C.-Y.; Cicek, E.; Vashaei, Z.; McClintock, R.; Razeghi, M.

2013-03-01

Indium Gallium Nitride (InGaN) based PV have the best fit to the solar spectrum of any alloy system and emerging LED lighting based on InGaN technology and has the potential to reduce energy consumption by nearly one half while enabling significant carbon emission reduction. However, getting the maximum benefit from GaN diode -based PV and LEDs will require wide-scale adoption. A key bottleneck for this is the device cost, which is currently dominated by the substrate (i.e. sapphire) and the epitaxy (i.e. GaN). This work investigates two schemes for reducing such costs. First, we investigated the integration of Zinc Oxide (ZnO) in InGaN-based diodes. (Successful growth of GaN on ZnO template layers (on sapphire) was illustrated. These templates can then be used as sacrificial release layers for chemical lift-off. Such an approach provides an alternative to laser lift-off for the transfer of GaN to substrates with a superior cost-performance profile, plus an added advantage of reclaiming the expensive single-crystal sapphire. It was also illustrated that substitution of low temperature n-type ZnO for n-GaN layers can combat indium leakage from InGaN quantum well active layers in inverted p-n junction structures. The ZnO overlayers can also double as transparent contacts with a nanostructured surface which enhances light in/out coupling. Thus ZnO was confirmed to be an effective GaN substitute which offers added flexibility in device design and can be used in order to simultaneously reduce the epitaxial cost and boost the device performance. Second, we investigated the use of GaN templates on patterned Silicon (100) substrates for reduced substrate cost LED applications. Controlled local metal organic chemical vapor deposition epitaxy of cubic phase GaN with on-axis Si(100) substrates was illustrated. Scanning electron microscopy and transmission electron microscopy techniques were used to investigate uniformity and examine the defect structure in the GaN. Our results suggest that groove structures are very promising for controlled local epitaxy of cubic phase GaN. Overall, it is concluded that there are significant opportunities for cost reduction in novel hybrid diodes based on ZnO-InGaN-Si hybridization.

In Situ Fabrication of 3D Ag@ZnO Nanostructures for Microfluidic Surface-Enhanced Raman Scattering Systems

PubMed Central

2015-01-01

In this work, we develop an in situ method to grow highly controllable, sensitive, three-dimensional (3D) surface-enhanced Raman scattering (SERS) substrates via an optothermal effect within microfluidic devices. Implementing this approach, we fabricate SERS substrates composed of Ag@ZnO structures at prescribed locations inside microfluidic channels, sites within which current fabrication of SERS structures has been arduous. Conveniently, properties of the 3D Ag@ZnO nanostructures such as length, packing density, and coverage can also be adjusted by tuning laser irradiation parameters. After exploring the fabrication of the 3D nanostructures, we demonstrate a SERS enhancement factor of up to ∼2 × 106 and investigate the optical properties of the 3D Ag@ZnO structures through finite-difference time-domain simulations. To illustrate the potential value of our technique, low concentrations of biomolecules in the liquid state are detected. Moreover, an integrated cell-trapping function of the 3D Ag@ZnO structures records the surface chemical fingerprint of a living cell. Overall, our optothermal-effect-based fabrication technique offers an effective combination of microfluidics with SERS, resolving problems associated with the fabrication of SERS substrates in microfluidic channels. With its advantages in functionality, simplicity, and sensitivity, the microfluidic-SERS platform presented should be valuable in many biological, biochemical, and biomedical applications. PMID:25402207

Study on the structural, optical, and electrical properties of the yellow light-emitting diode grown on free-standing (0001) GaN substrate

NASA Astrophysics Data System (ADS)

Deng, Gaoqiang; Zhang, Yuantao; Yu, Ye; Yan, Long; Li, Pengchong; Han, Xu; Chen, Liang; Zhao, Degang; Du, Guotong

2018-04-01

In this paper, GaN-based yellow light-emitting diodes (LEDs) were homoepitaxially grown on free-standing (0001) GaN substrates by metal-organic chemical vapor deposition. X-ray diffraction (XRD), photoluminescence (PL), and electroluminescence (EL) measurements were conducted to investigate the structural, optical, and electrical properties of the yellow LED. The XRD measurement results showed that the InGaN/GaN multiple quantum wells (MQWs) in the LED structure have good periodicity because the distinct MQWs related higher order satellite peaks can be clearly observed from the profile of 2θ-ω XRD scan. The low temperature (10 K) and room temperature PL measurement results yield an internal quantum efficiency of 16% for the yellow LED. The EL spectra of the yellow LED present well Gaussian distribution with relatively low linewidth (47-55 nm), indicating the homogeneous In-content in the InGaN quantum well layers in the yellow LED structure. It is believed that this work will aid in the future development of GaN on GaN LEDs with long emission wavelength.

Structural and chemical ordering of Heusler C o x M n y G e z epitaxial films on Ge (111): Quantitative study using traditional and anomalous x-ray diffraction techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins, B. A.; Chu, Y. S.; He, L.

2015-12-01

Epitaxial films of CoxMnyGez grown on Ge (111) substrates by molecular-beam-epitaxy techniques have been investigated as a continuous function of composition using combinatorial synchrotron x-ray diffraction (XRD) and x-ray fluorescence (XRF) spectroscopy techniques. A high-resolution ternary epitaxial phase diagram is obtained, revealing a small number of structural phases stabilized over large compositional regions. Ordering of the constituent elements in the compositional region near the full Heusler alloy Co2MnGe has been examined in detail using both traditional XRD and a new multiple-edge anomalous diffraction (MEAD) technique. Multiple-edge anomalous diffraction involves analyzing the energy dependence of multiple reflections across each constituent absorptionmore » edge in order to detect and quantify the elemental distribution of occupation in specific lattice sites. Results of this paper show that structural and chemical ordering are very sensitive to the Co : Mn atomic ratio, such that the ordering is the highest at an atomic ratio of 2 but significantly reduced even a few percent off this ratio. The in-plane lattice is nearly coherent with that of the Ge substrate, while the approximately 2% lattice mismatch is accommodated by the out-of-plane tetragonal strain. The quantitative MEAD analysis further reveals no detectable amount (< 0.5%) of Co-Mn site swapping, but instead high levels (26%) of Mn-Ge site swapping. Increasing Ge concentration above the Heusler stoichiometry (Co0.5Mn0.25Ge0.25) is shown to correlate with increased lattice vacancies, antisites, and stacking faults, but reduced lattice relaxation. The highest degree of chemical ordering is observed off the Heusler stoichiometry with a Ge enrichment of 5 at.%.« less

Growth of diamond by RF plasma-assisted chemical vapor deposition

NASA Technical Reports Server (NTRS)

Meyer, Duane E.; Ianno, Natale J.; Woollam, John A.; Swartzlander, A. B.; Nelson, A. J.

1988-01-01

A system has been designed and constructed to produce diamond particles by inductively coupled radio-frequency, plasma-assisted chemical vapor deposition. This is a low-pressure, low-temperature process used in an attempt to deposit diamond on substrates of glass, quartz, silicon, nickel, and boron nitride. Several deposition parameters have been varied including substrate temperature, gas concentration, gas pressure, total gas flow rate, RF input power, and deposition time. Analytical methods employed to determine composition and structure of the deposits include scanning electron microscopy, absorption spectroscopy, scanning Auger microprobe spectroscopy, and Raman spectroscopy. Analysis indicates that particles having a thin graphite surface, as well as diamond particles with no surface coatings, have been deposited. Deposits on quartz have exhibited optical bandgaps as high as 4.5 eV. Scanning electron microscopy analysis shows that particles are deposited on a pedestal which Auger spectroscopy indicates to be graphite. This is a phenomenon that has not been previously reported in the literature.

Robust forests of vertically aligned carbon nanotubes chemically assembled on carbon substrates.

PubMed

Garrett, David J; Flavel, Benjamin S; Shapter, Joseph G; Baronian, Keith H R; Downard, Alison J

2010-02-02

Forests of vertically aligned carbon nanotubes (VACNTs) have been chemically assembled on carbon surfaces. The structures show excellent stability over a wide potential range and are resistant to degradation from sonication in acid, base, and organic solvent. Acid-treated single-walled carbon nanotubes (SWCNTs) were assembled on amine-terminated tether layers covalently attached to pyrolyzed photoresist films. Tether layers were electrografted to the carbon substrate by reduction of the p-aminobenzenediazonium cation and oxidation of ethylenediamine. The amine-modified surfaces were incubated with cut SWCNTs in the presence of N,N'-dicyclohexylcarbodiimide (DCC), giving forests of vertically aligned carbon nanotubes (VACNTs). The SWCNT assemblies were characterized by scanning electron microscopy, atomic force microscopy, and electrochemistry. Under conditions where the tether layers slow electron transfer between solution-based redox probes and the underlying electrode, the assembly of VACNTs on the tether layer dramatically increases the electron-transfer rate at the surface. The grafting procedure, and hence the preparation of VACNTs, is applicable to a wide range of materials including metals and semiconductors.

Growth and microstructural investigation of multiwall carbon nanotubes fabricated using electrodeposited nickel nanodeposits and chemical vapor deposition method

NASA Astrophysics Data System (ADS)

Zanganeh, Navid; Rajabi, Armin; Torabi, Morteza; Allahkarami, Masoud; Moghaddas, Arshak; Sadrnezhaad, S. K.

2014-09-01

This study proposes a common approach for growing multiwall carbon nanotubes (MWCNTs) on nickel nanodeposits. MWCNT growth was performed in two separate stages. In the first stage, nickel nanodeposits were electrodeposited on n-Si(1 1 1):H substrate in the presence of sulfuric acid. Based on atomic force microscopy (AFM) observations, the nickel deposits had a fairly polygonal morphology and were distributed on the prepared n-Si(1 1 1):H substrate. In the second stage, acetylene gas was decomposed on the surfaces of the nickel nanodeposits using chemical vapor deposition method at 700 °C. When carbon is saturated in a catalyst, it acts as a primary nucleating element for MWCNT growth. The structure of the MWCNTs was also investigated using scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, and Raman spectroscopy. Results showed that the synthesized MWCNTs had a small wall thickness and were formed under the experimental conditions applied to the system.

Substrate Vibrations as Promoters of Chemical Reactivity on Metal Surfaces.

PubMed

Campbell, Victoria L; Chen, Nan; Guo, Han; Jackson, Bret; Utz, Arthur L

2015-12-17

Studies exploring how vibrational energy (Evib) promotes chemical reactivity most often focus on molecular reagents, leaving the role of substrate atom motion in heterogeneous interfacial chemistry underexplored. This combined theoretical and experimental study of methane dissociation on Ni(111) shows that lattice atom motion modulates the reaction barrier height during each surface atom's vibrational period, which leads to a strong variation in the reaction probability (S0) with surface temperature (Tsurf). State-resolved beam-surface scattering studies at Tsurf = 90 K show a sharp threshold in S0 at translational energy (Etrans) = 42 kJ/mol. When Etrans decreases from 42 kJ/mol to 34 kJ/mol, S0 decreases 1000-fold at Tsurf = 90 K, but only 2-fold at Tsurf = 475 K. Results highlight the mechanism for this effect, provide benchmarks for DFT calculations, and suggest the potential importance of surface atom induced barrier height modulation in heterogeneously catalyzed reactions, particularly on structurally labile nanoscale particles and defect sites.

Homogeneity of Ge-rich nanostructures as characterized by chemical etching and transmission electron microscopy.

PubMed

Bollani, Monica; Chrastina, Daniel; Montuori, Valeria; Terziotti, Daniela; Bonera, Emiliano; Vanacore, Giovanni M; Tagliaferri, Alberto; Sordan, Roman; Spinella, Corrado; Nicotra, Giuseppe

2012-02-03

The extension of SiGe technology towards new electronic and optoelectronic applications on the Si platform requires that Ge-rich nanostructures be obtained in a well-controlled manner. Ge deposition on Si substrates usually creates SiGe nanostructures with relatively low and inhomogeneous Ge content. We have realized SiGe nanostructures with a very high (up to 90%) Ge content. Using substrate patterning, a regular array of nanostructures is obtained. We report that electron microscopy reveals an abrupt change in Ge content of about 20% between the filled pit and the island, which has not been observed in other Ge island systems. Dislocations are mainly found within the filled pit and only rarely in the island. Selective chemical etching and electron energy-loss spectroscopy reveal that the island itself is homogeneous. These Ge-rich islands are possible candidates for electronic applications requiring locally induced stress, and optoelectronic applications which exploit the Ge-like band structure of Ge-rich SiGe.

Structure formation and surface chemistry of ionic liquids on model electrode surfaces—Model studies for the electrode | electrolyte interface in Li-ion batteries

NASA Astrophysics Data System (ADS)

Buchner, Florian; Uhl, Benedikt; Forster-Tonigold, Katrin; Bansmann, Joachim; Groß, Axel; Behm, R. Jürgen

2018-05-01

Ionic liquids (ILs) are considered as attractive electrolyte solvents in modern battery concepts such as Li-ion batteries. Here we present a comprehensive review of the results of previous model studies on the interaction of the battery relevant IL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP]+[TFSI]-) with a series of structurally and chemically well-defined model electrode surfaces, which are increasingly complex and relevant for battery applications [Ag(111), Au(111), Cu(111), pristine and lithiated highly oriented pyrolytic graphite (HOPG), and rutile TiO2(110)]. Combining surface science techniques such as high resolution scanning tunneling microscopy and X-ray photoelectron spectroscopy for characterizing surface structure and chemical composition in deposited (sub-)monolayer adlayers with dispersion corrected density functional theory based calculations, this work aims at a molecular scale understanding of the fundamental processes at the electrode | electrolyte interface, which are crucial for the development of the so-called solid electrolyte interphase (SEI) layer in batteries. Performed under idealized conditions, in an ultrahigh vacuum environment, these model studies provide detailed insights on the structure formation in the adlayer, the substrate-adsorbate and adsorbate-adsorbate interactions responsible for this, and the tendency for chemically induced decomposition of the IL. To mimic the situation in an electrolyte, we also investigated the interaction of adsorbed IL (sub-)monolayers with coadsorbed lithium. Even at 80 K, postdeposited Li is found to react with the IL, leading to decomposition products such as LiF, Li3N, Li2S, LixSOy, and Li2O. In the absence of a [BMP]+[TFSI]- adlayer, it tends to adsorb, dissolve, or intercalate into the substrate (metals, HOPG) or to react with the substrate (TiO2) above a critical temperature, forming LiOx and Ti3+ species in the latter case. Finally, the formation of stable decomposition products was found to sensitively change the equilibrium between surface Li and Li+ intercalated in the bulk, leading to a deintercalation from lithiated HOPG in the presence of an adsorbed IL adlayer at >230 K. Overall, these results provide detailed insights into the surface chemistry at the solid | electrolyte interface and the initial stages of SEI formation at electrode surfaces in the absence of an applied potential, which is essential for the further improvement of future Li-ion batteries.

Selenization of CIS and CIGS layers deposited by chemical spray pyrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babu, B. J.; Egaas, B.; Velumani, S.

Cu(In1-xGax)Se2 (CIGS) thin films with x=0 (CIS) and x=0.3 (CIGS) were prepared on Mo-coated glass substrate by using chemical spray pyrolysis at a substrate temperature of 350 degrees C, followed by selenization treatment at 550 degrees C in selenium environment under N2 gas flow. X-ray diffraction patterns of as-deposited CIGS layers on Mo showed polycrystalline chalcopyrite phase with an intense (112) plane. Splitting of (204)/(220) and (116)/(312) planes for the film with x=0.3 reveals deviation of tetragonal nature. Field emission scanning electron microscopy cross-sectional images of selenized films showed clear re-crystallization of grains. During the selenization process of the CIGSmore » absorber, a thin interface layer of MoSe2 is formed. Line mapping of Mo/CIGS layer showed more gallium segregation at the interface of back contact resulting in band gap grading. Chemical composition and mapping of the as-deposited and selenized samples were determined by energy dispersive analysis of X-rays. This work leads to fabrication of low cost and large scale Mo/CIGS/CdS/ZnO/ZnO:Al device structure.« less

Combined use of confocal laser scanning microscopy (CLSM) and Raman microscopy (RM): investigations on EPS-Matrix.

PubMed

Wagner, Michael; Ivleva, Natalia P; Haisch, Christoph; Niessner, Reinhard; Horn, Harald

2009-01-01

Confocal laser scanning microscopy (CLSM) was applied in combination with Raman microscopy (RM) for the characterization of heterotrophic biofilms. Compared to CLSM, RM allows for a deeper insight into the chemical structure of extracellular polymeric substances (EPS) of the biofilm matrix. A low load of glucose (2 g m(-2)d(-1)) was applied as substrate to ensure small growth rates of the heterotrophic biofilm. To investigate the influence of hydrodynamic conditions on the chemical composition of EPS, a three funnel flow system was used, wherein biofilms were grown at Reynolds numbers of 1000, 2500 and 4000, respectively. 31 and 92 days after inoculation with activated sludge supernatant RM was applied as an additional technique to standard CLSM measurements for a more detailed analysis of the biofilm matrix. Polysaccharide-related Raman bands are in good agreement with the lectin binding analysis from CLSM. For the older biofilm, lectin binding analysis showed no change in the composition of EPS, whereas Raman spectra pointed out a change of EPS composition from predominantly polysaccharides to predominantly (glyco) proteins. For the applied substrate condition no significant influence of the Reynolds number on the chemical properties was observed.

Sb2S3 grown by ultrasonic spray pyrolysis and its application in a hybrid solar cell

PubMed Central

Katerski, Atanas; Oja Acik, Ilona; Mere, Arvo; Mikli, Valdek; Krunks, Malle

2016-01-01

Chemical spray pyrolysis (CSP) is a fast wet-chemical deposition method in which an aerosol is guided by carrier gas onto a hot substrate where the decomposition of the precursor chemicals occurs. The aerosol is produced using an ultrasonic oscillator in a bath of precursor solution and guided by compressed air. The use of the ultrasonic CSP resulted in the growth of homogeneous and well-adhered layers that consist of submicron crystals of single-phase Sb2S3 with a bandgap of 1.6 eV if an abundance of sulfur source is present in the precursor solution (SbCl3/SC(NH2)2 = 1:6) sprayed onto the substrate at 250 °C in air. Solar cells with glass-ITO-TiO2-Sb2S3-P3HT-Au structure and an active area of 1 cm2 had an open circuit voltage of 630 mV, short circuit current density of 5 mA/cm2, a fill factor of 42% and a conversion efficiency of 1.3%. Conversion efficiencies up to 1.9% were obtained from solar cells with smaller areas. PMID:28144515

Deep-Ultraviolet Luminescence of Rocksalt-Structured Mg x Zn1-x O (x > 0.5) Films on MgO Substrates

NASA Astrophysics Data System (ADS)

Kaneko, Kentaro; Tsumura, Keiichi; Ishii, Kyohei; Onuma, Takayoshi; Honda, Tohru; Fujita, Shizuo

2018-04-01

Rocksalt-structured Mg x Zn1-x O films with Mg composition x of 0.47, 0.57, and 0.64 were grown on (100)-oriented MgO substrates using mist chemical vapor deposition. Cathodoluminescence measurements showed deep ultraviolet (DUV) emission peaking at 4.88 eV (254 nm), 5.15 eV (241 nm), and 5.21 eV (238 nm), respectively, at 12 K. The peak energies were lower than the band gap energies by ca. 1 eV, suggesting that the deep ultraviolet (DUV) emission may be recognized as near band edge luminescence but is associated with impurities, defects, or band fluctuations. The use of carbon-free precursors in the growth is suggested to eliminate carbon impurities and to improve the optical properties of Mg x Zn1-x O.

Optimization of a growth process for as-grown 2D materials-based devices

NASA Astrophysics Data System (ADS)

Lindquist, Miles; Khadka, Sudiksha; Aleithan, Shrouq; Blumer, Ari; Wickramasinghe, Thushan; Thorat, Ruhi; Kordesch, Martin; Stinaff, Eric

We will present the effects of varying key parameters of a deterministic growth method for producing self-contacted 2D transition metal dichalcogenides. Chemical vapor deposition is used to grow a film of 2D material nucleated around and seeded from metallic features prepared by photolithography and sputtering on a Si/SiO2 substrate prior to growth. We will focus on a particular method of growing variable MoS2 based device structures. The goal of this work is to arrive at robust platform for growing a variety of device structures by systematically altering parameters such as the amount of reactants used, the heat of the substrate and oxide powder, and the flow rate of argon gas used. These results will help advance a comprehensive process for the scalable production of as-grown, complex, 2D materials-based device architectures.

The controlled growth of GaN microrods on Si(111) substrates by MOCVD

NASA Astrophysics Data System (ADS)

Foltynski, Bartosz; Garro, Nuria; Vallo, Martin; Finken, Matthias; Giesen, Christoph; Kalisch, Holger; Vescan, Andrei; Cantarero, Andrés; Heuken, Michael

2015-03-01

In this paper, a selective area growth (SAG) approach for growing GaN microrods on patterned SiNx/Si(111) substrates by metal-organic chemical vapor deposition (MOCVD) is studied. The surface morphology, optical and structural properties of vertical GaN microrods terminated by pyramidal shaped facets (six { 10 1 bar 1} planes) were characterized using scanning electron microscopy (SEM), room temperature photoluminescence (PL) and Raman spectroscopy, respectively. Measurements revealed high-quality GaN microcolumns grown with silane support. Characterized structures were grown nearly strain-free (central frequency of Raman peak of 567±1 cm-1) with crystal quality comparable to bulk crystals (FWHM=4.2±1 cm-1). Such GaN microrods might be used as a next-generation device concept for solid-state lighting (SSL) applications by realizing core-shell InGaN/GaN multi-quantum wells (MQWs) on the n-GaN rod base.

Hydrothermal epitaxy and resultant properties of EuTiO3 films on SrTiO3(001) substrate

PubMed Central

2014-01-01

We report a novel epitaxial growth of EuTiO3 films on SrTiO3(001) substrate by hydrothermal method. The morphological, structural, chemical, and magnetic properties of these epitaxial EuTiO3 films were examined by scanning electron microscopy, transmission electron microscopy, high-resolution X-ray diffractometry, X-ray photoelectron spectroscopy, and superconducting quantum interference device magnetometry, respectively. As-grown EuTiO3 films with a perovskite structure were found to show an out-of-plane lattice shrinkage and room-temperature ferromagnetism, possibly resulting from an existence of Eu3+. Postannealing at 1,000°C could reduce the amount of Eu3+, relax the out-of-plane lattice shrinkage, and impact the magnetic properties of the films. PACS 81.10.Aj; 81.15.-z; 61.05.-a PMID:24948889

In-situ integrated processing and characterization of thin films of high temperature superconductors, dielectrics and semiconductors by MOCVD

NASA Technical Reports Server (NTRS)

Singh, R.; Sinha, S.; Hsu, N. J.; Thakur, R. P. S.; Chou, P.; Kumar, A.; Narayan, J.

1990-01-01

In this strategy of depositing the basic building blocks of superconductors, semiconductors, and dielectric having common elements, researchers deposited superconducting films of Y-Ba-Cu-O, semiconductor films of Cu2O, and dielectric films of BaF2 and Y2O3 by metal oxide chemical vapor deposition (MOCVD). By switching source materials entering the chamber, and by using direct writting capability, complex device structures like three-terminal hybrid semiconductors/superconductors transistors can be fabricated. The Y-Ba-Cu-O superconducting thin films on BaF2/YSZ substrates show a T(sub c) of 80 K and are textured with most of the grains having their c-axis or a-axis perpendicular to the substrate. Electrical characteristics as well as structural characteristics of superconductors and related materials obtained by x-ray defraction, electron microscopy, and energy dispersive x-ray analysis are discussed.

In-situ integrated processing and characterization of thin films of high temperature superconductors, dielectrics and semiconductors by MOCVD

NASA Technical Reports Server (NTRS)

Singh, R.; Sinha, S.; Hsu, N. J.; Thakur, R. P. S.; Chou, P.; Kumar, A.; Narayan, J.

1991-01-01

In this strategy of depositing the basic building blocks of superconductors, semiconductors, and dielectrics having common elements, researchers deposited superconducting films of Y-Ba-Cu-O, semiconductor films of Cu2O, and dielectric films of BaF2 and Y2O3 by metal oxide chemical vapor deposition (MOCVD). By switching source materials entering the chamber, and by using direct writing capability, complex device structures like three terminal hybrid semiconductor/superconductor transistors can be fabricated. The Y-Ba-Cu-O superconducting thin films on BaF2/YSZ substrates show a T(sub c) of 80 K and are textured with most of the grains having their c-axis or a-axis perpendicular to the substrate. Electrical characteristics as well as structural characteristics of superconductors and related materials obtained by x-ray deffraction, electron microscopy, and energy dispersive x-ray analysis are discussed.

Structural transformation of Si-rich SiNx film on Si via swift heavy ions irradiation

NASA Astrophysics Data System (ADS)

Murzalinov, D.; Akilbekov, A.; Dauletbekova, A.; Vlasukova, L.; Makhavikov, M.; Zdorovets, M.

2018-03-01

The effects of 200 MeV-Xe+ irradiation with fluencies of (109–1014) cm‑2 on the phase-structural transformation of Si-rich SiNx film deposited on Si substrate by low-pressure chemical vapor deposition have been reported. It has been shown from Raman scattering data that the swift heavy ions irradiation results in the dissolution of amorphous Si nanoclusters in nitride matrix. It has been shown, too, that the swift heavy ion irradiation leads to quenching a visual photoluminescence from nitride films.

The scanning tunnelling microscope as an operative tool: doing physics and chemistry with single atoms and molecules.

PubMed

Rieder, Karl-Heinz; Meyer, Gerhard; Hla, Saw-Wai; Moresco, Francesca; Braun, Kai F; Morgenstern, Karina; Repp, Jascha; Foelsch, Stefan; Bartels, Ludwig

2004-06-15

The scanning tunnelling microscope, initially invented to image surfaces down to the atomic scale, has been further developed in the last few years to an operative tool, with which atoms and molecules can be manipulated at will at low substrate temperatures in different manners to create and investigate artificial structures, whose properties can be investigated employing spectroscopic dI/dV measurements. The tunnelling current can be used to selectively break chemical bonds, but also to induce chemical association. These possibilities give rise to startling new opportunities for physical and chemical experiments on the single atom and single molecule level. Here we provide a short overview on recent results obtained with these techniques.

The effect of steel chemistry on the formation of Fe-Zn intermetallic compounds of galvanneal-coated steel sheets

NASA Astrophysics Data System (ADS)

Lin, C. S.; Meshii, M.

1994-10-01

The effects of steel chemistry on the formation of Fe-Zn intermetallic compounds in the galvanneal coatings have been investigated by examining the microstructure of galvanneal coat-ings on extra-low-carbon (ELC) steel, interstitial-free (IF) steel, and interstitial-free rephos-phorized (IFP) steel. The layer structure of the coatings was revealed by chemical etching. Phases present in each layer were then identified using electron diffraction in transmission elec-tron microscopy (TEM). A two-layer structure, one consisting of the δ phase with a small fraction of the ζ, phase dispersed on the surface and Γ phases and another consisting of the δ and Γ1 phases, was observed in the ELC sample and the IFP sample, respectively. A three-layer structure consisting of the δ, Γ1 + δ, and Γ phases was observed in the IF sample. The presence of C in the steel substrate retarded the alloying between Fe and Zn; while P in the steel favored the formation of the Γ1, phase over the Γ phase by its surface segregation in the steel substrate. The orientation relationship between coating and substrate was also studied by electron diffraction. Three α-Fe/Γ orientation relationships were frequently observed.

Highly stretchable strain sensor based on polyurethane substrate using hydrogen bond-assisted laminated structure for monitoring of tiny human motions

NASA Astrophysics Data System (ADS)

Huang, Ying; Zhao, Yunong; Wang, Yang; Guo, Xiaohui; Zhang, Yangyang; Liu, Ping; Liu, Caixia; Zhang, Yugang

2018-03-01

Strain sensors used as flexible and wearable electronic devices have improved prospects in the fields of artificial skin, robotics, human-machine interfaces, and healthcare. This work introduces a highly stretchable fiber-based strain sensor with a laminated structure made up of a graphene nanoplatelet layer and a carbon black/single-walled carbon nanotube synergetic conductive network layer. An ultrathin, flexible, and elastic two-layer polyurethane (PU) yarn substrate was successively deposited by a novel chemical bonding-based layered dip-coating process. These strain sensors demonstrated high stretchability (˜350%), little hysteresis, and long-term durability (over 2400 cycles) due to the favorable tensile properties of the PU substrate. The linearity of the strain sensor could reach an adjusted R-squared of 0.990 at 100% strain, which is better than most of the recently reported strain sensors. Meanwhile, the strain sensor exhibited good sensibility, rapid response, and a lower detection limit. The lower detection limit benefited from the hydrogen bond-assisted laminated structure and continuous conductive path. Finally, a series of experiments were carried out based on the special features of the PU strain sensor to show its capacity of detecting and monitoring tiny human motions.

Scalable transfer of vertical graphene nanosheets for flexible supercapacitor applications

NASA Astrophysics Data System (ADS)

Sahoo, Gopinath; Ghosh, Subrata; Polaki, S. R.; Mathews, Tom; Kamruddin, M.

2017-10-01

Vertical graphene nanosheets (VGN) are the material of choice for application in next-generation electronic devices. The growing demand for VGN-based flexible devices for the electronics industry brings in restriction on VGN growth temperature. The difficulty associated with the direct growth of VGN on flexible substrates can be overcome by adopting an effective strategy of transferring the well-grown VGN onto arbitrary flexible substrates through a soft chemistry route. In the present study, we report an inexpensive and scalable technique for the polymer-free transfer of VGN onto arbitrary substrates without disrupting its morphology, structure, and properties. After transfer, the morphology, chemical structure, and electrical properties are analyzed by scanning electron microscopy, Raman spectroscopy, x-ray photoelectron spectroscopy, and four-probe resistive methods, respectively. The wetting properties are studied from the water contact angle measurements. The observed results indicate the retention of morphology, surface chemistry, structure, and electronic properties. Furthermore, the storage capacity of the transferred VGN-based binder-free and current collector-free flexible symmetric supercapacitor device is studied. A very low sheet resistance of 670 Ω/□ and excellent supercapacitance of 158 μF cm-2 with 86% retention after 10 000 cycles show the prospect of the damage-free VGN transfer approach for the fabrication of flexible nanoelectronic devices.

Heme Structural Perturbation of PEG-Modified Horseradish Peroxidase C in Aromatic Organic Solvents Probed by Optical Absorption and Resonance Raman Dispersion Spectroscopy

PubMed Central

Huang, Qing; Al-Azzam, Wasfi; Griebenow, Kai; Schweitzer-Stenner, Reinhard

2003-01-01

The heme structure perturbation of poly(ethylene glycol)-modified horseradish peroxidase (HRP-PEG) dissolved in benzene and toluene has been probed by resonance Raman dispersion spectroscopy. Analysis of the depolarization ratio dispersion of several Raman bands revealed an increase of rhombic B1g distortion with respect to native HRP in water. This finding strongly supports the notion that a solvent molecule has moved into the heme pocket where it stays in close proximity to one of the heme's pyrrole rings. The interactions between the solvent molecule, the heme, and the heme cavity slightly stabilize the hexacoordinate high spin state without eliminating the pentacoordinate quantum mixed spin state that is dominant in the resting enzyme. On the contrary, the model substrate benzohydroxamic acid strongly favors the hexacoordinate quantum mixed spin state and induces a B2g-type distortion owing to its position close to one of the heme methine bridges. These results strongly suggest that substrate binding must have an influence on the heme geometry of HRP and that the heme structure of the enzyme-substrate complex (as opposed to the resting state) must be the key to understanding the chemical reactivity of HRP. PMID:12719258

Nanoengineered Polystyrene Surfaces with Nanopore Array Pattern Alters Cytoskeleton Organization and Enhances Induction of Neural Differentiation of Human Adipose-Derived Stem Cells.

PubMed

Jung, Ae Ryang; Kim, Richard Y; Kim, Hyung Woo; Shrestha, Kshitiz Raj; Jeon, Seung Hwan; Cha, Kyoung Je; Park, Yong Hyun; Kim, Dong Sung; Lee, Ji Youl

2015-07-01

Human adipose-derived stem cells (hADSCs) can differentiate into various cell types depending on chemical and topographical cues. One topographical cue recently noted to be successful in inducing differentiation is the nanoengineered polystyrene surface containing nanopore array-patterned substrate (NP substrate), which is designed to mimic the nanoscale topographical features of the extracellular matrix. In this study, efficacies of NP and flat substrates in inducing neural differentiation of hADSCs were examined by comparing their substrate-cell adhesion rates, filopodia growth, nuclei elongation, and expression of neural-specific markers. The polystyrene nano Petri dishes containing NP substrates were fabricated by a nano injection molding process using a nickel electroformed nano-mold insert (Diameter: 200 nm. Depth of pore: 500 nm. Center-to-center distance: 500 nm). Cytoskeleton and filopodia structures were observed by scanning electron microscopy and F-actin staining, while cell adhesion was tested by vinculin staining after 24 and 48 h of seeding. Expression of neural specific markers was examined by real-time quantitative polymerase chain reaction and immunocytochemistry. Results showed that NP substrates lead to greater substrate-cell adhesion, filopodia growth, nuclei elongation, and expression of neural specific markers compared to flat substrates. These results not only show the advantages of NP substrates, but they also suggest that further study into cell-substrate interactions may yield great benefits for biomaterial engineering.

Solar-induced chemical vapor deposition of diamond-type carbon films

DOEpatents

Pitts, J.R.; Tracy, C.E.; King, D.E.; Stanley, J.T.

1994-09-13

An improved chemical vapor deposition method for depositing transparent continuous coatings of sp[sup 3]-bonded diamond-type carbon films, comprises: (a) providing a volatile hydrocarbon gas/H[sub 2] reactant mixture in a cold wall vacuum/chemical vapor deposition chamber containing a suitable substrate for said films, at pressure of about 1 to 50 Torr; and (b) directing a concentrated solar flux of from about 40 to about 60 watts/cm[sup 2] through said reactant mixture to produce substrate temperatures of about 750 C to about 950 C to activate deposition of the film on said substrate. 11 figs.

Solar-induced chemical vapor deposition of diamond-type carbon films

DOEpatents

Pitts, J. Roland; Tracy, C. Edwin; King, David E.; Stanley, James T.

1994-01-01

An improved chemical vapor deposition method for depositing transparent continuous coatings of sp.sup.3 -bonded diamond-type carbon films, comprising: a) providing a volatile hydrocarbon gas/H.sub.2 reactant mixture in a cold wall vacuum/chemical vapor deposition chamber containing a suitable substrate for said films, at pressure of about 1 to 50 Torr; and b) directing a concentrated solar flux of from about 40 to about 60 watts/cm.sup.2 through said reactant mixture to produce substrate temperatures of about 750.degree. C. to about 950.degree. C. to activate deposition of the film on said substrate.

A priori calculations of the free energy of formation from solution of polymorphic self-assembled monolayers.

PubMed

Reimers, Jeffrey R; Panduwinata, Dwi; Visser, Johan; Chin, Yiing; Tang, Chunguang; Goerigk, Lars; Ford, Michael J; Sintic, Maxine; Sum, Tze-Jing; Coenen, Michiel J J; Hendriksen, Bas L M; Elemans, Johannes A A W; Hush, Noel S; Crossley, Maxwell J

2015-11-10

Modern quantum chemical electronic structure methods typically applied to localized chemical bonding are developed to predict atomic structures and free energies for meso-tetraalkylporphyrin self-assembled monolayer (SAM) polymorph formation from organic solution on highly ordered pyrolytic graphite surfaces. Large polymorph-dependent dispersion-induced substrate-molecule interactions (e.g., -100 kcal mol(-1) to -150 kcal mol(-1) for tetratrisdecylporphyrin) are found to drive SAM formation, opposed nearly completely by large polymorph-dependent dispersion-induced solvent interactions (70-110 kcal mol(-1)) and entropy effects (25-40 kcal mol(-1) at 298 K) favoring dissolution. Dielectric continuum models of the solvent are used, facilitating consideration of many possible SAM polymorphs, along with quantum mechanical/molecular mechanical and dispersion-corrected density functional theory calculations. These predict and interpret newly measured and existing high-resolution scanning tunnelling microscopy images of SAM structure, rationalizing polymorph formation conditions. A wide range of molecular condensed matter properties at room temperature now appear suitable for prediction and analysis using electronic structure calculations.

Compositional depth profile of a native oxide LPCVD MNOS structure using X-ray photoelectron spectroscopy and chemical etching

NASA Technical Reports Server (NTRS)

Wurzbach, J. A.; Grunthaner, F. J.

1983-01-01

It is pointed out that there is no report of an unambiguous analysis of the composition and interfacial structure of MNOS (metal-nitride oxide semiconductor) systems, despite the technological importance of these systems. The present investigation is concerned with a study of an MNOS structure on the basis of a technique involving the use of X-ray photoelectron spectroscopy (XPS) with a controlled stopped-flow chemical-etching procedure. XPS is sensitive to the structure of surface layers, while stopped-flow etching permits the controlled removal of overlying material on a scale of atomic layers, to expose new surface layers as a function of thickness. Therefore, with careful analysis of observed intensities at measured depths, this combination of techniques provides depth resolution between 5 and 10 A. According to the obtained data there is intact SiO2 at the substrate interface. There appears to be a thin layer containing excess bonds to silicon on top of the SiO2.

Reactive metal-oxide interfaces: A microscopic view

NASA Astrophysics Data System (ADS)

Picone, A.; Riva, M.; Brambilla, A.; Calloni, A.; Bussetti, G.; Finazzi, M.; Ciccacci, F.; Duò, L.

2016-03-01

Metal-oxide interfaces play a fundamental role in determining the functional properties of artificial layered heterostructures, which are at the root of present and future technological applications. Magnetic exchange and magnetoelectric coupling, spin filtering, metal passivation, catalytic activity of oxide-supported nano-particles are just few examples of physical and chemical processes arising at metal-oxide hybrid systems, readily exploited in working devices. These phenomena are strictly correlated with the chemical and structural characteristics of the metal-oxide interfacial region, making a thorough understanding of the atomistic mechanisms responsible of its formation a prerequisite in order to tailor the device properties. The steep compositional gradient established upon formation of metal-oxide heterostructures drives strong chemical interactions at the interface, making the metal-oxide boundary region a complex system to treat, both from an experimental and a theoretical point of view. However, once properly mastered, interfacial chemical interactions offer a further degree of freedom for tuning the material properties. The goal of the present review is to provide a summary of the latest achievements in the understanding of metal/oxide and oxide/metal layered systems characterized by reactive interfaces. The influence of the interface composition on the structural, electronic and magnetic properties will be highlighted. Particular emphasis will be devoted to the discussion of ultra-thin epitaxial oxides stabilized on highly oxidizable metals, which have been rarely exploited as oxide supports as compared to the much more widespread noble and quasi noble metallic substrates. In this frame, an extensive discussion is devoted to the microscopic characterization of interfaces between epitaxial metal oxides and the Fe(001) substrate, regarded from the one hand as a prototypical ferromagnetic material and from the other hand as a highly oxidizable metal.

Dynamics Govern Specificity of a Protein-Protein Interface: Substrate Recognition by Thrombin.

PubMed

Fuchs, Julian E; Huber, Roland G; Waldner, Birgit J; Kahler, Ursula; von Grafenstein, Susanne; Kramer, Christian; Liedl, Klaus R

2015-01-01

Biomolecular recognition is crucial in cellular signal transduction. Signaling is mediated through molecular interactions at protein-protein interfaces. Still, specificity and promiscuity of protein-protein interfaces cannot be explained using simplistic static binding models. Our study rationalizes specificity of the prototypic protein-protein interface between thrombin and its peptide substrates relying solely on binding site dynamics derived from molecular dynamics simulations. We find conformational selection and thus dynamic contributions to be a key player in biomolecular recognition. Arising entropic contributions complement chemical intuition primarily reflecting enthalpic interaction patterns. The paradigm "dynamics govern specificity" might provide direct guidance for the identification of specific anchor points in biomolecular recognition processes and structure-based drug design.

Deposition of device quality low H content, amorphous silicon films

DOEpatents

Mahan, A.H.; Carapella, J.C.; Gallagher, A.C.

1995-03-14

A high quality, low hydrogen content, hydrogenated amorphous silicon (a-Si:H) film is deposited by passing a stream of silane gas (SiH{sub 4}) over a high temperature, 2,000 C, tungsten (W) filament in the proximity of a high temperature, 400 C, substrate within a low pressure, 8 mTorr, deposition chamber. The silane gas is decomposed into atomic hydrogen and silicon, which in turn collides preferably not more than 20--30 times before being deposited on the hot substrate. The hydrogenated amorphous silicon films thus produced have only about one atomic percent hydrogen, yet have device quality electrical, chemical, and structural properties, despite this lowered hydrogen content. 7 figs.

Deposition of device quality low H content, amorphous silicon films

DOEpatents

Mahan, Archie H.; Carapella, Jeffrey C.; Gallagher, Alan C.

1995-01-01

A high quality, low hydrogen content, hydrogenated amorphous silicon (a-Si:H) film is deposited by passing a stream of silane gas (SiH.sub.4) over a high temperature, 2000.degree. C., tungsten (W) filament in the proximity of a high temperature, 400.degree. C., substrate within a low pressure, 8 mTorr, deposition chamber. The silane gas is decomposed into atomic hydrogen and silicon, which in turn collides preferably not more than 20-30 times before being deposited on the hot substrate. The hydrogenated amorphous silicon films thus produced have only about one atomic percent hydrogen, yet have device quality electrical, chemical, and structural properties, despite this lowered hydrogen content.

Material-Independent Nanotransfer onto a Flexible Substrate Using Mechanical-Interlocking Structure.

PubMed

Seo, Min-Ho; Choi, Seon-Jin; Park, Sang Hyun; Yoo, Jae-Young; Lim, Sung Kyu; Lee, Jae-Shin; Choi, Kwang-Wook; Jo, Min-Seung; Kim, Il-Doo; Yoon, Jun-Bo

2018-05-22

Nanowire-transfer technology has received much attention thanks to its capability to fabricate high-performance flexible nanodevices with high simplicity and throughput. However, it is still challenging to extend the conventional nanowire-transfer method to the fabrication of a wide range of devices since a chemical-adhesion-based nanowire-transfer mechanism is complex and time-consuming, hindering successful transfer of diverse nanowires made of various materials. Here, we introduce a material-independent mechanical-interlocking-based nanowire-transfer (MINT) method, fabricating ultralong and fully aligned nanowires on a large flexible substrate (2.5 × 2 cm 2 ) in a highly robust manner. For the material-independent nanotransfer, we developed a mechanics-based nanotransfer method, which employs a dry-removable amorphous carbon (a-C) sacrificial layer between a vacuum-deposited nanowire and the underlying master mold. The controlled etching of the sacrificial layer enables the formation of a mechanical-interlocking structure under the nanowire, facilitating peeling off of the nanowire from the master mold robustly and reliably. Using the developed MINT method, we successfully fabricated various metallic and semiconductor nanowire arrays on flexible substrates. We further demonstrated that the developed method is well suited to the reliable fabrication of highly flexible and high-performance nanoelectronic devices. As examples, a fully aligned gold (Au) microheater array exhibited high bending stability (10 6 cycling) and ultrafast (∼220 ms) heating operation up to ∼100 °C. An ultralong Au heater-embedded cuprous-oxide (Cu 2 O) nanowire chemical gas sensor showed significantly improved reversible reaction kinetics toward NO 2 with 10-fold enhancement in sensitivity at 100 °C.

Chemical Sensing Systems that Utilize Soft Electronics on Thin Elastomeric Substrates with Open Cellular Designs

PubMed Central

Lee, Yoon Kyeung; Jang, Kyung-In; Ma, Yinji; Koh, Ahyeon; Chen, Hang; Jung, Han Na; Kim, Yerim; Kwak, Jean Won; Wang, Liang; Xue, Yeguang; Yang, Yiyuan; Tian, Wenlong; Jiang, Yu; Zhang, Yihui; Feng, Xue; Huang, Yonggang

2017-01-01

A collection of materials and device architectures are introduced for thin, stretchable arrays of ion sensors that mount on open cellular substrates to facilitate solution exchange for use in biointegrated electronics. The results include integration strategies and studies of fundamental characteristics in chemical sensing and mechanical response. The latter involves experimental measurements and theoretical simulations that establish important considerations in the design of low modulus, stretchable properties in cellular substrates, and in the realization of advanced capabilities in spatiotemporal mapping of chemicals' gradients. As the chemical composition of extracellular fluids contains valuable information related to biological function, the concepts introduced here have potential utility across a range of skin- and internal-organ-integrated electronics where soft mechanics, fluidic permeability, and advanced chemical sensing capabilities are key requirements. PMID:28989338

Deposition and characterization of silicon thin-films by aluminum-induced crystallization

NASA Astrophysics Data System (ADS)

Ebil, Ozgenc

Polycrystalline silicon (poly-Si) as a thin-film solar cell material could have major advantages compared to non-silicon thin-film technologies. In theory, thin-film poly-Si may retain the performance and stability of c-Si while taking advantage of established manufacturing techniques. However, poly-Si films deposited onto foreign substrates at low temperatures typically have an average grain size of 10--50 nm. Such a grain structure presents a potential problem for device performance since it introduces an excessive number of grain boundaries which, if left unpassivated, lead to poor solar cell properties. Therefore, for optimum device performance, the grain size of the poly-Si film should be at least comparable to the thickness of the films. For this project, the objectives were the deposition of poly-Si thin-films with 2--5 mum grain size on glass substrates using in-situ and conventional aluminum-induced crystallization (AIC) and the development of a model for AIC process. In-situ AIC experiments were performed using Hot-Wire Chemical Vapor Deposition (HWCVD) both above and below the eutectic temperature (577°C) of Si-Al binary system. Conventional AIC experiments were performed using a-Si layers deposited on aluminum coated glass substrates by Electron-beam deposition, Plasma Enhanced Chemical Vapor Deposition (PECVD) and HWCVD. Continuous poly-Si films with an average grain size of 10 mum on glass substrates were achieved by both in-situ and conventional aluminum-induced crystallization of Si below eutectic temperature. The grain size was determined by three factors; the grain structure of Al layer, the nature of the interfacial oxide, and crystallization temperature. The interface oxide was found to be crucial for AIC process but not necessary for crystallization itself. The characterization of interfacial oxide layer formed on Al films revealed a bilayer structure containing Al2O3 and Al(OH)3 . The effective activation energy for AIC process was determined to be 0.9 eV and depended on the nature of the interfacial oxide layer. Poly-Si layers prepared by AIC technique can be used as seed layers for epitaxial growth of bulk Si layer or as back contacts in c-Si based solar cells.

Method of producing catalytic material for fabricating nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seals, Roland D.; Menchhofer, Paul A.; Howe, Jane Y.

Methods of fabricating nano-catalysts are described. In some embodiments the nano-catalyst is formed from a powder-based substrate material and is some embodiments the nano-catalyst is formed from a solid-based substrate material. In some embodiments the substrate material may include metal, ceramic, or silicon or another metalloid. The nano-catalysts typically have metal nanoparticles disposed adjacent the surface of the substrate material. The methods typically include functionalizing the surface of the substrate material with a chelating agent, such as a chemical having dissociated carboxyl functional groups (--COO), that provides an enhanced affinity for metal ions. The functionalized substrate surface may then bemore » exposed to a chemical solution that contains metal ions. The metal ions are then bound to the substrate material and may then be reduced, such as by a stream of gas that includes hydrogen, to form metal nanoparticles adjacent the surface of the substrate.« less

Method of producing catalytic materials for fabricating nanostructures

DOEpatents

Seals, Roland D; Menchhofer, Paul A; Howe, Jane Y; Wang, Wei

2013-02-19

Methods of fabricating nano-catalysts are described. In some embodiments the nano-catalyst is formed from a powder-based substrate material and is some embodiments the nano-catalyst is formed from a solid-based substrate material. In some embodiments the substrate material may include metal, ceramic, or silicon or another metalloid. The nano-catalysts typically have metal nanoparticles disposed adjacent the surface of the substrate material. The methods typically include functionalizing the surface of the substrate material with a chelating agent, such as a chemical having dissociated carboxyl functional groups (--COO), that provides an enhanced affinity for metal ions. The functionalized substrate surface may then be exposed to a chemical solution that contains metal ions. The metal ions are then bound to the substrate material and may then be reduced, such as by a stream of gas that includes hydrogen, to form metal nanoparticles adjacent the surface of the substrate.

Laser-driven fusion etching process

DOEpatents

Ashby, Carol I. H.; Brannon, Paul J.; Gerardo, James B.

1989-01-01

The surfaces of solid ionic substrates are etched by a radiation-driven chemical reaction. The process involves exposing an ionic substrate coated with a layer of a reactant material on its surface to radiation, e.g. a laser, to induce localized melting of the substrate which results in the occurrance of a fusion reaction between the substrate and coating material. The resultant reaction product and excess reactant salt are then removed from the surface of the substrate with a solvent which is relatively inert towards the substrate. The laser-driven chemical etching process is especially suitable for etching ionic salt substrates, e.g., a solid inorganic salt such as LiNbO.sub.3, such as used in electro-optical/acousto-optic devices. It is also suitable for applications wherein the etching process is required to produce an etched ionic substrate having a smooth surface morphology or when a very rapid etching rate is desired.

Strategies for an enzyme immobilization on electrodes: Structural and electrochemical characterizations

NASA Astrophysics Data System (ADS)

Ganesh, V.; Muthurasu, A.

2012-04-01

In this paper, we propose various strategies for an enzyme immobilization on electrodes (both metal and semiconductor electrodes). In general, the proposed methodology involves two critical steps viz., (1) chemical modification of substrates using functional monolayers [Langmuir - Blodgett (LB) films and/or self-assembled monolayers (SAMs)] and (2) anchoring of a target enzyme using specific chemical and physical interactions by attacking the terminal functionality of the modified films. Basically there are three ways to immobilize an enzyme on chemically modified electrodes. First method consists of an electrostatic interaction between the enzyme and terminal functional groups present within the chemically modified films. Second and third methods involve the introduction of nanomaterials followed by an enzyme immobilization using both the physical and chemical adsorption processes. As a proof of principle, in this work we demonstrate the sensing and catalytic activity of horseradish peroxidase (HRP) anchored onto SAM modified indium tin oxide (ITO) electrodes towards hydrogen peroxide (H2O2). Structural characterization of such modified electrodes is performed using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle measurements. The binding events and the enzymatic reactions are monitored using electrochemical techniques mainly cyclic voltammetry (CV).

III-nitride core–shell nanorod array on quartz substrates

PubMed Central

Bae, Si-Young; Min, Jung-Wook; Hwang, Hyeong-Yong; Lekhal, Kaddour; Lee, Ho-Jun; Jho, Young-Dahl; Lee, Dong-Seon; Lee, Yong-Tak; Ikarashi, Nobuyuki; Honda, Yoshio; Amano, Hiroshi

2017-01-01

We report the fabrication of near-vertically elongated GaN nanorods on quartz substrates. To control the preferred orientation and length of individual GaN nanorods, we combined molecular beam epitaxy (MBE) with pulsed-mode metal–organic chemical vapor deposition (MOCVD). The MBE-grown buffer layer was composed of GaN nanograins exhibiting an ordered surface and preferred orientation along the surface normal direction. Position-controlled growth of the GaN nanorods was achieved by selective-area growth using MOCVD. Simultaneously, the GaN nanorods were elongated by the pulsed-mode growth. The microstructural and optical properties of both GaN nanorods and InGaN/GaN core–shell nanorods were then investigated. The nanorods were highly crystalline and the core–shell structures exhibited optical emission properties, indicating the feasibility of fabricating III-nitride nano-optoelectronic devices on amorphous substrates. PMID:28345641

Hydroxyapatite-based porous aggregates: physico-chemical nature, structure, texture and architecture.

PubMed

Fabbri, M; Celotti, G C; Ravaglioli, A

1995-02-01

At the request of medical teams from the maxillofacial sector, a highly porous ceramic support based on hydroxyapatite of around 70-80% porosity was produced with a pore size distribution similar to bone texture (< 10 microns, approximately 3 vol%; 10-150 microns, approximately 110 vol%; > 150 microns, approximately 86 vol%). The ceramic substrates were conceived not only as a fillers for bone cavities, but also for use as drug dispensers and as supports to host cells to produce particular therapeutic agents. A method is suggested to obtain a substrate of high porosity, exploiting the impregnation of spongy substrate with hydroxyapatite ceramic particles. X-ray and scanning electron microscopy analyses were carried out to evaluate the nature of the new ceramic support in comparison with the most common commercial product; pore size distribution and porosity were controlled to known hydroxyapatite ceramic architecture for the different possible uses.

Epitaxial Ge Solar Cells Directly Grown on Si (001) by MOCVD Using Isobutylgermane

NASA Astrophysics Data System (ADS)

Kim, Youngjo; Kim, Kangho; Lee, Jaejin; Kim, Chang Zoo; Kang, Ho Kwan; Park, Won-Kyu

2018-03-01

Epitaxial Ge layers have been grown on Si (001) substrates by metalorganic chemical vapor deposition (MOCVD) using an isobutylgermane (IBuGe) metalorganic source. Low and high temperature two-step growth and post annealing techniques are employed to overcome the lattice mismatch problem between Ge and Si. It is demonstrated that high quality Ge epitaxial layers can be grown on Si (001) by using IBuGe with surface RMS roughness of 2 nm and an estimated threading dislocation density of 4.9 × 107 cm -2. Furthermore, single-junction Ge solar cells have been directly grown on Si substrates with an in situ MOCVD growth. The epitaxial Ge p- n junction structures are investigated with transmission electron microscopy and electrochemical C- V measurements. As a result, a power conversion efficiency of 1.69% was achieved for the Ge solar cell directly grown on Si substrate under AM1.5G condition.

Force-Manipulation Single-Molecule Spectroscopy Studies of Enzymatic Dynamics

NASA Astrophysics Data System (ADS)

Lu, H. Peter; He, Yufan; Lu, Maolin; Cao, Jin; Guo, Qing

2014-03-01

Subtle conformational changes play a crucial role in protein functions, especially in enzymatic reactions involving complex substrate-enzyme interactions and chemical reactions. We applied AFM-enhanced and magnetic tweezers-correlated single-molecule spectroscopy to study the mechanisms and dynamics of enzymatic reactions involved with kinase and lysozyme proteins. Enzymatic reaction turnovers and the associated structure changes of individual protein molecules were observed simultaneously in real-time by single-molecule FRET detections. Our single-molecule spectroscopy measurements of enzymatic conformational dynamics have revealed time bunching effect and intermittent coherence in conformational state change dynamics involving in enzymatic reaction cycles. The coherent conformational state dynamics suggests that the enzymatic catalysis involves a multi-step conformational motion along the coordinates of substrate-enzyme complex formation and product releasing. Our results support a multiple-conformational state model, being consistent with a complementary conformation selection and induced-fit enzymatic loop-gated conformational change mechanism in substrate-enzyme active complex formation.

The compositional and evolutionary logic of metabolism

NASA Astrophysics Data System (ADS)

Braakman, Rogier; Smith, Eric

2013-02-01

Metabolism is built on a foundation of organic chemistry, and employs structures and interactions at many scales. Despite these sources of complexity, metabolism also displays striking and robust regularities in the forms of modularity and hierarchy, which may be described compactly in terms of relatively few principles of composition. These regularities render metabolic architecture comprehensible as a system, and also suggests the order in which layers of that system came into existence. In addition metabolism also serves as a foundational layer in other hierarchies, up to at least the levels of cellular integration including bioenergetics and molecular replication, and trophic ecology. The recapitulation of patterns first seen in metabolism, in these higher levels, motivates us to interpret metabolism as a source of causation or constraint on many forms of organization in the biosphere. Many of the forms of modularity and hierarchy exhibited by metabolism are readily interpreted as stages in the emergence of catalytic control by living systems over organic chemistry, sometimes recapitulating or incorporating geochemical mechanisms. We identify as modules, either subsets of chemicals and reactions, or subsets of functions, that are re-used in many contexts with a conserved internal structure. At the small molecule substrate level, module boundaries are often associated with the most complex reaction mechanisms, catalyzed by highly conserved enzymes. Cofactors form a biosynthetically and functionally distinctive control layer over the small-molecule substrate. The most complex members among the cofactors are often associated with the reactions at module boundaries in the substrate networks, while simpler cofactors participate in widely generalized reactions. The highly tuned chemical structures of cofactors (sometimes exploiting distinctive properties of the elements of the periodic table) thereby act as ‘keys’ that incorporate classes of organic reactions within biochemistry. Module boundaries provide the interfaces where change is concentrated, when we catalogue extant diversity of metabolic phenotypes. The same modules that organize the compositional diversity of metabolism are argued, with many explicit examples, to have governed long-term evolution. Early evolution of core metabolism, and especially of carbon-fixation, appears to have required very few innovations, and to have used few rules of composition of conserved modules, to produce adaptations to simple chemical or energetic differences of environment without diverse solutions and without historical contingency. We demonstrate these features of metabolism at each of several levels of hierarchy, beginning with the small-molecule metabolic substrate and network architecture, continuing with cofactors and key conserved reactions, and culminating in the aggregation of multiple diverse physical and biochemical processes in cells.

Improved Optical Transmittance and Crystal Characteristics of ZnS:TbOF Thin Film on Bi4Ti3O12/Indium Tin Oxide/Glass Substrate by Using a SiO2 Buffer Layer

NASA Astrophysics Data System (ADS)

Chia, Wei‑Kuo; Yokoyama, Meiso; Yang, Cheng‑Fu; Chiang, Wang‑Ta; Chen, Ying‑Chung

2006-07-01

Bi4Ti3O12 thin films are deposited on indium tin oxide (ITO)/glass substrates using RF magnetron sputtering technology and are annealed at 675 °C in a rapid thermal annealing furnace in an oxygen atmosphere. The resulting films have high optical transmittances and good crystalline characteristics. ZnS:TbOF films are then deposited on the Bi4Ti3O12 films, causing the originally highly transparent specimens to blacken and to resemble a glass surface coated with carbon powder. The optical transmittance of the specimen is less than 15% under the visible wavelength range, and neither a crystalline phase nor a distinct ZnS grain structure is evident in X-ray diffractometer (XRD) and scanning electronic microscope (SEM). Secondary ion mass spectrometer (SIMS) analysis reveals the occurrence of interdiffusion between the ZnS and Bi4Ti3O12 layers. This suggests that one or more unknown chemical reactions take place among the elements Bi, S, and O at the interface during the deposition of ZnS:TbOF film on a Bi4Ti3O12/ITO/glass substrate. These reactions cause the visible transmittance of the specimens to deteriorate dramatically. To prevent interdiffusion, a silicon dioxide (SiO2) buffer layer 100 nm thick was grown on the Bi4Ti3O12/ITO/glass substrate using plasma-enhanced chemical vapor deposition (PECVD), then the ZnS:TbOF film was grown on the SiO2 buffer layer. The transmittance of the resulting specimen is enhanced approximately 8-fold in the visible region. XRD patterns reveal the ZnS(111)-oriented phase is dominant. Furthermore, dense, crack-free ZnS:TbOF grains are observed by SEM. The results imply that the SiO2 buffer layer sandwiched between the ZnS:TbOF and Bi4Ti3O2 layers effectively separates the two layers. Therefore, interdiffusion and chemical reactions are prevented at the interface of the two layers, and the crystalline characteristics of the ZnS:TbOF layer and the optical transmittance of the specimen are improved as a result. Finally, the dielectric constant of the stacked structure is lower than that of the single layer structure without SiO2, but the dielectric breakdown strength is enhanced.

Automated Inference of Chemical Discriminants of Biological Activity.

PubMed

Raschka, Sebastian; Scott, Anne M; Huertas, Mar; Li, Weiming; Kuhn, Leslie A

2018-01-01

Ligand-based virtual screening has become a standard technique for the efficient discovery of bioactive small molecules. Following assays to determine the activity of compounds selected by virtual screening, or other approaches in which dozens to thousands of molecules have been tested, machine learning techniques make it straightforward to discover the patterns of chemical groups that correlate with the desired biological activity. Defining the chemical features that generate activity can be used to guide the selection of molecules for subsequent rounds of screening and assaying, as well as help design new, more active molecules for organic synthesis.The quantitative structure-activity relationship machine learning protocols we describe here, using decision trees, random forests, and sequential feature selection, take as input the chemical structure of a single, known active small molecule (e.g., an inhibitor, agonist, or substrate) for comparison with the structure of each tested molecule. Knowledge of the atomic structure of the protein target and its interactions with the active compound are not required. These protocols can be modified and applied to any data set that consists of a series of measured structural, chemical, or other features for each tested molecule, along with the experimentally measured value of the response variable you would like to predict or optimize for your project, for instance, inhibitory activity in a biological assay or ΔG binding . To illustrate the use of different machine learning algorithms, we step through the analysis of a dataset of inhibitor candidates from virtual screening that were tested recently for their ability to inhibit GPCR-mediated signaling in a vertebrate.

Enzyme-specific sensors via aggregation of charged p-phenylene ethynylenes.

PubMed

Hill, Eric H; Zhang, Yue; Evans, Deborah G; Whitten, David G

2015-03-11

Chemical and biological sensors are sought for their ability to detect enzymes as biomarkers for symptoms of various disorders, or the presence of chemical pollutants or poisons. p-Phenylene ethynylene oligomers with pendant charged groups have been recently shown to have ideal photophysical properties for sensing. In this study, one anionic and one cationic oligomer are combined with substrates that are susceptible to enzymatic degradation by phospholipases or acetylcholinesterases. The photophysical properties of the J-aggregated oligomers with the substrate are ideal for sensing, with fluorescence quantum yields of the sensors enhanced between 30 and 66 times compared to the oligomers without substrate. The phospholipase sensor was used to monitor the activity of phospholipase A1 and A2 and obtain kinetic information, though phospholipase C did not degrade the sensor. The acetylcholinesterase sensor was used to monitor enzyme activity and was also used to detect the inhibition of acetylcholinesterase by three different inhibitors. Phospholipase A2 is a biomarker for heart and circulatory disease, and acetylcholinesterase is a biomarker for Alzheimer's, and indicative of exposure to certain pesticides and nerve agents. This work shows that phenylene ethynylene oligomers can be tailored to enzyme-specific sensors by careful selection of substrates that induce formation of a molecular aggregate, and that the sensing of enzymes can be extended to enzyme kinetics and detection of inhibition. Furthermore, the aggregates were studied through all-atom molecular dynamics, providing a molecular-level view of the formation of the molecular aggregates and their structure.

Interfacial interactions between calcined hydroxyapatite nanocrystals and substrates.

PubMed

Okada, Masahiro; Furukawa, Keiko; Serizawa, Takeshi; Yanagisawa, Yoshihiko; Tanaka, Hidekazu; Kawai, Tomoji; Furuzono, Tsutomu

2009-06-02

Interfacial interactions between calcined hydroxyapatite (HAp) nanocrystals and surface-modified substrates were investigated by measuring adsorption behavior and adhesion strength with a quartz crystal microbalance (QCM) and a contact-mode atomic force microscope (AFM), respectively. The goal was to develop better control of HAp-nanocrystal coatings on biomedical materials. HAp nanocrystals with rodlike or spherical morphology were prepared by a wet chemical process followed by calcination at 800 degrees C with an antisintering agent to prevent the formation of sintered polycrystals. The substrate surface was modified by chemical reaction with a low-molecular-weight compound, or graft polymerization with a functional monomer. QCM measurement showed that the rodlike HAp nanocrystals adsorbed preferentially onto anionic COOH-modified substrates compared to cationic NH2- or hydrophobic CH3-modified substrates. On the other hand, the spherical nanocrystals adsorbed onto NH2- and COOH-modified substrates, which indicates that the surface properties of the HAp nanocrystals determined their adsorption behavior. The adhesion strength, which was estimated from the force required to move the nanocrystal in contact-mode AFM, on a COOH-grafted substrate prepared by graft polymerization was almost 9 times larger than that on a COOH-modified substrate prepared by chemical reaction with a low-molecular-weight compound, indicating that the long-chain polymer grafted on the substrate mitigated the surface roughness mismatch between the nanocrystal and the substrate. The adhesion strength of the nanocrystal bonded covalently by the coupling reaction to a Si(OCH3)-grafted substrate prepared by graft polymerization was approximately 1.5 times larger than that when adsorbed on the COOH-grafted substrate.

Laser-driven fusion etching process

DOEpatents

Ashby, C.I.H.; Brannon, P.J.; Gerardo, J.B.

1987-08-25

The surfaces of solids are etched by a radiation-driven chemical reaction. The process involves exposing a substrate coated with a layer of a reactant material on its surface to radiation, e.g., a laser, to induce localized melting of the substrate which results in the occurrence of a fusion reaction between the substrate and coating material. The resultant reaction product and excess reactant salt are then removed from the surface of the substrate with a solvent which is relatively inert towards the substrate. The laser-driven chemical etching process is especially suitable for etching ionic substrates, e.g., LiNbO/sub 3/, such as used in electro-optical/acousto-optic devices. It is also suitable for applications wherein the etching process is required to produce an etched ionic substrate having a smooth surface morphology or when a very rapid etching rate is desired.

Systems biology and the origins of life? part II. Are biochemical networks possible ancestors of living systems? networks of catalysed chemical reactions: non-equilibrium, self-organization and evolution.

PubMed

Ricard, Jacques

2010-01-01

The present article discusses the possibility that catalysed chemical networks can evolve. Even simple enzyme-catalysed chemical reactions can display this property. The example studied is that of a two-substrate proteinoid, or enzyme, reaction displaying random binding of its substrates A and B. The fundamental property of such a system is to display either emergence or integration depending on the respective values of the probabilities that the enzyme has bound one of its substrate regardless it has bound the other substrate, or, specifically, after it has bound the other substrate. There is emergence of information if p(A)>p(AB) and p(B)>p(BA). Conversely, if p(A)

Plasma Amino Acid Coatings for a Conformal Growth of Titania Nanoparticles

DTIC Science & Technology

2010-04-01

of dry nitrogen. Periodic porous polymer SU8 templates fabricated using multi-beam IL according to published procedures have been supplied by Thomas...3D periodic polymer structures via plasma enhanced chemical vapor deposition. We demonstrate the efficient utilization of this functional amino acid...nanoparticles were grown directly on histidine-functionalized planar and 3D polymer substrates by a wet-chemistry method that showed uniform surface

Interface Properties of Wide Bandgap Semiconductor Structures

DTIC Science & Technology

1993-12-01

oxyacetylene torch and a water cooled substrate. Studying and controlling this chemical vapor deposition (CVD) process, however, can be frustrating because the...the carbide heat of formation. The precursors of chlorinated methylsilanes coupled with bias were used to deposit C films on Si(100). Textured C (lll...films were also achieved using an oxyacetylene torch . Cu forms an epitaxial rectifyingIcontact to diamond with a Schottky barrier height (SBH) of

Conversion of Lignocellulosic Biomass to Nanocellulose: Structure and Chemical Process

PubMed Central

Lee, H. V.; Hamid, S. B. A.; Zain, S. K.

2014-01-01

Lignocellulosic biomass is a complex biopolymer that is primary composed of cellulose, hemicellulose, and lignin. The presence of cellulose in biomass is able to depolymerise into nanodimension biomaterial, with exceptional mechanical properties for biocomposites, pharmaceutical carriers, and electronic substrate's application. However, the entangled biomass ultrastructure consists of inherent properties, such as strong lignin layers, low cellulose accessibility to chemicals, and high cellulose crystallinity, which inhibit the digestibility of the biomass for cellulose extraction. This situation offers both challenges and promises for the biomass biorefinery development to utilize the cellulose from lignocellulosic biomass. Thus, multistep biorefinery processes are necessary to ensure the deconstruction of noncellulosic content in lignocellulosic biomass, while maintaining cellulose product for further hydrolysis into nanocellulose material. In this review, we discuss the molecular structure basis for biomass recalcitrance, reengineering process of lignocellulosic biomass into nanocellulose via chemical, and novel catalytic approaches. Furthermore, review on catalyst design to overcome key barriers regarding the natural resistance of biomass will be presented herein. PMID:25247208

Chemically Deposited Thin-Film Solar Cell Materials

NASA Technical Reports Server (NTRS)

Raffaelle, R.; Junek, W.; Gorse, J.; Thompson, T.; Harris, J.; Hehemann, D.; Hepp, A.; Rybicki, G.

2005-01-01

We have been working on the development of thin film photovoltaic solar cell materials that can be produced entirely by wet chemical methods on low-cost flexible substrates. P-type copper indium diselenide (CIS) absorber layers have been deposited via electrochemical deposition. Similar techniques have also allowed us to incorporate both Ga and S into the CIS structure, in order to increase its optical bandgap. The ability to deposit similar absorber layers with a variety of bandgaps is essential to our efforts to develop a multi-junction thin-film solar cell. Chemical bath deposition methods were used to deposit a cadmium sulfide (CdS) buffer layers on our CIS-based absorber layers. Window contacts were made to these CdS/CIS junctions by the electrodeposition of zinc oxide (ZnO). Structural and elemental determinations of the individual ZnO, CdS and CIS-based films via transmission spectroscopy, x-ray diffraction, x-ray photoelectron spectroscopy and energy dispersive spectroscopy will be presented. The electrical characterization of the resulting devices will be discussed.

Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse.

PubMed

Agarwal, Vinayak; Miles, Zachary D; Winter, Jaclyn M; Eustáquio, Alessandra S; El Gamal, Abrahim A; Moore, Bradley S

2017-04-26

Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

The influence of H{sub 2}O{sub 2} concentration to the structure of silicon nanowire growth by metal-assisted chemical etching

DOE Office of Scientific and Technical Information (OSTI.GOV)

Omar, Hafsa, E-mail: mrshafsaomar@gmail.com; Jani, Abdul Mutalib Md., E-mail: abdmutalib@perlis.uitm.edu.my; Abdullah, Saifollah, E-mail: saifollah@salam.utm.edu.my

2016-07-06

A simple and low cost method to produce well aligned silicon nanowires at large areas using Ag-assisted chemical etching at room temperature were presented. The structure of silicon nanowires growth by metal-assisted chemical etching was observed. Prior to the etching, the silicon nanowires were prepared by electroless metal deposited (EMD) in solution containing hydrofluoric acid and hydrogen peroxide in Teflon vessel. The silver particle was deposited on substrate by immersion in hydrofluoric acid and silver nitrate solution for sixty second. The silicon nanowires were growth in different hydrogen peroxide concentration which are 0.3M, 0.4M, 0.5M and 0.6M and 0.7M.The influencemore » of hydrogen peroxide concentration to the formation of silicon nanowires was studied. The morphological properties of silicon nanowires were investigated using field emission scanning electron microscopy (FESEM) and Energy Dispersive X-Ray Spectroscopy (EDS).« less

Boron Arsenide and Boron Phosphide for High Temperature and Luminescent Devices. [semiconductor devices - crystal growth/crystal structure

NASA Technical Reports Server (NTRS)

Chu, T. L.

1975-01-01

The crystal growth of boron arsenide and boron phosphide in the form of bulk crystals and epitaxial layers on suitable substrates is discussed. The physical, chemical, and electrical properties of the crystals and epitaxial layers are examined. Bulk crystals of boron arsenide were prepared by the chemical transport technique, and their carrier concentration and Hall mobility were measured. The growth of boron arsenide crystals from high temperature solutions was attempted without success. Bulk crystals of boron phosphide were also prepared by chemical transport and solution growth techniques. Techniques required for the fabrication of boron phosphide devices such as junction shaping, diffusion, and contact formation were investigated. Alloying techniques were developed for the formation of low-resistance ohmic contacts to boron phosphide. Four types of boron phosphide devices were fabricated: (1) metal-insulator-boron phosphide structures, (2) Schottky barriers; (3) boron phosphide-silicon carbide heterojunctions; and (4) p-n homojunctions. Easily visible red electroluminescence was observed from both epitaxial and solution grown p-n junctions.

Computational Modeling in Structural Materials Processing

NASA Technical Reports Server (NTRS)

Meyyappan, Meyya; Arnold, James O. (Technical Monitor)

1997-01-01

High temperature materials such as silicon carbide, a variety of nitrides, and ceramic matrix composites find use in aerospace, automotive, machine tool industries and in high speed civil transport applications. Chemical vapor deposition (CVD) is widely used in processing such structural materials. Variations of CVD include deposition on substrates, coating of fibers, inside cavities and on complex objects, and infiltration within preforms called chemical vapor infiltration (CVI). Our current knowledge of the process mechanisms, ability to optimize processes, and scale-up for large scale manufacturing is limited. In this regard, computational modeling of the processes is valuable since a validated model can be used as a design tool. The effort is similar to traditional chemically reacting flow modeling with emphasis on multicomponent diffusion, thermal diffusion, large sets of homogeneous reactions, and surface chemistry. In the case of CVI, models for pore infiltration are needed. In the present talk, examples of SiC nitride, and Boron deposition from the author's past work will be used to illustrate the utility of computational process modeling.

Control of a chemical reaction (photodegradation of the p3ht polymer) with nonlocal dielectric environments

PubMed Central

Peters, V. N.; Tumkur, T. U.; Zhu, G.; Noginov, M. A.

2015-01-01

Proximity to metallic surfaces, plasmonic structures, cavities and other inhomogeneous dielectric environments is known to control spontaneous emission, energy transfer, scattering, and many other phenomena of practical importance. The aim of the present study was to demonstrate that, in spirit of the Marcus theory, the rates of chemical reactions can, too, be influenced by nonlocal dielectric environments, such as metallic films and metal/dielectric bilayer or multilayer structures. We have experimentally shown that metallic, composite metal/dielectric substrates can, indeed, control ordering as well as photodegradation of thin poly-3-hexylthiophene (p3ht) films. In many particular experiments, p3ht films were separated from metal by a dielectric spacer, excluding conventional catalysis facilitated by metals and making modification of the nonlocal dielectric environment a plausible explanation for the observed phenomena. This first step toward understanding of a complex relationship between chemical reactions and nonlocal dielectric environments is to be followed by the theory development and a broader scope of thorough experimental studies. PMID:26434679

Influence of Ta doping in resistive switching behavior of TiO2

NASA Astrophysics Data System (ADS)

Barman, Arabinda; Saini, Chetan P.; Deshmukh, Sujit; Dhar, Sankar; Kanjilal, Aloke

An approach has been made to understand the resistive switching behavior in Ta-doped TiO2 films on Pt substrates. Prior to thin film deposition, Ta-doped TiO2 powder has been synthesized chemically using Ta and Ti precursor solutions. However, the Ta doping has seriously been affected by increasing Ta concentration above 1 at% due to the segregation of Ta2O5 phase. The Ta-doped TiO2 targets have been prepared for pulsed laser deposition of the films on Pt substrates using an excitation wavelength of 248 nm. The structural and chemical properties of the Ta-doped TiO2 films have been investigated in details with the help of XRD, SIMS, XAS and XPS. The stoichiometry of the Ta-doped TiO2 films with increasing depth has been verified initially by SIMS. The electrical study of the corresponding device structures further suggests that the optimized resistive switching effect can be accomplished up to a threshold Ta-doping of 1 at%. Nevertheless, a highly conducting behavior has been shown when the TiO2 films are doped with 2 at% Ta. These results will be discussed in details in the light of defect induced resistive switching phenomenon.

2D or not 2D? The impact of nanoscale roughness and substrate interactions on the tribological properties of graphene and MoS2

NASA Astrophysics Data System (ADS)

Elinski, Meagan B.; Liu, Zhuotong; Spear, Jessica C.; Batteas, James D.

2017-03-01

The use of 2D nanomaterials for controlling friction and wear at interfaces has received increased attention over the past few years due to their unique structural, thermal, electrical and mechanical properties. These materials proffer potential critical solutions to challenges in boundary lubrication across numerous platforms ranging from engines, to biomedical implants and micro- and nano-scaled machines that will play a major role in the Internet of Things. There has been significant work on a range of 2D nanomaterials, such as graphene and molybdenum disulfide (MoS2). From these studies, their frictional properties have been shown to be highly dependent on numerous factors, such as substrate structure, strain, and competing chemical interactions between the interfaces in sliding contact. Moreover, when considering real contacts in machined interfaces, these surfaces are often composed of nanoscaled asperities, whose intermittent contact dominates the tribochemical processes that result in wear. In this review we aim to capture recent work on the tribological properties of graphene and MoS2 and to discuss the impacts of surface roughness (from the atomic scale to the nanoscale) and chemical interactions at interfaces on their frictional properties, and their use in designing advanced boundary lubrication schemes.

Site-directed introduction of disulfide groups on antibodies for highly sensitive immunosensors.

PubMed

Acero Sánchez, Josep Ll; Fragoso, Alex; Joda, Hamdi; Suárez, Guillaume; McNeil, Calum J; O'Sullivan, Ciara K

2016-07-01

The interface between the sample and the transducer surface is critical to the performance of a biosensor. In this work, we compared different strategies for covalent self-assembly of antibodies onto bare gold substrates by introducing disulfide groups into the immunoglobulin structure, which acted as anchor molecules able to chemisorb spontaneously onto clean gold surfaces. The disulfide moieties were chemically introduced to the antibody via the primary amines, carboxylic acids, and carbohydrates present in its structure. The site-directed modification via the carbohydrate chains exhibited the best performance in terms of analyte response using a model system for the detection of the stroke marker neuron-specific enolase. SPR measurements clearly showed the potential for creating biologically active densely packed self-assembled monolayers (SAMs) in a one-step protocol compared to both mixed SAMs of alkanethiol compounds and commercial immobilization layers. The ability of the carbohydrate strategy to construct an electrochemical immunosensor was investigated using electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV) transduction. Graphical Abstract Left: Functionalization strategies of bare gold substrates via direct bio-SAM using disulfide-containing antibody chemically modified via their primary amines (A), carbohydrates (B) and carboxylic acids (C). Right: Dependence of the peak height with NSE concentration at NSE21-CHO modified electrochemical immunosensor. Inset: Logarithmic calibration plot.