Mechanism of bonding and debonding using surface activated bonding method with Si intermediate layer

NASA Astrophysics Data System (ADS)

Takeuchi, Kai; Fujino, Masahisa; Matsumoto, Yoshiie; Suga, Tadatomo

2018-04-01

Techniques of handling thin and fragile substrates in a high-temperature process are highly required for the fabrication of semiconductor devices including thin film transistors (TFTs). In our previous study, we proposed applying the surface activated bonding (SAB) method using Si intermediate layers to the bonding and debonding of glass substrates. The SAB method has successfully bonded glass substrates at room temperature, and the substrates have been debonded after heating at 450 °C, in which TFTs are fabricated on thin glass substrates for LC display devices. In this study, we conducted the bonding and debonding of Si and glass in order to understand the mechanism in the proposed process. Si substrates are also successfully bonded to glass substrates at room temperature and debonded after heating at 450 °C using the proposed bonding process. By the composition analysis of bonding interfaces, it is clarified that the absorbed water on the glass forms interfacial voids and cause the decrease in bond strength.

Interconnect mechanisms in microelectronic packaging

NASA Astrophysics Data System (ADS)

Roma, Maria Penafrancia C.

Global economic, environmental and market developments caused major impact in the microelectronics industry. Astronomical rise of gold metal prices over the last decade shifted the use of copper and silver alloys as bonding wires. Environmental legislation on the restriction of the use of Pb launched worldwide search for lead-free solders and platings. Finally, electrical and digital uses demanded smaller, faster and cheaper devices. Ultra-fine pitch bonding, decreasing bond wire sizes and hard to bond substrates have put the once-robust stitch bond in the center of reliability issues due to stitch bond lift or open wires .Unlike the ball bond, stitch bonding does not lead to intermetallic compound formation but adhesion is dependent on mechanical deformation, interdiffusion, solid solution formation, void formation and mechanical interlocking depending on the wire material, bond configuration, substrate type , thickness and surface condition. Using Au standoff stitch bonds on NiPdAu plated substrates eliminated stitch bond lift even when the Au and Pd layers are reduced. Using the Matano-Boltzmann analysis on a STEM (Scanning Transmission Analysis) concentration profile the interdiffusion coefficient is measured to be 10-16 cm 2/s. Wire pull strength data showed that the wire pull strength is 0.062N and increases upon stress testing. Meanwhile, coating the Cu wire with Pd, not only increases oxidation resistance but also improved adhesion due to the formation of a unique interfacial adhesion layers. Adhesion strength as measured by pull showed the Cu wire bonded to Ag plated Cu substrate (0.132N) to be stronger than the Au wire bonded on the same substrate (0.124N). Ag stitch bonded to Au is predicted to be strong but surface modification made the adhesion stronger. However, on the Ag ball bonded to Al showed multiple IMC formation with unique morphology exposed by ion milling and backscattered scanning electron microscopy. Adding alloying elements in the Ag wire alloy showed differences in adhesion strength and IMC formation. Bond strength by wire pull testing showed the 95Ag alloy with higher values while shear bond testing showed the 88Ag higher bond strength. Use of Cu pillars in flip chips and eutectic bonding in wafer level chip scale packages are direct consequences of diminishing interconnect dimension as a result of the drive for miniaturization. The combination of Cu-Sn interdiffusion, Kirkendall mechanism and heterogeneous vacancy precipitation are the main causes of IMC and void formation in Cu pillar - Sn solder - Cu lead frame sandwich structure. However, adding a Ni barrier agent showed less porous IMC layer as well as void formation as a result of the modified Cu and Sn movement well as the void formation. Direct die to die bonding using Al-Ge eutectic bonds is necessary when 3D integration is needed to reduce the footprint of a package. Hermeticity and adhesion strength are a function of the Al/Ge thickness ratio, bonding pressure, temperature and time. Scanning Electron Microscope (SEM) and Focused Ion Beam (FIB) allowed imaging of interfacial microstructures, porosity, grain morphology while Scanning Transmission Electron microscope (STEM) provided diffusion profile and confirmed interdiffusion. Ion polishing technique provided information on porosity and when imaged using backscattered mode, grain structure confirmed mechanical deformation of the bonds. Measurements of the interfacial bond strength are made by wire pull tests and ball shear tests based on existing industry standard tests. However, for the Al-Ge eutectic bonds, no standard strength is available so a test is developed using the stud pull test method using the Dage 4000 Plus to yield consistent results. Adhesion strengths of 30-40 MPa are found for eutectic bonded packages however, as low as 20MPa was measured in low temperature bonded areas.

Cellular volume regulation and substrate stiffness modulate the detachment dynamics of adherent cells

NASA Astrophysics Data System (ADS)

Yang, Yuehua; Jiang, Hongyuan

2018-03-01

Quantitative characterizations of cell detachment are vital for understanding the fundamental mechanisms of cell adhesion. Experiments have found that cell detachment shows strong rate dependence, which is mostly attributed to the binding-unbinding kinetics of receptor-ligand bond. However, our recent study showed that the cellular volume regulation can significantly regulate the dynamics of adherent cell and cell detachment. How this cellular volume regulation contributes to the rate dependence of cell detachment remains elusive. Here, we systematically study the role of cellular volume regulation in the rate dependence of cell detachment by investigating the cell detachments of nonspecific adhesion and specific adhesion. We find that the cellular volume regulation and the bond kinetics dominate the rate dependence of cell detachment at different time scales. We further test the validity of the traditional Johnson-Kendall-Roberts (JKR) contact model and the detachment model developed by Wyart and Gennes et al (W-G model). When the cell volume is changeable, the JKR model is not appropriate for both the detachments of convex cells and concave cells. The W-G model is valid for the detachment of convex cells but is no longer applicable for the detachment of concave cells. Finally, we show that the rupture force of adherent cells is also highly sensitive to substrate stiffness, since an increase in substrate stiffness will lead to more associated bonds. These findings can provide insight into the critical role of cell volume in cell detachment and might have profound implications for other adhesion-related physiological processes.

Flip Chip Bonding of 68 x 68 MWIR LED Arrays

DTIC Science & Technology

2009-01-01

transmission of IR light through GaSb material varies between 5%–30% and depends on the type of substrate dopants (n- or p-type). Hence, for bottom...emission regions (8.9/16 monolayer’s (ml) InAs/GaSb) separated by (n InAs/GaSb super lattice grade)/(p+ GaSb) tunnel junctions. Graded super lattices were...flip chip bonding process. Besides four corner LED test pads, there are 296 bonding pads in the CMOS driver to bias each LED pixel independently. The

Effect of Storage Time on Bond Strength and Nanoleakage Expression of Universal Adhesives Bonded to Dentin and Etched Enamel.

PubMed

Makishi, P; André, C B; Ayres, Apa; Martins, A L; Giannini, M

2016-01-01

To investigate bond strength and nanoleakage expression of universal adhesives (UA) bonded to dentin and etched enamel. Extracted human third molars were sectioned and ground to obtain flat surfaces of dentin (n = 36) and enamel (n = 48). Dentin and etched enamel surfaces were bonded with one of two UAs, All-Bond Universal (ABU) or Scotchbond Universal (SBU); or a two-step self-etching adhesive, Clearfil SE Bond (CSEB). A hydrophobic bonding resin, Adper Scotchbond Multi-Purpose Bond (ASMP Bond) was applied only on etched enamel. Following each bonding procedure, resin composite blocks were built up incrementally. The specimens were sectioned and subjected to microtensile bond strength (MTBS) testing after 24 hours or one year water storage, or immersed into ammoniacal silver nitrate solution after aging with 10,000 thermocycles and observed using scanning electron microscopy. The percentage distribution of silver particles at the adhesive/tooth interface was calculated using digital image-analysis software. The MTBS (CSEB = SBU > ABU, for dentin; and CSEB > ABU = SBU = ASMP Bond, for etched enamel) differed significantly between the adhesives after 24 hours. After one year, MTBS values were reduced significantly within the same adhesive for both substrates (analysis of variance, Bonferroni post hoc, p<0.05), and no significant differences were found among the adhesives for etched enamel. Silver particles could be detected within the adhesive/dentin interface of all specimens tested. Kruskal-Wallis mean ranks for nanoleakage in ABU, SBU, and CSEB were 16.9, 18.5 and 11, respectively (p>0.05). In the short term, MTBS values were material and dental-substrate dependent. After aging, a decrease in bonding effectiveness was observed in all materials, with nanoleakage at the adhesive/dentin interface. The bonding of the UAs was equal or inferior to that of the conventional restorative systems when applied to either substrate and after either storage period.

Method and system for evaluating integrity of adherence of a conductor bond to a mating surface of a substrate

DOEpatents

Telschow, K.L.; Siu, B.K.

1996-07-09

A method of evaluating integrity of adherence of a conductor bond to a substrate includes: (a) impinging a plurality of light sources onto a substrate; (b) detecting optical reflective signatures emanating from the substrate from the impinged light; (c) determining location of a selected conductor bond on the substrate from the detected reflective signatures; (d) determining a target site on the selected conductor bond from the detected reflective signatures; (e) optically imparting an elastic wave at the target site through the selected conductor bond and into the substrate; (f) optically detecting an elastic wave signature emanating from the substrate resulting from the optically imparting step; and (g) determining integrity of adherence of the selected conductor bond to the substrate from the detected elastic wave signature emanating from the substrate. A system is disclosed which is capable of conducting the method. 13 figs.

Method and system for evaluating integrity of adherence of a conductor bond to a mating surface of a substrate

DOEpatents

Telschow, Kenneth L.; Siu, Bernard K.

1996-01-01

A method of evaluating integrity of adherence of a conductor bond to a substrate includes: a) impinging a plurality of light sources onto a substrate; b) detecting optical reflective signatures emanating from the substrate from the impinged light; c) determining location of a selected conductor bond on the substrate from the detected reflective signatures; d) determining a target site on the selected conductor bond from the detected reflective signatures; e) optically imparting an elastic wave at the target site through the selected conductor bond and into the substrate; f) optically detecting an elastic wave signature emanating from the substrate resulting from the optically imparting step; and g) determining integrity of adherence of the selected conductor bond to the substrate from the detected elastic wave signature emanating from the substrate. A system is disclosed which is capable of conducting the method.

Reductive dehalogenase structure suggests a mechanism for B12-dependent dehalogenation

PubMed Central

Fisher, Karl; Dunstan, Mark S; Collins, Fraser A; Sjuts, Hanno; Levy, Colin; Hay, Sam; Rigby, Stephen EJ; Leys, David

2015-01-01

Organohalide chemistry underpins many industrial and agricultural processes, and a large proportion of environmental pollutants are organohalides1. Nevertheless, organohalide chemistry is not exclusively of anthropogenic origin, with natural abiotic and biological processes contributing to the global halide cycle2–3. Reductive dehalogenases are responsible for biological dehalogenation in organohalide respiring bacteria4–5, with substrates including the notorious polychlorinated biphenyls (PCBs) or dioxins6–7. These proteins form a distinct subfamily of cobalamin (B12) dependent enzymes that are usually membrane-associated and oxygen-sensitive, hindering detailed studies8–12. We report the characterisation of a soluble, oxygen-tolerant reductive dehalogenase and, by combining structure determination with EPR spectroscopy and simulation, show that a direct interaction between the cobalamin cobalt and the substrate halogen underpins catalysis. In contrast to the carbon-Co bond chemistry catalyzed by the other cobalamin-dependent subfamilies13 we propose that reductive dehalogenases achieve reduction of the organohalide substrate via halogen-Co bond formation. This presents a new paradigm in both organohalide and cobalamin (bio)chemistry that will guide future exploitation of these enzymes in bioremediation or biocatalysis. PMID:25327251

The change in hydrogen bond strength accompanying charge rearrangement: Implications for enzymatic catalysis

PubMed Central

Shan, Shu-ou; Herschlag, Daniel

1996-01-01

The equilibrium for formation of the intramolecular hydrogen bond (KHB) in a series of substituted salicylate monoanions was investigated as a function of ΔpKa, the difference between the pKa values of the hydrogen bond donor and acceptor, in both water and dimethyl sulfoxide. The dependence of log KHB upon ΔpKa is linear in both solvents, but is steeper in dimethyl sulfoxide (slope = 0.73) than in water (slope = 0.05). Thus, hydrogen bond strength can undergo substantially larger increases in nonaqueous media than aqueous solutions as the charge density on the donor or acceptor atom increases. These results support a general mechanism for enzymatic catalysis, in which hydrogen bonding to a substrate is strengthened as charge rearranges in going from the ground state to the transition state; the strengthening of the hydrogen bond would be greater in a nonaqueous enzymatic active site than in water, thus providing a rate enhancement for an enzymatic reaction relative to the solution reaction. We suggest that binding energy of an enzyme is used to fix the substrate in the low-dielectric active site, where the strengthening of the hydrogen bond in the course of a reaction is increased. PMID:8962076

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

Wertsching, Alan Kevin; Trantor, Troy Joseph; Ebner, Matthias Anthony

A method and device for producing secure, high-density tritium bonded with carbon. A substrate comprising carbon is provided. A precursor is intercalated between carbon in the substrate. The precursor intercalated in the substrate is irradiated until at least a portion of the precursor, preferably a majority of the precursor, is transmutated into tritium and bonds with carbon of the substrate forming bonded tritium. The resulting bonded tritium, tritium bonded with carbon, produces electrons via beta decay. The substrate is preferably a substrate from the list of substrates consisting of highly-ordered pyrolytic graphite, carbon fibers, carbon nanotunes, buckministerfullerenes, and combinations thereof.more » The precursor is preferably boron-10, more preferably lithium-6. Preferably, thermal neutrons are used to irradiate the precursor. The resulting bonded tritium is preferably used to generate electricity either directly or indirectly.« less

Vacuum pull down method for an enhanced bonding process

DOEpatents

Davidson, James C.; Balch, Joseph W.

1999-01-01

A process for effectively bonding arbitrary size or shape substrates. The process incorporates vacuum pull down techniques to ensure uniform surface contact during the bonding process. The essence of the process for bonding substrates, such as glass, plastic, or alloys, etc., which have a moderate melting point with a gradual softening point curve, involves the application of an active vacuum source to evacuate interstices between the substrates while at the same time providing a positive force to hold the parts to be bonded in contact. This enables increasing the temperature of the bonding process to ensure that the softening point has been reached and small void areas are filled and come in contact with the opposing substrate. The process is most effective where at least one of the two plates or substrates contain channels or grooves that can be used to apply vacuum between the plates or substrates during the thermal bonding cycle. Also, it is beneficial to provide a vacuum groove or channel near the perimeter of the plates or substrates to ensure bonding of the perimeter of the plates or substrates and reduce the unbonded regions inside the interior region of the plates or substrates.

Different redox sensitivity of endoplasmic reticulum associated degradation clients suggests a novel role for disulphide bonds in secretory proteins.

PubMed

Medraño-Fernandez, Iria; Fagioli, Claudio; Mezghrani, Alexandre; Otsu, Mieko; Sitia, Roberto

2014-04-01

To maintain proteostasis in the endoplasmic reticulum (ER), terminally misfolded secretory proteins must be recognized, partially unfolded, and dislocated to the cytosol for proteasomal destruction, in a complex process called ER-associated degradation (ERAD). Dislocation implies reduction of inter-chain disulphide bonds. When in its reduced form, protein disulphide isomerase (PDI) can act not only as a reductase but also as an unfoldase, preparing substrates for dislocation. PDI oxidation by Ero1 favours substrate release and transport across the ER membrane. Here we addressed the redox dependency of ERAD and found that DTT stimulates the dislocation of proteins with DTT-resistant disulphide bonds (i.e., orphan Ig-μ chains) but stabilizes a ribophorin mutant (Ri332) devoid of them. DTT promotes the association of Ri332, but not of Ig-µ, with PDI. This discrepancy may suggest that disulphide bonds in cargo proteins can be utilized to oxidize PDI, hence facilitating substrate detachment and degradation also in the absence of Ero1. Accordingly, Ero1 silencing retards Ri332 degradation, but has little if any effect on Ig-µ. Thus, some disulphides can increase the stability and simultaneously favour quality control of secretory proteins.

Numerical investigations on the rebound phenomena and the bonding mechanisms in cold spray processes

NASA Astrophysics Data System (ADS)

Viscusi, A.

2018-05-01

Cold spray technology is a relatively new additive process allowing to create high quality metallic coatings, on both metallic and non-metallic substrates, without extensive heating of the powders sprayed. Upon impact with a target surface, conversion of kinetic energy to plastic deformation occurs, the solid particles deform and bond together. The actual bonding mechanism for cold spray particles is still not well understood, a high number of works has been carried out during the past two decades, several theories have been proposed to explain the adhesion/rebound mechanisms making the system ineffective for industrial applications. Therefore, the aim of this research activity is to better explain the complex adhesion/rebound phenomena into cold spray impact processes through numerical simulations; for this purpose, on the base of simplified hypothesis and results found in literature, an original 3D Finite Element Method (FEM) model of an aluminium particle impacting on an aluminium substrate was proposed. A cohesive behaviour algorithm was implemented in the particle-substrate contact regions aiming to simulate the bonding between the impacting particle and the substrate under specific working conditions. A rebound coefficient was also defined representing the particle residual energy. Different simulations were performed using a range of impact velocities and varying the interfacial cohesive strength. It was shown that at low impact velocities the rebound phenomenon is governed by the elastic energy stored in the system, meanwhile at high impact velocities, the rebound phenomenon is mainly due to the strain rate effects making the system mechanically stronger; therefore, a specific range of bonding velocities depending on substrate-particle contact area were found.

Nanowire surface fastener fabrication on flexible substrate.

PubMed

Toku, Yuhki; Uchida, Keita; Morita, Yasuyuki; Ju, Yang

2018-07-27

The market for wearable devices has increased considerably in recent years. In response to this demand, flexible electronic circuit technology has become more important. The conventional bonding technology in electronic assembly depends on high-temperature processes such as reflow soldering, which result in undesired thermal damages and residual stress at a bonding interface. In addition, it exhibits poor compatibility with bendable or stretchable device applications. Therefore, there is an urgent requirement to attach electronic parts on printed circuit boards with good mechanical and electrical properties at room temperature. Nanowire surface fasteners (NSFs) are candidates for resolving these problems. This paper describes the fabrication of an NSF on a flexible substrate, which can be used for room temperature conductive bonding. The template method is used for preparing high-density nanowire arrays. A Cu thin film is layered on the template as the flexible substrate. After etching the template, a Cu NSF is obtained on the Cu film substrate. In addition, the electrical and mechanical properties of the Cu NSF are studied under various fabrication conditions. The Cu NSF exhibits high shear adhesion strength (∼234 N cm -2 ) and low contact resistivity (2.2 × 10 -4 Ω cm 2 ).

Nanowire surface fastener fabrication on flexible substrate

NASA Astrophysics Data System (ADS)

Toku, Yuhki; Uchida, Keita; Morita, Yasuyuki; Ju, Yang

2018-07-01

The market for wearable devices has increased considerably in recent years. In response to this demand, flexible electronic circuit technology has become more important. The conventional bonding technology in electronic assembly depends on high-temperature processes such as reflow soldering, which result in undesired thermal damages and residual stress at a bonding interface. In addition, it exhibits poor compatibility with bendable or stretchable device applications. Therefore, there is an urgent requirement to attach electronic parts on printed circuit boards with good mechanical and electrical properties at room temperature. Nanowire surface fasteners (NSFs) are candidates for resolving these problems. This paper describes the fabrication of an NSF on a flexible substrate, which can be used for room temperature conductive bonding. The template method is used for preparing high-density nanowire arrays. A Cu thin film is layered on the template as the flexible substrate. After etching the template, a Cu NSF is obtained on the Cu film substrate. In addition, the electrical and mechanical properties of the Cu NSF are studied under various fabrication conditions. The Cu NSF exhibits high shear adhesion strength (∼234 N cm‑2) and low contact resistivity (2.2 × 10‑4 Ω cm2).

Plates for vacuum thermal fusion

DOEpatents

Davidson, James C.; Balch, Joseph W.

2002-01-01

A process for effectively bonding arbitrary size or shape substrates. The process incorporates vacuum pull down techniques to ensure uniform surface contact during the bonding process. The essence of the process for bonding substrates, such as glass, plastic, or alloys, etc., which have a moderate melting point with a gradual softening point curve, involves the application of an active vacuum source to evacuate interstices between the substrates while at the same time providing a positive force to hold the parts to be bonded in contact. This enables increasing the temperature of the bonding process to ensure that the softening point has been reached and small void areas are filled and come in contact with the opposing substrate. The process is most effective where at least one of the two plates or substrates contain channels or grooves that can be used to apply vacuum between the plates or substrates during the thermal bonding cycle. Also, it is beneficial to provide a vacuum groove or channel near the perimeter of the plates or substrates to ensure bonding of the perimeter of the plates or substrates and reduce the unbonded regions inside the interior region of the plates or substrates.

Endoplasmic reticulum-dependent redox reactions control endoplasmic reticulum-associated degradation and pathogen entry.

PubMed

Walczak, Christopher P; Bernardi, Kaleena M; Tsai, Billy

2012-04-15

Protein misfolding within the endoplasmic reticulum (ER) is managed by an ER quality control system that retro-translocates aberrant proteins into the cytosol for proteasomal destruction. This process, known as ER-associated degradation, utilizes the action of ER redox enzymes to accommodate the disulfide-bonded nature of misfolded proteins. Strikingly, various pathogenic viruses and toxins co-opt these redox components to reach the cytosol during entry. These redox factors thus regulate critical cellular homeostasis and host-pathogen interactions. Recent studies identify specific members of the protein disulfide isomerase (PDI) family, which use their chaperone and catalytic activities, in engaging both misfolded ER proteins and pathogens. The precise molecular mechanism by which a dedicated PDI family member disrupts the disulfide bonds in the misfolded ER proteins and pathogens, as well as how they act to unfold these substrates to promote their ER-to-cytosol membrane transport, remain poorly characterized. How PDI family members distinguish folded versus misfolded ER substrates remains enigmatic. What physical characteristics surrounding a substrate's disulfide bond instruct PDI that it is mispaired or native? For the pathogens, as their disulfide bonds normally serve a critical role in providing physical support, what conformational changes experienced in the host enable their disulfide bonds to be disrupted? A combination of more rigorous biochemical and high-resolution structural studies should begin to address these questions.

An active-site phenylalanine directs substrate binding and C-H cleavage in the alpha-ketoglutarate-dependent dioxygenase TauD.

PubMed

McCusker, Kevin P; Klinman, Judith P

2010-04-14

Enzymes that cleave C-H bonds are often found to depend on well-packed hydrophobic cores that influence the distance between the hydrogen donor and acceptor. Residue F159 in taurine alpha-ketoglutarate dioxygenase (TauD) is demonstrated to play an important role in the binding and orientation of its substrate, which undergoes a hydrogen atom transfer to the active site Fe(IV)=O. Mutation of F159 to smaller hydrophobic side chains (L, V, A) leads to substantially reduced rates for substrate binding and for C-H bond cleavage, as well as increased contribution of the chemical step to k(cat) under steady-state turnover conditions. The greater sensitivity of these substrate-dependent processes to mutation at position 159 than observed for the oxygen activation process supports a previous conclusion of modularity of function within the active site of TauD (McCusker, K. P.; Klinman, J. P. Proc. Natl. Acad. Sci. U.S.A. 2009, 106, 19791-19795). Extraction of intrinsic deuterium kinetic isotope effects (KIEs) using single turnover transients shows 2- to 4-fold increase in the size of the KIE for F159V in relation to wild-type and F159L. It appears that there is a break in behavior following removal of a single methylene from the side chain of F159L to generate F159V, whereby the protein active site loses its ability to restore the internuclear distance between substrate and Fe(IV)=O that supports optimal hydrogenic wave function overlap.

Photovoltaic solar concentrator

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

Nielson, Gregory N.; Cruz-Campa, Jose Luis; Okandan, Murat

A process including forming a photovoltaic solar cell on a substrate, the photovoltaic solar cell comprising an anchor positioned between the photovoltaic solar cell and the substrate to suspend the photovoltaic solar cell from the substrate. A surface of the photovoltaic solar cell opposite the substrate is attached to a receiving substrate. The receiving substrate may be bonded to the photovoltaic solar cell using an adhesive force or a metal connecting member. The photovoltaic solar cell is then detached from the substrate by lifting the receiving substrate having the photovoltaic solar cell attached thereto and severing the anchor connecting themore » photovoltaic solar cell to the substrate. Depending upon the type of receiving substrate used, the photovoltaic solar cell may be removed from the receiving substrate or remain on the receiving substrate for use in the final product.« less

Analysis of splicing complexes on native gels.

PubMed

Ares, Manuel

2013-10-01

Splicing requires a complex set of ATP-dependent macromolecular associations that lead to the rearrangement of just a few covalent bonds in the pre-mRNA substrate. Seeing only the covalent bonds breaking and forming is seeing only a very small part of the process. Analysis of native splicing complexes into which the radiolabeled substrate has been assembled, but not necessarily completely reacted, has provided a good understanding of the process. This protocol describes a gel method for detecting and analyzing yeast splicing complexes formed in vitro on a radiolabeled pre-mRNA substrate. Complexes formed during the splicing reaction are quenched by dilution and addition of an excess of RNA, which is thought to strip nonspecifically bound proteins from the labeled substrate RNA. After loading on a low-percentage, low-cross-linking ratio composite agarose-acrylamide gel (in 10% glycerol), labeled bands are detected. These can be extracted and shown to contain small nuclear RNAs (snRNAs) and partly reacted pre-mRNA.

An ATP-dependent ligase with substrate flexibility involved in assembly of the peptidyl nucleoside antibiotic polyoxin

USDA-ARS?s Scientific Manuscript database

Polyoxin (POL) is an unusual nucleoside antibiotic, in which peptidyl moiety and nucleoside skeleton are linked by an amide bond. However, their biosynthesis remains poorly understood. Here, we report the deciphering of PolG as an ATP-dependent ligase responsible for the assembly of POL. A polG muta...

Method for applying a high-temperature bond coat on a metal substrate, and related compositions and articles

DOEpatents

Hasz, Wayne Charles; Sangeeta, D

2006-04-18

A method for applying a bond coat on a metal-based substrate is described. A slurry which contains braze material and a volatile component is deposited on the substrate. The slurry can also include bond coat material. Alternatively, the bond coat material can be applied afterward, in solid form or in the form of a second slurry. The slurry and bond coat are then dried and fused to the substrate. A repair technique using this slurry is also described, along with related compositions and articles.

Method for applying a high-temperature bond coat on a metal substrate, and related compositions and articles

DOEpatents

Hasz, Wayne Charles; Sangeeta, D

2002-01-01

A method for applying a bond coat on a metal-based substrate is described. A slurry which contains braze material and a volatile component is deposited on the substrate. The slurry can also include bond coat material. Alternatively, the bond coat material can be applied afterward, in solid form or in the form of a second slurry. The slurry and bond coat are then dried and fused to the substrate. A repair technique using this slurry is also described, along with related compositions and articles.

Vacuum die attach for integrated circuits

DOEpatents

Schmitt, E.H.; Tuckerman, D.B.

1991-09-10

A thin film eutectic bond for attaching an integrated circuit die to a circuit substrate is formed by coating at least one bonding surface on the die and substrate with an alloying metal, assembling the die and substrate under compression loading, and heating the assembly to an alloying temperature in a vacuum. A very thin bond, 10 microns or less, which is substantially void free, is produced. These bonds have high reliability, good heat and electrical conduction, and high temperature tolerance. The bonds are formed in a vacuum chamber, using a positioning and loading fixture to compression load the die, and an IR lamp or other heat source. For bonding a silicon die to a silicon substrate, a gold silicon alloy bond is used. Multiple dies can be bonded simultaneously. No scrubbing is required. 1 figure.

Vacuum die attach for integrated circuits

DOEpatents

Schmitt, Edward H.; Tuckerman, David B.

1991-01-01

A thin film eutectic bond for attaching an integrated circuit die to a circuit substrate is formed by coating at least one bonding surface on the die and substrate with an alloying metal, assembling the die and substrate under compression loading, and heating the assembly to an alloying temperature in a vacuum. A very thin bond, 10 microns or less, which is substantially void free, is produced. These bonds have high reliability, good heat and electrical conduction, and high temperature tolerance. The bonds are formed in a vacuum chamber, using a positioning and loading fixture to compression load the die, and an IR lamp or other heat source. For bonding a silicon die to a silicon substrate, a gold silicon alloy bond is used. Multiple dies can be bonded simultaneously. No scrubbing is required.

High performance InAs quantum dot lasers on silicon substrates by low temperature Pd-GaAs wafer bonding

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

Wang, Zihao; Preble, Stefan F.; Yao, Ruizhe

2015-12-28

InAs quantum dot (QD) laser heterostructures have been grown by molecular beam epitaxy system on GaAs substrates, and then transferred to silicon substrates by a low temperature (250 °C) Pd-mediated wafer bonding process. A low interfacial resistivity of only 0.2 Ω cm{sup 2} formed during the bonding process is characterized by the current-voltage measurements. The InAs QD lasers on Si exhibit comparable characteristics to state-of-the-art QD lasers on silicon substrates, where the threshold current density J{sub th} and differential quantum efficiency η{sub d} of 240 A/cm{sup 2} and 23.9%, respectively, at room temperature are obtained with laser bars of cavity length and waveguide ridgemore » of 1.5 mm and 5 μm, respectively. The InAs QD lasers also show operation up to 100 °C with a threshold current density J{sub th} and differential quantum efficiency η{sub d} of 950 A/cm{sup 2} and 9.3%, respectively. The temperature coefficient T{sub 0} of 69 K from 60 to 100 °C is characterized from the temperature dependent J{sub th} measurements.« less

Process Of Bonding Copper And Tungsten

DOEpatents

Slattery, Kevin T.; Driemeyer, Daniel E.; Davis, John W.

2000-07-18

Process for bonding a copper substrate to a tungsten substrate by providing a thin metallic adhesion promoting film bonded to a tungsten substrate and a functionally graded material (FGM) interlayer bonding the thin metallic adhesion promoting film to the copper substrate. The FGM interlayer is formed by sintering a stack of individual copper and tungsten powder blend layers having progressively higher copper content/tungsten content, by volume, ratio values in successive powder blend layers in a lineal direction extending from the tungsten substrate towards the copper substrate. The resulting copper to tungsten joint well accommodates the difference in the coefficient of thermal expansion of the materials.

Current-Assisted Diffusion Bonding of Extruded Ti-22Al-25Nb Alloy by Spark Plasma Sintering: Interfacial Microstructure and Mechanical Properties

NASA Astrophysics Data System (ADS)

Yang, Jianlei; Wang, Guofeng; Jiao, Xueyan; Gu, Yibin; Liu, Qing; Li, You

2018-05-01

Spark plasma sintering (SPS) technology was used to current-assisted bond extruded Ti-22Al-25Nb alloy. The effects of bonding temperature (920-980 °C) and bonding time (10-30 min) on the microstructure evolution and shear strength of this alloy were investigated systematically. The temperature distribution in the specimen during the current-assisted bonding process was also analyzed by numerical simulation. It is noted that the highest temperature was obtained at the bonding interface. As the bonding temperature and bonding time increased, the voids in the interface shrank increasingly until they vanished. A complete metallurgical bonding interface could be produced at 960 °C/20 min/10 MPa, exhibiting the highest shear strength of 269.3 MPa. In addition, the shear strength of the bonded specimen depended on its interfacial microstructure. With increased bonding temperature, the fracture mode transformed from the intergranular fracture at the bonding interface to the cleavage fracture in the substrate.

Metal-dielectric interactions

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1979-01-01

Metal direlectric surface interactions and dielectric films on metal substrates were investigated. Since interfacial interaction depends so heavily on the nature of the surfaces, analytical surface tools such as Auger emission spectroscopy, X-ray photoelectron spectroscopy and field ion microscopy were used to assist in surface and interfacial characterization. The results indicate that with metals contacting certain glasses in the clean state interfacial, bonding produces fractures in the glasses while when a film such as water is present, fractures occur in the metal near the interface. Friction forces were used to measure the interfacial bond strengths. Studies with metals contacting polymers using field ion microscopy revealed that strong bonding forces could develop being between a metal and polymer surface with polymer transferring to the metal surface in various ways depending upon the forces applied to the surface in contact. With the deposition of refractory carbides, silicides and borides onto metal and alloy substrates the presence of oxides at the interface or active gases in the deposition plasma were shown to alter interfacial properties and chemistry. Auger ion depth profile analysis indicated the chemical composition at the interface and this could be related to the mechanical, friction, and wear behavior of the coating.

Mechanism of ribonucleotide reductase from Herpes simplex virus type 1. Evidence for 3' carbon-hydrogen bond cleavage and inactivation by nucleotide analogs

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

Ator, M.A.; Stubbe, J.; Spector, T.

1986-03-15

Isotope effects of 2.5, 2.1, and 1.0 were measured on the conversion of (3'-3H)ADP, (3'-H)UDP, and (5-3H) UDP to the corresponding 2'-deoxynucleotides by herpes simplex virus type 1 ribonucleotide reductase. These results indicate that the reduction of either purine or pyrimidine nucleotides requires cleavage of the 3' carbon-hydrogen bond of the substrate. The substrate analogs 2'-chloro-2'-deoxyuridine 5'-diphosphate (ClUDP), 2'-deoxy-2'-fluorouridine 5'-diphosphate, and 2'-azido-2'-deoxyuridine 5'-diphosphate were time-dependent inactivators of the herpes simplex virus type 1 ribonucleotide reductase. Incubation of (3'-3H)ClUDP with the enzyme was accompanied by time-dependent release of 3H to the solvent. Reaction of (beta-32P)ClUDP with the reductase resulted in themore » production of inorganic pyrophosphate. These results are consistent with the enzyme-mediated cleavage of the 3' carbon-hydrogen bond of ClUDP and the subsequent conversion of the nucleotide to 2-methylene-3(2H)furanone, as previously reported with the Escherichia coli ribonucleotide reductase.« less

Superstrong encapsulated monolayer graphene by the modified anodic bonding

NASA Astrophysics Data System (ADS)

Jung, Wonsuk; Yoon, Taeshik; Choi, Jongho; Kim, Soohyun; Kim, Yong Hyup; Kim, Taek-Soo; Han, Chang-Soo

2013-12-01

We report a superstrong adhesive of monolayer graphene by modified anodic bonding. In this bonding, graphene plays the role of a superstrong and ultra-thin adhesive between SiO2 and glass substrates. As a result, monolayer graphene presented a strong adhesion energy of 1.4 J m-2 about 310% that of van der Waals bonding (0.45 J m-2) to SiO2 and glass substrates. This flexible solid state graphene adhesive can tremendously decrease the adhesive thickness from about several tens of μm to 0.34 nm for epoxy or glue at the desired bonding area. As plausible causes of this superstrong adhesion, we suggest conformal contact with the rough surface of substrates and generation of C-O chemical bonding between graphene and the substrate due to the bonding process, and characterized these properties using optical microscopy, atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy.We report a superstrong adhesive of monolayer graphene by modified anodic bonding. In this bonding, graphene plays the role of a superstrong and ultra-thin adhesive between SiO2 and glass substrates. As a result, monolayer graphene presented a strong adhesion energy of 1.4 J m-2 about 310% that of van der Waals bonding (0.45 J m-2) to SiO2 and glass substrates. This flexible solid state graphene adhesive can tremendously decrease the adhesive thickness from about several tens of μm to 0.34 nm for epoxy or glue at the desired bonding area. As plausible causes of this superstrong adhesion, we suggest conformal contact with the rough surface of substrates and generation of C-O chemical bonding between graphene and the substrate due to the bonding process, and characterized these properties using optical microscopy, atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03822j

Adhesion, friction, and deformation of ion-beam-deposited boron nitride films

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa; Buckley, Donald H.; Alterovitz, Samuel A.; Pouch, John J.; Liu, David C.

1987-01-01

The tribological properties and mechanical strength of boron nitride films were investigated. The BN films were predominantly amorphous and nonstoichiometric and contained small amounts of oxides and carbides. It was found that the yield pressure at full plasticity, the critical load to fracture, and the shear strength of interfacial adhesive bonds (considered as adhesion) depended on the type of metallic substrate on which the BN was deposited. The harder the substrate, the greater the critical load and the adhesion. The yield pressures of the BN film were 12 GPa for the 440C stainless steel substrate, 4.1 GPa for the 304 stainless steel substrate, and 3.3 GPa for the titanium substrate.

Adhesion, friction and deformation of ion-beam-deposited boron nitride films

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.; Alterovitz, S. A.; Pouch, J. J.; Liu, D. C.

1987-01-01

The tribological properties and mechanical strength of boron nitride films were investigated. The BN films were predominantly amorphous and nonstoichiometric and contained small amounts of oxides and carbides. It was found that the yield pressure at full plasticity, the critical load to fracture, and the shear strength of interfacial adhesive bonds (considered as adhesion) depended on the type of metallic substrate on which the BN was deposited. The harder the substrate, the greater the critical load and the adhesion. The yield pressures of the BN film were 12 GPa for the 440C stainless steel substrate, 4.1 GPa for the 304 stainless steel substrate, and 3.3 GPa for the titanium substrate.

The Important Role of Halogen Bond in Substrate Selectivity of Enzymatic Catalysis

NASA Astrophysics Data System (ADS)

Jiang, Shuiqin; Zhang, Lujia; Cui, Dongbin; Yao, Zhiqiang; Gao, Bei; Lin, Jinping; Wei, Dongzhi

2016-10-01

The use of halogen bond is widespread in drug discovery, design, and clinical trials, but is overlooked in drug biosynthesis. Here, the role of halogen bond in the nitrilase-catalyzed synthesis of ortho-, meta-, and para-chlorophenylacetic acid was investigated. Different distributions of halogen bond induced changes of substrate binding conformation and affected substrate selectivity. By engineering the halogen interaction, the substrate selectivity of the enzyme changed, with the implication that halogen bond plays an important role in biosynthesis and should be used as an efficient and reliable tool in enzymatic drug synthesis.

Extended reaction scope of thiamine diphosphate dependent cyclohexane-1,2-dione hydrolase: from C-C bond cleavage to C-C bond ligation.

PubMed

Loschonsky, Sabrina; Wacker, Tobias; Waltzer, Simon; Giovannini, Pier Paolo; McLeish, Michael J; Andrade, Susana L A; Müller, Michael

2014-12-22

ThDP-dependent cyclohexane-1,2-dione hydrolase (CDH) catalyzes the CC bond cleavage of cyclohexane-1,2-dione to 6-oxohexanoate, and the asymmetric benzoin condensation between benzaldehyde and pyruvate. One of the two reactivities of CDH was selectively knocked down by mutation experiments. CDH-H28A is much less able to catalyze the CC bond formation, while the ability for CC bond cleavage is still intact. The double variant CDH-H28A/N484A shows the opposite behavior and catalyzes the addition of pyruvate to cyclohexane-1,2-dione, resulting in the formation of a tertiary alcohol. Several acyloins of tertiary alcohols are formed with 54-94 % enantiomeric excess. In addition to pyruvate, methyl pyruvate and butane-2,3-dione are alternative donor substrates for CC bond formation. Thus, the very rare aldehyde-ketone cross-benzoin reaction has been solved by design of an enzyme variant. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Engineering Environmentally-Stable Proteases to Specifically Neutralize Protein Toxins

DTIC Science & Technology

2013-10-01

acids. These sites constitute a variable environment, with the effect of mutations largely isolated to effects on interactions with the P4 side chain. 2...desires to cut. We observe, however, sequence-specific cleavage is much more subtle, depending upon how side chain interactions influence not only...first five substrate amino acids on the acyl side of the scissile bond (denoted P1 through P5, numbering from the scissile bond toward the N-terminus

Engineering Environmentally-Stable Proteases to Specifically Neutralize Protein Toxins

DTIC Science & Technology

2012-10-14

effect of mutations largely isolated to effects on interactions with the P4 side chain. 2) Most mutations at some sites (e.g. 126, 128) decrease...to cut. We observe, however, sequence-specific cleavage is much more subtle, depending upon how side chain interactions influence not only ground...five substrate amino acids on the acyl side of the scissile bond (denoted P1 through P5, numbering from the scissile bond toward the N-terminus of the

Thermoplastic Ribbon-Ply Bonding Model

NASA Technical Reports Server (NTRS)

Hinkley, Jeffrey A.; Marchello, Joseph M.; Messier, Bernadette C.

1996-01-01

The aim of the present work was to identify key variables in rapid weldbonding of thermoplastic tow (ribbon) and their relationship to matrix polymer properties and to ribbon microstructure. Theoretical models for viscosity, establishment of ply-ply contact, instantaneous (Velcro) bonding, molecular interdiffusion (healing), void growth suppression, and gap filling were reviewed and synthesized. Consideration of the theoretical bonding mechanisms and length scales and of the experimental weld/peel data allow the prediction of such quantities as the time and pressure required to achieve good contact between a ribbon and a flat substrate, the time dependence of bond strength, pressures needed to prevent void growth from dissolved moisture and conditions for filling gaps and smoothing overlaps.

Initial and long-term bond strengths of one-step self-etch adhesives with silane coupling agent to enamel-dentin-composite in combined situation.

PubMed

Mamanee, Teerapong; Takahashi, Masahiro; Nakajima, Masatoshi; Foxton, Richard M; Tagami, Junji

2015-01-01

This study evaluated the effect of adding silane coupling agent on initial and long-term bond strengths of one-step self-etch adhesives to enamel-dentin-composite in combined situation. Cervical cavities were prepared on extracted molars and filled with Clearfil AP-X. After water-storage for one-week, the filled teeth were sectioned in halves to expose enamel, dentin and composite surfaces and then enamel-dentin-composite surface was totally applied with one of adhesive treatments (Clearfil SE One, Clearfil SE One with Clearfil Porcelain Bond Activator, Beautibond Multi, Beautibond Multi with Beautibond Multi PR Plus and Scotchbond Universal). After designed period, micro-shear bond strengths (µSBSs) to each substrate were determined. For each period of water-storage, additive silane treatments significantly increased µSBS to composite (p<0.001). On the other hand, they significantly decreased µSBS to dentin (p<0.001), although did not have adverse effect on µSBS to enamel (p>0.05). Moreover, the stability of µSBS was depended on materials and substrates used.

Method of making reflecting film reflector

DOEpatents

Cottingham, James G.

1980-01-01

A reflector of the reflecting film type is disclosed and which may be used in a heliostatic system for concentrating solar energy and comprising a reflecting film bonded to an appropriate rigid substrate in such a way that specularity of a very high order is achieved. A method of bonding the reflecting film to the substrate is also disclosed and comprises the steps of initially adhering the film to a smooth, clean flat rigid surface with a non-bonding liquid between the rigid surface and film, and then bonding the substrate and film. The non-bonding liquid has a molecular adhesion greater than any stresses due to handling or curing of the bonding agent which is applied between the film and the opposing surface of the rigid substrate.

Asymmetrical bonding in cold spraying of dissimilar materials

NASA Astrophysics Data System (ADS)

Nikbakht, R.; Seyedein, S. H.; Kheirandish, S.; Assadi, H.; Jodoin, B.

2018-06-01

Characteristics of particle bonding, especially for dissimilar materials, remains a key question in cold spray deposition. There are limited reports in direct correlation to particle/substrate bonding and peripheral shear zones. Cold spraying experiments and numerical simulations are conducted to characterise and analyse the correlation between bonding and peripheral shear zones for asymmetric particle/substrate pairs of intermetallic-forming elements of nickel and titanium. The correlation between metallic bonding and highly strained areas is explored in view of the growth of the intermetallic phase at the particle/substrate interface during subsequent heat treatments. Characterisation of the as-sprayed samples reveal that for the Ni(particle)/Ti(substrate) pair, plastic deformation of the particle is dominating over substrate deformation. However, for the Ti(particle)/Ni(substrate) pair, it is observed that the substrate and particle deform to similar extents. Characterisation of the samples after a brief heat treatment at 700 °C indicate that intermetallic formation, and hence metallurgical bonding of the pairs is more likely to occur at the particle peripheries where the interface areas are highly strained, and rarely achieved at the particle base. Results also reveal that bonding extends from peripheries toward the central part of the interfaces with increasing the impact velocity. The kinetics of interfacial intermetallic formation at peripheral areas and its correlation to particle bonding is discussed in view of deformation-enhanced interdiffusion.

Microfabrication of plastic-PDMS microfluidic devices using polyimide release layer and selective adhesive bonding

DOE PAGES

Wang, Shuyu; Yu, Shifeng; Lu, Ming; ...

2017-03-15

In this study, we present an improved method to bond poly(dimethylsiloxane) (PDMS) with polyimide (PI) to develop flexible substrate microfluidic devices. The PI film was separately fabricated on a silicon wafer by spin coating followed by thermal treatment to avoid surface unevenness of the flexible substrate. In this way, we could also integrate flexible substrate into standard micro-electromechanical systems (MEMS) fabrication. Meanwhile, the adhesive epoxy was selectively transferred to the PDMS microfluidic device by a stamp-and-stick method to avoid epoxy clogging the microfluidic channels. To spread out the epoxy evenly on the transferring substrate, we used superhydrophilic vanadium oxide filmmore » coated glass as the transferring substrate. After the bonding process, the flexible substrate could easily be peeled off from the rigid substrate. Contact angle measurement was used to characterize the hydrophicity of the vanadium oxide film. X-ray photoelectron spectroscopy analysis was conducted to study the surface of the epoxy. We further evaluated the bonding quality by peeling tests, which showed a maximum bonding strength of 100 kPa. By injecting with black ink, the plastic microfluidic device was confirmed to be well bonded with no leakage for a day under 1 atm. Finally, this proposed versatile method could bond the microfluidic device and plastic substrate together and be applied in the fabrication of some biosensors and lab-on-a-chip systems.« less

Microfabrication of plastic-PDMS microfluidic devices using polyimide release layer and selective adhesive bonding

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

Wang, Shuyu; Yu, Shifeng; Lu, Ming

In this study, we present an improved method to bond poly(dimethylsiloxane) (PDMS) with polyimide (PI) to develop flexible substrate microfluidic devices. The PI film was separately fabricated on a silicon wafer by spin coating followed by thermal treatment to avoid surface unevenness of the flexible substrate. In this way, we could also integrate flexible substrate into standard micro-electromechanical systems (MEMS) fabrication. Meanwhile, the adhesive epoxy was selectively transferred to the PDMS microfluidic device by a stamp-and-stick method to avoid epoxy clogging the microfluidic channels. To spread out the epoxy evenly on the transferring substrate, we used superhydrophilic vanadium oxide filmmore » coated glass as the transferring substrate. After the bonding process, the flexible substrate could easily be peeled off from the rigid substrate. Contact angle measurement was used to characterize the hydrophicity of the vanadium oxide film. X-ray photoelectron spectroscopy analysis was conducted to study the surface of the epoxy. We further evaluated the bonding quality by peeling tests, which showed a maximum bonding strength of 100 kPa. By injecting with black ink, the plastic microfluidic device was confirmed to be well bonded with no leakage for a day under 1 atm. Finally, this proposed versatile method could bond the microfluidic device and plastic substrate together and be applied in the fabrication of some biosensors and lab-on-a-chip systems.« less

Removing bonded skin from a substrate

NASA Technical Reports Server (NTRS)

Chartier, E. N.

1980-01-01

Metal skin is peeled off like sardine-can cover with key. Method is useful in removing bonded skins from any substrate where substrate is strong enough not to buckle or tear when bonded skin is rolled free. Also, it is useful for removing sections of damaged skin where bladders of other equipment below substrate might be damaged if saw or router were used to cut completely through skin.

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.

Wafer bonded virtual substrate and method for forming the same

DOEpatents

Atwater, Jr., Harry A.; Zahler, James M [Pasadena, CA; Morral, Anna Fontcuberta i [Paris, FR

2007-07-03

A method of forming a virtual substrate comprised of an optoelectronic device substrate and handle substrate comprises the steps of initiating bonding of the device substrate to the handle substrate, improving or increasing the mechanical strength of the device and handle substrates, and thinning the device substrate to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. The handle substrate is typically Si or other inexpensive common substrate material, while the optoelectronic device substrate is formed of more expensive and specialized electro-optic material. Using the methodology of the invention a wide variety of thin film electro-optic materials of high quality can be bonded to inexpensive substrates which serve as the mechanical support for an optoelectronic device layer fabricated in the thin film electro-optic material.

Wafer bonded virtual substrate and method for forming the same

NASA Technical Reports Server (NTRS)

Atwater, Jr., Harry A. (Inventor); Zahler, James M. (Inventor); Morral, Anna Fontcuberta i (Inventor)

2007-01-01

A method of forming a virtual substrate comprised of an optoelectronic device substrate and handle substrate comprises the steps of initiating bonding of the device substrate to the handle substrate, improving or increasing the mechanical strength of the device and handle substrates, and thinning the device substrate to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. The handle substrate is typically Si or other inexpensive common substrate material, while the optoelectronic device substrate is formed of more expensive and specialized electro-optic material. Using the methodology of the invention a wide variety of thin film electro-optic materials of high quality can be bonded to inexpensive substrates which serve as the mechanical support for an optoelectronic device layer fabricated in the thin film electro-optic material.

Optimization of Cold Spray Deposition of High-Density Polyethylene Powders

NASA Astrophysics Data System (ADS)

Bush, Trenton B.; Khalkhali, Zahra; Champagne, Victor; Schmidt, David P.; Rothstein, Jonathan P.

2017-10-01

When a solid, ductile particle impacts a substrate at sufficient velocity, the resulting heat, pressure and plastic deformation can produce bonding between the particle and the substrate. The use of a cool supersonic gas flow to accelerate these solid particles is known as cold spray deposition. The cold spray process has been commercialized for some metallic materials, but further research is required to unlock the exciting potential material properties possible with polymeric particles. In this work, a combined computational and experimental study was employed to study the cold spray deposition of high-density polyethylene powders over a wide range of particle temperatures and impact velocities. Cold spray deposition of polyethylene powders was demonstrated across a range broad range of substrate materials including several different polymer substrates with different moduli, glass and aluminum. A material-dependent window of successful deposition was determined for each substrate as a function of particle temperature and impact velocity. Additionally, a study of deposition efficiency revealed the optimal process parameters for high-density polyethylene powder deposition which yielded a deposition efficiency close to 10% and provided insights into the physical mechanics responsible for bonding while highlighting paths toward future process improvements.

Precise Nanoelectronics with Adatom Chains

NASA Technical Reports Server (NTRS)

Yamada, Toshishige

1999-01-01

Adatom chains on an atomically regulated substrate will be building components in future precise nanoelectronics. Adatoms need to be secured with chemical bonding, but then electronic isolation between the adatom and substrate systems is not guaranteed. A one-dimensional model shows that good isolation with existence of surface states is expected on an s-p crossing substrate such as Si, Ge, or GaAs, reflecting the bulk nature of the substrate. Isolation is better if adatoms are electronically similar to the substrate atoms, and can be manipulated by hydrogenation. Chain structures with group IV adatoms with two chemical bonds, or group III adatoms with one chemical bond, are semiconducting, reflecting the surface nature of the substrate. These structures are unintentionally doped due to the charge transfer across the chemical bonds. Physical properties of adatom chains have to be determined for the unified adatom-substrate system.

Pharmacophore, QSAR, and binding mode studies of substrates of human cytochrome P450 2D6 (CYP2D6) using molecular docking and virtual mutations and an application to chinese herbal medicine screening.

PubMed

Mo, Sui-Lin; Liu, Wei-Feng; Li, Chun-Guang; Zhou, Zhi-Wei; Luo, Hai-Bin; Chew, Helen; Liang, Jun; Zhou, Shu-Feng

2012-07-01

The highly polymorphic human cytochrome P450 2D6 (CYP2D6) metabolizes about 25% of currently used drugs. In this study, we have explored the interaction of a large number of substrates (n = 120) with wild-type and mutated CYP2D6 by molecular docking using the CDOCKER module. Before we conducted the molecular docking and virtual mutations, the pharmacophore and QSAR models of CYP2D6 substrates were developed and validated. Finally, we explored the interaction of a traditional Chinese herbal formula, Fangjifuling decoction, with CYP2D6 by virtual screening. The optimized pharmacophore model derived from 20 substrates of CYP2D6 contained two hydrophobic features and one hydrogen bond acceptor feature, giving a relevance ratio of 76% when a validation set of substrates were tested. However, our QSAR models gave poor prediction of the binding affinity of substrates. Our docking study demonstrated that 117 out of 120 substrates could be docked into the active site of CYP2D6. Forty one out of 117 substrates (35.04%) formed hydrogen bonds with various active site residues of CYP2D6 and 53 (45.30%) substrates formed a strong π-π interaction with Phe120 (53/54), with only carvedilol showing π-π interaction with Phe483. The active site residues involving hydrogen bond formation with substrates included Leu213, Lys214, Glu216, Ser217, Gln244, Asp301, Ser304, Ala305, Phe483, and Phe484. Furthermore, the CDOCKER algorithm was further applied to study the impact of mutations of 28 active site residues (mostly non-conserved) of CYP2D6 on substrate binding modes using five probe substrates including bufuralol, debrisoquine, dextromethorphan, sparteine, and tramadol. All mutations of the residues examined altered the hydrogen bond formation and/or aromatic interactions, depending on the probe used in molecular docking. Apparent changes of the binding modes have been observed with the Glu216Asp and Asp301Glu mutants. Overall, 60 compounds out of 130 from Fangjifuling decoction matched our pharmacophore model for CYP2D6 substrates. Fifty four out of these 60 compounds could be docked into the active site of CYP2D6 and 24 of 54 compounds formed hydrogen bonds with Glu216, Asp301, Ser304, and Ala305 in CYP2D6. These results have provided further insights into the factors that determining the binding modes of substrates to CYP2D6. Screening of high-affinity ligands for CYP2D6 from herbal formula using computational models is a useful approach to identify potential herb-drug interactions.

Solvent-free thermoplastic-poly(dimethylsiloxane) bonding mediated by UV irradiation followed by gas-phase chemical deposition of an adhesion linker

NASA Astrophysics Data System (ADS)

Ahn, S. Y.; Lee, N. Y.

2015-07-01

Here, we introduce a solvent-free strategy for bonding various thermoplastic substrates with poly(dimethylsiloxane) (PDMS) using ultraviolet (UV) irradiation followed by the gas-phase chemical deposition of aminosilane on the UV-irradiated thermoplastic substrates. The thermoplastic substrates were first irradiated with UV for surface hydrophilic treatment and were then grafted with vacuum-evaporated aminosilane, where the alkoxysilane side reacted with the oxidized surface of the thermoplastic substrate. Next, the amine-terminated thermoplastic substrates were treated with corona discharge to oxidize the surface and were bonded with PDMS, which was also oxidized via corona discharge. The two substrates were then hermetically sealed and pressed under atmospheric pressure for 30 min at 60 °C. This process enabled the formation of a robust siloxane bond (Si-O-Si) between the thermoplastic substrate and PDMS under relatively mild conditions using an inexpensive and commercially available UV lamp and Tesla coil. Various thermoplastic substrates were examined for bonding with PDMS, including poly(methylmethacrylate) (PMMA), polycarbonate (PC), poly(ethyleneterephthalate) (PET) and polystyrene (PS). Surface characterizations were performed by measuring the contact angle and performing x-ray photoelectron spectroscopy analysis, and the bond strength was analyzed by conducting various mechanical force measurements such as pull, delamination, leak and burst tests. The average bond strengths for the PMMA-PDMS, PC-PDMS, PET-PDMS and PS-PDMS assemblies were measured at 823.6, 379.3, 291.2 and 229.0 kPa, respectively, confirming the highly reliable performance of the introduced bonding strategy.

Microstructure, Tensile Adhesion Strength and Thermal Shock Resistance of TBCs with Different Flame-Sprayed Bond Coat Materials Onto BMI Polyimide Matrix Composite

NASA Astrophysics Data System (ADS)

Abedi, H. R.; Salehi, M.; Shafyei, A.

2017-10-01

In this study, thermal barrier coatings (TBCs) composed of different bond coats (Zn, Al, Cu-8Al and Cu-6Sn) with mullite top coats were flame-sprayed and air-plasma-sprayed, respectively, onto bismaleimide matrix composites. These polyimide matrix composites are of interest to replace PMR-15, due to concerns about the toxicity of the MDA monomer from which PMR-15 is made. The results showed that pores and cracks appeared at the bond coat/substrate interface for the Al-bonded TBC because of its high thermal conductivity and diffusivity resulting in transferring of high heat flux and temperature to the polymeric substrate during top coat deposition. The other TBC systems due to the lower conductivity and diffusivity of bonding layers could decrease the adverse thermal effect on the polymer substrate during top coat deposition and exhibited adhesive bond coat/substrate interfaces. The tensile adhesion test showed that the adhesion strength of the coatings to the substrate is inversely proportional to the level of residual stress in the coatings. However, the adhesion strength of Al bond-coated sample decreased strongly after mullite top coat deposition due to thermal damage at the bond coat/substrate interface. TBC system with the Cu-6Sn bond coat exhibited the best thermal shock resistance, while Al-bonded TBC showed the lowest. It was inferred that thermal mismatch stresses and oxidation of the bond coats were the main factors causing failure in the thermal shock test.

Superstrong encapsulated monolayer graphene by the modified anodic bonding.

PubMed

Jung, Wonsuk; Yoon, Taeshik; Choi, Jongho; Kim, Soohyun; Kim, Yong Hyup; Kim, Taek-Soo; Han, Chang-Soo

2014-01-07

We report a superstrong adhesive of monolayer graphene by modified anodic bonding. In this bonding, graphene plays the role of a superstrong and ultra-thin adhesive between SiO2 and glass substrates. As a result, monolayer graphene presented a strong adhesion energy of 1.4 J m(-2) about 310% that of van der Waals bonding (0.45 J m(-2)) to SiO2 and glass substrates. This flexible solid state graphene adhesive can tremendously decrease the adhesive thickness from about several tens of μm to 0.34 nm for epoxy or glue at the desired bonding area. As plausible causes of this superstrong adhesion, we suggest conformal contact with the rough surface of substrates and generation of C-O chemical bonding between graphene and the substrate due to the bonding process, and characterized these properties using optical microscopy, atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy.

Process Of Bonding Copper And Tungsten

DOEpatents

Slattery, Kevin T.; Driemeyer, Daniel E.

1999-11-23

Process for bonding a copper substrate to a tungsten substrate by providing a thin metallic adhesion promoting film bonded to a tungsten substrate and a functionally graded material (FGM) interlayer bonding the thin metallic adhesion promoting film to the copper substrate. The FGM interlayer is formed by thermal plasma spraying mixtures of copper powder and tungsten powder in a varied blending ratio such that the blending ratio of the copper powder and the tungsten powder that is fed to a plasma torch is intermittently adjusted to provide progressively higher copper content/tungsten content, by volume, ratio values in the interlayer in a lineal direction extending from the tungsten substrate towards the copper substrate. The resulting copper to tungsten joint well accommodates the difference in the coefficient of thermal expansion of the materials.

Composition of RF-sputtered refractory compounds determined by X-ray photoelectron spectroscopy

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Brainard, W. A.

1978-01-01

RF-sputtered coatings of CrB2, MoSi2, Mo2C, TiC, and MoS2 were examined by X-ray photoelectron spectroscopy (XPS). Data on stoichiometry, impurity content, and chemical bonding were obtained. The influences of sputtering target history, deposition time, RF power level, and substrate bias were studied. Significant deviations from stoichiometry and high oxide levels were related to target outgassing. The effect of substrate bias depended on the particular coating material studied.

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.

Surface instability of an imperfectly bonded thin elastic film under surface van der Waals forces

NASA Astrophysics Data System (ADS)

Wang, Xu; Jing, Rong

2017-02-01

This paper studies surface instability of a thin elastic film imperfectly bonded to a rigid substrate interacting with a rigid contactor through van der Waals forces under plane strain conditions. The film-substrate interface is modeled as a linear spring with vanishing thickness described in terms of the normal and tangential interface parameters. Depending on the ratio of the two imperfect interface parameters, the critical value of the Poisson's ratio for the occurrence of surface wrinkling in the absence of surface energy can be greater than, equal to, or smaller than 0.25, which is the critical Poisson's ratio for a perfect film-substrate interface. The critical surface energy for the inhibition of the surface wrinkling is also obtained. Finally, we propose a very simple and effective method to study the surface instability of a multilayered elastic film with imperfect interfaces interacting with a rigid contactor or with another multilayered elastic film (or a multilayered simply supported plate) with imperfect interfaces.

Development and Characterization of the Bonding and Integration Technologies Needed for Fabricating Silicon Carbide Based Injector Components

NASA Technical Reports Server (NTRS)

Halbig,Michael C.; Singh, Mrityunjay

2008-01-01

Advanced ceramic bonding and integration technologies play a critical role in the fabrication and application of silicon carbide based components for a number of aerospace and ground based applications. One such application is a lean direct injector for a turbine engine to achieve low NOx emissions. Ceramic to ceramic diffusion bonding and ceramic to metal brazing technologies are being developed for this injector application. For the diffusion bonding technology, titanium interlayers (coatings and foils) were used to aid in the joining of silicon carbide (SiC) substrates. The influence of such variables as surface finish, interlayer thickness, and processing time were investigated. Electron microprobe analysis was used to identify the reaction formed phases. In the diffusion bonds, an intermediate phase, Ti5Si3Cx, formed that is thermally incompatible in its thermal expansion and caused thermal stresses and cracking during the processing cool-down. Thinner interlayers of pure titanium and/or longer processing times resulted in an optimized microstructure. Tensile tests on the joined materials resulted in strengths of 13-28 MPa depending on the SiC substrate material. Nondestructive evaluation using ultrasonic immersion showed well formed bonds. For the joining technology of brazing Kovar fuel tubes to silicon carbide, preliminary development of the joining approach has begun. Various technical issues and requirements for the injector application are addressed.

Nitro-Assisted Brønsted Acid Catalysis: Application to a Challenging Catalytic Azidation.

PubMed

Dryzhakov, Marian; Hellal, Malik; Wolf, Eléna; Falk, Florian C; Moran, Joseph

2015-08-05

A cocatalytic effect of nitro compounds is described for the B(C6F5)3·H2O catalyzed azidation of tertiary aliphatic alcohols, enabling catalyst turnover for the first time and with a broad range of substrates. Kinetic investigations into this surprising effect reveal that nitro compounds induce a switch from first order concentration dependence in Brønsted acid to second order concentration dependence in Brønsted acid and second order dependence in the nitro compounds. Kinetic, electronic, and spectroscopic evidence suggests that higher order hydrogen-bonded aggregates of nitro compounds and acids are the kinetically competent Brønsted acid catalysts. Specific weak H-bond accepting additives may offer a new general approach to accelerating Brønsted acid catalysis in solution.

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.

Effect of tooth substrate and porcelain thickness on porcelain veneer failure loads in vitro.

PubMed

Ge, Chunling; Green, Chad C; Sederstrom, Dalene A; McLaren, Edward A; Chalfant, James A; White, Shane N

2017-12-19

Bonded porcelain veneers are widely used esthetic restorations. High success and survival rates have been reported, but failures do occur. Fractures are the commonest failure mode. Minimally invasive or thin veneers have gained popularity. Increased enamel and porcelain thickness improve the strength of veneers bonded to enamel, but less is known about dentin or mixed substrates. The purpose of this in vitro study was to measure the influences of tooth substrate type (all-enamel, all-dentin, or half-dentin-half-enamel) and veneer thickness on the loads needed to cause initial and catastrophic porcelain veneer failure. Model discoid porcelain veneer specimens of varying thicknesses were bonded to the flattened facial surfaces of incisors with different enamel and dentin tooth substrates, artificially aged, and loaded to failure with a small sphere. Initial and catastrophic fracture events were identified and analyzed statistically and fractographically. Fracture events included initial Hertzian cracks, intermediate radial cracks, and catastrophic gross failure. All specimens retained some porcelain after catastrophic failure. Cement failure occurred at the cement-porcelain interface not at the cement-tooth interface. Porcelain veneers bonded to enamel were substantially stronger and more damage-tolerant than those bonded to dentin or mixed substrates. Increased porcelain thickness substantially raised the loads to catastrophic failure on enamel substrates but only moderately raised the loads to catastrophic failure on dentin or mixed substrates. The veneers bonded to half-dentin-half-enamel behaved remarkably like those bonded wholly to dentin. Porcelain veneers bonded to enamel were substantially stronger and more damage-tolerant than those bonded to dentin or half-enamel-half dentin. Copyright © 2017 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Shear sensitive monomer-polymer laminate structure and method of using same

NASA Technical Reports Server (NTRS)

Singh, Jag J. (Inventor); Eftekhari, Abe (Inventor); Parmar, Devendra S. (Inventor)

1993-01-01

Monomer cholesteric liquid crystals have helical structures which result in a phenomenon known as selective reflection, wherein incident white light is reflected in such a way that its wavelength is governed by the instantaneous pitch of the helix structure. The pitch is dependent on temperature and external stress fields. It is possible to use such monomers in flow visualization and temperature measurement. However, the required thin layers of these monomers are quickly washed away by a flow, making their application time dependent for a given flow rate. The laminate structure according to the present invention comprises a liquid crystal polymer substrate attached to a test surface of an article. A light absorbing coating is applied to the substrate and is thin enough to permit bonding steric interaction between the liquid crystal polymer substrate and an overlying liquid crystal monomer thin film. Light is directed through and reflected by the liquid crystal monomer thin film and unreflected light is absorbed by the underlying coating. The wavelength of the reflected light is indicative of the shear stress experienced by the test surface. Novel aspects of the invention include its firm bonding of a liquid crystal monomer to a model and its use of a coating to reduce interference from light unreflected by the monomer helical structure.

[Characterization of polygalacturonase covalently bonded to Sepharose].

PubMed

Bock, W; Krause, M; Anger, H; Flemming, C

1981-01-01

For the soluble endo-polygalacturonase (EC 3.2.1.15.) from Aspergillus spec., investigated in the present work, the defined substrate turnover U at 50% loss of viscosity if 0.2% and is independent on the reaction temperature. In the case of the covalently-bonded enzyme, the following linear equation applies to U, depending on the specific activity A and in the limits from A = O [U] and Amax: U = [U] + S square root of A. U is influenced by the kind of linkage, the conditions of immobilization and the properties of the carrier: it is a measure of the postulated conformational change of the polygalacturonase. The characteristic limiting value for the substrate turnover at A = O [U] is also temperature-independent and proves to be a true increment of binding, whereas Amax depends essentially on the porosity of the carrier. Polygalacturonase-sepharose complexes with a real substrate turnover U of 3--20% were prepared by varying systematically the kind of linkage and the specific activity A. It was found that with increasing U these complexes were, as a rule, inhibited to a lesser extent by a non-competitive pectinase inhibitor than the soluble polygalacturonase. Furthermore, their ability to liberate or enrich oligomeric galacturonic acids with a degree of polymerization greater than 3 was markedly reduced.

Initiated chemical vapor deposited nanoadhesive for bonding National Ignition Facility's targets

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

Lee, Tom

Currently, the target fabrication scientists in National Ignition Facility Directorate at Lawrence Livermore National Laboratory (LLNL) is studying the propagation force resulted from laser impulses impacting a target. To best study this, they would like the adhesive used to glue the target substrates to be as thin as possible. The main objective of this research project is to create adhesive glue bonds for NIF’s targets that are ≤ 1 μm thick. Polyglycidylmethacrylate (PGMA) thin films were coated on various substrates using initiated chemical vapor deposition (iCVD). Film quality studies using white light interferometry reveal that the iCVD PGMA films weremore » smooth. The coated substrates were bonded at 150 °C under vacuum, with low inflow of Nitrogen. Success in bonding most of NIF’s mock targets at thicknesses ≤ 1 μm indicates that our process is feasible in bonding the real targets. Key parameters that are required for successful bonding were concluded from the bonding results. They include inert bonding atmosphere, sufficient contact between the PGMA films, and smooth substrates. Average bond strength of 0.60 MPa was obtained from mechanical shearing tests. The bonding failure mode of the sheared interfaces was observed to be cohesive. Future work on this project will include reattempt to bond silica aerogel to iCVD PGMA coated substrates, stabilize carbon nanotube forests with iCVD PGMA coating, and kinetics study of PGMA thermal crosslinking.« less

Bonding and Integration Technologies for Silicon Carbide Based Injector Components

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Singh, Mrityunjay

2008-01-01

Advanced ceramic bonding and integration technologies play a critical role in the fabrication and application of silicon carbide based components for a number of aerospace and ground based applications. One such application is a lean direct injector for a turbine engine to achieve low NOx emissions. Ceramic to ceramic diffusion bonding and ceramic to metal brazing technologies are being developed for this injector application. For the diffusion bonding, titanium interlayers (PVD and foils) were used to aid in the joining of silicon carbide (SiC) substrates. The influence of such variables as surface finish, interlayer thickness (10, 20, and 50 microns), processing time and temperature, and cooling rates were investigated. Microprobe analysis was used to identify the phases in the bonded region. For bonds that were not fully reacted an intermediate phase, Ti5Si3Cx, formed that is thermally incompatible in its thermal expansion and caused thermal stresses and cracking during the processing cool-down. Thinner titanium interlayers and/or longer processing times resulted in stable and compatible phases that did not contribute to microcracking and resulted in an optimized microstructure. Tensile tests on the joined materials resulted in strengths of 13-28 MPa depending on the SiC substrate material. Non-destructive evaluation using ultrasonic immersion showed well formed bonds. For the joining technology of brazing Kovar fuel tubes to silicon carbide, preliminary development of the joining approach has begun. Various technical issues and requirements for the injector application are addressed.

Substrate specificity in enzymatic fluorination. The fluorinase from Streptomyces cattleya accepts 2′-deoxyadenosine substrates†

PubMed Central

Cobb, Steven L.; Deng, Hai; McEwan, Andrew R.; Naismith, James H.; O’Hagan, David; Robinson, David A.

2012-01-01

The fluorinase enzyme from Streptomyces cattleya displays an unusual ability in biocatalysis in that it forms a C–F bond. We now report that the enzyme will accept 2′-deoxyadenosine in place of adenosine substrates, and structural evidence reveals a reorganisation in hydrogen bonding to accommodate this substrate series. It emerges from this study that the enzyme does not require a planar ribose conformation of the substrate to catalyse C–F bond formation. PMID:16604208

Dislocation-free strained silicon-on-silicon by in-place bonding

NASA Astrophysics Data System (ADS)

Cohen, G. M.; Mooney, P. M.; Paruchuri, V. K.; Hovel, H. J.

2005-06-01

In-place bonding is a technique where silicon-on-insulator (SOI) slabs are bonded by hydrophobic attraction to the underlying silicon substrate when the buried oxide is undercut in dilute HF. The bonding between the exposed surfaces of the SOI slab and the substrate propagates simultaneously with the buried oxide etching. As a result, the slabs maintain their registration and are referred to as "bonded in-place". We report the fabrication of dislocation-free strained silicon slabs from pseudomorphic trilayer Si/SiGe/SOI by in-place bonding. Removal of the buried oxide allows the compressively strained SiGe film to relax elastically and induce tensile strain in the top and bottom silicon films. The slabs remain bonded to the substrate by van der Waals forces when the wafer is dried. Subsequent annealing forms a covalent bond such that when the upper Si and the SiGe layer are removed, the bonded silicon slab remains strained.

Biofriendly bonding processes for nanoporous implantable SU-8 microcapsules for encapsulated cell therapy.

PubMed

Nemani, Krishnamurthy; Kwon, Joonbum; Trivedi, Krutarth; Hu, Walter; Lee, Jeong-Bong; Gimi, Barjor

2011-01-01

Mechanically robust, cell encapsulating microdevices fabricated using photolithographic methods can lead to more efficient immunoisolation in comparison to cell encapsulating hydrogels. There is a need to develop adhesive bonding methods which can seal such microdevices under physiologically friendly conditions. We report the bonding of SU-8 based substrates through (i) magnetic self assembly, (ii) using medical grade photocured adhesive and (iii) moisture and photochemical cured polymerization. Magnetic self-assembly, carried out in biofriendly aqueous buffers, provides weak bonding not suitable for long term applications. Moisture cured bonding of covalently modified SU-8 substrates, based on silanol condensation, resulted in weak and inconsistent bonding. Photocured bonding using a medical grade adhesive and of acrylate modified substrates provided stable bonding. Of the methods evaluated, photocured adhesion provided the strongest and most stable adhesion.

Substrate Effects for Atomic Chain Electronics

NASA Technical Reports Server (NTRS)

Yamada, Toshishige; Saini, Subhash (Technical Monitor)

1998-01-01

A substrate for future atomic chain electronics, where adatoms are placed at designated positions and form atomically precise device components, is studied theoretically. The substrate has to serve as a two-dimensional template for adatom mounting with a reasonable confinement barrier and also provide electronic isolation, preventing unwanted coupling between independent adatom structures. For excellent structural stability, we demand chemical bonding between the adatoms and substrate atoms, but then good electronic isolation may not be guaranteed. Conditions are clarified for good isolation. Because of the chemical bonding, fundamental adatom properties are strongly influenced: a chain with group IV adatoms having two chemical bonds, or a chain with group III adatoms having one chemical bond is semiconducting. Charge transfer from or to the substrate atoms brings about unintentional doping, and the electronic properties have to be considered for the entire combination of the adatom and substrate systems even if the adatom modes are well localized at the surface.

Ultra-thin Polyethylene glycol Coatings for Stem Cell Culture

NASA Astrophysics Data System (ADS)

Schmitt, Samantha K.

Human mesenchymal stem cells (hMSCs) are a widely accessible and a clinically relevant cell type that are having a transformative impact on regenerative medicine. However, current clinical expansion methods can lead to selective changes in hMSC phenotype resulting from relatively undefined cell culture surfaces. Chemically defined synthetic surfaces can aid in understanding stem cell behavior. In particular we have developed chemically defined ultra-thin coatings that are stable over timeframes relevant to differentiation of hMSCs (several weeks). The approach employs synthesis of a copolymer with distinct chemistry in solution before application to a substrate. This provides wide compositional flexibility and allows for characterization of the orthogonal crosslinking and peptide binding groups. Characterization is done in solution by proton NMR and after crosslinking by X-ray photoelectron spectroscopy (XPS). The solubility of the copolymer in ethanol and low temperature crosslinking, expands its applicability to plastic substrates, in addition to silicon, glass, and gold. Cell adhesive peptides, namely Arg-Gly-Asp (RGD) fragments, are coupled to coating via different chemistries resulting in the urethane, amide or the thioester polymer-peptide bonds. Development of azlactone-based chemistry allowed for coupling in water at low peptide concentrations and resulted in either an amide or thioester bonds, depending on reactants. Characterization of the peptide functionalized coating by XPS, infrared spectroscopy and cell culture assays, showed that the amide linkages can present peptides for multiple weeks, while shorter-term presentation of a few days is possible using the more labile thioester bond. Regardless, coatings promoted initial adhesion and spreading of hMSCs in a peptide density dependent manner. These coatings address the following challenges in chemically defined cell culture simultaneously: (i) substrate adaptability, (ii) scalability over large areas, (ii) quantification of peptides, (iv) chemically defined passage of hMSCs, (v) stability of peptide-polymer bonds, and (vi) long-term coating stability. These coating platforms can potentially elucidate cell-material interactions in vitro and have far-reaching effects on stem cell culture methods.

Coated substrates and process

DOEpatents

Chu, Wei-kan; Childs, Charles B.

1991-01-01

Disclosed herein is a coated substrate and a process for forming films on substrates and for providing a particularly smooth film on a substrate. The method of this invention involves subjecting a surface of a substrate to contact with a stream of ions of an inert gas having sufficient force and energy to substantially change the surface characteristics of said substrate, and then exposing a film-forming material to a stream of ions of an inert gas having sufficient energy to vaporize the atoms of said film-forming material and to transmit the vaporized atoms to the substrate surface with sufficient force to form a film bonded to the substrate. This process is particularly useful commercially because it forms strong bonds at room temperature. This invention is particularly useful for adhering a gold film to diamond and forming ohmic electrodes on diamond, but also can be used to bond other films to substrates.

Interface thermal conductance of van der Waals monolayers on amorphous substrates

NASA Astrophysics Data System (ADS)

Correa, Gabriela C.; Foss, Cameron J.; Aksamija, Zlatan

2017-03-01

Heterostructures based on atomic monolayers are emerging as leading materials for future energy efficient and multifunctional electronics. Due to the single atom thickness of monolayers, their properties are strongly affected by interactions with the external environment. We develop a model for interface thermal conductance (ITC) in an atomic monolayer van der Waals bonded to a disordered substrate. Graphene on SiO2 is initially used in our model and contrasted against available experimental data; the model is then applied to monolayer molybdenum disulfide (MoS2) on SiO2 substrate. Our findings show the dominant carrier of heat in both graphene and MoS2 in the cross-plane direction is the flexural (ZA) phonon mode, owing to the large overlap between graphene ZA and substrate vibrational density of states. The rate of phonon transfer across the interface depends quadratically on the substrate coupling constant K a , but this interaction also causes a lifting of the lowest flexural phonon modes. As a result, ITC depends roughly linearly on the strength of the coupling between a monolayer and its substrate. We conclude that, in both graphene and MoS2 on SiO2, substrate adhesion plays a strong role in determining ITC, requiring further study of substrate coupling in TMDCs.

Rapid bonding of Pyrex glass microchips.

PubMed

Akiyama, Yoshitake; Morishima, Keisuke; Kogi, Atsuna; Kikutani, Yoshikuni; Tokeshi, Manabu; Kitamori, Takehiko

2007-03-01

A newly developed vacuum hot press system has been specially designed for the thermal bonding of glass substrates in the fabrication process of Pyrex glass microchemical chips. This system includes a vacuum chamber equipped with a high-pressure piston cylinder and carbon plate heaters. A temperature of up to 900 degrees C and a force of as much as 9800 N could be applied to the substrates in a vacuum atmosphere. The Pyrex substrates bonded with this system under different temperatures, pressures, and heating times were evaluated by tensile strength tests, by measurements of thickness, and by observations of the cross-sectional shapes of the microchannels. The optimal bonding conditions of the Pyrex glass substrates were 570 degrees C for 10 min under 4.7 N/mm(2) of applied pressure. Whereas more than 16 h is required for thermal bonding with a conventional furnace, the new system could complete the whole bonding processes within just 79 min, including heating and cooling periods. Such improvements should considerably enhance the production rate of Pyrex glass microchemical chips. Whereas flat and dust-free surfaces are required for conventional thermal bonding, especially without long and repeated heating periods, our hot press system could press a fine dust into glass substrates so that even the areas around the dust were bonded. Using this capability, we were able to successfully integrate Pt/Ti thin film electrodes into a Pyrex glass microchip.

Lactate Dehydrogenase Undergoes a Substantial Structural Change to Bind its Substrate

PubMed Central

Qiu, Linlin; Gulotta, Miriam; Callender, Robert

2007-01-01

Employing temperature-jump relaxation spectroscopy, we investigate the kinetics and thermodynamics of the formation of a very early ternary binding intermediate formed when lactate dehydrogenase (LDH) binds a substrate mimic on its way to forming the productive LDH/NADH·substrate Michaelis complex. Temperature-jump scans show two distinct submillisecond processes are involved in the formation of this ternary binding intermediate, called the encounter complex here. The on-rate of the formation of the encounter complex from LDH/NADH with oxamate (a substrate mimic) is determined as a function of temperature and in the presence of small concentrations of a protein destabilizer (urea) and protein stabilizer (TMAO). It shows a strong temperature dependence with inverse Arrhenius behavior and a temperature-dependent enthalpy (heat capacity of 610 ± 84 cal/Mol K), is slowed in the presence of TMAO and speeded up in the presence of urea. These results suggest that LDH/NADH occupies a range of conformations, some competent to bind substrate (open structure; a minority population) and others noncompetent (closed), in fast equilibrium with each other in accord with a select fit model of binding. From the thermodynamic results, the two species differ in the rearrangement of low energy hydrogen bonds as would arise from changes in internal hydrogen bonding and/or increases in the solvation of the protein structure. The binding-competent species can bind ligand at or very near diffusion-limited speeds, suggesting that the binding pocket is substantially exposed to solvent in these species. This would be in contrast to the putative closed structure where the binding pocket resides deep within the protein interior. PMID:17483169

Study of the Fracture Mechanisms of Electroplated Metallization Systems Using In Situ Microtension Test

NASA Astrophysics Data System (ADS)

Msolli, Sabeur; Kim, Heung Soo

2018-07-01

This framework assesses the mechanical behavior of some potential thin/thick metallization systems in use as either ohmic contacts for diamond semi-conductors or for metallization on copper double bounded ceramic substrates present in the next-generation power electronics packaging. The interesting and unique characteristic of this packaging is the use of diamond as a semi-conductor material instead of silicon to increase the lifetime of embedded power converters for use in aeronautical applications. Theoretically, such packaging is able to withstand temperatures of up to 300 °C without breaking the semi-conductor, provided that the constitutive materials of the packaging are compatible. Metallization is very important to protect the chips and substrates. Therefore, we address this issue in the present work. The tested metallization systems are Ni/Au, Ni/Cr/Au and Ni/Cr. These specific systems were studied since they can be used in conjunction with existing bonding technologies, including AuGe soldering, Ag-In Transient liquid Phase Bonding and silver nanoparticle sintering. The metallization is achieved via electrodeposition, and a mechanical test, consisting of a microtension technique, is carried out at room temperature inside a scanning electron microscopy chamber. The technique permits observations the cracks initiation and growth in the metallization to locate the deformation zones and identify the fracture mechanisms. Different failure mechanisms were shown to occur depending on the metallic layers deposited on top of the copper substrate. The density of these cracks depends on the imposed load and the involved metallization. These observations will help choose the metallization that is compatible with the particular bonding material, and manage mechanical stress due to thermal cycling so that they can be used as a constitutive component for high-temperature power electronics packaging.

Protein farnesyltransferase isoprenoid substrate discrimination is dependent on isoprene double bonds and branched methyl groups.

PubMed

Micali, E; Chehade, K A; Isaacs, R J; Andres, D A; Spielmann, H P

2001-10-16

Farnesylation is a posttranslational lipid modification in which a 15-carbon farnesyl isoprenoid is linked via a thioether bond to specific cysteine residues of proteins in a reaction catalyzed by protein farnesyltransferase (FTase). We synthesized the benzyloxyisoprenyl pyrophosphate (BnPP) series of transferable farnesyl pyrophosphate (FPP) analogues (1a-e) to test the length dependence of the isoprenoid substrate on the FTase-catalyzed transfer of lipid to protein substrate. Kinetic analyses show that pyrophosphates 1a-e and geranyl pyrophosphate (GPP) transfer with a lower efficiency than FPP whereas geranylgeranyl pyrophosphate (GGPP) does not transfer at all. While a correlation was found between K(m) and analogue hydrophobicity and length, there was no correlation between k(cat) and these properties. Potential binding geometries of FPP, GPP, GGPP, and analogues 1a-e were examined by modeling the molecules into the active site of the FTase crystal structure. We found that analogue 1d displaces approximately the same volume of the active site as does FPP, whereas GPP and analogues 1a-c occupy lesser volumes and 1e occupies a slightly larger volume. Modeling also indicated that GGPP adopts a different conformation than the farnesyl chain of FPP, partially occluding the space occupied by the Ca(1)a(2)X peptide in the ternary X-ray crystal structure. Within the confines of the FTase pocket, the double bonds and branched methyl groups of the geranylgeranyl chain significantly restrict the number of possible conformations relative to the more flexible lipid chain of analogues 1a-e. The modeling results also provide a molecular explanation for the observation that an aromatic ring is a good isostere for the terminal isoprene of FPP.

Study of the Fracture Mechanisms of Electroplated Metallization Systems Using In Situ Microtension Test

NASA Astrophysics Data System (ADS)

Msolli, Sabeur; Kim, Heung Soo

2018-03-01

This framework assesses the mechanical behavior of some potential thin/thick metallization systems in use as either ohmic contacts for diamond semi-conductors or for metallization on copper double bounded ceramic substrates present in the next-generation power electronics packaging. The interesting and unique characteristic of this packaging is the use of diamond as a semi-conductor material instead of silicon to increase the lifetime of embedded power converters for use in aeronautical applications. Theoretically, such packaging is able to withstand temperatures of up to 300 °C without breaking the semi-conductor, provided that the constitutive materials of the packaging are compatible. Metallization is very important to protect the chips and substrates. Therefore, we address this issue in the present work. The tested metallization systems are Ni/Au, Ni/Cr/Au and Ni/Cr. These specific systems were studied since they can be used in conjunction with existing bonding technologies, including AuGe soldering, Ag-In Transient liquid Phase Bonding and silver nanoparticle sintering. The metallization is achieved via electrodeposition, and a mechanical test, consisting of a microtension technique, is carried out at room temperature inside a scanning electron microscopy chamber. The technique permits observations the cracks initiation and growth in the metallization to locate the deformation zones and identify the fracture mechanisms. Different failure mechanisms were shown to occur depending on the metallic layers deposited on top of the copper substrate. The density of these cracks depends on the imposed load and the involved metallization. These observations will help choose the metallization that is compatible with the particular bonding material, and manage mechanical stress due to thermal cycling so that they can be used as a constitutive component for high-temperature power electronics packaging.

The effects of dentin and intaglio indirect ceramic optimized polymer restoration surface treatment on the shear bond strength of resin cement

NASA Astrophysics Data System (ADS)

Puspitarini, A.; Suprastiwi, E.; Usman, M.

2017-08-01

Ceramic optimized polymer (ceromer) bonds to the tooth substrate through resin cements. The bond strength between dentin, resin cement, and ceromer depends on the applied surface treatment. To analyze the effects of dentin and intaglio ceromer surface treatment on the shear bond strength self-adhesive resin cement. Forty-five dentin premolar and ceromer specimens were bonded with resin cement and divided into three groups as follows: in group 1, no treatment was applied; in group 2, dentin surface treatment was carried out with acid etching and a bonding agent; and in group 3, dentin surface treatment was carried out with acid etching, a bonding agent, and intaglio ceromer surface treatment with etching and silane. All specimens were incubated at 37 °C for 24 hours, and the shear bond strength was measured using a universal testing machine. Group 3 showed the highest shear bond strength, followed by group 2. The surface treatment of dentin and intaglio ceromer showed significantly improved shear bond strength in the group comparison. Dentin and intaglio ceromer surface treatment can improved the shear bond strength self-adhesive resin cement.

Alkyl Aryl Ether Bond Formation with PhenoFluor**

PubMed Central

Shen, Xiao; Neumann, Constanze N.; Kleinlein, Claudia; Claudia, Nathaniel W.; Ritter, Tobias

2015-01-01

An alkyl aryl ether bond formation reaction between phenols and primary and secondary alcohols with PhenoFluor has been developed. The reaction features a broad substrate scope and tolerates many functional groups, and substrates that are challenging for more conventional ether bond forming processes may be coupled. A preliminary mechanistic study indicates reactivity distinct from conventional ether bond formation. PMID:25800679

[Biological and neural bases of partner preferences in rodents: models to understand human pair bonds].

PubMed

Coria-Avila, G A; Hernández-Aguilar, M E; Toledo-Cárdenas, R; García-Hernández, L I; Manzo, J; Pacheco, P; Miquel, M; Pfaus, J G

To analyse the biological and neural bases of partner preference formation in rodents as models to understand human pair bonding. Rodents are social individuals, capable of forming short- or long-lasting partner preferences that develop slowly by stimuli like cohabitation, or rapidly by stimuli like sex and stress. Dopamine, corticosteroids, oxytocin, vasopressin, and opioids form the neurochemical substrate for pair bonding in areas like the nucleus accumbens, the prefrontal cortex, the piriform cortex, the medial preoptic area, the ventral tegmental area and the medial amygdala, among others. Additional areas may participate depending on the nature of the conditioned stimuli by which and individual recognizes a preferred partner. Animal models help us understand that the capacity of an individual to display long-lasting and selective preferences depends on neural bases, selected throughout evolution. The challenge in neuroscience is to use this knowledge to create new solutions for mental problems associated with the incapacity of an individual to display a social bond, keep one, or cope with the disruption of a consolidated one.

A novel bonding method for large scale poly(methyl methacrylate) micro- and nanofluidic chip fabrication

NASA Astrophysics Data System (ADS)

Qu, Xingtian; Li, Jinlai; Yin, Zhifu

2018-04-01

Micro- and nanofluidic chips are becoming increasing significance for biological and medical applications. Future advances in micro- and nanofluidics and its utilization in commercial applications depend on the development and fabrication of low cost and high fidelity large scale plastic micro- and nanofluidic chips. However, the majority of the present fabrication methods suffer from a low bonding rate of the chip during thermal bonding process due to air trapping between the substrate and the cover plate. In the present work, a novel bonding technique based on Ar plasma and water treatment was proposed to fully bond the large scale micro- and nanofluidic chips. The influence of Ar plasma parameters on the water contact angle and the effect of bonding conditions on the bonding rate and the bonding strength of the chip were studied. The fluorescence tests demonstrate that the 5 × 5 cm2 poly(methyl methacrylate) chip with 180 nm wide and 180 nm deep nanochannels can be fabricated without any block and leakage by our newly developed method.

Method of using a germanium layer transfer to Si for photovoltaic applications and heterostructure made thereby

DOEpatents

Atwater, Jr., Harry A.; Zahler, James M.

2006-11-28

Ge/Si and other nonsilicon film heterostructures are formed by hydrogen-induced exfoliation of the Ge film which is wafer bonded to a cheaper substrate, such as Si. A thin, single-crystal layer of Ge is transferred to Si substrate. The bond at the interface of the Ge/Si heterostructures is covalent to ensure good thermal contact, mechanical strength, and to enable the formation of an ohmic contact between the Si substrate and Ge layers. To accomplish this type of bond, hydrophobic wafer bonding is used, because as the invention demonstrates the hydrogen-surface-terminating species that facilitate van der Waals bonding evolves at temperatures above 600.degree. C. into covalent bonding in hydrophobically bound Ge/Si layer transferred systems.

Applying a biodeposition layer to increase the bond of a repair mortar on a mortar substrate.

PubMed

Snoeck, D; Wang, J; Bentz, D P; De Belie, N

2018-02-01

One of the major concerns in infrastructure repair is a sufficient bond between the substrate and the repair material, especially for the long-term performance and durability of the repaired structure. In this study, the bond of the repair material on the mortar substrate is promoted via the biodeposition of a calcium carbonate layer by a ureolytic bacterium. X-ray diffraction and scanning electron microscopy were used to examine the interfaces between the repair material and the substrate, as well as the polymorph of the deposited calcium carbonate. The approximately 50 μm thick biodeposition film on the mortar surface mostly consisted of calcite and vaterite. Both the repair material and the substrate tended to show a good adherence to that layer. The bond, as assessed by slant shear specimen testing, was improved by the presence of the biodeposition layer. A further increase was found when engineering the substrate surface using a structured pattern layer of biodeposition.

Catalytic strategy for carbon−carbon bond scission by the cytochrome P450 OleT

PubMed Central

Grant, Job L.; Mitchell, Megan E.; Makris, Thomas Michael

2016-01-01

OleT is a cytochrome P450 that catalyzes the hydrogen peroxide-dependent metabolism of Cn chain-length fatty acids to synthesize Cn-1 1-alkenes. The decarboxylation reaction provides a route for the production of drop-in hydrocarbon fuels from a renewable and abundant natural resource. This transformation is highly unusual for a P450, which typically uses an Fe4+−oxo intermediate known as compound I for the insertion of oxygen into organic substrates. OleT, previously shown to form compound I, catalyzes a different reaction. A large substrate kinetic isotope effect (≥8) for OleT compound I decay confirms that, like monooxygenation, alkene formation is initiated by substrate C−H bond abstraction. Rather than finalizing the reaction through rapid oxygen rebound, alkene synthesis proceeds through the formation of a reaction cycle intermediate with kinetics, optical properties, and reactivity indicative of an Fe4+−OH species, compound II. The direct observation of this intermediate, normally fleeting in hydroxylases, provides a rationale for the carbon−carbon scission reaction catalyzed by OleT. PMID:27555591

Evaluation of flexural, diametral tensile, and shear bond strength of composite repairs.

PubMed

Imbery, T A; Gray, T; DeLatour, F; Boxx, C; Best, A M; Moon, P C

2014-01-01

Repairing composite restorations may be a more conservative treatment than replacing the entire restoration. The objective of this in vitro study was to determine the best repair method by measuring flexural, diametral tensile, and shear bond strength of repaired composites in which the surfaces were treated with chemical primers (Add & Bond or Silane Bond Enhancer), a bonding agent (Optibond Solo Plus [OBSP]), or mechanical retention with a bonding agent. Filtek Supreme Ultra shade B1B was placed in special molds to fabricate specimens that served to test the flexural, diametral tensile, or shear strength of the inherent resin substrate. The same molds were modified to make specimens for testing repair strength of the resin. Repairs were made immediately or after aging in deionized water at 37°C for seven days. All repair sites were finished with coarse Sof-Lex discs to simulate finishing new restorations or partially removing aged restorations. Repair surfaces were treated with one of the following: 1) phosphoric-acid etching and OBSP; 2) Add & Bond; 3) phosphoric-acid etching, Silane Bond Enhancer, and OBSP; or 4) quarter round bur, phosphoric-acid etching, and OBSP. Specimens were placed back in the original molds to fabricate specimens for diametral tensile or flexural testing or in an Ultradent jig to make specimens for shear bond testing. Composite resin in shade B5B was polymerized against the treated surfaces to make repairs. Two negative control groups for the three testing methods consisted of specimens in which repairs were made immediately or after aging without any surface treatments. Controls and experimental repairs were aged (water 37°C, 24 hours) before flexural, diametral tensile, or shear testing in an Instron Universal testing machine at a crosshead speed of 0.5 mm/min. Experimental flexural repair strengths ranged from 26.4% to 88.6% of the inherent substrate strength. Diametral tensile repair strengths ranged from 40% to 80% of the inherent substrate strength, and shear bond strength repairs ranged from 56% to 102%. Geometric means were statistically analyzed with two-way analysis of variance on their log-transformed values. Significant differences were determined using Tukey honestly significant difference (p<0.05). Depending on the mechanical property being tested, surface treatments produced different results. OBSP produced more consistent results than chemical primers.

The Influence of Pre-Heated Treatment to Improve Adhesion Bond Coating Strength of Fly Ash Based Geopolymer Ceramic

NASA Astrophysics Data System (ADS)

Jamaludin, L.; Abdullah, M. M. A. B.; Hussin, K.; Kadir, A. Abdul

2018-06-01

The study focus on effect of pre-heated ceramic surface on the adhesion bond strength between geopolymer coating coating and ceramic substrates. Ceramic substrates was pre-heated at different temperature (400 °C, 600 °C, 800 °C and 1000 °C). Fly ash geopolymer coating material potential used to protect surface used in exposure conditions after sintering at high temperature. Fly ash and alkali activator (Al2O3/Na2SiO3) were mixed with 2.0 solids-to-liquid ratios to prepare geopolymer coating material at constant NaOH concentration of 12M. Adhesion test was conducted to determine the adhesion bond between ceramic substrates and fly ash coating material. The results showed the pre-heated ceramic substrates effect the adhesion bond of coating compared with untreated substrates with increasing of strength up to 20 % for temperature 600 °C.

Joining of Silicon Carbide: Diffusion Bond Optimization and Characterization

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Singh, Mrityunjay

2008-01-01

Joining and integration methods are critically needed as enabling technologies for the full utilization of advanced ceramic components in aerospace and aeronautics applications. One such application is a lean direct injector for a turbine engine to achieve low NOx emissions. In the application, several SiC substrates with different hole patterns to form fuel and combustion air channels are bonded to form the injector. Diffusion bonding is a joining approach that offers uniform bonds with high temperature capability, chemical stability, and high strength. Diffusion bonding was investigated with the aid of titanium foils and coatings as the interlayer between SiC substrates to aid bonding. The influence of such variables as interlayer type, interlayer thickness, substrate finish, and processing time were investigated. Optical microscopy, scanning electron microscopy, and electron microprobe analysis were used to characterize the bonds and to identify the reaction formed phases.

Thermodynamics of cell adhesion. II. Freely mobile repellers.

PubMed Central

Torney, D C; Dembo, M; Bell, G I

1986-01-01

The equilibrium adhesion of a cell or vesicle to a substrate is analyzed in a theoretical model in which two types of mobile molecules in the cell membrane are of interest: receptors that can form bonds with fixed ligands in the substrate and repellers that repel the substrate. If the repulsion between the repeller molecule and substrate is greater than kT, there is substantial redistribution of the repellers from the contact area. Coexisting equilibrium states are observed having comparable free energies (a) with unstretched bonds and repeller redistribution and (b) with stretched bonds and partial redistribution. PMID:3955182

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.

Low-Cost High-Efficiency Solar Cells with Wafer Bonding and Plasmonic Technologies

NASA Astrophysics Data System (ADS)

Tanake, Katsuaki

We fabricated a direct-bond interconnected multijunction solar cell, a two-terminal monolithic GaAs/InGaAs dual-junction cell, to demonstrate a proof-of-principle for the viability of direct wafer bonding for solar cell applications. The bonded interface is a metal-free n+GaAs/n +InP tunnel junction with highly conductive Ohmic contact suitable for solar cell applications overcoming the 4% lattice mismatch. The quantum efficiency spectrum for the bonded cell was quite similar to that for each of unbonded GaAs and InGaAs subcells. The bonded dual-junction cell open-circuit voltage was equal to the sum of the unbonded subcell open-circuit voltages, which indicates that the bonding process does not degrade the cell material quality since any generated crystal defects that act as recombination centers would reduce the open-circuit voltage. Also, the bonded interface has no significant carrier recombination rate to reduce the open circuit voltage. Engineered substrates consisting of thin films of InP on Si handle substrates (InP/Si substrates or epitaxial templates) have the potential to significantly reduce the cost and weight of compound semiconductor solar cells relative to those fabricated on bulk InP substrates. InGaAs solar cells on InP have superior performance to Ge cells at photon energies greater than 0.7 eV and the current record efficiency cell for 1 sun illumination was achieved using an InGaP/GaAs/InGaAs triple junction cell design with an InGaAs bottom cell. Thermophotovoltaic (TPV) cells from the InGaAsP-family of III-V materials grown epitaxially on InP substrates would also benefit from such an InP/Si substrate. Additionally, a proposed four-junction solar cell fabricated by joining subcells of InGaAs and InGaAsP grown on InP with subcells of GaAs and AlInGaP grown on GaAs through a wafer-bonded interconnect would enable the independent selection of the subcell band gaps from well developed materials grown on lattice matched substrates. Substitution of InP/Si substrates for bulk InP in the fabrication of such a four-junction solar cell could significantly reduce the substrate cost since the current prices for commercial InP substrates are much higher than those for Si substrates by two orders of magnitude. Direct heteroepitaxial growth of InP thin films on Si substrates has not produced the low dislocation-density high quality layers required for active InGaAs/InP in optoelectronic devices due to the ˜8% lattice mismatch between InP and Si. We successfully fabricated InP/Si substrates by He implantation of InP prior to bonding to a thermally oxidized Si substrate and annealing to exfoliate an InP thin film. The thickness of the exfoliated InP films was only 900 nm, which means hundreds of the InP/Si substrates could be prepared from a single InP wafer in principle. The photovoltaic current-voltage characteristics of the In0.53Ga0.47As cells fabricated on the wafer-bonded InP/Si substrates were comparable to those synthesized on commercially available epi-ready InP substrates, and had a ˜20% higher short-circuit current which we attribute to the high reflectivity of the InP/SiO2/Si bonding interface. This work provides an initial demonstration of wafer-bonded InP/Si substrates as an alternative to bulk InP substrates for solar cell applications. We have observed photocurrent enhancements up to 260% at 900 nm for a GaAs cell with a dense array of Ag nanoparticles with 150 nm diameter and 20 nm height deposited through porous alumina membranes by thermal evaporation on top of the cell, relative to reference GaAs cells with no metal nanoparticle array. This dramatic photocurrent enhancement is attributed to the effect of metal nanoparticles to scatter the incident light into photovoltaic layers with a wide range of angles to increase the optical path length in the absorber layer. GaAs solar cells with metallic structures at the bottom of the photovoltaic active layers, not only at the top, using semiconductor-metal direct bonding have been fabricated. These metallic back structures could incouple the incident light into surface plasmon mode propagating at the semiconductor/metal interface to increase the optical path, as well as simply act as back reflector, and we have observed significantly increased short-circuit current relative to reference cells without these metal components. (Abstract shortened by UMI.)

Atomic-Level Properties of Thermal Barrier Coatings: Characterization of Metal-Ceramic Interfaces

DTIC Science & Technology

2001-01-01

these cases metal - metal bonds were stronger than metal - substrate bonds, thus predicting a 3D (cluster) growth mode as opposed to layer-by-layer...coat layer must be deposited. The top coat serves as the insulator and the bond coat mediates contact between the top coat and metal alloy substrate ...in thermomechanical properties between a YSZ top coat and a metal -alloy substrate is enough to require the introduction of an intermediate layer. This

Controlled Thermal Expansion Coat for Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Brindley, William J. (Inventor); Miller, Robert A. (Inventor); Aikin, Beverly J. M. (Inventor)

1999-01-01

A improved thermal barrier coating and method for producing and applying such is disclosed herein. The thermal barrier coating includes a high temperature substrate, a first bond coat layer applied to the substrate of MCrAlX, and a second bond coat layer of MCrAlX with particles of a particulate dispersed throughout the MCrAlX and the preferred particulate is Al2O3. The particles of the particulate dispersed throughout the second bond coat layer preferably have a diameter of less then the height of the peaks of the second bond coat layer, or a diameter of less than 5 microns. The method of producing the second bond coat layer may either include the steps of mechanical alloying of particles throughout the second bond coat layer, attrition milling the particles of the particulate throughout the second bond coat layer, or using electrophoresis to disperse the particles throughout the second bond coat layer. In the preferred embodiment of the invention, the first bond coat layer is applied to the substrate, and then the second bond coat layer is thermally sprayed onto the first bond coat layer. Further, in a preferred embodiment of die invention, a ceramic insulating layer covers the second bond coat layer.

A review: Application of adhesive bonding on semiconductor interconnection joints

NASA Astrophysics Data System (ADS)

Suppiah, Sarveshvaran; Ong, Nestor Rubio; Sauli, Zaliman; Sarukunaselan, Karunavani; Alcain, Jesselyn Barro; Shahimin, Mukhzeer Mohamad; Retnasamy, Vithyacharan

2017-09-01

A comprehensive review on adhesive die bonding is presented in this paper. Adhesive bonding technique involved electrically conductive adhesives that bond by evaporation of a solvent or by curing a bonding agent with three main parameters; heat, pressure, and time. Isotropic conductive adhesive (ICA) and anisotropic conductive adhesive (ACA) are the commonly used adhesive in this technique. In order to achieve and promote a better adhesion of die on the substrate, surface cleaning steps and methods were very crucial. The major challenge faced by this technique is entrapment of the conductive particles between the die and substrate. An adequate amount of conductive particle is needed between the die and substrate in order to avoid increase in contact resistance.

Bonding by Hydroxide-Catalyzed Hydration and Dehydration

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung

2008-01-01

A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to have exposed hydroxyl groups and that can be chemically linked, by hydroxide catalysis, to a silicate-like network. The silicate-like network could be generated in situ from the filling material and/or substrate material, or could be originally present in the bonding material.

Methods of Antimicrobial Coating of Diverse Materials

NASA Technical Reports Server (NTRS)

Akse, James R.; Holtsnider, John T.; Kliestik, Helen

2011-01-01

Methods of coating diverse substrate materials with antimicrobial agents have been developed. Originally intended to reduce health risks to astronauts posed by pathogenic microorganisms that can grow on surfaces in spacecraft, these methods could also be used on Earth for example, to ensure sterility of surgical inserts and other medical equipment. The methods involve, generally, chemical preparation of substrate surfaces to enable attachment of antimicrobial molecules to the substrate surfaces via covalent bonds. Substrate materials that have been treated successfully include aluminum, glass, a corrosion-resistant nickel alloy, stainless steel, titanium, and poly(tetrafluoroethylene). Antimicrobial agents that have been successfully immobilized include antibiotics, enzymes, bacteriocins, bactericides, and fungicides. A variety of linkage chem istries were employed. Activity of antimicrobial coatings against gram-positive bacteria, gram-negative bacteria, and fungi was demonstrated. Results of investigations indicate that the most suitable combination of antimicrobial agent, substrate, and coating method depends upon the intended application.

Investigation of a Hybrid Wafer Scale Integration Technique that Mounts Discrete Integrated Circuit Die in a Silicon Substrate.

DTIC Science & Technology

1988-03-01

Polyimides as Planarizing and Insulative Coatings 2-21 III. Experimental Procedure, Equipment, and Materials 3-1 Wet Orientation Dependent Etching Study 3...1 Die Bond Adhesives Study .3-7 Fabrication of Samples for Electrical Testing 3-21 Evaluation of the Final Samples 3-45 IV. Experimental Results and...Discussion .. 4-1 We :ientation Dependent Etching Study Results 4-1 Die Attach Adhesives Study Results 4-21 Fabrication of Samples for Electrical

Influence of Nd:YAG laser on the bond strength of self-etching and conventional adhesive systems to dental hard tissues.

PubMed

Marimoto, A K; Cunha, L A; Yui, K C K; Huhtala, M F R L; Barcellos, D C; Prakki, A; Gonçalves, S E P

2013-01-01

The aim of this study was to investigate the influence of Nd:YAG laser on the shear bond strength to enamel and dentin of total and self-etch adhesives when the laser was applied over the adhesives, before they were photopolymerized, in an attempt to create a new bonding layer by dentin-adhesive melting. One-hundred twenty bovine incisors were ground to obtain flat surfaces. Specimens were divided into two substrate groups (n=60): substrate E (enamel) and substrate D (dentin). Each substrate group was subdivided into four groups (n=15), according to the surface treatment accomplished: X (Xeno III self-etching adhesive, control), XL (Xeno III + laser Nd:YAG irradiation at 140 mJ/10 Hz for 60 seconds + photopolymerization, experimental), S (acid etching + Single Bond conventional adhesive, Control), and SL (acid etching + Single Bond + laser Nd:YAG at 140 mJ/10 Hz for 60 seconds + photopolymerization, experimental). The bonding area was delimited with 3-mm-diameter adhesive tape for the bonding procedures. Cylinders of composite were fabricated on the bonding area using a Teflon matrix. The teeth were stored in water at 37°C/48 h and submitted to shear testing at a crosshead speed of 0.5 mm/min in a universal testing machine. Results were analyzed with three-way analysis of variance (ANOVA; substrate, adhesive, and treatment) and Tukey tests (α=0.05). ANOVA revealed significant differences for the substrate, adhesive system, and type of treatment: lased or unlased (p<0.05). The mean shear bond strength values (MPa) for the enamel groups were X=20.2 ± 5.61, XL=23.6 ± 4.92, S=20.8 ± 4.55, SL=22.1 ± 5.14 and for the dentin groups were X=14.1 ± 7.51, XL=22.2 ± 6.45, S=11.2 ± 5.77, SL=15.9 ± 3.61. For dentin, Xeno III self-etch adhesive showed significantly higher shear bond strength compared with Single Bond total-etch adhesive; Nd:YAG laser irradiation showed significantly higher shear bond strength compared with control (unlased). Nd:YAG laser application prior to photopolymerization of adhesive systems significantly increased the bond strength to dentin.

Effect of different adhesion strategies on bond strength of resin composite to composite-dentin complex.

PubMed

Özcan, M; Pekkan, G

2013-01-01

Service life of discolored and abraded resin composite restorations could be prolonged by repair or relayering actions. Composite-composite adhesion can be achieved successfully using some surface conditioning methods, but the most effective adhesion protocol for relayering is not known when the composite restorations are surrounded with dentin. This study evaluated the effect of three adhesion strategies on the bond strength of resin composite to the composite-dentin complex. Intact maxillary central incisors (N=72, n=8 per subgroup) were collected and the coronal parts of the teeth were embedded in autopolymerized poly(methyl tfr54methacrylate) surrounded by a polyvinyl chloride cylinder. Cylindrical cavities (diameter: 2.6 mm; depth: 2 mm) were opened in the middle of the labial surfaces of the teeth using a standard diamond bur, and the specimens were randomly divided into three groups. Two types of resin composite, namely microhybrid (Quadrant Anterior Shine; AS) and nanohybrid (Grandio; G), were photo-polymerized incrementally in the cavities according to each manufacturer's recommendations. The composite-enamel surfaces were ground finished to 1200-grit silicone carbide paper until the dentin was exposed. The surfaces of the substrate composites and the surrounding dentin were conditioned according to one of the following adhesion protocols: protocol 1: acid-etching (dentin) + silica coating (composite) + silanization (composite) + primer (dentin) + bonding agent (dentin + composite); protocol 2: silica coating (composite) + acid-etching (dentin) + silanization (composite) + primer (dentin) + bonding agent (dentin + composite); and protocol 3: acid-etching (dentin) + primer (dentin) + silanization (composite) + bonding agent (dentin + composite). Applied primer and bonding agents were the corresponding materials of the composite manufacturer. Silica coating (CoJet sand, 30 μm) was achieved using a chairside air-abrasion device (distance: 10 mm; duration: four seconds in circular motion). After conditioning protocols, the repair resin was adhered to the substrate surfaces using transparent polyethylene molds (diameter: 3.6 mm) incrementally and photo-polymerized. The substrate-adherend combinations were as follows: AS-AS, G-G, AS-G. Shear force was applied to the adhesive interface in a Universal Testing Machine (crosshead speed: 1 mm/min). The types of failures were further evaluated and categorized as follows: 1) cohesive in the composite substrate and 2) adhesive at the interface. Bond strength values (MPa) were statistically analyzed using two-way analysis of variance and least significant difference post hoc tests (α=0.05). Significant effects of the adhesion strategy (p=0.006) and the composite type (p=0.000) were found. Interaction terms were not significant (p=0.292). Regardless of the substrate-adherend combination, protocol 1 (17-22 MPa) showed significantly higher results than did protocols 2 (15-17 MPa) and 3 (11-17 MPa) (p=0.028, p=0.002, respectively). The highest results were obtained from the G-G combination after all three protocols (17-22 MPa). The incidence of cohesive failures was more common when the substrate and the adherend were the same composite type (AS-AS: 87.5%, 87.5%, 75%; G-G: 100%, 75%, 50% for protocols 1, 2, and 3, respectively). When substrate and adherend were used interchangeably, adhesive failures were more frequent (25%, 50%, and 100% for protocol 1, 2, and 3, respectively). When the substrate and the adherend are of the same type, greater repair strength could be expected. In the repair of composites next to the dentin, depending on the composite type, conditioning the composite with silica coating and silanization after etching the dentin adds to the repair strength compared to the results obtained with silane application only.

A short review on thermosonic flip chip bonding

NASA Astrophysics Data System (ADS)

Suppiah, Sarveshvaran; Ong, Nestor Rubio; Sauli, Zaliman; Sarukunaselan, Karunavani; Alcain, Jesselyn Barro; Shahimin, Mukhzeer Mohamad; Retnasamy, Vithyacharan

2017-09-01

This review is to study the evolution and key findings, critical technical challenges, solutions and bonding equipment of thermosonic flip chip bonding. Based on the review done, it was found that ultrasonic power, bonding time and force are the three main critical parameters need to be optimized in order to achieve sound and reliable bonding between the die and substrate. A close monitoring of the ultrasonic power helped to prevent over bonding phenomena on flexible substrate. Gold stud bumping is commonly used in thermosonic bonding compared to solder due to its better reliability obtained in the LED and optoelectronic packages. The review comprised short details on the available thermosonic bonding equipment in the semiconductor industry as well.

Shear Bond Strength between Fiber-Reinforced Composite and Veneering Resin Composites with Various Adhesive Resin Systems.

PubMed

AlJehani, Yousef A; Baskaradoss, Jagan K; Geevarghese, Amrita; AlShehry, Marey A; Vallittu, Pekka K

2016-07-01

The aim of this research was to evaluate the shear bond strength of different laboratory resin composites bonded to a fiber-reinforced composite substrate with some intermediate adhesive resins. Mounted test specimens of a bidirectional continuous fiber-reinforced substrate (StickNet) were randomly assigned to three equal groups. Three types of commercially available veneering resin composites - BelleGlass®, Sinfony®, and GC Gradia® were bonded to these specimens using four different adhesive resins. Half the specimens per group were stored for 24 hours; the remaining were stored for 30 days. There were 10 specimens in the test group (n). The shear bond strengths were calculated and expressed in MPa. Data were analyzed statistically, and variations in bond strength within each group were additionally evaluated by calculating the Weibull modulus. Shear bond values of those composites are influenced by the different bonding resins and different indirect composites. There was a significant difference in the shear bond strengths using different types of adhesive resins (p = 0.02) and using different veneering composites (p < 0.01). Belle-Glass® had the highest mean shear bond strength when bonded to StickNet substrate using both Prime & Bond NT and OptiBond Solo Plus. Sinfony® composite resin exhibited the lowest shear bond strength values when used with the same adhesive resins. The adhesive mode of failure was higher than cohesive with all laboratory composite resins bonded to the StickNet substructure at both storage times. Water storage had a tendency to lower the bond strengths of all laboratory composites, although the statistical differences were not significant. Within the limitations of this study, it was found that bonding of the veneering composite to bidirectional continuous fiber-reinforced substrate is influenced by the brand of the adhesive resin and veneering composite. © 2015 by the American College of Prosthodontists.

Effect of substrate bending on the piezoelectric measurement of PZT thin film

NASA Astrophysics Data System (ADS)

Xu, Xiaohui; Tang, Jianhong; He, Liangna

2009-05-01

Bonding conditions between PZT thin film and sample holder greatly affect the strain measurement of the PZT sample. The influence of various bonding conditions on the measured displacement were analyzed using finite element analysis (FEA). One-end fixed sample induces the maximum bending displacement. Experiments were performed on sol-gel derived PZT thin film. The voltage-displacement curve and "butterfly" loop were measured using laser Doppler method with phase detection. Experimental results agreed well with the simulated ones. The measured frequency dependence of piezoelectric response of PZT thin film indicated that, if the operating frequency was lower than 2 kHz, good bonding effect could be obtained when the entire back surface of the sample was glued to a rigid supporter using epoxy resin. A simple bonding model which considered the adhesives as a spring was used to estimate the frequency response of PZT thin film sample.

Apparatus for Precise Indium-Bump Bonding of Microchips

NASA Technical Reports Server (NTRS)

Wild, Larry; Mulder, Jerry; Alvarado, Nicholas

2005-01-01

An improved apparatus has been designed and built for use in precise positioning and pressing of a microchip onto a substrate (which could, optionally, be another microchip) for the purpose of indium-bump bonding. The apparatus (see figure) includes the following: A stereomicroscope, A stage for precise positioning of the microchip in rotation angle (theta) about the nominally vertical pressing axis and in translation along two nominally horizontal coordinate axes (x and y), and An actuator system that causes a bonding tip to press the microchip against the substrate with a precisely controlled force. In operation, the microscope and the stage are used to position the microchip under the bonding tip and to align the indium bumps on the chip and the substrate, then the actuator system is used to apply a prescribed bonding force for a prescribed time. The improved apparatus supplants a partly similar prior apparatus that operated with less precision and repeatability, producing inconsistent and unreliable bonds. Results of the use of the prior apparatus included broken microchips, uneven bonds, and bonds characterized, variously, by overcompression or undercompression. In that apparatus, the bonding force was generated and controlled by use of a micrometer head positioned over the center of a spring-loaded scale, and the force was applied to the microchip via the scale, which was equipped for digital readout of the force. The inconsistency of results was attributed to the following causes: It was not possible to control the bonding force with sufficient precision or repeatability. Particularly troublesome was the inability to control the force at levels less than the weight of 150 g. Excessive compliance in the spring-loaded scale, combined with deviations from parallelarity of the substrate and bonding-tip surfaces, gave rise to nonuniformity in the pressure applied to the microchip, thereby generating excessive stresses and deformations in the microchip. In the improved apparatus, the bonding tip and the components that hold the substrate and the microchip are more rigid and precise than in the prior apparatus, so as to ensure less deviation from parallelarity of the bonding-tip and substrate surfaces, thereby ensuring more nearly uniform distribution of bonding force over the area of the microchip. The bonding force is now applied through, and measured by, a load cell that makes it possible to exert finer control over the force. The force can be set at any value between 0 and the weight of 800 g in increments of 0.2 g.

Diffusion Bonding of Silicon Carbide for MEMS-LDI Applications

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Singh, Mrityunjay; Shpargel, Tarah P.; Kiser, J. Douglas

2007-01-01

A robust joining approach is critically needed for a Micro-Electro-Mechanical Systems-Lean Direct Injector (MEMS-LDI) application which requires leak free joints with high temperature mechanical capability. Diffusion bonding is well suited for the MEMS-LDI application. Diffusion bonds were fabricated using titanium interlayers between silicon carbide substrates during hot pressing. The interlayers consisted of either alloyed titanium foil or physically vapor deposited (PVD) titanium coatings. Microscopy shows that well adhered, crack free diffusion bonds are formed under optimal conditions. Under less than optimal conditions, microcracks are present in the bond layer due to the formation of intermetallic phases. Electron microprobe analysis was used to identify the reaction formed phases in the diffusion bond. Various compatibility issues among the phases in the interlayer and substrate are discussed. Also, the effects of temperature, pressure, time, silicon carbide substrate type, and type of titanium interlayer and thickness on the microstructure and composition of joints are discussed.

Hydrogen-Bonding Catalysis and Inhibition by Simple Solvents in the Stereoselective Kinetic Epoxide-Opening Spirocyclization of Glycal Epoxides to Form Spiroketals

PubMed Central

Wurst, Jacqueline M.; Liu, Guodong; Tan, Derek S.

2011-01-01

Mechanistic investigations of a MeOH-induced kinetic epoxide-opening spirocyclization of glycal epoxides have revealed dramatic, specific roles for simple solvents in hydrogen-bonding catalysis of this reaction to form spiroketal products stereoselectively with inversion of configuration at the anomeric carbon. A series of electronically-tuned C1-aryl glycal epoxides was used to study the mechanism of this reaction based on differential reaction rates and inherent preferences for SN2 versus SN1 reaction manifolds. Hammett analysis of reaction kinetics with these substrates is consistent with an SN2 or SN2-like mechanism (ρ = −1.3 vs. ρ = −5.1 for corresponding SN1 reactions of these substrates). Notably, the spirocyclization reaction is second-order dependent on MeOH and the glycal ring oxygen is required for second-order MeOH catalysis. However, acetone cosolvent is a first-order inhibitor of the reaction. A transition state consistent with the experimental data is proposed in which one equivalent of MeOH activates the epoxide electrophile via a hydrogen bond while a second equivalent of MeOH chelates the sidechain nucleophile and glycal ring oxygen. A paradoxical previous observation that decreased MeOH concentration leads to increased competing intermolecular methyl glycoside formation is resolved by the finding that this side reaction is only first-order dependent on MeOH. This study highlights the unusual abilities of simple solvents to act as hydrogen-bonding catalysts and inhibitors in epoxide-opening reactions, providing both stereoselectivity and discrimination between competing reaction manifolds. This spirocyclization reaction provides efficient, stereocontrolled access to spiroketals that are key structural motifs in natural products. PMID:21539313

Composition and functional group characterization of extracellular polymeric substances (EPS) in activated sludge: the impacts of polymerization degree of proteinaceous substrates.

PubMed

Wang, Bin-Bin; Liu, Xue-Ting; Chen, Jian-Meng; Peng, Dang-Cong; He, Feng

2018-02-01

Characteristics of extracellular polymeric substances (EPS) in activated sludge strongly depend on wastewater substrates. Proteinaceous substrates (ProS) present in heterogeneous polymeric form are intrinsic and important parts of wastewater substrates for microorganisms in activated sludge systems. However, correlations between ProS and characteristics of EPS are scarce. This study systematically explored the impacts of monomeric (Mono-), low polymeric (LoP-) and high polymeric (HiP-) ProS on compositions and functional groups of EPS in activated sludge. The results showed that the change of polymerization degree of ProS significantly altered the composition of EPS. Compared to EPS Mono-ProS , the proportion of proteins in EPS LoP-ProS and EPS HiP-ProS increased by 12.8% and 27.7%, respectively, while that of polysaccharides decreased by 22.9% and 63.6%, respectively. Moreover, the proportion of humic compounds in EPS LoP-ProS and EPS HiP-ProS were ∼6 and ∼16-fold higher than that in EPS Mono-ProS , respectively. The accumulation of humic compounds in EPS increased the unsaturation degree of EPS molecules, and thereby reduced the energy requirement for electrons transition of amide bonds and aromatic groups. Size exclusion chromatography (SEC) analyses detected more molecular clusters in EPS HiP-ProS , indicating more complex composition of EPS in HiP-ProS fed activated sludge. Spectroscopic characterization revealed the dominance of hydrocarbon, protein, polysaccharide and aromatic associated bonds in all three EPS. Nevertheless, with the increase of polymerization degree of ProS, the protein associated bonds (such as CONH, CO, NC, NH) increased, while the polysaccharide associated bonds (such as COC, COH, OCOH) decreased. This paper paves a path to understand the role of ProS in affecting the production and characteristics of EPS in biological wastewater treatment systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Method of Producing Controlled Thermal Expansion Coat for Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Brindley, William J. (Inventor); Miller, Robert A. (Inventor); Aikin, Beverly J. M. (Inventor)

2000-01-01

An improved thermal barrier coating and method for producing and applying such is disclosed herein. The thermal barrier coatings includes a high temperature substrate, a first bond coat layer applied to the substrate of MCrAlX and a second bond coat layer of MCrAlX with particles of a particulate dispersed throughout the MCrAlX and the preferred particulate is Al2O3. The particles of the particulate dispersed throughout the second bond coat layer preferably have a diameter of less then the height of the peaks of the second bond coat layer or a diameter of less than 5 micron. The method of producing the second bond coat layer may either include the steps of mechanical alloying of particles throughout the second bond coat layer, attrition milling the particles of the particulate throughout the second bond coat layer, or using electrophoresis to disperse the particles throughout the second bond coat layer. In the preferred embodiment of the invention the first bond coat layer is applied to the substrate. and then the second bond coat layer is thermally sprayed onto the first bond coat layer. Further, in a preferred embodiment of the invention a ceramic insulating layer covers the second bond coat layer.

Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

NASA Astrophysics Data System (ADS)

Murphy, Colin J.; Carrasco, Javier; Lawton, Timothy J.; Liriano, Melissa L.; Baber, Ashleigh E.; Lewis, Emily A.; Michaelides, Angelos; Sykes, E. Charles H.

2014-07-01

Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells.

Surface Analysis Evaluation of Handwipe Cleaning for the Space Shuttle RSRM

NASA Technical Reports Server (NTRS)

Lesley, Michael W.; Anderson, Erin L.; McCool, Alex (Technical Monitor)

2001-01-01

In this paper we discuss the role of surface-sensitive spectroscopy (electron spectroscopy for chemical analysis, or ESCA) in the selection of solvents to replace 1,1,1-trichloroethane in handwipe cleaning of bonding surfaces on NASA's Space Shuttle Reusable Solid Rocket Motor (RSRM). Removal of common process soils from a wide variety of metallic and polymeric substrates was characterized. The cleaning efficiency was usually more dependent on the type of substrate being cleaned and the specific process soil than on the solvent used. A few substrates that are microscopically rough or porous proved to be difficult to clean with any cleaner, and some soils were very tenacious and difficult to remove from any substrate below detection limits. Overall, the work showed that a wide variety of solvents will perform at least as well as 1,1,1-trichloroethane.

Combining Solvent Isotope Effects with Substrate Isotope Effects in Mechanistic Studies of Alcohol and Amine Oxidation by Enzymes*

PubMed Central

Fitzpatrick, Paul F.

2014-01-01

Oxidation of alcohols and amines is catalyzed by multiple families of flavin-and pyridine nucleotide-dependent enzymes. Measurement of solvent isotope effects provides a unique mechanistic probe of the timing of the cleavage of the OH and NH bonds, necessary information for a complete description of the catalytic mechanism. The inherent ambiguities in interpretation of solvent isotope effects can be significantly decreased if isotope effects arising from isotopically labeled substrates are measured in combination with solvent isotope effects. The application of combined solvent and substrate (mainly deuterium) isotope effects to multiple enzymes is described here to illustrate the range of mechanistic insights that such an approach can provide. PMID:25448013

Editing disulphide bonds: error correction using redox currencies.

PubMed

Ito, Koreaki

2010-01-01

The disulphide bond-introducing enzyme of bacteria, DsbA, sometimes oxidizes non-native cysteine pairs. DsbC should rearrange the resulting incorrect disulphide bonds into those with correct connectivity. DsbA and DsbC receive oxidizing and reducing equivalents, respectively, from respective redox components (quinones and NADPH) of the cell. Two mechanisms of disulphide bond rearrangement have been proposed. In the redox-neutral 'shuffling' mechanism, the nucleophilic cysteine in the DsbC active site forms a mixed disulphide with a substrate and induces disulphide shuffling within the substrate part of the enzyme-substrate complex, followed by resolution into a reduced enzyme and a disulphide-rearranged substrate. In the 'reduction-oxidation' mechanism, DsbC reduces those substrates with wrong disulphides so that DsbA can oxidize them again. In this issue of Molecular Microbiology, Berkmen and his collaborators show that a disulphide reductase, TrxP, from an anaerobic bacterium can substitute for DsbC in Escherichia coli. They propose that the reduction-oxidation mechanism of disulphide rearrangement can indeed operate in vivo. An implication of this work is that correcting errors in disulphide bonds can be coupled to cellular metabolism and is conceptually similar to the proofreading processes observed with numerous synthesis and maturation reactions of biological macromolecules.

Room-temperature bonding of epitaxial layer to carbon-cluster ion-implanted silicon wafers for CMOS image sensors

NASA Astrophysics Data System (ADS)

Koga, Yoshihiro; Kadono, Takeshi; Shigematsu, Satoshi; Hirose, Ryo; Onaka-Masada, Ayumi; Okuyama, Ryousuke; Okuda, Hidehiko; Kurita, Kazunari

2018-06-01

We propose a fabrication process for silicon wafers by combining carbon-cluster ion implantation and room-temperature bonding for advanced CMOS image sensors. These carbon-cluster ions are made of carbon and hydrogen, which can passivate process-induced defects. We demonstrated that this combination process can be used to form an epitaxial layer on a carbon-cluster ion-implanted Czochralski (CZ)-grown silicon substrate with a high dose of 1 × 1016 atoms/cm2. This implantation condition transforms the top-surface region of the CZ-grown silicon substrate into a thin amorphous layer. Thus, an epitaxial layer cannot be grown on this implanted CZ-grown silicon substrate. However, this combination process can be used to form an epitaxial layer on the amorphous layer of this implanted CZ-grown silicon substrate surface. This bonding wafer has strong gettering capability in both the wafer-bonding region and the carbon-cluster ion-implanted projection range. Furthermore, this wafer inhibits oxygen out-diffusion to the epitaxial layer from the CZ-grown silicon substrate after device fabrication. Therefore, we believe that this bonding wafer is effective in decreasing the dark current and white-spot defect density for advanced CMOS image sensors.

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

Bosserman, Mary A.; Downey, Theresa; Noinaj, Nicholas

Baeyer–Villiger monooxygenases (BVMOs) have been shown to play key roles for the biosynthesis of important natural products. MtmOIV, a homodimeric FAD- and NADPH-dependent BVMO, catalyzes the key frame-modifying steps of the mithramycin biosynthetic pathway, including an oxidative C–C bond cleavage, by converting its natural substrate premithramycin B into mithramycin DK, the immediate precursor of mithramycin. The drastically improved protein structure of MtmOIV along with the high-resolution structure of MtmOIV in complex with its natural substrate premithramycin B are reported here, revealing previously undetected key residues that are important for substrate recognition and catalysis. Kinetic analyses of selected mutants allowed usmore » to probe the substrate binding pocket of MtmOIV and also to discover the putative NADPH binding site. This is the first substrate-bound structure of MtmOIV providing new insights into substrate recognition and catalysis, which paves the way for the future design of a tailored enzyme for the chemo-enzymatic preparation of novel mithramycin analogues.« less

Composite used for thermal spray instrumentation and method for making the same

NASA Technical Reports Server (NTRS)

Gregory, Otto J. (Inventor); Downey, Markus A. (Inventor)

2011-01-01

A superalloy article which comprises a substrate comprised of a superalloy, a bond coat comprised of MCrAlY wherein M is a metal selected from the group consisting of cobalt, nickel and mixtures thereof applied onto at least a portion of the substrate and a ceramic top coat applied over at least a portion of the bond coat. The bond coat is exposed to a temperature of within the range of between about 1600-1800.degree. F. subsequent to its application onto the substrate.

Myosin-cross-reactive antigen (MCRA) protein from Bifidobacterium breve is a FAD-dependent fatty acid hydratase which has a function in stress protection.

PubMed

Rosberg-Cody, Eva; Liavonchanka, Alena; Göbel, Cornelia; Ross, R Paul; O'Sullivan, Orla; Fitzgerald, Gerald F; Feussner, Ivo; Stanton, Catherine

2011-02-17

The aim of this study was to determine the catalytic activity and physiological role of myosin-cross-reactive antigen (MCRA) from Bifidobacterium breve NCIMB 702258. MCRA from B. breve NCIMB 702258 was cloned, sequenced and expressed in heterologous hosts (Lactococcus and Corynebacterium) and the recombinant proteins assessed for enzymatic activity against fatty acid substrates. MCRA catalysed the conversion of palmitoleic, oleic and linoleic acids to the corresponding 10-hydroxy fatty acids, but shorter chain fatty acids were not used as substrates, while the presence of trans-double bonds and double bonds beyond the position C12 abolished hydratase activity. The hydroxy fatty acids produced were not metabolised further. We also found that heterologous Lactococcus and Corynebacterium expressing MCRA accumulated increasing amounts of 10-HOA and 10-HOE in the culture medium. Furthermore, the heterologous cultures exhibited less sensitivity to heat and solvent stresses compared to corresponding controls. MCRA protein in B. breve can be classified as a FAD-containing double bond hydratase, within the carbon-oxygen lyase family, which may be catalysing the first step in conjugated linoleic acid (CLA) production, and this protein has an additional function in bacterial stress protection.

Descriptions of crack growth behaviors in glass-ZrO2 bilayers under thermal residual stresses.

PubMed

Belli, Renan; Wendler, Michael; Zorzin, José I; Petschelt, Anselm; Tanaka, Carina B; Meira, Josete; Lohbauer, Ulrich

2016-09-01

This study was intended to separate residual stresses arising from the mismatch in coefficients of thermal expansion between glass and zirconia (ZrO2) from those stresses arising solely from the cooling process. Slow crack growth experimentes were undertaken to demonstrate how cracks grow in different residual stress fields. Aluminosilicate glass discs were sintered onto ZrO2 to form glass-ZrO2 bilayers. Glass discs were allowed to bond to the ZrO2 substrate during sintering or prevented from bonding by means of coating the ZrO2 with a thin boron nitrade coating. Residual stress gradients on "bonded" and "unbonded" bilayers were assessed using birefringence measurements. Unbonded glass discs were further tested under biaxial flexure in dynamic fatigue conditions in order to evaluate the effect of residual stress on the slow crack growth behavior. When fast-ccoling was induced, residual tensile stresses on the glass increased significantly on the side toward the ZrO2 substrate. By allowing the bond between glass and ZrO2, those tensile stresses observed in unbonded specimens are overwhelmed by the contraction mismatch stresses between the ZrO2 substrate and the glassy overlayer. Specimens containing residual tensile stresses on the bending surface showed a time-dependent strength increase in relation to stress-free annealed samples in the dynamic biaxial bending test, with this effect being dependent on the magnitude of the residual tensile stress. The phenomenon observed is explained here on the basis of the water toughening effect, in which water diffuses into the glass promoting local swelling. An additional residual tensile stress at the crack tip adds an applied-stress-independent (Kres) term to the total tip stress intensity factor (Ktip), increasing the stress-enhanced diffusion and the shielding of the crack tip through swelling of the crack faces. Residual stresses in the glass influence the crack growth behavior of veneered-ZrO2 bilayered dental prostheses. The role of water in crack growth might be of higher complexity when residual stresses are present in the glass layer. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A non-modular type B feruloyl esterase from Neurospora crassa exhibits concentration-dependent substrate inhibition.

PubMed Central

Crepin, Valerie F; Faulds, Craig B; Connerton, Ian F

2003-01-01

Feruloyl esterases, a subclass of the carboxylic acid esterases (EC 3.1.1.1), are able to hydrolyse the ester bond between the hydroxycinnamic acids and sugars present in the plant cell wall. The enzymes have been classified as type A or type B, based on their substrate specificity for aromatic moieties. We show that Neurospora crassa has the ability to produce multiple ferulic acid esterase activities depending upon the length of fermentation with either sugar beet pulp or wheat bran substrates. A gene identified on the basis of its expression on sugar beet pulp has been cloned and overexpressed in Pichia pastoris. The gene encodes a single-domain ferulic acid esterase, which represents the first report of a non-modular type B enzyme (fae-1 gene; GenBank accession no. AJ293029). The purified recombinant protein has been shown to exhibit concentration-dependent substrate inhibition (K(m) 0.048 mM, K (i) 2.5 mM and V(max) 8.2 units/mg against methyl 3,4-dihydroxycinnamate). The kinetic behaviour of the non-modular enzyme is discussed in terms of the diversity in the roles of the feruloyl esterases in the mobilization of plant cell wall materials and their respective modes of action. PMID:12435269

Hydroxide-catalyzed bonding

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung (Inventor)

2003-01-01

A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

Interface bonding of NiCrAlY coating on laser modified H13 tool steel surface

NASA Astrophysics Data System (ADS)

Reza, M. S.; Aqida, S. N.; Ismail, I.

2016-06-01

Bonding strength of thermal spray coatings depends on the interfacial adhesion between bond coat and substrate material. In this paper, NiCrAlY (Ni-164/211 Ni22 %Cr10 %Al1.0 %Y) coatings were developed on laser modified H13 tool steel surface using atmospheric plasma spray (APS). Different laser peak power, P p, and duty cycle, DC, were investigated in order to improve the mechanical properties of H13 tool steel surface. The APS spraying parameters setting for coatings were set constant. The coating microstructure near the interface was analyzed using IM7000 inverted optical microscope. Interface bonding of NiCrAlY was investigated by interfacial indentation test (IIT) method using MMT-X7 Matsuzawa Hardness Tester Machine with Vickers indenter. Diffusion of atoms along NiCrAlY coating, laser modified and substrate layers was investigated by energy-dispersive X-ray spectroscopy (EDXS) using Hitachi Tabletop Microscope TM3030 Plus. Based on IIT method results, average interfacial toughness, K avg, for reference sample was 2.15 MPa m1/2 compared to sample L1 range of K avg from 6.02 to 6.96 MPa m1/2 and sample L2 range of K avg from 2.47 to 3.46 MPa m1/2. Hence, according to K avg, sample L1 has the highest interface bonding and is being laser modified at lower laser peak power, P p, and higher duty cycle, DC, prior to coating. The EDXS analysis indicated the presence of Fe in the NiCrAlY coating layer and increased Ni and Cr composition in the laser modified layer. Atomic diffusion occurred in both coating and laser modified layers involved in Fe, Ni and Cr elements. These findings introduce enhancement of coating system by substrate surface modification to allow atomic diffusion.

Remote site-selective C-H activation directed by a catalytic bifunctional template

NASA Astrophysics Data System (ADS)

Zhang, Zhipeng; Tanaka, Keita; Yu, Jin-Quan

2017-03-01

In chemical syntheses, the activation of carbon-hydrogen (C-H) bonds converts them directly into carbon-carbon or carbon-heteroatom bonds without requiring any prior functionalization. C-H activation can thus substantially reduce the number of steps involved in a synthesis. A single specific C-H bond in a substrate can be activated by using a ‘directing’ (usually a functional) group to obtain the desired product selectively. The applicability of such a C-H activation reaction can be severely curtailed by the distance of the C-H bond in question from the directing group, and by the shape of the substrate, but several approaches have been developed to overcome these limitations. In one such approach, an understanding of the distal and geometric relationships between the functional groups and C-H bonds of a substrate has been exploited to achieve meta-selective C-H activation by using a covalently attached, U-shaped template. However, stoichiometric installation of this template has not been feasible in the absence of an appropriate functional group on which to attach it. Here we report the design of a catalytic, bifunctional nitrile template that binds a heterocyclic substrate via a reversible coordination instead of a covalent linkage. The two metal centres coordinated to this template have different roles: one reversibly anchors substrates near the catalyst, and the other cleaves remote C-H bonds. Using this strategy, we demonstrate remote, site-selective C-H olefination of heterocyclic substrates that do not have the necessary functional groups for covalently attaching templates.

Remote site-selective C-H activation directed by a catalytic bifunctional template.

PubMed

Zhang, Zhipeng; Tanaka, Keita; Yu, Jin-Quan

2017-03-23

In chemical syntheses, the activation of carbon-hydrogen (C-H) bonds converts them directly into carbon-carbon or carbon-heteroatom bonds without requiring any prior functionalization. C-H activation can thus substantially reduce the number of steps involved in a synthesis. A single specific C-H bond in a substrate can be activated by using a 'directing' (usually a functional) group to obtain the desired product selectively. The applicability of such a C-H activation reaction can be severely curtailed by the distance of the C-H bond in question from the directing group, and by the shape of the substrate, but several approaches have been developed to overcome these limitations. In one such approach, an understanding of the distal and geometric relationships between the functional groups and C-H bonds of a substrate has been exploited to achieve meta-selective C-H activation by using a covalently attached, U-shaped template. However, stoichiometric installation of this template has not been feasible in the absence of an appropriate functional group on which to attach it. Here we report the design of a catalytic, bifunctional nitrile template that binds a heterocyclic substrate via a reversible coordination instead of a covalent linkage. The two metal centres coordinated to this template have different roles: one reversibly anchors substrates near the catalyst, and the other cleaves remote C-H bonds. Using this strategy, we demonstrate remote, site-selective C-H olefination of heterocyclic substrates that do not have the necessary functional groups for covalently attaching templates.

Cryogenic High Pressure Sensor Module

NASA Technical Reports Server (NTRS)

Chapman, John J. (Inventor); Shams, Qamar A. (Inventor); Powers, William T. (Inventor)

1999-01-01

A pressure sensor is provided for cryogenic, high pressure applications. A highly doped silicon piezoresistive pressure sensor is bonded to a silicon substrate in an absolute pressure sensing configuration. The absolute pressure sensor is bonded to an aluminum nitride substrate. Aluminum nitride has appropriate coefficient of thermal expansion for use with highly doped silicon at cryogenic temperatures. A group of sensors, either two sensors on two substrates or four sensors on a single substrate are packaged in a pressure vessel.

Cryogenic, Absolute, High Pressure Sensor

NASA Technical Reports Server (NTRS)

Chapman, John J. (Inventor); Shams. Qamar A. (Inventor); Powers, William T. (Inventor)

2001-01-01

A pressure sensor is provided for cryogenic, high pressure applications. A highly doped silicon piezoresistive pressure sensor is bonded to a silicon substrate in an absolute pressure sensing configuration. The absolute pressure sensor is bonded to an aluminum nitride substrate. Aluminum nitride has appropriate coefficient of thermal expansion for use with highly doped silicon at cryogenic temperatures. A group of sensors, either two sensors on two substrates or four sensors on a single substrate are packaged in a pressure vessel.

Process Of Bonding A Metal Brush Structure To A Planar Surface Of A Metal Substrate

DOEpatents

Slattery, Kevin T.; Driemeyer, Daniel E.; Wille; Gerald W.

1999-11-02

Process for bonding a metal brush structure to a planar surface of a metal substrate in which an array of metal rods are retained and immobilized at their tips by a common retention layer formed of metal, and the brush structure is then joined to a planar surface of a metal substrate via the retention layer.

Superconducting articles of manufacture and method of producing same

DOEpatents

Newkirk, Lawrence R.; Valencia, Flavio A.

1980-01-01

Bulk coatings of Nb.sub.3 Ge with high superconducting transition temperatures bonded to metallic substrates and a chemical vapor deposition method for producing such coatings on metallic substrates are disclosed. In accordance with the method, a Nb.sub.3 Ge coating having a transition temperature in excess of 21.5 K may be tightly bonded to a copper substrate.

Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts.

PubMed

Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier

2016-08-19

Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity.

Yeast ribonuclease III uses a network of multiple hydrogen bonds for RNA binding and cleavage.

PubMed

Lavoie, Mathieu; Abou Elela, Sherif

2008-08-19

Members of the bacterial RNase III family recognize a variety of short structured RNAs with few common features. It is not clear how this group of enzymes supports high cleavage fidelity while maintaining a broad base of substrates. Here we show that the yeast orthologue of RNase III (Rnt1p) uses a network of 2'-OH-dependent interactions to recognize substrates with different structures. We designed a series of bipartite substrates permitting the distinction between binding and cleavage defects. Each substrate was engineered to carry a single or multiple 2'- O-methyl or 2'-fluoro ribonucleotide substitutions to prevent the formation of hydrogen bonds with a specific nucleotide or group of nucleotides. Interestingly, introduction of 2'- O-methyl ribonucleotides near the cleavage site increased the rate of catalysis, indicating that 2'-OH are not required for cleavage. Substitution of nucleotides in known Rnt1p binding site with 2'- O-methyl ribonucleotides inhibited cleavage while single 2'-fluoro ribonucleotide substitutions did not. This indicates that while no single 2'-OH is essential for Rnt1p cleavage, small changes in the substrate structure are not tolerated. Strikingly, several nucleotide substitutions greatly increased the substrate dissociation constant with little or no effect on the Michaelis-Menten constant or rate of catalysis. Together, the results indicate that Rnt1p uses a network of nucleotide interactions to identify its substrate and support two distinct modes of binding. One mode is primarily mediated by the dsRNA binding domain and leads to the formation of stable RNA/protein complex, while the other requires the presence of the nuclease and N-terminal domains and leads to RNA cleavage.

Selective neurotensin-derived internally quenched fluorogenic substrates for neurolysin (EC 3.4.24.16): comparison with thimet oligopeptidase (EC 3.4.24.15) and neprilysin (EC 3.4.24.11).

PubMed

Oliveira, V; Campos, M; Hemerly, J P; Ferro, E S; Camargo, A C; Juliano, M A; Juliano, L

2001-05-15

Internally quenched fluorescent peptides derived from neurotensin (pELYENKPRRPYIL) sequence were synthesized and assayed as substrates for neurolysin (EC 3.4.24.16), thimet oligopeptidase (EC 3.4.24.15 or TOP), and neprilysin (EC 3.4.24.11 or NEP). Abz-LYENKPRRPYILQ-EDDnp (where EDDnp is N-(2,4-dinitrophenyl)ethylenediamine and Abz is ortho-aminobenzoic acid) was derived from neurotensin by the introduction of Q-EDDnp at the C-terminal end of peptide and by the substitution of the pyroglutamic (pE) residue at N-terminus for Abz and a series of shorter peptides was obtained by deletion of amino acids residues from C-terminal, N-terminal, or both sides. Neurolysin and TOP hydrolyzed the substrates at P--Y or Y--I or R--R bonds depending on the sequence and size of the peptides, while NEP cleaved P-Y or Y-I bonds according to its S'(1) specificity. One of these substrates, Abz-NKPRRPQ-EDDnp was a specific and sensitive substrate for neurolysin (k(cat) = 7.0 s(-1), K(m) = 1.19 microM and k(cat)/K(m) = 5882 mM(-1). s(-1)), while it was completely resistant to NEP and poorly hydrolyzed by TOP and also by prolyl oligopeptidase (EC 3.4.21.26). Neurolysin concentrations as low as 1 pM were detected using this substrate under our conditions and its analogue Abz-NKPRAPQ-EDDnp was hydrolyzed by neurolysin with k(cat) = 14.03 s(-1), K(m) = 0.82 microM, and k(cat)/K(m) = 17,110 mM(-1). s(-1), being the best substrate so far described for this peptidase. Copyright 2001 Academic Press.

The impact of artificially caries-affected dentin on bond strength of multi-mode adhesives

PubMed Central

Follak, Andressa Cargnelutti; Miotti, Leonardo Lamberti; Lenzi, Tathiane Larissa; Rocha, Rachel de Oliveira; Maxnuck Soares, Fabio Zovico

2018-01-01

Aim: The aim of this study is to evaluate the impact of dentin condition on bond strength of multi-mode adhesive systems (MMAS) to sound and artificially induced caries-affected dentin (CAD). Methods: Flat dentin surfaces of 112 bovine incisors were assigned to 16 subgroups (n = 7) according to the substrate condition (sound and CAD– pH-cycling for 14 days); adhesive systems (Scotchbond Universal, All-Bond Universal, Prime and Bond Elect, Adper Single Bond Plus and Clearfil SE Bond) and etching strategy (etch-and-rinse and self-etch). All systems were applied according to the manufacturer's instructions, and resin composite restorations were built. After 24 h of water storage, specimens were sectioned (0.8 mm2) and submitted to the microtensile test. Statistical Analysis: Data (MPa) were analyzed using three-way analysis of variance and Tukey's test (α = 0.05). Results: MMAS presented similar bond strength values, regardless etching strategy in each substrate condition. Bond strength values were lower when MMAS were applied to CAD in the etch-and-rinse strategy. Conclusion: The etching strategy did not influence the bond strength of MMAS to sound or CAD, considering each substrate separately. However, CAD impact negatively on bond strength of MMAS in etch-and rinse mode. PMID:29674813

Vibrational Studies of Adsorbate-Induced Reconstruction on Molybdenum Surfaces.

NASA Astrophysics Data System (ADS)

Lopinski, Gregory Peter

Adsorbate-induced rearrangement of the substrate structure strongly modifies the adsorbate-substrate and adsorbate-adsorbate interactions, leading to the complex behavior observed in many chemisorption systems. In this thesis the H/Mo(211), O/Mo(211) and Na/Mo(100) systems have been studied using high resolution electron energy loss spectroscopy (HREELS) to observe vibrations of the adsorbed atoms. The vibrational data is correlated with observations of the long-range order probed by LEED as well as the work function changes induced by adsorption. Adsorbate -induced substrate reconstruction plays an important role in all three of these systems. Studies of the coadsorption systems O+H/Mo(211) and Na+O/Mo(100) indicate how these effects can influence interactions between adsorbates. For H/Mo(211), above 1ML a (1 x 1) to (1 x 2) transition is observed and attributed to modification of the substrate periodicity. Below 1ML, H atoms are bridge bonded and induce local distortions of the substrate. The transition to the (1 x 2) phase involves the ordering of these displacements and occupation of three-fold sites partially populated by conversion of the bridge bonded species. This conversion accounts for the sawtooth-like coverage dependence of the work function. The structural model proposed for this system is also supported by the desorption parameters and partial molar entropy extracted from adsorption isobars. Oxygen adsorption on Mo(211) involves the occupation of multiple binding sites, with both the long-range order and the local geometry of the adsorbate phases strongly temperature dependent. Coadsorption of low coverages of oxygen and hydrogen leads to segregation of the two adsorbates which can be understood in terms of a substrate-mediated repulsive interaction between O and H. For Na/Mo(100), the frequency of the Na-Mo symmetric stretch mode does not shift with coverage although the mode intensity is strongly coverage dependent. The absence of a frequency shift as well as the form of the observed coverage dependence differ from the predictions of the traditional charge transfer model of alkali adsorption. The relevance of the vibrational results to the Na-induced structural changes observed on this surface are also discussed. Na adsorption has been found to dramatically alter the interaction of oxygen with this surface, due to the presence of a strong attractive interaction between Na and O that forces O atoms to occupy a different binding site than on a clean surface.

Systems and methods for using a boehmite bond-coat with polyimide membranes for gas separation

DOEpatents

Polishchuk, Kimberly Ann

2013-03-05

The subject matter disclosed herein relates to gas separation membranes and, more specifically, to polyimide gas separation membranes. In an embodiment, a gas separation membrane includes a porous substrate, a substantially continuous polyimide membrane layer, and one or more layers of boehmite nanoparticles disposed between the porous substrate and the polyimide membrane layer to form a bond-coat layer. The bond-coat layer is configured to improve the adhesion of the polyimide membrane layer to the porous substrate, and the polyimide membrane layer has a thickness approximately 100 nm or less.

Power module packaging with double sided planar interconnection and heat exchangers

DOEpatents

Liang, Zhenxian; Marlino, Laura D.; Ning, Puqi; Wang, Fei

2015-05-26

A double sided cooled power module package having a single phase leg topology includes two IGBT and two diode semiconductor dies. Each IGBT die is spaced apart from a diode semiconductor die, forming a switch unit. Two switch units are placed in a planar face-up and face-down configuration. A pair of DBC or other insulated metallic substrates is affixed to each side of the planar phase leg semiconductor dies to form a sandwich structure. Attachment layers are disposed on outer surfaces of the substrates and two heat exchangers are affixed to the substrates by rigid bond layers. The heat exchangers, made of copper or aluminum, have passages for carrying coolant. The power package is manufactured in a two-step assembly and heating process where direct bonds are formed for all bond layers by soldering, sintering, solid diffusion bonding or transient liquid diffusion bonding, with a specially designed jig and fixture.

Metal-ceramic bond strength between a feldspathic porcelain and a Co-Cr alloy fabricated with Direct Metal Laser Sintering technique.

PubMed

Dimitriadis, Konstantinos; Spyropoulos, Konstantinos; Papadopoulos, Triantafillos

2018-02-01

The aim of the present study was to record the metal-ceramic bond strength of a feldspathic dental porcelain and a Co-Cr alloy, using the Direct Metal Laser Sintering technique (DMLS) for the fabrication of metal substrates. Ten metal substrates were fabricated with powder of a dental Co-Cr alloy using DMLS technique (test group) in dimensions according to ISO 9693. Another ten substrates were fabricated with a casing dental Co-Cr alloy using classic casting technique (control group) for comparison. Another three substrates were fabricated using each technique to record the Modulus of Elasticity ( E ) of the used alloys. All substrates were examined to record external and internal porosity. Feldspathic porcelain was applied on the substrates. Specimens were tested using the three-point bending test. The failure mode was determined using optical and scanning electron microscopy. The statistical analysis was performed using t-test. Substrates prepared using DMLS technique did not show internal porosity as compared to those produced using the casting technique. The E of control and test group was 222 ± 5.13 GPa and 227 ± 3 GPa, respectively. The bond strength was 51.87 ± 7.50 MPa for test group and 54.60 ± 6.20 MPa for control group. No statistically significant differences between the two groups were recorded. The mode of failure was mainly cohesive for all specimens. Specimens produced by the DMLS technique cover the lowest acceptable metal-ceramic bond strength of 25 MPa specified in ISO 9693 and present satisfactory bond strength for clinical use.

Electroless epitaxial etching for semiconductor applications

DOEpatents

McCarthy, Anthony M.

2002-01-01

A method for fabricating thin-film single-crystal silicon on insulator substrates using electroless etching for achieving efficient etch stopping on epitaxial silicon substrates. Microelectric circuits and devices are prepared on epitaxial silicon wafers in a standard fabrication facility. The wafers are bonded to a holding substrate. The silicon bulk is removed using electroless etching leaving the circuit contained within the epitaxial layer remaining on the holding substrate. A photolithographic operation is then performed to define streets and wire bond pad areas for electrical access to the circuit.

Active site remodeling during the catalytic cycle in metal-dependent fructose-1,6-bisphosphate aldolases.

PubMed

Jacques, Benoit; Coinçon, Mathieu; Sygusch, Jurgen

2018-03-28

Crystal structures of two bacterial metal (Zn) dependent D-fructose 1,6-bisphosphate (FBP) aldolases in complex with substrate, analogues, and triose-P reaction products were determined to 1.5-2.0 Å resolution. The ligand complexes cryotrapped in native or mutant H. pylori aldolase crystals enabled a novel mechanistic description of FBP C 3 -C 4 bond cleavage. The reaction mechanism uses active site remodelling during the catalytic cycle implicating relocation of the Zn cofactor that is mediated by conformational changes of active site loops. Substrate binding initiates conformational changes, triggered upon P 1 -phosphate binding, which liberates the Zn chelating His180, allowing it to act as a general base for the proton abstraction at the FBP C 4 -hydroxyl group. A second zinc chelating His83 hydrogen bonds the substrate C 4 - hydroxyl group and assists cleavage by stabilizing the developing negative charge during proton abstraction. Cleavage is concerted with relocation of the metal cofactor from an interior to a surface exposed site, thereby stabilizing the nascent enediolate form. Conserved residue Glu142 is essential for protonation of the enediolate form, prior to product release. A D-tagatose 1,6-bisphosphate enzymatic complex reveals how His180 mediated proton abstraction controls stereospecificity of the cleavage reaction. Recognition and discrimination of the reaction products, dihydroxyacetone-P and D-glyceraldehyde-3-P, occurs via charged hydrogen bonds between hydroxyl groups of the triose-Ps and conserved residues, Asp82 and Asp255, respectively, and are crucial aspects of the enzyme's role in gluconeogenesis. Conformational changes in mobile loops β5-α7 and β6-α8 (containing catalytic residues Glu142 and His180, respectively) drive active site remodelling enabling the relocation of the metal cofactor. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

Microbead-regulated surface wrinkling patterns in a film-substrate system

NASA Astrophysics Data System (ADS)

Zhang, Cheng; Wang, Jiawen; Cao, Yan-Ping; Lu, Conghua; Li, Bo; Feng, Xi-Qiao

2017-10-01

The control of surface wrinkling patterns at the microscale is a concern in many applications. In this letter, we regulate surface wrinkling patterns on a film-substrate system by introducing microbeads atop the film. Both experiments and theoretical analysis reveal the changes in surface wrinkles induced by microbeads. Under equibiaxial compression, the film-substrate system without microbeads bonded on its upper surface often buckles into global, uniform labyrinths, whereas the labyrinthine pattern locally gives way to radial stripes emanating from the microbeads. This regulation of surface wrinkles depends on the sizes and spacing of microbeads. We combine the finite element method and the Fourier spectral method to explore the physical mechanisms underlying the phenomena. This study offers a viable technique for engineering surfaces with tunable functions.

Surface texturing of fluoropolymers

NASA Technical Reports Server (NTRS)

Banks, B. A.; Mirtich, M. J.; Sovey, J. S. (Inventor)

1982-01-01

A method is disclosed for improving surface texture for adhesive bonding, metal bonding, substrate plating, decal substrate preparation, and biomedical implant applications. The surface to be bonded is dusted in a controlled fashion to produce a disbursed layer of fine mesh particles which serve as masks. The surface texture is produced by impinging gas ions on the masked surface. The textured surface takes the form of pillars or cones. The bonding material, such as a liquid epoxy, flows between the pillars which results in a bond having increased strength. For bonding metals a thin film of metal is vapor or sputter deposited onto the textured surface. Electroplating or electroless plating is then used to increase the metal thickness in the desired amount.

Shear bond strength of veneering porcelain to zirconia: Effect of surface treatment by CNC-milling and composite layer deposition on zirconia.

PubMed

Santos, R L P; Silva, F S; Nascimento, R M; Souza, J C M; Motta, F V; Carvalho, O; Henriques, B

2016-07-01

The purpose of this study was to evaluate the shear bond strength of veneering feldspathic porcelain to zirconia substrates modified by CNC-milling process or by coating zirconia with a composite interlayer. Four types of zirconia-porcelain interface configurations were tested: RZ - porcelain bonded to rough zirconia substrate (n=16); PZ - porcelain bonded to zirconia substrate with surface holes (n=16); RZI - application of a composite interlayer between the veneering porcelain and the rough zirconia substrate (n=16); PZI - application of a composite interlayer between the porcelain and the zirconia substrate treated by CNC-milling (n=16). The composite interlayer was composed of zirconia particles reinforced porcelain (30%, vol%). The mechanical properties of the ceramic composite have been determined. The shear bond strength test was performed at 0.5mm/min using a universal testing machine. The interfaces of fractured and untested specimens were examined by FEG-SEM/EDS. Data was analyzed with Shapiro-Wilk test to test the assumption of normality. The one-way ANOVA followed by Tukey HSD multiple comparison test was used to compare shear bond strength results (α=0.05). The shear bond strength of PZ (100±15MPa) and RZI (96±11MPa) specimens were higher than that recorded for RZ (control group) specimens (89±15MPa), although not significantly (p>0.05). The highest shear bond strength values were recorded for PZI specimens (138±19MPa), yielding a significant improvement of 55% relative to RZ specimens (p<0.05). This study shows that it is possible to highly enhance the zirconia-porcelain bond strength - even by ~55% - by combining surface holes in zirconia frameworks and the application of a proper ceramic composite interlayer. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Role of the Substrate on Photophysical Properties of Highly Ordered 15R-SiC Thin Films

NASA Astrophysics Data System (ADS)

Mourya, Satyendra; Jaiswal, Jyoti; Malik, Gaurav; Kumar, Brijesh; Chandra, Ramesh

2018-06-01

We report on the structural optimization and photophysical properties of in situ RF-sputtered single crystalline 15R-SiC thin films deposited on various substrates (ZrO2, MgO, SiC, and Si). The role of the substrates on the structural, electronic, and photodynamic behavior of the grown films have been demonstrated using x-ray diffraction, photoluminescence (PL) and time-resolved photoluminescence spectroscopy. The appropriate bonding order and the presence of native oxide on the surface of the grown samples are confirmed by x-ray photoelectron spectroscopy measurement. A deep-blue PL emission has been observed corresponding to the Si-centered defects occurring in the native oxide. Deconvolution of the PL spectra manifested two decay mechanisms corresponding to the radiative recombination. The PL intensity and carrier lifetime were found to be substrate- dependent which may be ascribed to the variation in the trap-density of the films grown on different substrates.

Formation of graphene on BN substrate by vapor deposition method and size effects on its structure

NASA Astrophysics Data System (ADS)

Giang, Nguyen Hoang; Hanh, Tran Thi Thu; Ngoc, Le Nhu; Nga, Nguyen To; Van Hoang, Vo

2018-04-01

We report MD simulation of the growth of graphene by the vapor deposition on a two-dimensional hBN substrate. The systems (containing carbon vapor and hBN substrate) are relaxed at high temperature (1500 K), and then it is cooled down to room one (300 K). Carbon atoms interact with the substrate via the Lennard-Jones potential while the interaction between carbon atoms is computed via the Tersoff potential. Depending on the size of the model, different crystalline honeycomb structures have been found. Structural properties of the graphene obtained at 300 K are studied by analyzing radial distribution functions (RDFs), coordination numbers, ring statistics, interatomic distances, bond-angle distributions and 2D visualization of atomic configurations. We find that the models containing various numbers of atoms have a honeycomb structure. Besides, differences in structural properties of graphene formed by the vapor deposition on the substrate and free standing one are found. Moreover, the size effect on the structure is significant.

Method of bonding silver to glass and mirrors produced according to this method

DOEpatents

Pitts, J.R.; Thomas, T.M.; Czanderna, A.W.

1984-07-31

A method for adhering silver to a glass substrate for producing mirrors includes attaining a silicon enriched substrate surface by reducing the oxygen therein in a vacuum and then vacuum depositing a silver layer onto the silicon enriched surface. The silicon enrichment can be attained by electron beam bombardment, ion beam bombardment, or neutral beam bombardment. It can also be attained by depositing a metal, such as aluminum, on the substrate surface, allowing the metal to oxidize by pulling oxygen from the substrate surface, thereby leaving a silicon enriched surface, and then etching or eroding the metal oxide layer away to expose the silicon enriched surface. Ultraviolet rays can be used to maintain dangling silicon bonds on the enriched surface until covalent bonding with the silver can occur. This disclosure also includes encapsulated mirrors with diffusion layers built therein. One of these mirrors is assembled on a polymer substrate.

Method of bonding silver to glass and mirrors produced according to this method

DOEpatents

Pitts, John R.; Thomas, Terence M.; Czanderna, Alvin W.

1985-01-01

A method for adhering silver to a glass substrate for producing mirrors includes attaining a silicon enriched substrate surface by reducing the oxygen therein in a vacuum and then vacuum depositing a silver layer onto the silicon enriched surface. The silicon enrichment can be attained by electron beam bombardment, ion beam bombardment, or neutral beam bombardment. It can also be attained by depositing a metal, such as aluminum, on the substrate surface, allowing the metal to oxidize by pulling oxygen from the substrate surface, thereby leaving a silicon enriched surface, and then etching or eroding the metal oxide layer away to expose the silicon enriched surface. Ultraviolet rays can be used to maintain dangling silicon bonds on the enriched surface until covalent bonding with the silver can occur. This disclosure also includes encapsulated mirrors with diffusion layers built therein. One of these mirrors is assembled on a polymer substrate.

Wafer bonded epitaxial templates for silicon heterostructures

DOEpatents

Atwater, Jr., Harry A.; Zahler, James M [Pasadena, CA; Morral, Anna Fontcubera I [Paris, FR

2008-03-11

A heterostructure device layer is epitaxially grown on a virtual substrate, such as an InP/InGaAs/InP double heterostructure. A device substrate and a handle substrate form the virtual substrate. The device substrate is bonded to the handle substrate and is composed of a material suitable for fabrication of optoelectronic devices. The handle substrate is composed of a material suitable for providing mechanical support. The mechanical strength of the device and handle substrates is improved and the device substrate is thinned to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. An upper portion of the device film exfoliated from the device substrate is removed to provide a smoother and less defect prone surface for an optoelectronic device. A heterostructure is epitaxially grown on the smoothed surface in which an optoelectronic device may be fabricated.

Wafer bonded epitaxial templates for silicon heterostructures

NASA Technical Reports Server (NTRS)

Atwater, Harry A., Jr. (Inventor); Zahler, James M. (Inventor); Morral, Anna Fontcubera I (Inventor)

2008-01-01

A heterostructure device layer is epitaxially grown on a virtual substrate, such as an InP/InGaAs/InP double heterostructure. A device substrate and a handle substrate form the virtual substrate. The device substrate is bonded to the handle substrate and is composed of a material suitable for fabrication of optoelectronic devices. The handle substrate is composed of a material suitable for providing mechanical support. The mechanical strength of the device and handle substrates is improved and the device substrate is thinned to leave a single-crystal film on the virtual substrate such as by exfoliation of a device film from the device substrate. An upper portion of the device film exfoliated from the device substrate is removed to provide a smoother and less defect prone surface for an optoelectronic device. A heterostructure is epitaxially grown on the smoothed surface in which an optoelectronic device may be fabricated.

The significance of nanoparticles on bond strength of polymer concrete to steel

DOE PAGES

Douba, A.; Genedy, M.; Matteo, E. N.; ...

2017-01-03

Here, polymer concrete (PC) is a commonly used material in construction due to its improved durability and good bond strength to steel substrate. PC has been suggested as a repair and seal material to restore the bond between the cement annulus and the steel casing in wells that penetrate formations under consideration for CO 2 sequestration. Nanoparticles including Multi-Walled Carbon Nano Tubes (MWCNTs), Aluminum Nanoparticles (ANPs) and Silica Nano particles (SNPs) were added to an epoxy-based PC to examine how the nanoparticles affect the bond strength of PC to a steel substrate. Slant shear tests were used to determine themore » bond strength of PC incorporating nanomaterials to steel; results reveal that PC incorporating nanomaterials has an improved bond strength to steel substrate compared with neat PC. In particular, ANPs improve the bond strength by 51% over neat PC. Local shear stresses, extracted from Finite Element (FE) analysis of the slant shear test, were found to be as much as twice the apparent/average shear/bond strength. These results suggest that the impact of nanomaterials is higher than that shown by the apparent strength. Fourier Transform Infrared (FTIR) measurements of epoxy with and without nanomaterials showed ANPs to influence curing of epoxy, which might explain the improved bond strength of PC incorporating ANPs.« less

The significance of nanoparticles on bond strength of polymer concrete to steel

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

Douba, A.; Genedy, M.; Matteo, E. N.

Here, polymer concrete (PC) is a commonly used material in construction due to its improved durability and good bond strength to steel substrate. PC has been suggested as a repair and seal material to restore the bond between the cement annulus and the steel casing in wells that penetrate formations under consideration for CO 2 sequestration. Nanoparticles including Multi-Walled Carbon Nano Tubes (MWCNTs), Aluminum Nanoparticles (ANPs) and Silica Nano particles (SNPs) were added to an epoxy-based PC to examine how the nanoparticles affect the bond strength of PC to a steel substrate. Slant shear tests were used to determine themore » bond strength of PC incorporating nanomaterials to steel; results reveal that PC incorporating nanomaterials has an improved bond strength to steel substrate compared with neat PC. In particular, ANPs improve the bond strength by 51% over neat PC. Local shear stresses, extracted from Finite Element (FE) analysis of the slant shear test, were found to be as much as twice the apparent/average shear/bond strength. These results suggest that the impact of nanomaterials is higher than that shown by the apparent strength. Fourier Transform Infrared (FTIR) measurements of epoxy with and without nanomaterials showed ANPs to influence curing of epoxy, which might explain the improved bond strength of PC incorporating ANPs.« less

Fabrication of complex nanoscale structures on various substrates

NASA Astrophysics Data System (ADS)

Han, Kang-Soo; Hong, Sung-Hoon; Lee, Heon

2007-09-01

Polymer based complex nanoscale structures were fabricated and transferred to various substrates using reverse nanoimprint lithography. To facilitate the fabrication and transference of the large area of the nanostructured layer to the substrates, a water-soluble polyvinyl alcohol mold was used. After generation and transference of the nanostructured layer, the polyvinyl alcohol mold was removed by dissolving in water. A residue-free, UV-curable, glue layer was formulated and used to bond the nanostructured layer onto the substrates. As a result, nanometer scale patterned polymer layers were bonded to various substrates and three-dimensional nanostructures were also fabricated by stacking of the layers.

GROUT-CONCRETE INTERFACE BOND PERFORMANCE: EFFECT OF INTERFACE MOISTURE ON THE TENSILE BOND STRENGTH AND GROUT MICROSTRUCTURE.

PubMed

De la Varga, I; Muñoz, J F; Bentz, D P; Spragg, R P; Stutzman, P E; Graybeal, B A

2018-05-01

Bond between two cementitious materials is crucial in applications such as repairs, overlays, and connections of prefabricated bridge elements (PBEs), to name just a few. It is the latter that has special interest to the authors of this paper. After performing a dimensional stability study on grout-like materials commonly used as connections between PBEs, it was observed that the so-called 'non-shrink' cementitious grouts showed a considerable amount of early-age shrinkage. This might have negative effects on the integrity of the structure, due not only to the grout material's early degradation, but also to a possible loss of bond between the grout and the prefabricated concrete element. Many factors affect the bond strength between two cementitious materials (e.g., grout-concrete), the presence of moisture at the existing concrete substrate surface being one of them. In this regard, pre-moistening the concrete substrate surface prior to the application of the grout material is sometimes recommended for bond enhancement. This topic has been the focus of numerous research studies in the past; however, there is still controversy among practitioners on the real benefits that this practice might provide. This paper evaluates the tensile bond performance of two non-shrink cementitious grouts applied to the exposed aggregate surface of a concrete substrate, and how the supply of moisture at the grout-concrete interface affects the bond strength. "Pull-off" bond results show increased tensile bond strength when the concrete surface is pre-moistened. Reasons to explain the observed increased bond strength are given after a careful microstructural analysis of the grout-concrete interface. Interfaces where sufficient moisture is provided to the concrete substrate such that moisture movement from the grout is prevented show reduced porosity and increased hydration on the grout side of the interface, which is thought to directly contribute to the increased tensile bond strength.

Asymmetric Stetter reactions catalyzed by thiamine diphosphate-dependent enzymes.

PubMed

Kasparyan, Elena; Richter, Michael; Dresen, Carola; Walter, Lydia S; Fuchs, Georg; Leeper, Finian J; Wacker, Tobias; Andrade, Susana L A; Kolter, Geraldine; Pohl, Martina; Müller, Michael

2014-12-01

The intermolecular asymmetric Stetter reaction is an almost unexplored transformation for biocatalysts. Previously reported thiamine diphosphate (ThDP)-dependent PigD from Serratia marcescens is the first enzyme identified to catalyze the Stetter reaction of α,β-unsaturated ketones (Michael acceptor substrates) and α-keto acids. PigD is involved in the biosynthesis of the potent cytotoxic agent prodigiosin. Here, we describe the investigation of two new ThDP-dependent enzymes, SeAAS from Saccharopolyspora erythraea and HapD from Hahella chejuensis. Both show a high degree of homology to the amino acid sequence of PigD (39 and 51 %, respectively). The new enzymes were heterologously overproduced in Escherichia coli, and the yield of soluble protein was enhanced by co-expression of the chaperone genes groEL/ES. SeAAS and HapD catalyze intermolecular Stetter reactions in vitro with high enantioselectivity. The enzymes possess a characteristic substrate range with respect to Michael acceptor substrates. This provides support for a new type of ThDP-dependent enzymatic activity, which is abundant in various species and not restricted to prodigiosin biosynthesis in different strains. Moreover, PigD, SeAAS, and HapD are also able to catalyze asymmetric carbon-carbon bond formation reactions of aldehydes and α-keto acids, resulting in 2-hydroxy ketones.

Integration of Indium Phosphide Based Devices with Flexible Substrates

NASA Astrophysics Data System (ADS)

Chen, Wayne Huai

2011-12-01

Flexible substrates have many advantages in applications where bendability, space, or weight play important roles or where rigid circuits are undesirable. However, conventional flexible thin film transistors are typically characterized as having low carrier mobility as compared to devices used in the electronics industry. This is in part due to the limited temperature tolerance of plastic flexible substrates, which commonly reduces the highest processing temperature to below 200°C. Common approaches of implementation include low temperature deposition of organic, amorphous, or polycrystalline semiconductors, all of which result in carrier mobility well below 100 cm2V -1s-1. High quality, single crystalline III-V semiconductors such as indium phosphide (InP), on the other hand, have carrier mobility well over 1000 cm 2V-1s-1 at room temperature, depending on carrier concentration. Recently, the ion-cut process has been used in conjunction with wafer bonding to integrate thin layers of III-V material onto silicon for optoelectronic applications. This approach has the advantage of high scalability, reusability of the initial III-V substrate, and the ability to tailor the location (depth) of the layer splitting. However, the transferred substrate usually suffers from hydrogen implantation damage. This dissertation demonstrates a new approach to enable integration of InP with various substrates, called the double-flip transfer process. The process combines ion-cutting with adhesive bonding. The problem of hydrogen implantation was overcome by patterned ion-cut transfer. In this type of transfer, areas of interest are shielded from implantation but still transferred by surrounding implanted regions. We found that patterned ion-cut transfer is strongly dependent upon crystal orientation and that using cleavage-plane oriented donors can be beneficial in transferring large areas of high quality semiconductor material. InP-based devices were fabricated to demonstrate the transfer process and test functionality following transfer. Passive devices (photodetectors) as well as active transistors were transferred and fabricated on various substrates. The transferred device layers were either implanted through with a blanket implant or protected with an ion-mask during implantation. Results demonstrate the viability of the double-flip ion-cut process in achieving very high electron mobility (˜2800 cm2V-1s-1) transistors on plastic flexible substrates.

Effect of the Cold-Sprayed Aluminum Coating-Substrate Interface Morphology on Bond Strength for Aircraft Repair Application

NASA Astrophysics Data System (ADS)

Blochet, Quentin; Delloro, Francesco; N'Guyen, Franck; Jeulin, Dominique; Borit, François; Jeandin, Michel

2017-04-01

This article is dealing with the effects of surface preparation of the substrate on aluminum cold-sprayed coating bond strength. Different sets of AA2024-T3 specimens have been coated with pure Al 1050 feedstock powder, using a conventional cold spray coating technique. The sets were grit-blasted (GB) before coating. The study focuses on substrate surface topography evolution before coating and coating-substrate interface morphology after coating. To study coating adhesion by LASAT® technique for each set, specimens with and without preceding GB treatment were tested in load-controlled conditions. Then, several techniques were used to evaluate the effects of substrate surface treatment on the final coating mechanical properties. Irregularities induced by the GB treatment modify significantly the interface morphology. Results showed that particle anchoring was improved dramatically by the presence of craters. The substrate surface was characterized by numerous anchors. Numerical simulation results exhibited the increasing deformation of particle onto the grit-blasted surface. In addition, results showed a strong relationship between the coating-substrate bond strength on the deposited material and surface preparation.

Mechanistic studies of ribonucleoside triphosphate reductase from Lactobacillus leichmannii

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

Harris, G.M.

1984-01-01

The mechanism of action of the adenosylcobalamin (AdoCbl)-dependent ribonucleoside triphosphate reductase (RTPR) was investigated using isotope effect and substrate specificity studies. These experiments were conducted on RTPR purified by a new method from Lactobacillus leichmannii. Isotope effect studies using (3{prime}-{sup 3}H)UTP and (3{prime}-{sup 3}H)ATP demonstrated that the 3{prime} C-H bond of the nucleotide is cleaved in order to cleave the 2{prime} C-OH bond. AdoCbl does not act as a direct H abstractor from the 3{prime} position of the substrate, but instead is thought to act as a radical chain initiator to generate an amino acid radical on the enzyme. Furthermore » support for this enzyme mediated cleavage of the 3{prime} C-H bond of the nucleotide and the novel role of AdoCbl came from studies using (3{prime}{sup 3}H)2{prime}-chloro-2{prime}-deoxyuridine 5{prime}-triphosphate ((3{prime}-{sup 3}H)CIUTP). Evidence is presented that during the course of this reaction, the {sup 3}H abstracted from the 3{prime} position of (3{prime}-{sup 3}H)CIUTP was either exchanged with the solvent or returned to the {beta} face of the 2{prime} position to produce (2{prime}{sup 3}H)-2{prime}-deoxy-3{prime}-ketoUTP. This result demonstrates that RTPR is capable of catalyzing a rearrangement reaction. The significance of the RTPR-catalyzed rearrangement with respect to the AdoCbl-dependent enzymes which catalyze rearrangements is discussed.« less

Carbon Conversion Efficiency and Limits of Productive Bacterial Degradation of Methyl tert-Butyl Ether and Related Compounds▿

PubMed Central

Müller, Roland H.; Rohwerder, Thore; Harms, Hauke

2007-01-01

The utilization of the fuel oxygenate methyl tert-butyl ether (MTBE) and related compounds by microorganisms was investigated in a mainly theoretical study based on the YATP concept. Experiments were conducted to derive realistic maintenance coefficients and Ks values needed to calculate substrate fluxes available for biomass production. Aerobic substrate conversion and biomass synthesis were calculated for different putative pathways. The results suggest that MTBE is an effective heterotrophic substrate that can sustain growth yields of up to 0.87 g g−1, which contradicts previous calculation results (N. Fortin et al., Environ. Microbiol. 3:407-416, 2001). Sufficient energy equivalents were generated in several of the potential assimilatory routes to incorporate carbon into biomass without the necessity to dissimilate additional substrate, efficient energy transduction provided. However, when a growth-related kinetic model was included, the limits of productive degradation became obvious. Depending on the maintenance coefficient ms and its associated biomass decay term b, growth-associated carbon conversion became strongly dependent on substrate fluxes. Due to slow degradation kinetics, the calculations predicted relatively high threshold concentrations, Smin, below which growth would not further be supported. Smin strongly depended on the maximum growth rate μmax, and b and was directly correlated with the half maximum rate-associated substrate concentration Ks, meaning that any effect impacting this parameter would also change Smin. The primary metabolic step, catalyzing the cleavage of the ether bond in MTBE, is likely to control the substrate flux in various strains. In addition, deficits in oxygen as an external factor and in reduction equivalents as a cellular variable in this reaction should further increase Ks and Smin for MTBE. PMID:17220260

Effect of Phosphoric Acid Pre-etching on Fatigue Limits of Self-etching Adhesives.

PubMed

Takamizawa, T; Barkmeier, W W; Tsujimoto, A; Scheidel, D D; Erickson, R L; Latta, M A; Miyazaki, M

2015-01-01

The purpose of this study was to use shear bond strength (SBS) and shear fatigue limit (SFL) testing to determine the effect of phosphoric acid pre-etching of enamel and dentin prior to application of self-etch adhesives for bonding resin composite to these substrates. Three self-etch adhesives--1) G- ænial Bond (GC Corporation, Tokyo, Japan); 2) OptiBond XTR (Kerr Corp, Orange, CA, USA); and 3) Scotchbond Universal (3M ESPE Dental Products, St Paul, MN, USA)--were used to bond Z100 Restorative resin composite to enamel and dentin surfaces. A stainless-steel metal ring with an inner diameter of 2.4 mm was used to bond the resin composite to flat-ground (4000 grit) tooth surfaces for determination of both SBS and SFL. Fifteen specimens each were used to determine initial SBS to human enamel/dentin, with and without pre-etching with a 35% phosphoric acid (Ultra-Etch, Ultradent Products Inc, South Jordan, UT, USA) for 15 seconds prior to the application of the adhesives. A staircase method of fatigue testing (25 specimens for each test) was then used to determine the SFL of resin composite bonded to enamel/dentin using a frequency of 10 Hz for 50,000 cycles or until failure occurred. A two-way analysis of variance and Tukey post hoc test were used for analysis of SBS data, and a modified t-test with Bonferroni correction was used for the SFL data. Scanning electron microscopy was used to examine the area of the bonded restorative/tooth interface. For all three adhesive systems, phosphoric acid pre-etching of enamel demonstrated significantly higher (p<0.05) SBS and SFL with pre-etching than it did without pre-etching. The SBS and SFL of dentin bonds decreased with phosphoric acid pre-etching. The SBS and SFL of bonds using phosphoric acid prior to application of self-etching adhesives clearly demonstrated different tendencies between enamel and dentin. The effect of using phosphoric acid, prior to the application of the self-etching adhesives, on SBS and SFL was dependent on the adhesive material and tooth substrate and should be carefully considered in clinical situations.

Effect of Pd Surface Roughness on the Bonding Process and High Temperature Reliability of Au Ball Bonds

NASA Astrophysics Data System (ADS)

Huang, Y.; Kim, H. J.; McCracken, M.; Viswanathan, G.; Pon, F.; Mayer, M.; Zhou, Y. N.

2011-06-01

A 0.3- μm-thick electrolytic Pd layer was plated on 1 μm of electroless Ni on 1 mm-thick polished and roughened Cu substrates with roughness values ( R a) of 0.08 μm and 0.5 μm, respectively. The rough substrates were produced with sand-blasting. Au wire bonding on the Ni/Pd surface was optimized, and the electrical reliability was investigated under a high temperature storage test (HTST) during 800 h at 250°C by measuring the ball bond contact resistance, R c. The average value of R c of optimized ball bonds on the rough substrate was 1.96 mΩ which was about 40.0% higher than that on the smooth substrate. The initial bondability increased for the rougher surface, so that only half of the original ultrasonic level was required, but the reliability was not affected by surface roughness. For both substrate types, HTST caused bond healing, reducing the average R c by about 21% and 27%, respectively. Au diffusion into the Pd layer was observed in scanning transmission electron microscopy/ energy dispersive spectroscopy (STEM-EDS) line-scan analysis after HTST. It is considered that diffusion of Au or interdiffusion between Au and Pd can provide chemically strong bonding during HTST. This is supported by the R c decrease measured as the aging time increased. Cu migration was indicated in the STEM-EDS analysis, but its effect on reliability can be ignored. Au and Pd tend to form a complete solid solution at the interface and can provide reliable interconnection for high temperature (250°C) applications.

Essential Factors Influencing the Bonding Strength of Cold-Sprayed Aluminum Coatings on Ceramic Substrates

NASA Astrophysics Data System (ADS)

Drehmann, R.; Grund, T.; Lampke, T.; Wielage, B.; Wüstefeld, C.; Motylenko, M.; Rafaja, D.

2018-02-01

The present work summarizes the most important results of a research project dealing with the comprehensive investigation of the bonding mechanisms between cold-sprayed Al coatings and various poly- and monocrystalline ceramic substrates (Al2O3, AlN, Si3N4, SiC, MgF2). Due to their exceptional combination of properties, metallized ceramics are gaining more and more importance for a wide variety of applications, especially in electronic engineering. Cold spray provides a quick, flexible, and cost-effective one-step process to apply metallic coatings on ceramic surfaces. However, since most of the existing cold-spray-related publications focus on metallic substrates, only very little is known about the bonding mechanisms acting between cold-sprayed metals and ceramic substrates. In this paper, the essential factors influencing the bonding strength in such composites are identified. Besides mechanical tensile strength testing, a thorough analysis of the coatings and especially the metal/ceramic interfaces was conducted by means of HRTEM, FFT, STEM, EDX, EELS, GAXRD, and EBSD. The influence of substrate material, substrate temperature, and particle size is evaluated. The results suggest that, apart from mechanical interlocking, the adhesion of cold-sprayed metallic coatings on ceramics is based on a complex interplay of different mechanisms such as quasiadiabatic shearing, static recrystallization, and heteroepitaxial growth.

Structural Studies of the Initial Stages of Fluoride Epitaxy on Silicon and GERMANIUM(111)

NASA Astrophysics Data System (ADS)

Denlinger, Jonathan David

The epitaxial growth of ionic insulators on semiconductor substrates is of interest due to fundamental issues of interface bonding and structure as well as to potential technological applications. The initial stages of Group IIa fluoride insulator growth on (111) Si and Ge substrates by molecular beam epitaxy are studied with the in situ combination of X-ray Photoelectron Spectroscopy (XPS) and Diffraction (XPD). While XPS probes the electronic structure, XPD reveals atomic structure. In addition, low energy electron diffraction (LEED) is used to probe surface order and a separate study using X-ray standing wave (XSW) fluorescence reveals interface cation bonding sites. Following the formation of a chemically-reacted interface layer in CaF_2 epitaxy on Si(111), the morphology of the subsequent bulk layers is found to be dependent on substrate temperature and incident flux rate. At temperatures >=600 ^circC a transition from three -dimensional island formation at low flux to laminar growth at higher flux is observed with bulk- and interface-resolved XPD. At lower substrate temperatures, laminar growth is observed at all fluxes, but with different bulk nucleation behavior due to changes in the stoichiometry of the interface layer. This new observation of kinetic effects on the initial nucleation in CaF_2 epitaxy has important ramifications for the formation of thicker heterostructures for scientific or device applications. XPS and XPD are also used to identify for the first time, surface core-level species of Ca and F, and a secondary interface-shifted F Auger component arising from a second-layer site directly above interface-layer Ca atoms. The effects of lattice mismatch (from -3% to 8%) are investigated with various growths of Ca_{rm x}Sr _{rm 1-x}F_2 on Si and Ge (111) substrates. Triangulation of (111) and (220) XSW indicates a predominance of 3-fold hollow Sr bonding sites coexisting with 4-fold top sites for monolayers of SrF_2 on Si. XSW and LEED reveal a lateral discommensuration of the overlayer for lattice mismatches of >5% relative to the substrate. XPD also reveals a transition from single - to mixed-domains of overlayer crystallographic orientation for mismatches >=3.5%.

The Enantiomers of 4-Amino-3-fluorobutanoic Acid as Substrates for γ-Aminobutyric Acid Aminotransferase. Conformational Probes for GABA Binding†

PubMed Central

Clift, Michael; Ji, Haitao; Deniau, Gildas P.; O’Hagan, David; Silverman, Richard B.

2008-01-01

γ-Aminobutyric acid aminotransferase (GABA-AT), a pyridoxal 5’-phosphate dependent enzyme, catalyzes the degradation of the inhibitory neurotransmitter γ-aminobutyric acid (GABA) to succinic semialdehyde with concomitant conversion of pyridoxal 5’-phosphate (PLP) to pyridoxamine 5’-phosphate (PMP). The enzyme then catalyzes the conversion of α-ketoglutarate to the excitatory neurotransmitter L-glutamate. Racemic 4-amino-3-fluorobutanoic acid (3-F-GABA) was shown previously to act as a substrate for GABA-AT, not for transamination, but for HF elimination. Here we report studies of the reaction catalyzed by GABA-AT on (R)- and (S)-3-F-GABA. Neither enantiomer is a substrate for transamination. Very little elimination from the (S)-enantiomer was detected using a coupled enzyme assay; The rate of elimination of HF from the (R)-enantiomer is at least 10 times greater than that for the (S)-enantiomer. The (R)-enantiomer is about 20 times more efficient as a substrate for GABA-AT catalyzed HF elimination than GABA is a substrate for transamination. The (R)-enantiomer also inhibits the transamination of GABA 10 times more effectively than the (S)-enantiomer. Using a combination of computer modeling and the knowledge that vicinal C-F and C-NH3+ bonds have a strong preference to align gauche rather than anti to each other, it is concluded that on binding of free 3-F-GABA to GABA-AT the optimal conformation places the C-NH3+ and C-F bonds gauche in the (R)-enantiomer but anti in the (S)-enantiomer. Furthermore, the dynamic binding process and the bioactive conformation of GABA bound to GABA-AT have been inferred based on the different biological behavior of the two enantiomers of 3-F-GABA when they bind to the enzyme. The present study suggests that the C-F bond can be utilized as a conformational probe to explore the dynamic binding process and provide insight into the bioactive conformation of substrates, which cannot be easily determined by other biophysical approaches. PMID:17988152

Some material structural properties of SOI substrates produced by SDB technology

NASA Astrophysics Data System (ADS)

Hui, Li; Guo-Liang, Sun; Juan, Zhan; Qin-Yi, Tong

1987-10-01

SOI substrates have been produced by silicon direct bonding (SDB) technology. Thermal oxides ranging in thickness from native oxide to 1 μm or even more, on either or both wafers have been bonded successfully. The fracture strength of the SOI layer is 130-200 kg/cm 2 which is similar to the value of intrinsic bulk silicon. Dislocations have been shown to be concentrated on the backsides of the substrate and no additional defects have been developed within 80 μm of the Si-SiO 2 bonding area. Mobility and minority carrier lifetime similar to that of the original bulk silicon have been obtained after annealing.

Peroxidase-type reactions suggest a heterolytic/nucleophilic O–O joining mechanism in the heme-dependent chlorite dismutase†

PubMed Central

Mayfield, Jeffrey A.; Blanc, Béatrice; Rodgers, Kenton R.; Lukat-Rodgers, Gudrun S.; DuBois, Jennifer L.

2015-01-01

Heme-containing chlorite dismutases (Clds) catalyze a highly unusual O–O bond forming reaction. The O–O cleaving reactions of hydrogen peroxide and peracetic acid (PAA) with the Cld from Dechloromonas aromatica (DaCld) were studied to better understand the Cl–O cleavage of the natural substrate and subsequent O–O bond formation. While reactions with H2O2 resulted in slow destruction of the heme, at acidic pH, heterolytic cleavage of the O–O bond of PAA cleanly yielded the ferryl porphyrin cation radical (Compound I). At alkaline pH, the reaction proceeds more rapidly and the first observed intermediate is a ferryl heme. Freezequench EPR confirmed that the latter has an uncoupled protein-based radical, indicating that Compound I is the first intermediate formed at all pH values and that radical migration is faster at alkaline pH. These results suggest by analogy that two-electron Cl–O bond cleavage to yield a ferryl-porphyrin cation radical is the most likely initial step in O–O bond formation from chlorite. PMID:24001266

Single-Crystal Material on Non-Single-Crystalline Substrate

DTIC Science & Technology

1999-02-01

point frit or solder glass can be deposited on a surface and bonded to a second surface using pressure and temperature. A sodium silicate material...interface. A metal or silicide at the bonding interface may be advantageous fQr electrical current conduction across the interface. 10 Applications...substrate, or a silicide or metal to aid bonding and vertical electrical current conduction. In some cases, it is difficult to polish the non- single

Metal-ceramic bond strength between a feldspathic porcelain and a Co-Cr alloy fabricated with Direct Metal Laser Sintering technique

PubMed Central

Spyropoulos, Konstantinos

2018-01-01

PURPOSE The aim of the present study was to record the metal-ceramic bond strength of a feldspathic dental porcelain and a Co-Cr alloy, using the Direct Metal Laser Sintering technique (DMLS) for the fabrication of metal substrates. MATERIALS AND METHODS Ten metal substrates were fabricated with powder of a dental Co-Cr alloy using DMLS technique (test group) in dimensions according to ISO 9693. Another ten substrates were fabricated with a casing dental Co-Cr alloy using classic casting technique (control group) for comparison. Another three substrates were fabricated using each technique to record the Modulus of Elasticity (E) of the used alloys. All substrates were examined to record external and internal porosity. Feldspathic porcelain was applied on the substrates. Specimens were tested using the three-point bending test. The failure mode was determined using optical and scanning electron microscopy. The statistical analysis was performed using t-test. RESULTS Substrates prepared using DMLS technique did not show internal porosity as compared to those produced using the casting technique. The E of control and test group was 222 ± 5.13 GPa and 227 ± 3 GPa, respectively. The bond strength was 51.87 ± 7.50 MPa for test group and 54.60 ± 6.20 MPa for control group. No statistically significant differences between the two groups were recorded. The mode of failure was mainly cohesive for all specimens. CONCLUSION Specimens produced by the DMLS technique cover the lowest acceptable metal-ceramic bond strength of 25 MPa specified in ISO 9693 and present satisfactory bond strength for clinical use. PMID:29503711

Screening method for selecting semiconductor substrates having defects below a predetermined level in an oxide layer

DOEpatents

Warren, William L.; Vanheusden, Karel J. R.; Schwank, James R.; Fleetwood, Daniel M.; Shaneyfelt, Marty R.; Winokur, Peter S.; Devine, Roderick A. B.

1998-01-01

A method for screening or qualifying semiconductor substrates for integrated circuit fabrication. The method comprises the steps of annealing at least one semiconductor substrate at a first temperature in a defect-activating ambient (e.g. hydrogen, forming gas, or ammonia) for sufficient time for activating any defects within on oxide layer of the substrate; measuring a defect-revealing electrical characteristic of at least a portion of the oxide layer for determining a quantity of activated defects therein; and selecting substrates for which the quantity of activated defects is below a predetermined level. The defect-revealing electrical characteristic may be a capacitance-versus-voltage (C-V) characteristic or a current-versus-voltage (I-V) characteristic that is dependent on an electrical charge in the oxide layer generated by the activated defects. Embodiments of the present invention may be applied for screening any type of semiconductor substrate or wafer having an oxide layer formed thereon or therein. This includes silicon-on-insulator substrates formed by a separation by the implantation of oxygen (SIMOX) process or the bond and etch back silicon-on-insulator (BESOI) process, as well as silicon substrates having a thermal oxide layer or a deposited oxide layer.

Mode of VAMP Substrate Recognition and Inhibition of Clostridium botulinum Neurotoxin F

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

Agarwal, R.; Schmidt, J; Stafford, R

2009-01-01

Clostridium botulinum neurotoxins (BoNTs) cleave neuronal proteins responsible for neurotransmitter release, causing the neuroparalytic disease botulism. BoNT serotypes B, D, F and G cleave and inactivate vesicle-associated membrane protein (VAMP), each at a unique peptide bond. The specificity of BoNTs depends on the mode of substrate recognition. We have investigated the mechanism of substrate recognition of BoNT F by determining the crystal structures of its complex with two substrate-based inhibitors, VAMP 22-58/Gln58D-cysteine and 27-58/Gln58D-cysteine. The inhibitors bind to BoNT F in the canonical direction (as seen for BoNTs A and E substrates) but are positioned specifically via three major exositesmore » away from the active site. The cysteine sulfur of the inhibitors interacts with the zinc and exists as sulfinic acid in the inhibitor VAMP 27-58/Gln58D-cysteine. Arg133 and Arg171, which form part of two separate exosites, are crucial for substrate binding and catalysis.« less

Structure of the carboxypeptidase B complex with N-sulfamoyl-L-phenylalanine - a transition state analog of non-specific substrate.

PubMed

Akparov, Valery; Timofeev, Vladimir; Khaliullin, Ilyas; Švedas, Vytas; Kuranova, Inna

2018-03-01

Carboxypeptidase B (EC 3.4.17.2) (CPB) is commonly used in the industrial insulin production and as a template for drug design. However, its ability to discriminate substrates with hydrophobic, hydrophilic, and charged side chains is not well understood. We report structure of CPB complex with a transition state analog N-sulfamoyl-L-phenylalanine solved at 1.74Å. The study provided an insight into structural basis of CPB substrate specificity. Ligand binding is affected by structure-depended conformational changes of Asp255 in S1'-subsite, interactions with Asn144 and Arg145 in C-terminal binding subsite, and Glu270 in the catalytic center. Side chain of the non-specific substrate analog SPhe in comparison with that of specific substrate analog SArg (reported earlier) not only loses favorable electrostatic interactions and two hydrogen bonds with Asp255 and three fixed water molecules, but is forced to be in the unfavorable hydrophilic environment. Thus, Ser207, Gly253, Tyr248, and Asp255 residues play major role in the substrate recognition by S1'-subsite.

X-Ray Fluorescence Solvent Detection at the Substrate-Adhesive Interface

NASA Technical Reports Server (NTRS)

Wurth, Laura; Evans, Kurt; Weber, Bart; Headrick, Sarah

2005-01-01

With environmental regulations limiting the use of volatile organic compounds, low-vapor pressure solvents have replaced traditional degreasing solvents for bond substrate preparation. When used to clean and prepare porous bond substrates such as phenolic composites, low vapor pressure solvents can penetrate deep into substrate pore networks and remain there for extended periods. Trapped solvents can interact with applied adhesives either prior to or during cure, potentially compromising bond properties. Currently, methods for characterizing solvent time-depth profiles in bond substrates are limited to bulk gravimetric or sectioning techniques. While sectioning techniques such as microtome allow construction of solvent depth profiles, their depth resolution and reliability are limited by substrate type. Sectioning techniques are particularly limited near the adhesive-substrate interface where depth resolution is further limited by adhesive-substrate hardness and, in the case of a partially cured adhesive, mechanical properties differences. Additionally, sectioning techniques cannot provide information about lateral solvent diffusion. Cross-section component mapping is an alternative method for measuring solvent migration in porous substrates that eliminates the issues associated with sectioning techniques. With cross-section mapping, the solvent-wiped substrate is sectioned perpendicular rather than parallel to the wiped surface, and the sectioned surface is analyzed for the solvent or solvent components of interest using a two-dimensional mapping or imaging technique. Solvent mapping can be performed using either direct or indirect methods. With a direct method, one or more solvent components are mapped using red or Raman spectroscopy together with a moveable sample stage and/or focal plane array detector. With an indirect method, an elemental "tag" not present in the substrate is added to the solvent before the substrate is wiped. Following cross sectioning, the tag element can then be mapped by its characteristic x-ray emission using either x-ray fluorescence, or electron-beam energy-and wavelength-dispersive x-ray spectrometry. The direct mapping techniques avoid issues of different diffusion or migration rates of solvents and elemental tags, while the indirect techniques avoid spectral resolution issues in cases where solvents and substrates have adjacent or overlapping peaks. In this study, cross-section component indirect mapping is being evaluated as a method for measuring migration of d-limonene based solvents in glass-cloth phenolic composite (GCP) prior to and during subsequent bonding and epoxy adhesive cure.

Fabrication and Characterization of Diffusion Bonds for Silicon Carbide

NASA Technical Reports Server (NTRS)

Halbig, Michael; Singh, Mrityunjay; Martin, Richard E.; Cosgriff, Laura M.

2007-01-01

Diffusion bonds of silicon carbide (SiC) were fabricated using several different types of titanium (Ti) based interlayers between the SiC substrates. The interlayers were an alloyed Ti foil, a pure Ti foil, and a physically vapor deposited (PVD) Ti coating. Microscopy was conducted to evaluate the cross-sections of the resulting bonds. Microprobe analysis identified reaction formed phases in the diffusion bonded region. Uniform and well adhered bonds were formed between the SiC substrates. In the case where the alloyed Ti foil or a thick Ti coating (i.e. 20 micron) was used as the interlayer, microcracks and several phases were present in the diffusion bonds. When a thinner interlayer was used (i.e. 10 micron PVD Ti), no microcracks were observed and only two reaction formed phases were present. The two phases were preferred and fully reacted phases that did not introduce thermal stresses or microcracks during the cool-down stage after processing. Diffusion bonded samples were evaluated with the non-destructive evaluation (NDE) methods of pulsed thermography and immersion ultrasonic testing. Joined SiC substrates that were fully bonded and that had simulated bond flaws in the interlayer were also evaluated using immersion ultrasound. Pull testing was conducted on the bonds to determine the tensile strength. To demonstrate the joining approach for a complex multilayered component for a low NOx injector application, the diffusion bonding approach was used to join three 4" diameter SiC discs that contained complex fuel and air flow channels.

Low-pressure, high-temperature thermal bonding of polymeric microfluidic devices and their applications for electrophoretic separation

NASA Astrophysics Data System (ADS)

Sun, Yi; Chian Kwok, Yien; Nguyen, Nam-Trung

2006-08-01

A new method for thermally bonding poly(methyl methacrylate) (PMMA) substrates has been demonstrated. PMMA substrates are first engraved by CO2-laser micromachining to form microchannels. Both channel width and depth can be adjusted by varying the laser power and scanning speed. Channel depths from 50 µm to 1500 µm and widths from 150 µm to 400 µm are attained. CO2 laser is also used for drilling and dicing of the PMMA parts. Considering the thermal properties of PMMA, a novel thermal bonding process with high temperature and low bonding pressure has been developed for assembling PMMA sheets. A high bonding strength of 2.15 MPa is achieved. Subsequent inspection of the cross sections of several microdevices reveals that the dimensions of the channels are well preserved during the bonding process. Electroosmotic mobility of the ablated channel is measured to be 2.47 × 10-4 cm2 V-1 s-1. The functionality of these thermally bonded microfluidic substrates is demonstrated by performing rapid and high-resolution electrophoretic separations of mixture of fluorescein and carboxyfluorescein as well as double-stranded DNA ladders (ΦX174-Hae III dsDNA digest). The performance of the CO2 laser ablated and thermally bonded PMMA devices compares favorably with those fabricated by other professional means.

A Substrate-Assisted Mechanism of Nucleophile Activation in a Ser-His-Asp Containing C-C Bond Hydrolase

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

Ruzzini, Antonio C.; Bhowmik, Shiva; Ghosh, Subhangi

The meta-cleavage product (MCP) hydrolases utilize a Ser–His–Asp triad to hydrolyze a carbon–carbon bond. Hydrolysis of the MCP substrate has been proposed to proceed via an enol-to-keto tautomerization followed by a nucleophilic mechanism of catalysis. Ketonization involves an intermediate, ES red, which possesses a remarkable bathochromically shifted absorption spectrum. We investigated the catalytic mechanism of the MCP hydrolases using DxnB2 from Sphingomonas wittichii RW1. Pre-steady-state kinetic and LC ESI/MS evaluation of the DxnB2-mediated hydrolysis of 2-hydroxy-6-oxo-6-phenylhexa-2,4-dienoic acid to 2-hydroxy-2,4-pentadienoic acid and benzoate support a nucleophilic mechanism catalysis. In DxnB2, the rate of ES red decay and product formation showed amore » solvent kinetic isotope effect of 2.5, indicating that a proton transfer reaction, assigned here to substrate ketonization, limits the rate of acylation. For a series of substituted MCPs, this rate was linearly dependent on MCP pK a2 (β nuc ~ 1). Structural characterization of DxnB2 S105A:MCP complexes revealed that the catalytic histidine is displaced upon substrate-binding. The results provide evidence for enzyme-catalyzed ketonization in which the catalytic His–Asp pair does not play an essential role. The data further suggest that ES red represents a dianionic intermediate that acts as a general base to activate the serine nucleophile. This substrate-assisted mechanism of nucleophilic catalysis distinguishes MCP hydrolases from other serine hydrolases.« less

LED Die-Bonded on the Ag/Cu Substrate by a Sn-BiZn-Sn Bonding System

NASA Astrophysics Data System (ADS)

Tang, Y. K.; Hsu, Y. C.; Lin, E. J.; Hu, Y. J.; Liu, C. Y.

2016-12-01

In this study, light emitting diode (LED) chips were die-bonded on a Ag/Cu substrate by a Sn-BixZn-Sn bonding system. A high die-bonding strength is successfully achieved by using a Sn-BixZn-Sn ternary system. At the bonding interface, there is observed a Bi-segregation phenomenon. This Bi-segregation phenomenon solves the problems of the brittle layer-type Bi at the joint interface. Our shear test results show that the bonding interface with Bi-segregation enhances the shear strength of the LED die-bonding joints. The Bi-0.3Zn and Bi-0.5Zn die-bonding cases have the best shear strength among all die-bonding systems. In addition, we investigate the atomic depth profile of the deposited Bi-xZn layer by evaporating Bi-xZn E-gun alloy sources. The initial Zn content of the deposited Bi-Zn alloy layers are much higher than the average Zn content in the deposited Bi-Zn layers.

Preparation and Bond Properties of Thermal Barrier Coatings on Mg Alloy with Sprayed Al or Diffused Mg-Al Intermetallic Interlayer

NASA Astrophysics Data System (ADS)

Fan, Xizhi; Wang, Ying; Zou, Binglin; Gu, Lijian; Huang, Wenzhi; Cao, Xueqiang

2014-02-01

Sprayed Al or diffused Mg-Al layer was designed as interlayer between the thermal barrier coatings (TBCs) and Mg alloy substrate. The effects of the interlayer on the bond properties of the coats were investigated. Al layers were prepared by arc spraying and atmospheric plasma spraying (APS), respectively. Mg-Al diffused layer was obtained after the heat treatment of the sprayed sample (Mg alloy with APS Al coat) at 400 °C. The results show that sprayed Al interlayer does not improve the bond stability of TBCs. The failure of the TBCs on Mg alloy with Al interlayer occurs mainly due to the low strength of Al layer. Mg-Al diffused layer improves corrosion resistance of substrate and the bond interface. The TBCs on Mg alloy with Mg-Al diffused interlayer shows better bond stability than the sample of which the TBCs is directly sprayed on Mg alloy substrate by APS.

Enhanced bonding property of cold-sprayed Zn-Al coating on interstitial-free steel substrate with a nanostructured surface layer

NASA Astrophysics Data System (ADS)

Liang, Y. L.; Wang, Z. B.; Zhang, J.; Zhang, J. B.; Lu, K.

2016-11-01

By means of surface mechanical attrition treatment (SMAT), a gradient nanostructured surface layer was fabricated on a hot-rolled interstitial-free steel plate. A Zn-Al coating was subsequently deposited on the SMAT sample by using cold spray process. The bonding property of the coating on the SMAT substrate was compared with that on the coarse-grained (CG) sample. Stud-pull tests showed that the bonding strength in the as-sprayed SMAT sample is ∼30% higher than that in the as-sprayed CG sample. No further improvement in bonding strength was achieved in the coated SMAT sample after annealing at 400 °C, mostly due to the formation of cracks and intermetallic compounds at the coating/substrate interface in an earlier stage (<30 min) and in a final stage (>90 min), respectively. The enhanced bonding property of the Zn-Al coating on the SMAT sample might be related with the promoted atomic diffusion and hardness in the nanostructured surface layer.

Thioredoxin-1 actively maintains the pseudokinase MLKL in a reduced state to suppress disulfide bond-dependent MLKL polymer formation and necroptosis.

PubMed

Reynoso, Eduardo; Liu, Hua; Li, Lin; Yuan, Anthony L; Chen, She; Wang, Zhigao

2017-10-20

Necroptosis is an immunogenic cell death program that is associated with a host of human diseases, including inflammation, infections, and cancer. Receptor-interacting protein kinase 3 (RIPK3) and its substrate mixed lineage kinase domain-like protein (MLKL) are required for necroptosis activation. Specifically, RIPK3-dependent MLKL phosphorylation promotes the assembly of disulfide bond-dependent MLKL polymers that drive the execution of necroptosis. However, how MLKL disulfide bond formation is regulated is not clear. In this study we discovered that the MLKL-modifying compound necrosulfonamide cross-links cysteine 86 of human MLKL to cysteine 32 of the thiol oxidoreductase thioredoxin-1 (Trx1). Recombinant Trx1 preferentially binds to monomeric MLKL and blocks MLKL disulfide bond formation and polymerization in vitro Inhibition of MLKL polymer formation requires the reducing activity of Trx1. Importantly, shRNA-mediated knockdown of Trx1 promotes MLKL polymerization and sensitizes cells to necroptosis. Furthermore, pharmacological inhibition of Trx1 with compound PX-12 induces necroptosis in multiple cancer cell lines. Altogether, these findings demonstrate that Trx1 is a critical regulator of necroptosis that suppresses cell death by maintaining MLKL in a reduced inactive state. Our results further suggest new directions for targeted cancer therapy in which thioredoxin inhibitors like PX-12 could potentially be used to specifically target cancers expressing high levels of MLKL or MLKL short isoforms. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Enormous Hydrogen Bond Strength Enhancement through π-Conjugation Gain: Implications for Enzyme Catalysis.

PubMed

Wu, Chia-Hua; Ito, Keigo; Buytendyk, Allyson M; Bowen, K H; Wu, Judy I

2017-08-22

Surprisingly large resonance-assistance effects may explain how some enzymes form extremely short, strong hydrogen bonds to stabilize reactive oxyanion intermediates and facilitate catalysis. Computational models for several enzymic residue-substrate interactions reveal that when a π-conjugated, hydrogen bond donor (XH) forms a hydrogen bond to a charged substrate (Y - ), XH can become significantly more π-electron delocalized, and this "extra" stabilization may boost the [XH···Y - ] hydrogen bond strength by ≥15 kcal/mol. This reciprocal relationship departs from the widespread pK a concept (i.e., the idea that short, strong hydrogen bonds form when the interacting moieties have matching pK a values), which has been the rationale for enzymic acid-base reactions. The findings presented here provide new insight into how short, strong hydrogen bonds could form in enzymes.

Medical implants and methods of making medical implants

DOEpatents

Shaw, Wendy J; Yonker, Clement R; Fulton, John L; Tarasevich, Barbara J; McClain, James B; Taylor, Doug

2014-09-16

A medical implant device having a substrate with an oxidized surface and a silane derivative coating covalently bonded to the oxidized surface. A bioactive agent is covalently bonded to the silane derivative coating. An implantable stent device including a stent core having an oxidized surface with a layer of silane derivative covalently bonded thereto. A spacer layer comprising polyethylene glycol (PEG) is covalently bonded to the layer of silane derivative and a protein is covalently bonded to the PEG. A method of making a medical implant device including providing a substrate having a surface, oxidizing the surface and reacting with derivitized silane to form a silane coating covalently bonded to the surface. A bioactive agent is then covalently bonded to the silane coating. In particular instances, an additional coating of bio-absorbable polymer and/or pharmaceutical agent is deposited over the bioactive agent.

Regulation of Proteolysis by Human Deubiquitinating Enzymes

PubMed Central

Eletr, Ziad M.; Wilkinson, Keith D.

2013-01-01

The post-translational attachment of one or several ubiquitin molecules to a protein generates a variety of targeting signals that are used in many different ways in the cell. Ubiquitination can alter the activity, localization, protein-protein interactions or stability of the targeted protein. Further, a very large number of proteins are subject to regulation by ubiquitin-dependent processes, meaning that virtually all cellular functions are impacted by these pathways. Nearly a hundred enzymes from five different gene families (the deubiquitinating enzymes or DUBs), reverse this modification by hydrolyzing the (iso)peptide bond tethering ubiquitin to itself or the target protein. Four of these families are thiol proteases and one is a metalloprotease. DUBs of the Ubiquitin C-terminal Hydrolase (UCH) family act on small molecule adducts of ubiquitin, process the ubiquitin proprotein, and trim ubiquitin from the distal end of a polyubiquitin chain. Ubiquitin Specific Proteases (USP) tend to recognize and encounter their substrates by interaction of the variable regions of their sequence with the substrate protein directly, or with scaffolds or substrate adapters in multiprotein complexes. Ovarian Tumor (OTU) domain DUBs show remarkable specificity for different Ub chain linkages and may have evolved to recognize substrates on the basis of those linkages. The Josephin family of DUBs may specialize in distinguishing between polyubiquitin chains of different lengths. Finally, the JAB1/MPN+/MOV34 (JAMM) domain metalloproteases cleave the isopeptide bond near the attachment point of polyubiquitin and substrate, as well as being highly specific for the K63 poly-Ub linkage. These DUBs regulate proteolysis by: directly interacting with and co-regulating E3 ligases; altering the level of substrate ubiquitination; hydrolyzing or remodeling ubiquitinated and poly-ubiquitinated substrates; acting in specific locations in the cell and altering the localization of the target protein; and acting on proteasome bound substrates to facilitate or inhibit proteolysis. Thus, the scope and regulation of the ubiquitin pathway is very similar to that of phosphorylation, with the DUBs serving the same functions as the phosphatase. PMID:23845989

Glutamic Acid Selective Chemical Cleavage of Peptide Bonds.

PubMed

Nalbone, Joseph M; Lahankar, Neelam; Buissereth, Lyssa; Raj, Monika

2016-03-04

Site-specific hydrolysis of peptide bonds at glutamic acid under neutral aqueous conditions is reported. The method relies on the activation of the backbone amide chain at glutamic acid by the formation of a pyroglutamyl (pGlu) imide moiety. This activation increases the susceptibility of a peptide bond toward hydrolysis. The method is highly specific and demonstrates broad substrate scope including cleavage of various bioactive peptides with unnatural amino acid residues, which are unsuitable substrates for enzymatic hydrolysis.

Testing Bonds Between Brittle And Ductile Films

NASA Technical Reports Server (NTRS)

Wheeler, Donald R.; Ohsaki, Hiroyuki

1989-01-01

Simple uniaxial strain test devised to measure intrinsic shear strength. Brittle film deposited on ductile stubstrate film, and combination stretched until brittle film cracks, then separates from substrate. Dimensions of cracked segments related in known way to tensile strength of brittle film and shear strength of bond between two films. Despite approximations and limitations of technique, tests show it yields semiquantitative measures of bond strengths, independent of mechanical properties of substrates, with results reproducible with plus or minus 6 percent.

Pre-patterned ZnO nanoribbons on soft substrates for stretchable energy harvesting applications

NASA Astrophysics Data System (ADS)

Ma, Teng; Wang, Yong; Tang, Rui; Yu, Hongyu; Jiang, Hanqing

2013-05-01

Three pre-patterned ZnO nanoribbons in different configurations were studied in this paper, including (a) straight ZnO nanoribbons uniformly bonded on soft substrates that form sinusoidal buckles, (b) straight ZnO nanoribbons selectively bonded on soft substrates that form pop-up buckles, and (c) serpentine ZnO nanoribbons bonded on soft substrates via anchors. The nonlinear dynamics and random analysis were conducted to obtain the fundamental frequencies and to evaluate their performance in energy harvesting applications. We found that pop-up buckles and overhanging serpentine structures are suitable for audio frequency energy harvesting applications. Remarkably, almost unchanged fundamental natural frequency upon strain is achieved by properly patterning ZnO nanoribbons, which initiates a new and exciting direction of stretchable energy harvesting using nano-scale materials in audio frequency range.

Integration of a Graphite/PMMA CompositeElectrode into a Poly(methyl methacrylate) (PMMA) Substrate for Electrochemical Detection in Microchips

PubMed Central

Regel, Anne; Lunte, Susan

2013-01-01

Traditional fabrication methods for polymer microchips, the bonding of two substrates together to form the microchip, can make the integration of carbon electrodes difficult. We have developed a simple and inexpensive method to integrate graphite/PMMA composite electrodes (GPCEs) into a PMMA substrate. These substrates can be bonded to other PMMA layers using a solvent-assisted thermal bonding method. The optimal composition of the GPCEs for electrochemical detection was determined using cyclic voltammetry with dopamine as a test analyte. Using the optimized GPCEs in an all-PMMA flow cell with flow injection analysis, it was possible to detect 50 nM dopamine under the best conditions. These electrodes were also evaluated for the detection of dopamine and catechol following separation by microchip electrophoresis (ME). PMID:23670816

Chip packaging technique

NASA Technical Reports Server (NTRS)

Jayaraj, Kumaraswamy (Inventor); Noll, Thomas E. (Inventor); Lockwood, Harry F. (Inventor)

2001-01-01

A hermetically sealed package for at least one semiconductor chip is provided which is formed of a substrate having electrical interconnects thereon to which the semiconductor chips are selectively bonded, and a lid which preferably functions as a heat sink, with a hermetic seal being formed around the chips between the substrate and the heat sink. The substrate is either formed of or includes a layer of a thermoplastic material having low moisture permeability which material is preferably a liquid crystal polymer (LCP) and is a multiaxially oriented LCP material for preferred embodiments. Where the lid is a heat sink, the heat sink is formed of a material having high thermal conductivity and preferably a coefficient of thermal expansion which substantially matches that of the chip. A hermetic bond is formed between the side of each chip opposite that connected to the substrate and the heat sink. The thermal bond between the substrate and the lid/heat sink may be a pinched seal or may be provided, for example by an LCP frame which is hermetically bonded or sealed on one side to the substrate and on the other side to the lid/heat sink. The chips may operate in the RF or microwave bands with suitable interconnects on the substrate and the chips may also include optical components with optical fibers being sealed into the substrate and aligned with corresponding optical components to transmit light in at least one direction. A plurality of packages may be physically and electrically connected together in a stack to form a 3D array.

Influence of Substrate Bonding and Surface Morphology on Dynamic Organic Layer Growth: Perylenetetracarboxylic Dianhydride on Au(111).

PubMed

Schmidt, Thomas; Marchetto, Helder; Groh, Ullrich; Fink, Rainer H; Freund, Hans-Joachim; Umbach, Eberhard

2018-05-15

We investigated the dynamics of the initial growth of the first epitaxial layers of perylenetetracarboxylic dianhydride (PTCDA) on the Au(111) surface with high lateral resolution using the aberration-corrected spectro-microscope SMART. With this instrument, we could simultaneously study the different adsorption behaviors and layer growth on various surface areas consisting of either a distribution of flat (111) terraces, separated by single atomic steps ("ideal surface"), or on areas with a high density of step bunches and defects ("realistic surface"). The combined use of photoemission electron microscopy, low-energy electron microscopy, and μ-spot X-ray absorption provided a wealth of new information, showing that the growth of the archetype molecule PTCDA not only has similarities but also has significant differences when comparing Au(111) and Ag(111) substrate surfaces. For instance, under otherwise identical preparation conditions, we observed different growth mechanisms on different surface regions, depending on the density of step bunches. In addition, we studied the spatially resolved desorption behavior which also depends on the substrate morphology.

Insights into the Phosphoryl Transfer Catalyzed by cAMP-Dependent Protein Kinase: An X-ray Crystallographic Study of Complexes with Various Metals and Peptide Substrate SP20

PubMed Central

2013-01-01

X-ray structures of several ternary substrate and product complexes of the catalytic subunit of cAMP-dependent protein kinase (PKAc) have been determined with different bound metal ions. In the PKAc complexes, Mg2+, Ca2+, Sr2+, and Ba2+ metal ions could bind to the active site and facilitate the phosphoryl transfer reaction. ATP and a substrate peptide (SP20) were modified, and the reaction products ADP and the phosphorylated peptide were found trapped in the enzyme active site. Finally, we determined the structure of a pseudo-Michaelis complex containing Mg2+, nonhydrolyzable AMP-PCP (β,γ-methyleneadenosine 5′-triphosphate) and SP20. The product structures together with the pseudo-Michaelis complex provide snapshots of different stages of the phosphorylation reaction. Comparison of these structures reveals conformational, coordination, and hydrogen bonding changes that might occur during the reaction and shed new light on its mechanism, roles of metals, and active site residues. PMID:23672593

Deciphering the chemoselectivity of nickel-dependent quercetin 2,4-dioxygenase.

PubMed

Wang, Wen-Juan; Wei, Wen-Jie; Liao, Rong-Zhen

2018-06-13

The reaction mechanism and chemoselectivity of nickel-dependent quercetin 2,4-dioxygenase (2,4-QueD) have been investigated using the QM/MM approach. The protonation state of the Glu74 residue, a first-shell ligand of Ni, has been considered to be either neutral or deprotonated. QM/MM calculations predict that Glu74 must be deprotonated to rationalize the chemoselectivity and steer the 2,4-dioxygenolytic cleavage of quercetin, which harvests the experimentally-observed product, 2-protocatechuoylphloroglucinol carboxylic acid, coupled with the release of carbon monoxide. If the enzyme has a neutral Glu74 residue, the undesired 2,3-dioxygenolytic cleavage of quercetin becomes the dominant pathway, leading to the formation of α-keto acid. The calculations suggest that the reaction takes place via three major steps: (1) attack of the superoxide on the C2 of the substrate pyrone ring to generate a NiII-peroxide intermediate; (2) formation of the second C-O bond between C4 and the peroxide to produce a peroxide bridge; (3) simultaneous cleavage of the C2-C3, C3-C4, and O1-O2 bonds with the formation of 2-protocatechuoylphloroglucinol carboxylic acid and carbon monoxide. The third step was found to be rate-limiting, with a barrier of 17.4 kcal mol-1, which is in very good agreement with the experimental kinetic data. For the second C-O bond formation, an alternative pathway is that the peroxide attacks the C3 of the substrate pyrone ring, leading to the formation of a four-membered ring intermediate, which then undergoes concerted C2-C3 and O1-O2 bond cleavages to produce an α-keto acid. This pathway is associated with a barrier of 30.6 kcal mol-1, which is much higher than the major pathway. When Glu74 is protonated, the 2,3-dioxygenolytic pathway, however, has a lower barrier (21.8 kcal mol-1) than the 2,4-dioxygenolytic pathway.

Bonding performance of universal adhesives to er,cr:YSGG laser-irradiated enamel.

PubMed

Ayar, Muhammet Kerim; Erdemir, Fatih

2017-04-01

Universal adhesives have been recently introduced for use as self-etch or etch-and-rinse adhesives depending on the dental substrate and clinical condition. However, their bonding effectiveness to laser-irradiated enamel is still not well-known. Thus, the aim of this study was to compare the shear bond strength (SBS) of universal adhesives (Single Bond Universal; Nova Compo-B Plus) applied to Er,Cr:YSGG laser-irradiated enamel with SBS of the same adhesives applied in self-etch and acid-etching modes, respectively. Crown segments of sixty bovine incisors were embedded into standardized acrylic blocks. Flattened enamel surfaces were prepared. Specimens were divided into six groups according to universal adhesives and application modes randomly (n = 10), as follows: Single Bond Universal/acid-etching mode; Nova Compo-B Plus/acid-etching mode; Single Bond Universal/self-etching mode; Nova Compo-B Plus/self-etching mode; and Single Bond Universal/Er,Cr:YSGG Laser-etching mode; Nova Compo-B Plus/Er,Cr:YSGG Laser-etching mode. After surface treatments, universal adhesives were applied onto surfaces. SBS was determined after storage in water for 24 h using a universal testing machine with a crosshead speed of 0.5 mm min -1 . Failure modes were evaluated using a stereomicroscope. Data was analyzed using two-way of analyses of variances (ANOVA) (p = 0.05). Two-way ANOVA revealed that adhesive had no effect on SBS (p = 0.88), but application mode significantly influenced SBS (p = 0.00). Acid-etching significantly increased SBS, whereas there are no significant differences between self-etch mode and laser-etching for both adhesives. The bond strength of universal adhesives may depend on application mode. Acid etching may significantly increase bond strength, while laser etching may provide similar bond strength when compared to self-etch mode. © 2016 Wiley Periodicals, Inc.

Method of bonding functional surface materials to substrates and applications in microtechnology and anti-fouling

DOEpatents

Feng, Xiangdong; Liu, Jun; Liang, Liang

2001-01-01

A simple and effective method to bond a thin coating of poly(N-isopropylacylamide) (NIPAAm) on a glass surface by UV photopolymerization, and the use of such a coated surface in nano and micro technology applications. A silane coupling agent with a dithiocarbamate group is provided as a photosensitizer preferably, (N,N'-diethylamine) dithiocarbamoylpropyl-(trimethoxy) silane (DATMS). The thiocarbamate group of the sensitizer is then bonded to the glass surface by coupling the silane agent with the hydroxyl groups on the glass surface. The modified surface is then exposed to a solution of NIPAAm and a crosslinking agent which may be any organic molecule having an acrylamide group and at least two double bonds in its structure, such as N, N'-methylenebisacrylamide, and a polar solvent which may be any polar liquid which will dissolve the monomer and the crosslinking agent such as acetone, water, ethanol, or combinations thereof. By exposing the glass surface to a UV light, free radicals are generated in the thiocarbamate group which then bonds to the crosslinking agent and the NIPAAm. Upon bonding, the crosslinking agent and the NIPAAm polymerize to form a thin coating of PNIPAAm bonded to the glass. Depending upon the particular configuration of the glass, the properties of the PNIPAAm allow applications in micro and nano technology.

Method of bonding functional surface materials to substrates and applications in microtechnology and antifouling

DOEpatents

Feng, Xiangdong; Liu, Jun; Liang, Liang

1999-01-01

A simple and effective method to bond a thin coating of poly(N-isopropylacylamide) (NIPAAm) on a glass surface by UV photopolymerization, and the use of such a coated surface in nano and micro technology applications. A silane coupling agent with a dithiocarbamate group is provided as a photosensitizer, preferably, (N,N'-diethylamine)dithiocarbamoylpropyl-(trimethoxy)silane (DATMS). The thiocarbamate group of the sensitizer is then bonded to the glass surface by coupling the silane agent with the hydroxyl groups on the glass surface. The modified surface is then exposed to a solution of NIPAAm and a crosslinking agent which may be any organic molecule having an acrylamide group and at least two double bonds in its structure, such as N,N'-methylenebisacrylamide, and a polar solvent which may be any polar liquid which will dissolve the monomer and the crosslinking agent such as acetone, water, ethanol, or combinations thereof. By exposing the glass surface to a UV light, free radicals are generated in the thiocarbamate group which then bonds to the crosslinking agent and the NIPAAm. Upon bonding, the crosslinking agent and the NIPAAm polymerize to form a thin coating of PNIPAAm bonded to the glass. Depending upon the particular configuration of the glass, the properties of the PNIPAAm allow applications in micro and nano technology.

Geometric Restraint Drives On- and Off-pathway Catalysis by the Escherichia coli Menaquinol:Fumarate Reductase*

PubMed Central

Tomasiak, Thomas M.; Archuleta, Tara L.; Andréll, Juni; Luna-Chávez, César; Davis, Tyler A.; Sarwar, Maruf; Ham, Amy J.; McDonald, W. Hayes; Yankovskaya, Victoria; Stern, Harry A.; Johnston, Jeffrey N.; Maklashina, Elena; Cecchini, Gary; Iverson, Tina M.

2011-01-01

Complex II superfamily members catalyze the kinetically difficult interconversion of succinate and fumarate. Due to the relative simplicity of complex II substrates and their similarity to other biologically abundant small molecules, substrate specificity presents a challenge in this system. In order to identify determinants for on-pathway catalysis, off-pathway catalysis, and enzyme inhibition, crystal structures of Escherichia coli menaquinol:fumarate reductase (QFR), a complex II superfamily member, were determined bound to the substrate, fumarate, and the inhibitors oxaloacetate, glutarate, and 3-nitropropionate. Optical difference spectroscopy and computational modeling support a model where QFR twists the dicarboxylate, activating it for catalysis. Orientation of the C2–C3 double bond of activated fumarate parallel to the C(4a)–N5 bond of FAD allows orbital overlap between the substrate and the cofactor, priming the substrate for nucleophilic attack. Off-pathway catalysis, such as the conversion of malate to oxaloacetate or the activation of the toxin 3-nitropropionate may occur when inhibitors bind with a similarly activated bond in the same position. Conversely, inhibitors that do not orient an activatable bond in this manner, such as glutarate and citrate, are excluded from catalysis and act as inhibitors of substrate binding. These results support a model where electronic interactions via geometric constraint and orbital steering underlie catalysis by QFR. PMID:21098488

Critical Amino Acids in the Active Site of Meprin Metalloproteinases for Substrate and Peptide Bond Specificity*

PubMed Central

Villa, James P.; Bertenshaw, Greg P.; Bond, Judith S.

2008-01-01

SUMMARY The protease domains of the evolutionarily-related α and ß subunits of meprin metalloproteases are approximately 55% identical at the amino acid level, however, their substrate and peptide bond specificities differ markedly. The meprin ß subunit favors acidic residues proximal to the scissile bond, while the α subunit prefers small or aromatic amino acids flanking the scissile bond. Thus gastrin, a peptide that contains a string of five Glu residues, is an excellent substrate for meprin ß while it is not hydrolyzed by meprin α. Work herein aimed to identify critical amino acids in the meprin active sites that determine the substrate specificity differences. Sequence alignments and homology models, based on the crystal structure of the crayfish astacin, showed electrostatic differences within the meprin active sites. Site-directed mutagenesis of active site residues demonstrated that replacement of a hydrophobic residue by a basic amino acid enabled the meprin α protease to cleave gastrin. The meprin αY199K mutant was most effective; the corresponding mutation of meprin ßK185Y resulted in decreased activity toward gastrin. Peptide cleavage site determinations and kinetic analyses using a variety of peptides extended evidence that meprin αTyr199/ßLys185 are substrate specificity determinants in meprin active sites. These studies shed light on the molecular basis for the substrate specificity differences of astacin metalloproteinases. PMID:12888571

Geometric Restraint Drives On- and Off-pathway Catalysis by the Escherichia coli Menaquinol:Fumarate Reductase

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

Tomasiak, Thomas M.; Archuleta, Tara L.; Andréll, Juni

2012-01-05

Complex II superfamily members catalyze the kinetically difficult interconversion of succinate and fumarate. Due to the relative simplicity of complex II substrates and their similarity to other biologically abundant small molecules, substrate specificity presents a challenge in this system. In order to identify determinants for on-pathway catalysis, off-pathway catalysis, and enzyme inhibition, crystal structures of Escherichia coli menaquinol:fumarate reductase (QFR), a complex II superfamily member, were determined bound to the substrate, fumarate, and the inhibitors oxaloacetate, glutarate, and 3-nitropropionate. Optical difference spectroscopy and computational modeling support a model where QFR twists the dicarboxylate, activating it for catalysis. Orientation of themore » C2-C3 double bond of activated fumarate parallel to the C(4a)-N5 bond of FAD allows orbital overlap between the substrate and the cofactor, priming the substrate for nucleophilic attack. Off-pathway catalysis, such as the conversion of malate to oxaloacetate or the activation of the toxin 3-nitropropionate may occur when inhibitors bind with a similarly activated bond in the same position. Conversely, inhibitors that do not orient an activatable bond in this manner, such as glutarate and citrate, are excluded from catalysis and act as inhibitors of substrate binding. These results support a model where electronic interactions via geometric constraint and orbital steering underlie catalysis by QFR.« less

Laser-Direct Writing of Silver Metal Electrodes on Transparent Flexible Substrates with High-Bonding Strength.

PubMed

Zhou, Weiping; Bai, Shi; Ma, Ying; Ma, Delong; Hou, Tingxiu; Shi, Xiaomin; Hu, Anming

2016-09-21

We demonstrate a novel approach to rapidly fabricate conductive silver electrodes on transparent flexible substrates with high-bonding strength by laser-direct writing. A new type of silver ink composed of silver nitrate, sodium citrate, and polyvinylpyrrolidone (PVP) was prepared in this work. The role of PVP was elucidated for improving the quality of silver electrodes. Silver nanoparticles and sintered microstructures were simultaneously synthesized and patterned on a substrate using a focused 405 nm continuous wave laser. The writing was completed through the transparent flexible substrate with a programmed 2D scanning sample stage. Silver electrodes fabricated by this approach exhibit a remarkable bonding strength, which can withstand an adhesive tape test at least 50 times. After a 1500 time bending test, the resistance only increased 5.2%. With laser-induced in-situ synthesis, sintering, and simultaneous patterning of silver nanoparticles, this technology is promising for the facile fabrication of conducting electronic devices on flexible substrates.

Enhancement of low pressure cold sprayed copper coating adhesion by laser texturing on aluminum substrates

NASA Astrophysics Data System (ADS)

Knapp, Wolfgang; Gillet, Vincent; Courant, Bruno; Aubignat, Emilie; Costil, Sophie; Langlade, Cécile

2017-02-01

Surface pre-treatment is fundamental in thermal spraying processes to obtain a sufficient bonding strength between substrate and coating. Different pre-treatments can be used, mostly grit-blasting for current industrial applications. This study is focused on Cu-Al2O3 coatings obtained by Low Pressure Cold Spray on AW5083 aluminum alloy substrate. Bonding strength is measured by tensile adhesion test, while deposition efficiency is measured. Substrates are textured by laser, using a pattern of equally spaced grooves with almost constant diameter and variations of depth. Results show that bonding strength is improved up to +81% compared to non-treated substrate, while deposition efficiency remains constant. The study of the samples after rupture reveals a modification of the failure mode, from mixed failure to cohesive failure. A modification of crack propagation is also noticed, the shape of laser textured grooves induces a deviation of cracks inside the coating instead of following the interface between the layers.

Breather cloth for vacuum curing

NASA Technical Reports Server (NTRS)

Reed, M. W.

1979-01-01

Finely-woven nylon cloth that has been treated with Teflon improves vacuum adhesive bonding of coatings to substrates. Cloth is placed over coating; entire assembly, including substrate, coating, and cloth, is placed in plastic vacuum bag for curing. Cloth allows coating to "breathe" when bag is evacuated. Applications include bonding film coatings to solar concentrators and collectors.

Low-Melt Poly(Amic Acids) and Polyimides and Their Uses

NASA Technical Reports Server (NTRS)

Parrish, Clyde F. (Inventor); Jolley, Scott T. (Inventor); Gibson, Tracy L. (Inventor); Snyder, Sarah J. (Inventor); Williams, Martha K. (Inventor)

2016-01-01

Provided are low-melt polyimides and poly(amic acids) (PAAs) for use as adhesives, and methods of using the materials for attaching two substrates. The methods typically form an adhesive bond that is hermetically sealed to both substrates. Additionally, the method typically forms a cross-linked bonding material that is flexible.

Process for protecting bonded components from plating shorts

DOEpatents

Tarte, Lisa A.; Bonde, Wayne L.; Carey, Paul G.; Contolini, Robert J.; McCarthy, Anthony M.

2000-01-01

A method which protects the region between a component and the substrate onto which the components is bonded using an electrically insulating fillet of photoresist. The fillet protects the regions from subsequent plating with metal and therefore shorting the plated conductors which run down the sides of the component and onto the substrate.

Improved Interfacial Bonding in Magnesium/Aluminum Overcasting Systems by Aluminum Surface Treatments

NASA Astrophysics Data System (ADS)

Zhang, Hui; Chen, Yiqing; Luo, Alan A.

2014-12-01

"Overcasting" technique is used to produce bimetallic magnesium/aluminum (Mg/Al) structures where lightweight Mg can be cast onto solid Al substrates. An inherent difficulty in creating strong Mg/Al interfacial bonding is the natural oxide film on the solid Al surfaces, which reduces the wettability between molten Mg and Al substrates during the casting process. In the paper, an "electropolishing + anodizing" surface treatment has been developed to disrupt the oxide film on a dilute Al-0.08 wt pct Ga alloy, improving the metallurgical bonding between molten Mg and Al substrates in the bimetallic experiments carried out in a high-vacuum test apparatus. The test results provided valuable information of the interfacial phenomena of the Mg/Al bimetallic samples. The results show significantly improved metallurgical bonding in the bimetallic samples with "electropolishing + anodizing" surface treatment and Ga alloying. It is recommended to adjust the pre-heating temperature and time of the Al substrates and the Mg melt temperature to control the interfacial reactions for optimum interfacial properties in the actual overcasting processes.

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.

Algicidal Activity of a Surface-Bonded Organosilicon Quaternary Ammonium Chloride

PubMed Central

Walters, P. A.; Abbott, E. A.; Isquith, A. J.

1973-01-01

The hydrolysis product of a quaternary amine-containing organosilicon salt, 3-(trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride, was found to exhibit algicidal activity while chemically bonded to a variety of substrates. Six representative species of Chlorophyta, Cyanophyta, and Chrysophyta were used to evaluate the algicidal activity. Substrate-bonded 14C-labeled organosilicon quaternary ammonium salt when attached to nonwoven fibers was durable to repeated washings, and algicidal activity could not be attributed to slow release of the chemical. Images PMID:4632852

Identification and cloning of an NADPH-dependent hydroxycinnamoyl-CoA double bond reductase involved in dihydrochalcone formation in Malus×domestica Borkh.

PubMed

Ibdah, Mwafaq; Berim, Anna; Martens, Stefan; Valderrama, Andrea Lorena Herrera; Palmieri, Luisa; Lewinsohn, Efraim; Gang, David R

2014-11-01

The apple tree (Malus sp.) is an agriculturally and economically important source of food and beverages. Many of the health beneficial properties of apples are due to (poly)phenolic metabolites that they contain, including various dihydrochalcones. Although many of the genes and enzymes involved in polyphenol biosynthesis are known in many plant species, the specific reactions that lead to the biosynthesis of the dihydrochalcone precursor, p-dihydrocoumaroyl-CoA (3), are unknown. To identify genes involved in the synthesis of these metabolites, existing genome databases of the Rosaceae were screened for apple genes with significant sequence similarity to Arabidopsis alkenal double bond reductases. Herein described are the isolation and characterization of a Malus hydroxycinnamoyl-CoA double bond reductase, which catalyzed the NADPH-dependent reduction of p-coumaroyl-CoA and feruloyl-CoA to p-dihydrocoumaroyl-CoA and dihydroferuloyl-CoA, respectively. Its apparent Km values for p-coumaroyl-CoA, feruloyl-CoA and NADPH were 96.6, 92.9 and 101.3μM, respectively. The Malus double bond reductase preferred feruloyl-CoA to p-coumaroyl-CoA as a substrate by a factor of 2.1 when comparing catalytic efficiencies in vitro. Expression analysis of the hydroxycinnamoyl-CoA double bond reductase gene revealed that its transcript levels showed significant variation in tissues of different developmental stages, but was expressed when expected for involvement in dihydrochalcone formation. Thus, the hydroxycinnamoyl-CoA double bond reductase appears to be responsible for the reduction of the α,β-unsaturated double bond of p-coumaroyl-CoA, the first step of dihydrochalcone biosynthesis in apple tissues, and may be involved in the production of these compounds. Copyright © 2014 Elsevier Ltd. All rights reserved.

Fabrication of silicon-on-diamond substrate with an ultrathin SiO2 bonding layer

NASA Astrophysics Data System (ADS)

Nagata, Masahiro; Shirahama, Ryouya; Duangchan, Sethavut; Baba, Akiyoshi

2018-06-01

We proposed and demonstrated a sputter etching method to prepare both a flat surface (root-mean-square surface roughness of approximately 0.2–0.3 nm) and an ultrathin SiO2 bonding layer at an accuracy of approximately 5 nm in thickness to fabricate a silicon-on-diamond substrate (SOD). We also investigated a plasma activation method on a SiO2 surface using various gases. We found that O2 plasma activation is more suitable for the bonding between SiO2 and Si than N2 or Ar plasma activation. We speculate that the concentration of hydroxyl groups on the SiO2 surface was increased by O2 plasma activation. We fabricated the SOD substrate with an ultrathin (15 nm in thickness) SiO2 bonding layer using the sputter etching and O2 plasma activation methods.

Low thermal resistance power module assembly

DOEpatents

Hassani, Vahab; Vlahinos, Andreas; Bharathan, Desikan

2007-03-13

A power module assembly with low thermal resistance and enhanced heat dissipation to a cooling medium. The assembly includes a heat sink or spreader plate with passageways or openings for coolant that extend through the plate from a lower surface to an upper surface. A circuit substrate is provided and positioned on the spreader plate to cover the coolant passageways. The circuit substrate includes a bonding layer configured to extend about the periphery of each of the coolant passageways and is made up of a substantially nonporous material. The bonding layer may be solder material which bonds to the upper surface of the plate to provide a continuous seal around the upper edge of each opening in the plate. The assembly includes power modules mounted on the circuit substrate on a surface opposite the bonding layer. The power modules are positioned over or proximal to the coolant passageways.

A thin porous substrate using bonded particles for reverse-emulsion electrophoretic displays

NASA Astrophysics Data System (ADS)

Ahumada, M.; Bryning, M.; Cromer, R.; Hartono, M.; Lee, S. J.

2012-03-01

A thin porous layer of bonded ceramic microparticles has been developed to provide structural integrity and a stationary matrix for use in reflective-mode reverse-emulsion electrophoretic displays (REED), based on self-assembled nanodroplets dispersed in a non-polar liquid. REED ink uses low-cost materials and manufacturing processes, yet is capable of video speed and low voltage operation below 10 V. Porous layers of titanium dioxide (TiO2) are prepared as thin as 10 microns by fluidizing the particles in a water-based slurry with polymeric adhesive. The slurry is distributed between glass shear plates, one of which serves as the substrate for the working device. Particle morphology is examined using scanning electron microscopy and layer uniformity is characterized by opacity measurements using a throughbeam fiber optic sensor. Performance of the bonded matrix with REED ink is compared to baseline performance of a paste mixture, comprised of the same ink and unbonded TiO2 particles. Results show that at 25% volume fraction, the bonded substrate improves image bistability and is better able to maintain both light and dark intensity after extensive switching. The same bonded substrate also improves image bistability when power is disconnected, even compared to a paste with 40% volume fraction of TiO2.

Flip-chip bonded optoelectronic integration based on ultrathin silicon (UTSi) CMOS

NASA Astrophysics Data System (ADS)

Hong, Sunkwang; Ho, Tawei; Zhang, Liping; Sawchuk, Alexander A.

2003-06-01

We describe the design and test of flip-chip bonded optoelectronic CMOS devices based on Peregrine Semiconductor's 0.5 micron Ultra-Thin Silicon on sapphire (UTSi) technology. The UTSi process eliminates the substrate leakage that typically results in crosstalk and reduces parasitic capacitance to the substrate, providing many benefits compared to bulk silicon CMOS. The low-loss synthetic sapphire substrate is optically transparent and has a coefficient of thermal expansion suitable for flip-chip bonding of vertical cavity surface emitting lasers (VCSELs) and detectors. We have designed two different UTSi CMOS chips. One contains a flip-chip bonded 1 x 4 photodiode array, a receiver array, a double edge triggered D-flip flop-based 2047-pattern pseudo random bit stream (PRBS) generator and a quadrature-phase LC-voltage controlled oscillator (VCO). The other chip contains a flip-chip bonded 1 x 4 VCSEL array, a driver array based on high-speed low-voltage differential signals (LVDS) and a full-balanced differential LC-VCO. Each VCSEL driver and receiver has individual input and bias voltage adjustments. Each UTSi chip is mounted on different printed circuit boards (PCBs) which have holes with about 1 mm radius for optical output and input paths through the sapphire substrate. We discuss preliminary testing of these chips.

Surface electronic states of low-temperature H-plasma-exposed Ge(100)

NASA Astrophysics Data System (ADS)

Cho, Jaewon; Nemanich, R. J.

1992-11-01

The surface of low-temperature H-plasma-cleaned Ge(100) was studied by angle-resolved UV-photoemission spectroscopy and low-energy electron diffraction (LEED). The surface was prepared by an ex situ preclean followed by an in situ H-plasma exposure at a substrate temperature of 150-300 °C. Auger-electron spectroscopy indicated that the in situ H-plasma clean removed the surface contaminants (carbon and oxygen) from the Ge(100) surface. The LEED pattern varied from a 1×1 to a sharp 2×1, as the substrate temperature was increased. The H-induced surface state was identified at ~5.6 eV below EF, which was believed to be mainly due to the ordered or disordered monohydride phases. The annealing dependence of the spectra showed that the hydride started to dissociate at a temperature of 190 °C, and the dangling-bond surface state was identified. A spectral shift upon annealing indicated that the H-terminated surfaces were unpinned. After the H-plasma clean at 300 °C the dangling-bond surface state was also observed directly with no evidence of H-induced states.

Very Hard Corrosion-Resistant Roll-Bonded Cr Coating on Mild Steel in Presence of Graphite

NASA Astrophysics Data System (ADS)

Kumar, Pankaj; Khara, S.; Shekhar, S.; Mondal, K.

2017-12-01

The present work discusses the development of very hard Cr and Cr-carbide coating by roll bonding of Cr powder on a mild steel followed by annealing at 800, 1000, 1100 and 1200 °C with and without the presence of graphite powder packing in argon environment. In addition, the effect of a roll skin pass of 5% prior to the application of coating was studied. The presence of graphite allows diffusion of both carbon and Cr in the mild steel substrate, leading to the formation of Cr-carbide on the outer surface, making the surface very hard (VHN 1800). Depending on the annealing temperature and processing condition, diffusion layer thickness of Cr is found to be in the range of 10-250 μm with Cr content of 12.5-15 wt.% across the diffusion layer. Excellent stable passivity of the coated surface is observed in 0.2 N H2SO4, which is comparable to a highly passivating 304 stainless steel, and very low corrosion rate of the coating is observed as compared to the substrate mild steel.

Molecular and thermodynamic mechanisms of the chloride-dependent human angiotensin-I-converting enzyme (ACE).

PubMed

Yates, Christopher J; Masuyer, Geoffrey; Schwager, Sylva L U; Akif, Mohd; Sturrock, Edward D; Acharya, K Ravi

2014-01-17

Somatic angiotensin-converting enzyme (sACE), a key regulator of blood pressure and electrolyte fluid homeostasis, cleaves the vasoactive angiotensin-I, bradykinin, and a number of other physiologically relevant peptides. sACE consists of two homologous and catalytically active N- and C-domains, which display marked differences in substrate specificities and chloride activation. A series of single substitution mutants were generated and evaluated under varying chloride concentrations using isothermal titration calorimetry. The x-ray crystal structures of the mutants provided details on the chloride-dependent interactions with ACE. Chloride binding in the chloride 1 pocket of C-domain ACE was found to affect positioning of residues from the active site. Analysis of the chloride 2 pocket R522Q and R522K mutations revealed the key interactions with the catalytic site that are stabilized via chloride coordination of Arg(522). Substrate interactions in the S2 subsite were shown to affect chloride affinity in the chloride 2 pocket. The Glu(403)-Lys(118) salt bridge in C-domain ACE was shown to stabilize the hinge-bending region and reduce chloride affinity by constraining the chloride 2 pocket. This work demonstrated that substrate composition to the C-terminal side of the scissile bond as well as interactions of larger substrates in the S2 subsite moderate chloride affinity in the chloride 2 pocket of the ACE C-domain, providing a rationale for the substrate-selective nature of chloride dependence in ACE and how this varies between the N- and C-domains.

Molecular and Thermodynamic Mechanisms of the Chloride-dependent Human Angiotensin-I-converting Enzyme (ACE)*

PubMed Central

Yates, Christopher J.; Masuyer, Geoffrey; Schwager, Sylva L. U.; Akif, Mohd; Sturrock, Edward D.; Acharya, K. Ravi

2014-01-01

Somatic angiotensin-converting enzyme (sACE), a key regulator of blood pressure and electrolyte fluid homeostasis, cleaves the vasoactive angiotensin-I, bradykinin, and a number of other physiologically relevant peptides. sACE consists of two homologous and catalytically active N- and C-domains, which display marked differences in substrate specificities and chloride activation. A series of single substitution mutants were generated and evaluated under varying chloride concentrations using isothermal titration calorimetry. The x-ray crystal structures of the mutants provided details on the chloride-dependent interactions with ACE. Chloride binding in the chloride 1 pocket of C-domain ACE was found to affect positioning of residues from the active site. Analysis of the chloride 2 pocket R522Q and R522K mutations revealed the key interactions with the catalytic site that are stabilized via chloride coordination of Arg522. Substrate interactions in the S2 subsite were shown to affect chloride affinity in the chloride 2 pocket. The Glu403-Lys118 salt bridge in C-domain ACE was shown to stabilize the hinge-bending region and reduce chloride affinity by constraining the chloride 2 pocket. This work demonstrated that substrate composition to the C-terminal side of the scissile bond as well as interactions of larger substrates in the S2 subsite moderate chloride affinity in the chloride 2 pocket of the ACE C-domain, providing a rationale for the substrate-selective nature of chloride dependence in ACE and how this varies between the N- and C-domains. PMID:24297181

Acoustic backing in 3-D integration of CMUT with front-end electronics.

PubMed

Berg, Sigrid; Rønnekleiv, Arne

2012-07-01

Capacitive micromachined ultrasonic transducers (CMUTs) have shown promising qualities for medical imaging. However, there are still some problems to be investigated, and some challenges to overcome. Acoustic backing is necessary to prevent SAWs excited in the surface of the silicon substrate from affecting the transmit pattern from the array. In addition, echoes resulting from bulk waves in the substrate must be removed. There is growing interest in integrating electronic circuits to do some of the beamforming directly below the transducer array. This may be easier to achieve for CMUTs than for traditional piezoelectric transducers. We will present simulations showing that the thickness of the silicon substrate and thicknesses and acoustic properties of the bonding material must be considered, especially when designing highfrequency transducers. Through simulations, we compare the acoustic properties of 3-D stacks bonded with three different bonding techniques; solid-liquid interdiffusion (SLID) bonding, direct fusion bonding, and anisotropic conductive adhesives (ACA). We look at a CMUT array with a center frequency of 30 MHz and three silicon wafers underneath, having a total silicon thickness of 100 μm. We find that fusion bonding is most beneficial if we want to prevent surface waves from damaging the array response, but SLID and ACA are also promising if bonding layer thicknesses can be reduced.

On Substrate for Atomic Chain Electronics

NASA Technical Reports Server (NTRS)

Yamada, Toshishige; Bauschlicher, Charles W., Jr.; Partridge, Harry; Saini, Subhash (Technical Monitor)

1998-01-01

A substrate for future atomic chain electronics, where adatoms are placed at designated positions and form atomically precise device components, is studied theoretically. The substrate has to serve as a two-dimensional template for adatom mounting with a reasonable confinement barrier and also provide electronic isolation, preventing unwanted coupling between independent adatom structures. However, the two requirements conflict. For excellent electronic isolation, we may seek adatom confinement via van der Waals interaction without chemical bonding to the substrate atoms, but the confinement turns out to be very weak and hence unsatisfactory. An alternative chemical bonding scheme with excellent structural strength is examined, but even fundamental adatom chain properties such as whether chains are semiconducting or metallic are strongly influenced by the nature of the chemical bonding, and electronic isolation is not always achieved. Conditions for obtaining semiconducting chains with well-localized surface-modes, leading to good isolation, are clarified and discussed.

APS TBC performance on directionally-solidified superalloy substrates with HVOF NiCoCrAlYHfSi bond coatings

DOE PAGES

Lance, Michael J.; Unocic, Kinga A.; Haynes, James A.; ...

2015-09-04

Directionally-solidified (DS) superalloy components with advanced thermal barrier coatings (TBC) to lower the metal operating temperature have the potential to replace more expensive single crystal superalloys for large land-based turbines. In order to assess relative TBC performance, furnace cyclic testing was used with superalloys 1483, X4 and Hf-rich DS 247 substrates and high velocity oxygen fuel (HVOF)-NiCoCrAlYHfSi bond coatings at 1100 °C with 1-h cycles in air with 10% H 2O. With these coating and test conditions, there was no statistically-significant effect of substrate alloy on the average lifetime of the air plasma sprayed (APS) yttria-stabilized zirconia (YSZ) top coatingsmore » on small coupons. Using photo-stimulated luminescence piezospectroscopy maps at regular cycling intervals, the residual compressive stress in the α-Al 2O 3 scale underneath the YSZ top coating and on a bare bond coating was similar for all three substrates and delaminations occurred at roughly the same rate and frequency. As a result, x-ray fluorescence (XRF) measurements collected from the bare bond coating surface revealed higher Ti interdiffusion occurring with the 1483 substrate, which contained the highest Ti content.« less

Protein kinase A catalytic subunit primed for action: Time-lapse crystallography of Michaelis complex formation

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

Das, Amit; Gerlits, Oksana O.; Parks, Jerry M.

The catalytic subunit of the cyclic AMP-dependent protein kinase A (PKAc) catalyzes the transfer of the γ-phosphate of bound Mg 2ATP to a serine or threonine residue of a protein substrate. Here, time-lapse X-ray crystallography was used to capture a series of complexes of PKAc with an oligopeptide substrate and unreacted Mg 2ATP, including the Michaelis complex, that reveal important geometric rearrangements in and near the active site preceding the phosphoryl transfer reaction. Contrary to the prevailing view, Mg 2+ binds first to the M1 site as a complex with ATP and is followed by Mg 2+ binding to themore » M2 site. Furthermore, the target serine hydroxyl of the peptide substrate rotates away from the active site toward the bulk solvent, which breaks the hydrogen bond with D166. In conclusion, the serine hydroxyl of the substrate rotates back toward D166 to form the Michaelis complex with the active site primed for phosphoryl transfer.« less

Protein kinase A catalytic subunit primed for action: Time-lapse crystallography of Michaelis complex formation

DOE PAGES

Das, Amit; Gerlits, Oksana O.; Parks, Jerry M.; ...

2015-11-12

The catalytic subunit of the cyclic AMP-dependent protein kinase A (PKAc) catalyzes the transfer of the γ-phosphate of bound Mg 2ATP to a serine or threonine residue of a protein substrate. Here, time-lapse X-ray crystallography was used to capture a series of complexes of PKAc with an oligopeptide substrate and unreacted Mg 2ATP, including the Michaelis complex, that reveal important geometric rearrangements in and near the active site preceding the phosphoryl transfer reaction. Contrary to the prevailing view, Mg 2+ binds first to the M1 site as a complex with ATP and is followed by Mg 2+ binding to themore » M2 site. Furthermore, the target serine hydroxyl of the peptide substrate rotates away from the active site toward the bulk solvent, which breaks the hydrogen bond with D166. In conclusion, the serine hydroxyl of the substrate rotates back toward D166 to form the Michaelis complex with the active site primed for phosphoryl transfer.« less

Biomechanics of leukocyte rolling

PubMed Central

Sundd, Prithu; Pospieszalska, Maria K.; Cheung, Luthur Siu-Lun; Konstantopoulos, Konstantinos; Ley, Klaus

2011-01-01

Leukocyte rolling on endothelial cells and other P-selectin substrates is mediated by P-selectin binding to P-selectin glycoprotein ligand-1 expressed on the tips of leukocyte microvilli. Leukocyte rolling is a result of rapid, yet balanced formation and dissociation of selectin-ligand bonds in the presence of hydrodynamic shear forces. The hydrodynamic forces acting on the bonds may either increase (catch bonds) or decrease (slip-bonds) their lifetimes. The force-dependent ‘catch-slip’ bond kinetics are explained using the ‘two pathway model’ for bond dissociation. Both the ‘sliding-rebinding’ and the ‘allosteric’ mechanisms attribute ‘catch-slip’ bond behavior to the force-induced conformational changes in the lectin-EGF domain hinge of selectins. Below a threshold shear stress, selectins cannot mediate rolling. This ‘shear-threshold’ phenomenon is a consequence of shear-enhanced tethering and catch-bond enhanced rolling. Quantitative dynamic footprinting microscopy has revealed that leukocytes rolling at venular shear stresses (> 0.6 Pa) undergo cellular deformation (large footprint) and form long tethers. The hydrodynamic shear force and torque acting on the rolling cell are thought to be synergistically balanced by the forces acting on tethers and stressed microvilli, however, their relative contribution remains to be determined. Thus, improvement beyond the current understanding requires in silico models that can predict both cellular and microvillus deformation and experiments that allow measurement of forces acting on individual microvilli and tethers. PMID:21515934

Effect of moisture on dental enamel in the interaction of two orthodontic bonding systems.

PubMed

Bertoz, André Pinheiro de Magalhães; de Oliveira, Derly Tescaro Narcizo; Gimenez, Carla Maria Melleiro; Briso, André Luiz Fraga; Bertoz, Francisco Antonio; Santos, Eduardo César Almada

2013-01-01

The purpose of this study was to assess by means of scanning electron microscopy (SEM) the remaining adhesive interface after debonding orthodontic attachments bonded to bovine teeth with the use of hydrophilic and hydrophobic primers under different dental substrate moisture conditions. Twenty mandibular incisors were divided into four groups (n = 5). In Group I, bracket bonding was performed with Transbond MIP hydrophilic primer and Transbond XT adhesive paste applied to moist substrate, and in Group II a bonding system comprising Transbond XT hydrophobic primer and adhesive paste was applied to moist substrate. Brackets were bonded to the specimens in Groups III and IV using the same adhesive systems, but on dry dental enamel. The images were qualitatively assessed by SEM. The absence of moisture in etched enamel enabled better interaction between bonding materials and the adamantine structure. The hydrophobic primer achieved the worst micromechanical interlocking results when applied to a moist dental structure, whereas the hydrophilic system proved versatile, yielding acceptable results in moist conditions and excellent interaction in the absence of contamination. The authors assert that the best condition for the application of primers to dental enamel occurs in the absence of moisture.

An allosteric disulfide bond is involved in enhanced activation of factor XI by protein disulfide isomerase.

PubMed

Zucker, M; Seligsohn, U; Yeheskel, A; Mor-Cohen, R

2016-11-01

Essentials Reduction of three disulfide bonds in factor (F) XI enhances chromogenic substrate cleavage. We measured FXI activity upon reduction and identified a bond involved in the enhanced activity. Reduction of FXI augments FIX cleavage, probably by faster conversion of FXI to FXIa. The Cys362-Cys482 disulfide bond is responsible for FXI enhanced activation upon its reduction. Background Reduction of factor (F) XI by protein disulfide isomerase (PDI) has been shown to enhance the ability of FXI to cleave its chromogenic substrate. Three disulfide bonds in FXI (Cys118-Cys147, Cys362-Cys482, and Cys321-Cys321) are involved in this augmented activation. Objectives To characterize the mechanisms by which PDI enhances FXI activity. Methods FXI activity was measured following PDI reduction. Thiols that were exposed in FXI after PDI reduction were labeled with 3-(N-maleimidopropionyl)-biocytin (MPB) and detected with avidin. The rate of conversion of FXI to activated FXI (FXIa) following thrombin activation was assessed with western blotting. FXI molecules harboring mutations that disrupt the three disulfide bonds (C147S, C321S, and C482S) were expressed in cells. The antigenicity of secreted FXI was measured with ELISA, and its activity was assessed by the use of a chromogenic substrate. The effect of disulfide bond reduction was analyzed by the use of molecular dynamics. Results Reduction of FXI by PDI enhanced cleavage of both its chromogenic substrate, S2366, and its physiologic substrate, FIX, and resulted in opening of the Cys362-Cys482 bond. The rate of conversion of FXI to FXIa was increased following its reduction by PDI. C482S-FXI showed enhanced activity as compared with both wild-type FXI and C321S-FXI. MD showed that disruption of the Cys362-Cys482 bond leads to a broader thrombin-binding site in FXI. Conclusions Reduction of FXI by PDI enhances its ability to cleave FIX, probably by causing faster conversion of FXI to FXIa. The Cys362-Cys482 disulfide bond is involved in enhancing FXI activation following its reduction, possibly by increasing thrombin accessibility to FXI. © 2016 International Society on Thrombosis and Haemostasis.

Microwave-assisted Ullmann C-S bond formation: synthesis of the P38alpha MAPK clinical candidate VX-745.

PubMed

Bagley, Mark C; Davis, Terence; Dix, Matthew C; Fusillo, Vincenzo; Pigeaux, Morgane; Rokicki, Michal J; Kipling, David

2009-11-06

Microwave irradiation promotes the rapid and efficient reaction of a thiophenol and aryl or heteroaryl halide using a copper or palladium catalyst and a range of ligands, depending upon substrate. Of particular utility is the use of copper(I) iodide (5 mol %) and trans-cyclohexane-1,2-diol as ligand under basic conditions and microwave irradiation to give the corresponding sulfide in high yield. This method for C-S bond formation is applied in the four-step synthesis of the clinical candidate VX-745 in 38% overall yield. The inhibitory activity of VX-745 against p38alpha MAPK is confirmed in Werner syndrome dermal fibroblasts at 1.0 microM concentration by immunoblot assay.

Plasma sprayed hydroxyapatite coatings on titanium substrates. Part 2: optimisation of coating properties.

PubMed

Tsui, Y C; Doyle, C; Clyne, T W

1998-11-01

Heat treatment and the introduction of a Ti bond coat have been applied to hydroxyapatite (HA) coatings sprayed using different plasma powers and gas mixtures. Attempts were made in this way to achieve optimal coating properties for orthopaedic implants. In particular, the effects on the degree of crystallinity, the adhesion, the OH ion content and the purity were evaluated. Heat treatment at 700 C for 1 h in air proved to be effective in increasing the crystallinity, regaining the OH- ion and removing other non-HA compounds, although it caused a significant decrease in the degree of adhesion (interfacial fracture toughness) for those specimens sprayed at high powers. This heat treatment was found to induce significant transformation of amorphous HA to the crystalline form, while not detrimentally changing the properties of the underlying Ti-6Al-4V substrates. Precoating with a 100 microm Ti layer increased the adhesion of the HA coatings on Ti-6Al-4V substrates, primarily by providing a rougher surface and promoting better mechanical interlocking. Changes in coating properties during immersion in biological fluids were also studied and were found to depend critically on the chemical composition of the fluids. Small precipitates formed on the coating surfaces when immersed in Ringers solution. These might account for the apparent drop in the degree of crystallinity when measured using X-ray diffraction. A significant drop in the interfacial adhesion was found for those coatings sprayed at high powers. This could be offset by prior precoating with a titanium bond coat and suitable heat treatment. In summary, the following processing sequence is suggested in order to achieve optimum coating properties: precoating the substrate with a layer of Ti (approximately 100 microm), spraying HA at a sufficiently high-power level (depending on particle size and gas mixture) and heat treatment at 700 degrees C for 1 h in air.

Organic photochemical storage of solar energy. Progress report, February 1, 1979-January 31, 1980

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

Jones, G. II

1980-02-01

Study of valence isomerization of organic compounds has focused on two mechanisms of photosensitization involving either electron donor-acceptor interaction or energy transfer. The quenching of fluorescent sensitizers by isomerizable substrates results in the formation of excited complexes. These sensitizer-substrate pairs are highly polarized, leading to changes in bond order for the substrates. For several substrates such as quadricyclene, hexamethyldewarbenzene, and a nonbornadiene derivative, this perturbation results in efficient valence isomerization. Isomerization observed on irradiation of charge transfer complexes of isomerizable substrates is consistent with a similar exciplex - template mechanism. The energy transfer mechanism of photosensitization has been studied bymore » measuring the temperature dependence of quantum yield for isomerization of dimethyl norbornadiene-2,3-dicarboxylate sensitized by benzanthrone. From temperature and quencher concentration profiles quenching constants have been obtained which are consistent with an endoergic triplet energy transfer mechanism. The thermal upconversion of the low energy triplet of benzanthrone results in a threefold increase in isomerization quantum yield over a 90/sup 0/ temperature range.« less

Intrinsic bond strength of metal films on polymer substrates

NASA Technical Reports Server (NTRS)

Wheeler, Donald R.; Osaki, Hiroyuki

1990-01-01

A semiquantitative method for the measurement of the intrinsic bond strength between elastic substrates and elastic films that fail by brittle fracture is described. Measurements on a polyethylene terephthalate (PET)-Ni couple were used to verify the essential features of the analysis. It was found that the interfacial shear strength of Ni on PET doubled after ion etching.

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.

Interfacial adhesion of dental ceramic-resin systems

NASA Astrophysics Data System (ADS)

Della Bona, Alvaro

The clinical success of resin bonding procedures for indirect ceramic restorations and ceramic repairs depends on the quality and durability of the bond between the ceramic and the resin. The quality of this bond will depend upon the bonding mechanisms that are controlled in part by the surface treatment that promotes micromechanical and/or chemical bonding to the substrate. The objective of this study is to correlate interfacial toughness (K A) with fracture surface morphological parameters of the dental ceramic-resin systems as a function of ceramic surface treatment. The analytical procedures focused on characterizing the microstructure and fracture properties of EmpressRTM ceramics (a leucite-based core ceramic, two lithia disilicate-based core ceramics, and a glass veneer) and determining the ceramic-resin adhesion zone bond strength characteristics. Microstructure and composition are controlling factors in the development of micromechanical retention produced by etching. Silane treated ceramics negated the effect of surface roughening produced by etching, inducing lower surface energy of the ceramic and, reduced bonding effectiveness. There was a positive correlation between WA, tensile bond strength (a), and KA, i.e., higher mean WA value, and higher mean sigma and KA values. This study suggests that (1) the sigma and KA values for ceramic bonded to resin are affected by the ceramic microstructure and the ceramic surface treatments; (2) the definition of the adhesion zone is essential to classify the modes of failure, which should be an integral component of all failure analyses; (3) the microtensile test may be preferable to conventional shear or flexural tests as an indicator of composite-ceramic bond quality; and (4) careful microscopic analysis of fracture surfaces and an x-ray dot map can produce a more consistent and complete description of the fracture process and interpretation of the modes of failure. The mode of failure and fractographic analyses provide important a more comprehensive assessment of mechanisms that control the survival times of dental adhesive systems. Thus, the quality of the bond should not be assessed based on bond strength data alone.

Probing the importance of hydrogen bonds in the active site of the subtilisin nattokinase by site-directed mutagenesis and molecular dynamics simulation

PubMed Central

Zheng, Zhong-liang; Ye, Mao-qing; Zuo, Zhen-yu; Liu, Zhi-gang; Tai, Keng-chang; Zou, Guo-lin

2006-01-01

Hydrogen bonds occurring in the catalytic triad (Asp32, His64 and Ser221) and the oxyanion hole (Asn155) are very important to the catalysis of peptide bond hydrolysis by serine proteases. For the subtilisin NK (nattokinase), a bacterial serine protease, construction and analysis of a three-dimensional structural model suggested that several hydrogen bonds formed by four residues function to stabilize the transition state of the hydrolysis reaction. These four residues are Ser33, Asp60, Ser62 and Thr220. In order to remove the effect of these hydrogen bonds, four mutants (Ser33→Ala33, Asp60→Ala60, Ser62→Ala62, and Thr220→Ala220) were constructed by site-directed mutagenesis. The results of enzyme kinetics indicated that removal of these hydrogen bonds increases the free-energy of the transition state (ΔΔGT). We concluded that these hydrogen bonds are more important for catalysis than for binding the substrate, because removal of these bonds mainly affects the kcat but not the Km values. A substrate, SUB1 (succinyl-Ala-Ala-Pro-Phe-p-nitroanilide), was used during enzyme kinetics experiments. In the present study we have also shown the results of FEP (free-energy perturbation) calculations with regard to the binding and catalysis reactions for these mutant subtilisins. The calculated difference in FEP also suggested that these four residues are more important for catalysis than binding of the substrate, and the simulated values compared well with the experimental values from enzyme kinetics. The results of MD (molecular dynamics) simulations further demonstrated that removal of these hydrogen bonds partially releases Asp32, His64 and Asn155 so that the stability of the transition state decreases. Another substrate, SUB2 (H-D-Val-Leu-Lys-p-nitroanilide), was used for FEP calculations and MD simulations. PMID:16411898

Probing the importance of hydrogen bonds in the active site of the subtilisin nattokinase by site-directed mutagenesis and molecular dynamics simulation.

PubMed

Zheng, Zhong-liang; Ye, Mao-qing; Zuo, Zhen-yu; Liu, Zhi-gang; Tai, Keng-chang; Zou, Guo-lin

2006-05-01

Hydrogen bonds occurring in the catalytic triad (Asp32, His64 and Ser221) and the oxyanion hole (Asn155) are very important to the catalysis of peptide bond hydrolysis by serine proteases. For the subtilisin NK (nattokinase), a bacterial serine protease, construction and analysis of a three-dimensional structural model suggested that several hydrogen bonds formed by four residues function to stabilize the transition state of the hydrolysis reaction. These four residues are Ser33, Asp60, Ser62 and Thr220. In order to remove the effect of these hydrogen bonds, four mutants (Ser33-->Ala33, Asp60-->Ala60, Ser62-->Ala62, and Thr220-->Ala220) were constructed by site-directed mutagenesis. The results of enzyme kinetics indicated that removal of these hydrogen bonds increases the free-energy of the transition state (DeltaDeltaG(T)). We concluded that these hydrogen bonds are more important for catalysis than for binding the substrate, because removal of these bonds mainly affects the kcat but not the K(m) values. A substrate, SUB1 (succinyl-Ala-Ala-Pro-Phe-p-nitroanilide), was used during enzyme kinetics experiments. In the present study we have also shown the results of FEP (free-energy perturbation) calculations with regard to the binding and catalysis reactions for these mutant subtilisins. The calculated difference in FEP also suggested that these four residues are more important for catalysis than binding of the substrate, and the simulated values compared well with the experimental values from enzyme kinetics. The results of MD (molecular dynamics) simulations further demonstrated that removal of these hydrogen bonds partially releases Asp32, His64 and Asn155 so that the stability of the transition state decreases. Another substrate, SUB2 (H-D-Val-Leu-Lys-p-nitroanilide), was used for FEP calculations and MD simulations.

Screening method for selecting semiconductor substrates having defects below a predetermined level in an oxide layer

DOEpatents

Warren, W.L.; Vanheusden, K.J.R.; Schwank, J.R.; Fleetwood, D.M.; Shaneyfelt, M.R.; Winokur, P.S.; Devine, R.A.B.

1998-07-28

A method is disclosed for screening or qualifying semiconductor substrates for integrated circuit fabrication. The method comprises the steps of annealing at least one semiconductor substrate at a first temperature in a defect-activating ambient (e.g. hydrogen, forming gas, or ammonia) for sufficient time for activating any defects within on oxide layer of the substrate; measuring a defect-revealing electrical characteristic of at least a portion of the oxide layer for determining a quantity of activated defects therein; and selecting substrates for which the quantity of activated defects is below a predetermined level. The defect-revealing electrical characteristic may be a capacitance-versus voltage (C-V) characteristic or a current-versus-voltage (I-V) characteristic that is dependent on an electrical charge in the oxide layer generated by the activated defects. Embodiments of the present invention may be applied for screening any type of semiconductor substrate or wafer having an oxide layer formed thereon or therein. This includes silicon-on-insulator substrates formed by a separation by the implantation of oxygen (SIMOX) process or the bond and etch back silicon-on-insulator (BESOI) process, as well as silicon substrates having a thermal oxide layer or a deposited oxide layer. 5 figs.

Neuropeptide Y, B-type natriuretic peptide, substance P and peptide YY are novel substrates of fibroblast activation protein-α.

PubMed

Keane, Fiona M; Nadvi, Naveed A; Yao, Tsun-Wen; Gorrell, Mark D

2011-04-01

Fibroblast activation protein-α (FAP) is a cell surface-expressed and soluble enzyme of the prolyl oligopeptidase family, which includes dipeptidyl peptidase 4 (DPP4). FAP is not generally expressed in normal adult tissues, but is found at high levels in activated myofibroblasts and hepatic stellate cells in fibrosis and in stromal fibroblasts of epithelial tumours. FAP possesses a rare catalytic activity, hydrolysis of the post-proline bond two or more residues from the N-terminus of target substrates. α(2)-antiplasmin is an important physiological substrate of FAP endopeptidase activity. This study reports the first natural substrates of FAP dipeptidyl peptidase activity. Neuropeptide Y, B-type natriuretic peptide, substance P and peptide YY were the most efficiently hydrolysed substrates and the first hormone substrates of FAP to be identified. In addition, FAP slowly hydrolysed other hormone peptides, such as the incretins glucagon-like peptide-1 and glucose-dependent insulinotropic peptide, which are efficient DPP4 substrates. FAP showed negligible or no hydrolysis of eight chemokines that are readily hydrolysed by DPP4. This novel identification of FAP substrates furthers our understanding of this unique protease by indicating potential roles in cardiac function and neurobiology. © 2011 The Authors Journal compilation © 2011 FEBS.

Systematization of material consumption norms in spray-coating

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

Lelyukh, I.M.

1995-03-01

Regulating the consumption of materials is particularly important in the economics and organization of spray-coating operations. Three main factors are taken into account when establishing norms for the consumption of the materials of the coating: the physicomechanical and chemical properties of the particles; the shape of the substrate; the dimensions of the substrate. The most important parameters of the spraying regime are the velocity and temperature of the particles. Given the same velocity, the optimum particle kinetic energy for producing a strong bond with the substrate depends on particle shape and size and the density of the materials being spray-coated.more » These parameters determine the heating of the particles in the plasma jet or, in the case of the use of a detonation gun, during collision with the surface of the part. Powders of fragmented or drop shape are used to obtain coatings by spraying.« less

Investigation of the donor and acceptor range for chiral carboligation catalyzed by the E1 component of the 2-oxoglutarate dehydrogenase complex

PubMed Central

Patel, Hetalben; Shim, Da Jeong; Farinas, Edgardo T.; Jordan, Frank

2013-01-01

The potential of thiamin diphosphate (ThDP)-dependent enzymes to catalyze C-C bond forming (carboligase) reactions with high enantiomeric excess has been recognized for many years. Here we report the application of the E1 component of the Escherichia coli 2-oxoglutarate dehydrogenase multienzyme complex in the synthesis of chiral compounds with multiple functional groups in good yield and high enantiomeric excess, by varying both the donor substrate (different 2-oxo acids) and the acceptor substrate (glyoxylate, ethyl glyoxylate and methyl glyoxal). Major findings include the demonstration that the enzyme can accept 2-oxovalerate and 2-oxoisovalerate in addition to its natural substrate 2-oxoglutarate, and that the tested acceptors are also acceptable in the carboligation reaction, thereby very much expanding the repertory of the enzyme in chiral synthesis. PMID:24277992

Thermal barrier coating for alloy systems

DOEpatents

Seals, Roland D.; White, Rickey L.; Dinwiddie, Ralph B.

2000-01-01

An alloy substrate is protected by a thermal barrier coating formed from a layer of metallic bond coat and a top coat formed from generally hollow ceramic particles dispersed in a matrix bonded to the bond coat.

A Discovery of Strong Metal-Support Bonding in Nanoengineered Au-Fe3O4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy.

PubMed

Han, Chang Wan; Choksi, Tej; Milligan, Cory; Majumdar, Paulami; Manto, Michael; Cui, Yanran; Sang, Xiahan; Unocic, Raymond R; Zemlyanov, Dmitry; Wang, Chao; Ribeiro, Fabio H; Greeley, Jeffrey; Ortalan, Volkan

2017-08-09

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous "strong metal-support bonding" between gold nanoparticles and "nano-engineered" Fe 3 O 4 substrates by in situ microscopy. During in situ vacuum annealing of Au-Fe 3 O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3 O 4 on Au nanoparticles, the gold nanoparticles transform into the gold thin films and wet the surface of nano-Fe 3 O 4 , as the surface reduction of nano-Fe 3 O 4 proceeds. This phenomenon results from a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3 O 4 and the extremely strong adhesion between Au and the reduced Fe 3 O 4 . This strong metal-support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and ultimately for the development of improved catalysts and functional nanostructures.

Compressive and bonding strength of fly ash based geopolymer mortar

NASA Astrophysics Data System (ADS)

Zailani, Warid Wazien Ahmad; Abdullah, Mohd Mustafa Al Bakri; Zainol, Mohd Remy Rozainy Mohd Arif; Razak, Rafiza Abd.; Tahir, Muhammad Faheem Mohd

2017-09-01

Geopolymer which is produced by synthesizing aluminosilicate source materials with an alkaline activator solution promotes sustainable and excellent properties of binder. The purpose of this paper is to determine the optimum binder to sand ratio of geopolymer mortars based on mechanical properties. In order to optimize the formulation of geopolymer mortar, various binder to sand ratios (0.25, 0.33, 0.5, 1.0, 2.0, 3.0, and 4.0) are prepared. The investigation on the effect of sand inclusion to the compressive and bonding strength of geopolymer mortar is approached. The experimental results show that the bonding strength performance of geopolymer is also depends on the various binder to sand ratio, where the optimum ratio 0.5 gives a highest strength of 12.73 MPa followed by 12.35 MPa, which corresponds the ratio 1.0 for geopolymer, while the compared value of OPC bonding strength is given by 9.3 MPa. The morphological structure at the interface zone is determined by Scanning Electron Microscope (SEM) and the homogenous bonding between geopolymer and substrate can be observed. Fly ash based geopolymers reveal a new category of mortar which has high potential to be used in the field of concrete repair and rehabilitation.

Structural and dynamical characterization of water on the Au (100) and graphene surfaces: A molecular dynamics simulation approach

NASA Astrophysics Data System (ADS)

Foroutan, Masumeh; Darvishi, Mehdi; Fatemi, S. Mahmood

2017-09-01

The positioning, adsorption, and movement of water on substrates is dependent upon the chemical nature and arrangement of the atoms of the surface. Therefore the behavior of water molecules on a substrate is a reflection of properties of the surface. Based on this premise, graphene and gold substrates were chosen to study this subject from a molecular perspective. In this work, the structural and dynamical behaviors of a water nanodroplet on Au (100) and the graphene interfaces have been studied by molecular dynamics simulation. The results have shown how the structural and dynamical behaviors of water molecules at the interface reflect the characteristics of these surfaces. The results have demonstrated that residence time and hydrogen bonds' lifetime at the water-Au (100) interface are bigger than at the water-graphene interface. Energy contour map analysis indicates a more uniform surface energy on graphene than on the gold surface. The obtained results illustrate that water clusters on gold and graphene form tetramer and hexamer structures, respectively. Furthermore, the water molecules are more ordered on the gold surface than on graphene. The study of hydrogen bonds showed that the order, stability, and the number of hydrogen bonds is higher on the gold surface. The positioning pattern of water molecules is also similar to the arrangement of gold atoms while no regularity was observed on graphene. The study of dynamical behavior of water molecules revealed that the movement of water on gold is much less than on graphene which is in agreement with the strong water-gold interaction in comparison to the water-graphene interaction.

Experimental and Numerical Study of the Influence of Substrate Surface Preparation on Adhesion Mechanisms of Aluminum Cold Spray Coatings on 300M Steel Substrates

NASA Astrophysics Data System (ADS)

Nastic, A.; Vijay, M.; Tieu, A.; Rahmati, S.; Jodoin, B.

2017-10-01

The effect of substrate surface topography on the creation of metallurgical bonds and mechanical anchoring points has been studied for the cold spray deposition of pure aluminum on 300M steel substrate material. The coatings adhesion strength showed a significant decrease from 31.0 ± 5.7 MPa on polished substrates to 6.9 ± 2.0 MPa for substrates with roughness of 2.2 ± 0.5 μm. Strengths in the vicinity of 45 MPa were reached for coatings deposited onto forced pulsed waterjet treated surfaces with roughnesses larger than 33.8 μm. Finite element analysis has confirmed the sole presence of mechanical anchoring in coating adhesion strength for all surface treatment except polished surfaces. Grit embedment has been shown to be non-detrimental to coating adhesion for the current deposited material combination. The particle deformation process during impacts has been studied through finite element analysis using the Preston-Tonks-Wallace (PTW) constitutive model. The obtained equivalent plastic strain (PEEQ), temperature, contact pressure and velocity vector were correlated to the particle ability to form metallurgical bonds. Favorable conditions for metallurgical bonding were found to be highest for particles deposited on polished substrates, as confirmed by fracture surface analysis.

Method for joining carbon-carbon composites to metals

DOEpatents

Lauf, Robert J.; McMillan, April D.; Moorhead, Arthur J.

1997-01-01

A method for joining carbon-carbon composites to metals by brazing. Conventional brazing of recently developed carbon-bonded carbon fiber (CBCF) material to a metal substrate is limited by the tendency of the braze alloy to "wick" into the CBCF composite rather than to form a strong bond. The surface of the CBCF composite that is to be bonded is first sealed with a fairly dense carbonaceous layer achieved by any of several methods. The sealed surface is then brazed to the metal substrate by vacuum brazing with a Ti-Cu-Be alloy.

Method for joining carbon-carbon composites to metals

DOEpatents

Lauf, R.J.; McMillan, A.D.; Moorhead, A.J.

1997-07-15

A method for joining carbon-carbon composites to metals by brazing. Conventional brazing of recently developed carbon-bonded carbon fiber (CBCF) material to a metal substrate is limited by the tendency of the braze alloy to ``wick`` into the CBCF composite rather than to form a strong bond. The surface of the CBCF composite that is to be bonded is first sealed with a fairly dense carbonaceous layer achieved by any of several methods. The sealed surface is then brazed to the metal substrate by vacuum brazing with a Ti-Cu-Be alloy. 1 fig.

Experimental investigations into cryosorption pumping of plasma exhaust

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

Perinic, D.; Mack, A.

1988-09-01

Within the framework of the European Fusion Technology Programme the Karlsruhe Nuclear Research Centre has been awarded a contract for the development of cryosorption panels for compound cryopumps of the NEt plasma exhaust pumping system. This task includes the development of a bonding technique for porous sorbent materials with metal substrates and a test programme for development and optimization of cryopanels. A variety of material combinations for sorbent, bonding and substrate were evaluated and listed in a test matrix. Bonding tests involving soldering, cementing and plasma spraying techniques have been carried out.

Metal oxide nanorod arrays on monolithic substrates

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

Gao, Pu-Xian; Guo, Yanbing; Ren, Zheng

A metal oxide nanorod array structure according to embodiments disclosed herein includes a monolithic substrate having a surface and multiple channels, an interface layer bonded to the surface of the substrate, and a metal oxide nanorod array coupled to the substrate surface via the interface layer. The metal oxide can include ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide. The substrate can include a glass substrate, a plastic substrate, a silicon substrate, a ceramic monolith, and a stainless steel monolith. The ceramic can include cordierite, alumina, tin oxide, and titania. The nanorod array structure can includemore » a perovskite shell, such as a lanthanum-based transition metal oxide, or a metal oxide shell, such as ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide, or a coating of metal particles, such as platinum, gold, palladium, rhodium, and ruthenium, over each metal oxide nanorod. Structures can be bonded to the surface of a substrate and resist erosion if exposed to high velocity flow rates.« less

Method for fabricating hafnia films

DOEpatents

Hu, Michael Z [Knoxville, TN

2007-08-21

The present invention comprises a method for fabricating hafnia film comprising the steps of providing a substrate having a surface that allows formation of a self-assembled monolayer thereon via covalent bonding; providing an aqueous solution that provides homogeneous hafnium ionic complexes and hafnium nanoclusters wherein the aqueous solution is capable of undergoing homogeneous precipitation under controlled conditions for a desired period of time at a controlled temperature and controlled solution acidity for desired nanocluster nucleation and growth kinetics, desired nanocluster size, desired growth rate of film thickness and desired film surface characteristics. The method further comprising forming the self-assembled monolayer on the surface of the substrate wherein the self-assembled monolayer comprises a plurality of hydrocarbon chains cross-linked together along the surface of the substrate, the hydrocarbon chains being uniformly spaced from one another and wherein each of the hydrocarbon chains having a functional anchoring group at a first end of the chain covalently bonded with the surface of the substrate and each of the hydrocarbon chains having a functional terminating group projected away from the surface wherein the functional terminating group provides a bonding site for the hafnium film to grow; and exposing the substrate to the aqueous solution for a desired period of time at a controlled temperature wherein the hafnium ionic complexes and the hafnium nanoclusters are deposited on the bonding site of the functional terminating group thereby forming the hafnia film wherein the hafnium bonded to the hydrocarbons and to one another provide a uniform ordered arrangement defined by the uniform arrangement of the hydrocarbons.

Film growth, adsorption and desorption kinetics of indigo on SiO2

PubMed Central

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2015-01-01

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer des orption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption. PMID:24832297

Film growth, adsorption and desorption kinetics of indigo on SiO{sub 2}

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

Scherwitzl, Boris, E-mail: b.scherwitzl@tugraz.at; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation ofmore » dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.« less

Film growth, adsorption and desorption kinetics of indigo on SiO2.

PubMed

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.

Sacrificial plastic mold with electroplatable base

DOEpatents

Domeier, Linda A.; Hruby, Jill M.; Morales, Alfredo M.

2002-01-01

A sacrificial plastic mold having an electroplatable backing is provided. One embodiment consists of the infusion of a softened or molten thermoplastic through a porous metal substrate (sheet, screen, mesh or foam) and into the features of a micro-scale molding tool contacting the porous metal substrate. Upon demolding, the porous metal substrate will be embedded within the thermoplastic and will project a plastic structure with features determined by the mold tool. This plastic structure, in turn, provides a sacrificial plastic mold mechanically bonded to the porous metal substrate which provides a conducting support suitable for electroplating either contiguous or non-contiguous metal replicates. After electroplating and lapping, the sacrificial plastic can be dissolved to leave the desired metal structure bonded to the porous metal substrate. Optionally, the electroplated structures may be debonded from the porous substrate by selective dissolution of the porous substrate or a coating thereon.

Sacrificial Plastic Mold With Electroplatable Base

DOEpatents

Domeier, Linda A.; Hruby, Jill M.; Morales, Alfredo M.

2005-08-16

A sacrificial plastic mold having an electroplatable backing is provided. One embodiment consists of the infusion of a softened or molten thermoplastic through a porous metal substrate (sheet, screen, mesh or foam) and into the features of a micro-scale molding tool contacting the porous metal substrate. Upon demolding, the porous metal substrate will be embedded within the thermoplastic and will project a plastic structure with features determined by the mold tool. This plastic structure, in turn, provides a sacrificial plastic mold mechanically bonded to the porous metal substrate which provides a conducting support suitable for electroplating either contiguous or non-contiguous metal replicates. After electroplating and lapping, the sacrificial plastic can be dissolved to leave the desired metal structure bonded to the porous metal substrate. Optionally, the electroplated structures may be debonded from the porous substrate by selective dissolution of the porous substrate or a coating thereon.

Continuous fiber reinforced mesh bond coat for environmental barrier coating system

DOEpatents

Zhang, James; Das, Rupak; Roberts III, Herbert Chidsey; Delvaux, John McConnell

2017-09-26

A gas turbine blade may have a bond coat applied to its surface. A porous substrate may be applied to the bond layer and one or more protective layers may be applied to the bond layer such that the fiber mesh is embedded between the bond layer and the protective layer to prevent creep.

Are epoxy-wood bonds durable enough?

Treesearch

Charles R. Frihart

2005-01-01

An important aspect of any adhesive bond is that the bond maintains its integrity during its end use. Epoxies form highly durable bonds with many substrates but are usually not considered capable of forming completely durable bonds with wood by standard accelerated tests. However, epoxies are sold for wood boat construction, and some data have indicated that epoxies...

Intrinsic Flexibility of Ubiquitin on Proliferating Cell Nuclear Antigen (PCNA) in Translesion Synthesis*

PubMed Central

Hibbert, Richard G.; Sixma, Titia K.

2012-01-01

Ubiquitin conjugation provides a crucial signaling role in hundreds of cellular pathways; however, a structural understanding of ubiquitinated substrates is lacking. One important substrate is monoubiquitinated PCNA (PCNA-Ub), which signals for recruitment of damage-tolerant polymerases in the translesion synthesis (TLS) pathway of DNA damage avoidance. We use a novel and efficient enzymatic method to produce PCNA-Ub at high yield with a native isopeptide bond and study its Usp1/UAF1-dependent deconjugation. In solution we find that the ubiquitin moiety is flexible relative to the PCNA, with its hydrophobic patch mostly accessible for recruitment of TLS polymerases, which promotes the interaction with polymerase η. The studies are a prototype for the nature of the ubiquitin modification. PMID:22989887

Optimal Design of Piezoelectric Materials for Maximal Energy Harvesting

DTIC Science & Technology

2015-06-01

Wright. . 22 Figure 3.1 Energy harvesting bimorph cantilever with distributed piezoelectric transducers (gray) bonded to a substrate ( white ). Adapted...certain materials, such as zinc blende, sodium chlorate, boracite, tourmaline, cane sugar, Rochelle salt, and quartz, mechanical stresses induce...cantilever with distributed piezoelectric transducers (gray) bonded to a substrate ( white ). Adapted from Dutoit, Wardle and Kim [16]. 25 The general equations

Communication: Surface-to-bulk diffusion of isolated versus interacting C atoms in Ni(111) and Cu(111) substrates: A first principle investigation.

PubMed

Harpale, Abhilash; Panesi, Marco; Chew, Huck Beng

2015-02-14

Using first principle calculations, we study the surface-to-bulk diffusion of C atoms in Ni(111) and Cu(111) substrates, and compare the barrier energies associated with the diffusion of an isolated C atom versus multiple interacting C atoms. We find that the preferential Ni-C bonding over C-C bonding induces a repulsive interaction between C atoms located at diagonal octahedral voids in Ni substrates. This C-C interaction accelerates C atom diffusion in Ni with a reduced barrier energy of ∼1 eV, compared to ∼1.4-1.6 eV for the diffusion of isolated C atoms. The diffusion barrier energy of isolated C atoms in Cu is lower than in Ni. However, bulk diffusion of interacting C atoms in Cu is not possible due to the preferential C-C bonding over C-Cu bonding, which results in C-C dimer pair formation near the surface. The dramatically different C-C interaction effects within the different substrates explain the contrasting growth mechanisms of graphene on Ni(111) and Cu(111) during chemical vapor deposition.

On the Interplay Between Adhesion Strength and Tensile Properties of Thermal Spray Coated Laminates—Part II: Low-Velocity Thermal Spray Coatings

NASA Astrophysics Data System (ADS)

Luo, Xiaotao; Smith, Gregory M.; Sampath, Sanjay

2018-02-01

In this two-part study, uniaxial tensile testing was used to evaluate coating/substrate bonding and compared with traditional ASTM C633 bond pull test results for thermal spray (TS) coated steel laminates. In Part I, the rationale, methodology, and applicability of the test to high-velocity TS coatings were demonstrated. In this Part II, the method was investigated for low-velocity TS processes (air plasma spray and arc spray) on equivalent materials. Ni and Ni-5wt.%Al coatings were deposited on steel substrates with three different roughness levels and tested using both uniaxial tensile and ASTM C633 methods. The results indicate the uniaxial tensile approach provides useful information about the nature of the coating/substrate bonding and goes beyond the traditional bond pull test in providing insightful information on the load sharing processes across the interface. Additionally, this proposed methodology alleviates some of the longstanding shortcomings and potentially reduces error associated with the traditional ASTM C633 test. The mechanisms governing the load transfer between the substrate and the coating were investigated, and the influence of Al in the coating material evaluated.

Selective aliphatic carbon-hydrogen bond activation of protected alcohol substrates by cytochrome P450 enzymes.

PubMed

Bell, Stephen G; Spence, Justin T J; Liu, Shenglan; George, Jonathan H; Wong, Luet-Lok

2014-04-21

Protected cyclohexanol and cyclohex-2-enol substrates, containing benzyl ether and benzoate ester moieties, were designed to fit into the active site of the Tyr96Ala mutant of cytochrome P450cam. The protected cyclohexanol substrates were efficiently and selectively hydroxylated by the mutant enzyme at the trans C-H bond of C-4 on the cyclohexyl ring. The selectivity of oxidation of the benzoate ester protected cyclohexanol could be altered by making alternative amino acid substitutions in the P450cam active site. The addition of the double bond in the cyclohexyl ring of the benzoate ester protected cyclohex-2-enol has a debilitative effect on the activity of the Tyr96Ala mutant with this substrate. However, the Phe87Ala/Tyr96Phe double mutant, which introduces space at a different location in the active site than the Tyr96Ala mutant, was able to efficiently hydroxylate the C-H bonds of 1-cyclohex-2-enyl benzoate at the allylic C-4 position. Mutations at Phe87 improved the selectivity of the oxidation of 1-phenyl-1-cyclohexylethylene to trans-4-phenyl-ethenylcyclohexanol (92%) when compared to single mutants at Tyr96 of P450cam.

Effect of grit-blasting on substrate roughness and coating adhesion

NASA Astrophysics Data System (ADS)

Varacalle, Dominic J.; Guillen, Donna Post; Deason, Douglas M.; Rhodaberger, William; Sampson, Elliott

2006-09-01

Statistically designed experiments were performed to compare the surface roughness produced by grit blasting A36/1020 steel using different abrasives. Grit blast media, blast pressure, and working distance were varied using a Box-type statistical design of experiment (SDE) approach. The surface textures produced by four metal grits (HG16, HG18, HG25, and HG40) and three conventional grits (copper slag, coal slag, and chilled iron) were compared. Substrate roughness was measured using surface profilometry and correlated with operating parameters. The HG16 grit produced the highest surface roughness of all the grits tested. Aluminum and zinc-aluminum coatings were deposited on the grit-blasted substrates using the twin-wire electric are (TWEA) process. Bond strength of the coatings was measured with a portable adhesion tester in accordance with ASTM standard D 4541. The coatings on substrates roughened with steel grit exhibit superior bond strength to those prepared with conventional grit. For aluminum coatings sprayed onto surfaces prepared with the HG16 grit, the bond strength was most influenced by current, spray distance, and spray gun pressure (in that order). The highest bond strength for the zinc-aluminum coatings was attained on surfaces prepared using the metal grits.

Fused silica GRISMs manufactured by hydrophilic direct bonding at moderate heating

NASA Astrophysics Data System (ADS)

Kalkowski, G.; Grabowski, K.; Harnisch, G.; Flügel-Paul, T.; Zeitner, U.; Risse, S.

2017-12-01

For high-resolution spectroscopy in space, GRISM elements—obtained by patterning gratings onto a prism surface—find increasing applications. We report on GRISM manufacturing by joining the individual functional elements—prisms and gratings—to suitable components by the technology of hydrophilic direct bonding. Fused silica was used as a substrate material and binary gratings were fabricated by standard e-beam lithography and dry etching. Alignment of the grating dispersion direction to the prism angle was realized by passive adjustment on dedicated bonding gear matched to the substrate geometry. Materials adapted bonds of high transmission, stiffness, and strength were obtained after heat treatment at temperatures of about 200 °C in vacuum. Examples for bonding uncoated as well as coated grating surfaces are given. The results illustrate the great potential of hydrophilic glass direct bonding for manufacturing transmission optics to be used in space or other heavy duty applications.

Hydration structure of the α-chymotrypsin substrate binding pocket: the impact of constrained geometry

NASA Astrophysics Data System (ADS)

Carey, Christina; Cheng, Yuen-Kit; Rossky, Peter J.

2000-08-01

The concave substrate binding pocket of α-chymotrypsin binds specifically hydrophobic side chains. In order to understand the hydration structure present in the absence of substrate, and elucidate the character of the solvent displaced on binding, molecular dynamics computer simulation of the solvent in a fully hydrated protein has been carried out and analyzed. The pocket is found to be characterized in terms of a mixed polar and apolar macromolecular surface. It is shown that the simulated solvent structure within it is spatially consistent with that seen via crystallography. The solvent structure is energetically characterized by large losses in hydrogen bonding among solvent molecules except at the mouth of the pocket where exposure to bulk-like solvent is possible. The loss in hydrogen bonding is attributed to the highly constrained geometry available to the solvent, preventing formation of a hydrogen bonding network, with only partial compensation by interactions with the macromolecular surface. The solvent displacement concomitant with substrate binding will therefore be associated with a large enthalpic driving force. This result is at the extreme of a continuum of variable cases of "hydrophobic" hydration, which differ most basically in surface curvature. These range from convex solute surfaces, inducing clathrate-like structures, with negligible hydrogen bond loss, to flat surfaces with significant interfacial loss, to the present concave case with hydrogen bonding losses exceeding 50%.

Hybrid Quantum/Classical Molecular Dynamics Simulations of the Proton Transfer Reactions Catalyzed by Ketosteroid Isomerase: Analysis of Hydrogen Bonding, Conformational Motions, and Electrostatics

PubMed Central

Chakravorty, Dhruva K.; Soudackov, Alexander V.; Hammes-Schiffer, Sharon

2009-01-01

Hybrid quantum/classical molecular dynamics simulations of the two proton transfer reactions catalyzed by ketosteroid isomerase are presented. The potential energy surfaces for the proton transfer reactions are described with the empirical valence bond method. Nuclear quantum effects of the transferring hydrogen increase the rates by a factor of ~8, and dynamical barrier recrossings decrease the rates by a factor of 3–4. For both proton transfer reactions, the donor-acceptor distance decreases substantially at the transition state. The carboxylate group of the Asp38 side chain, which serves as the proton acceptor and donor in the first and second steps, respectively, rotates significantly between the two proton transfer reactions. The hydrogen bonding interactions within the active site are consistent with the hydrogen bonding of both Asp99 and Tyr14 to the substrate. The simulations suggest that a hydrogen bond between Asp99 and the substrate is present from the beginning of the first proton transfer step, whereas the hydrogen bond between Tyr14 and the substrate is virtually absent in the first part of this step but forms nearly concurrently with the formation of the transition state. Both hydrogen bonds are present throughout the second proton transfer step until partial dissociation of the product. The hydrogen bond between Tyr14 and Tyr55 is present throughout both proton transfer steps. The active site residues are more mobile during the first step than during the second step. The van der Waals interaction energy between the substrate and the enzyme remains virtually constant along the reaction pathway, but the electrostatic interaction energy is significantly stronger for the dienolate intermediate than for the reactant and product. Mobile loop regions distal to the active site exhibit significant structural rearrangements and, in some cases, qualitative changes in the electrostatic potential during the catalytic reaction. These results suggest that relatively small conformational changes of the enzyme active site and substrate strengthen the hydrogen bonds that stabilize the intermediate, thereby facilitating the proton transfer reactions. Moreover, the conformational and electrostatic changes associated with these reactions are not limited to the active site but rather extend throughout the entire enzyme. PMID:19799395

Castable plastic mold with electroplatable base

DOEpatents

Domeier, Linda A.; Morales, Alfredo M.; Gonzales, Marcela G.; Keifer, Patrick M.

2004-01-20

A sacrificial plastic mold having an electroplatable backing is provided as are methods of making such a mold via the infusion of a castable liquid formulation through a porous metal substrate (sheet, screen, mesh or foam) and into the features of a micro-scale master mold. Upon casting and demolding, the porous metal substrate is embedded within the cast formulation and projects a plastic structure with features determined by the mold tool. The plastic structure provides a sacrificial plastic mold mechanically bonded to the porous metal substrate, which provides a conducting support suitable for electroplating either contiguous or non-contiguous metal replicates. After electroplating and lapping, the sacrificial plastic can be dissolved, leaving the desired metal structure bonded to the porous metal substrate. Optionally, the electroplated structures may be debonded from the porous substrate by selective dissolution of the porous substrate or a coating thereon.

Thermal barrier coatings with (Al2O3-Y2O3)/(Pt or Pt-Au) composite bond coat and 8YSZ top coat on Ni-based superalloy

NASA Astrophysics Data System (ADS)

Yao, Junqi; He, Yedong; Wang, Deren; Peng, Hui; Guo, Hongbo; Gong, Shengkai

2013-12-01

Developing new bond coat has been acknowledged as an effective way to extend the service life of thermal barrier coating (TBC) during high temperature. In this study, novel thermal barrier coating system, which is composed with an (Al2O3-Y2O3)/(Pt or Pt-Au) composite bond coat and a YSZ top coat on Ni-based superalloy, has been prepared by magnetron sputtering and EB-PVD, respectively. It is demonstrated, from the cyclic oxidation tests in air at 1100 °C for 200 h, that the YSZ top coat and alloy substrate can be bonded together effectively by the (Al2O3-Y2O3)/(Pt or Pt-Au) composite coating, showing excellent resistance to oxidation, cracking and buckling. These beneficial results can be attributed to the sealing effect of such composite coating, by which the alloy substrate can be protected from oxidation and the interdiffusion between the bond coat and alloy substrate can be avoided; and the toughening effect of noble metals and composite structure of bond coat, by which the micro-cracks propagation can be inhibited and the stress in bond coat can be relaxed. This ceramic/noble metal composite coating can be a considerable structure which would has great application prospect in the TBC.

Durability of bonds and clinical success of adhesive restorations

PubMed Central

Carvalho, Ricardo M.; Manso, Adriana P.; Geraldeli, Saulo; Tay, Franklin R.; Pashley, David H.

2013-01-01

Resin-dentin bond strength durability testing has been extensively used to evaluate the effectiveness of adhesive systems and the applicability of new strategies to improve that property. Clinical effectiveness is determined by the survival rates of restorations placed in non-carious cervical lesions (NCCL). While there is evidence that the bond strength data generated in laboratory studies somehow correlates with the clinical outcome of NCCL restorations, it is questionable whether the knowledge of bonding mechanisms obtained from laboratory testing can be used to justify clinical performance of resin-dentin bonds. There are significant morphological and structural differences between the bonding substrate used in in vitro testing versus the substrate encountered in NCCL. These differences qualify NCCL as a hostile substrate for bonding, yielding bond strengths that are usually lower than those obtained in normal dentin. However, clinical survival time of NCCL restorations often surpass the durability of normal dentin tested in the laboratory. Likewise, clinical reports on the long-term survival rates of posterior composite restorations defy the relatively rapid rate of degradation of adhesive interfaces reported in laboratory studies. This article critically analyzes how the effectiveness of adhesive systems is currently measured, to identify gaps in knowledge where new research could be encouraged. The morphological and chemical analysis of bonded interfaces of resin composite restorations in teeth that had been in clinical service for many years, but were extracted for periodontal reasons, could be a useful tool to observe the ultrastructural characteristics of restorations that are regarded as clinically acceptable. This could help determine how much degradation is acceptable for clinical success. PMID:22192252

Fabrication of high aspect grating using bonded substrate for X-ray refraction imaging by Talbot-Lau interferometer

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

Tada, Takuji; Murakoshi, Dai; Ishii, Hiroyasu

2012-07-31

In order to improve the image quality of X-ray refraction images using a Talbot-Lau interferometer, we have been attempting to fabricate gratings with high aspect ratio. In our attempt, deep grooves of grating structure were channeled on a Si substrate bonded by Au diffusion bonding method, and the grooves were filled with Au where the Au layer used for the bonding Si substrate was acting as a seed layer of Au electroplating. From the results of a visibility measurement and a cross sectional SEM image, it was confirmed that the grooves with a pitch of 5.8 {mu}m and a depthmore » of 100 {mu}m could be successfully filled with Au over a large area of 72 Multiplication-Sign 80 mm{sup 2}. Using this grating, the X-ray refraction images for the cartilage of a knee joint of a livestock pig could be obtained where SPS method was employed for the single-shot image acquisition.« less

Low thermal resistance power module assembly

DOEpatents

Hassani, Vahab; Vlahinos, Andreas; Bharathan, Desikan

2010-12-28

A power module assembly (400) with low thermal resistance and enhanced heat dissipation to a cooling medium. The assembly includes a heat sink or spreader plate (410) with passageways or openings (414) for coolant that extend through the plate from a lower surface (411) to an upper surface (412). A circuit substrate (420) is provided and positioned on the spreader plate (410) to cover the coolant passageways. The circuit substrate (420) includes a bonding layer (422) configured to extend about the periphery of each of the coolant passageways and is made up of a substantially nonporous material. The bonding layer (422) may be solder material which bonds to the upper surface (412) of the plate to provide a continuous seal around the upper edge of each opening (414) in the plate. The assembly includes power modules (430) mounted on the circuit substrate (420) on a surface opposite the bonding layer (422). The power modules (430) are positioned over or proximal to the coolant passageways.

Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E [Kennewick, WA; Zemanian, Thomas S [Richland, WA; Liu, Jun [West Richland, WA; Shin, Yongsoon [Richland, WA

2003-03-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-05-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-06-22

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2005-01-25

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Evaluation of Tack Coat Bond Strength Tests

DOT National Transportation Integrated Search

2018-05-01

Poor bonding between asphalt pavement overlays and the substrate pavement layer can greatly influence the long term performance of hot mix asphalt (HMA) in the form of premature cracking and fatigue. The primary method to achieve bonding between laye...

Second generation engineering of transketolase for polar aromatic aldehyde substrates.

PubMed

Payongsri, Panwajee; Steadman, David; Hailes, Helen C; Dalby, Paul A

2015-04-01

Transketolase has significant industrial potential for the asymmetric synthesis of carboncarbon bonds with new chiral centres. Variants evolved on propanal were found previously with nascent activity on polar aromatic aldehydes 3-formylbenzoic acid (3-FBA), 4-formylbenzoic acid (4-FBA), and 3-hydroxybenzaldehyde (3-HBA), suggesting a potential novel route to analogues of chloramphenicol. Here we evolved improved transketolase activities towards aromatic aldehydes, by saturation mutagenesis of two active-site residues (R358 and S385), predicted to interact with the aromatic substituents. S385 variants selectively controlled the aromatic substrate preference, with up to 13-fold enhanced activities, and KM values comparable to those of natural substrates with wild-type transketolase. S385E even completely removed the substrate inhibition for 3-FBA, observed in all previous variants. The mechanisms of catalytic improvement were both mutation type and substrate dependent. S385E improved 3-FBA activity via kcat, but reduced 4-FBA activity via KM. Conversely, S385Y/T improved 3-FBA activity via KM and 4-FBA activity via kcat. This suggested that both substrate proximity and active-site orientation are very sensitive to mutation. Comparison of all variant activities on each substrate indicated different binding modes for the three aromatic substrates, supported by computational docking. This highlights a potential divergence in the evolution of different substrate specificities, with implications for enzyme engineering. Copyright © 2015 Elsevier Inc. All rights reserved.

Key Durability Issues with Mullite-Based Environmental Barrier Coatings for Si-Based Ceramics

NASA Technical Reports Server (NTRS)

Lee, Kang N.

1999-01-01

Plasma-sprayed mullite (3Al2O3 central dot 2SiO2) and mullite/yttria-stabilized-zirconia (YSZ) dual layer coatings have been developed to protect silicon-based ceramics from environmental attack. Mullite-based coating systems show excellent durability in air. However, in combustion environments, corrosive species such as molten salt or water vapor penetrate through cracks in the coating and attack the Si-based ceramics along the interface, Thus modification of the coating system for enhanced crack-resistance is necessary for long-term durability in combustion environments. Other key durability issues include interfacial contamination and coating/substrate bonding. Interfacial contamination leads to enhanced oxidation and interfacial pore formation, while weak coating/substrate bonding leads to rapid attack of the interface by corrosive species, both of which can cause premature failure of the coating. Interfacial contamination can be minimized by limiting impurities in coating and substrate materials. The interface may be modified to improve the coating/substrate bond.

Key Durability Issues with Mullite-Based Environmental Barrier Coatings for Si-Based Ceramics

NASA Technical Reports Server (NTRS)

Lee, Kang N.

2000-01-01

Plasma-sprayed mullite (3Al2O3.2SiO2) and mullite/yttria-stabilized-zirconia (YSZ) dual layer coatings have been developed to protect silicon -based ceramics from environmental attack. Mullite-based coating systems show excellent durability in air. However, in combustion environments, corrosive species such as molten salt or water vapor penetrate through cracks in the coating and attack the Si-based ceramics along the interface. Thus the modification of the coating system for enhanced crack-resistance is necessary for long-term durability in combustion environments. Other key durability issues include interfacial contamination and coating/substrate bonding. Interfacial contamination leads to enhanced oxidation and interfacial pore formation, while a weak coating/substrate bonding leads to rapid attack of the interface by corrosive species, both of which can cause a premature failure of the coating. Interfacial contamination can be minimized by limiting impurities in coating and substrate materials. The interface may be modified to improve the coating/substrate bond.

One-step femtosecond laser welding and internal machining of three glass substrates

NASA Astrophysics Data System (ADS)

Tan, Hua; Duan, Ji'an

2017-05-01

In this paper, it demonstrated one-step femtosecond laser welding and internal machining of three fused silica substrates in the optical- and non-optical-contact regimes by focusing 1030-nm laser pulses at the middle of the second substrate. Focusing laser pulses within the second glass in optical-contact and non-optical-contact samples induces permanent internal structural modification, leading to the three glass substrates bonding together simultaneously. The bonding mechanism is based on the internal modification of glass, and this mechanism is different from that of ordinary glass welding at the interface. Welding-spot size is affected by not only the gap distance (ablation effect) and heat transmission, but also by gravity through examining the sizes of the welding spots on the four contact welding surfaces. The maximum bonding strength of the lower interface (56.2 MPa) in the optical-contact regime is more than double that (27.6 MPa) in the non-optical-contact regime.

RF sputtering for controlling dihydride and monohydride bond densities in amorphous silicon hydride

DOEpatents

Jeffery, F.R.; Shanks, H.R.

1980-08-26

A process is described for controlling the dihydride and monohydride bond densities in hydrogenated amorphous silicone produced by reactive rf sputtering of an amorphous silicon target. There is provided a chamber with an amorphous silicon target and a substrate therein with the substrate and the target positioned such that when rf power is applied to the target the substrate is in contact with the sputtering plasma produced thereby. Hydrogen and argon are fed to the chamber and the pressure is reduced in the chamber to a value sufficient to maintain a sputtering plasma therein, and then rf power is applied to the silicon target to provide a power density in the range of from about 7 watts per square inch to about 22 watts per square inch to sputter an amorphous solicone hydride onto the substrate, the dihydride bond density decreasing with an increase in the rf power density. Substantially pure monohydride films may be produced.

Recombinant S. cerevisiae expressing Old Yellow Enzymes from non-conventional yeasts: an easy system for selective reduction of activated alkenes

PubMed Central

2014-01-01

Background Old Yellow Enzymes (OYEs) are flavin-dependent enoate reductases (EC 1.6.99.1) that catalyze the stereoselective hydrogenation of electron-poor alkenes. Their ability to generate up to two stereocenters by the trans-hydrogenation of the C = C double bond is highly demanded in asymmetric synthesis. Isolated redox enzymes utilization require the addition of cofactors and systems for their regeneration. Microbial whole-cells may represent a valid alternative combining desired enzymatic activity and efficient cofactor regeneration. Considerable efforts were addressed at developing novel whole-cell OYE biocatalysts, based on recombinant Saccharomyces cerevisiae expressing OYE genes. Results Recombinant S. cerevisiae BY4741∆Oye2 strains, lacking endogenous OYE and expressing nine separate OYE genes from non-conventional yeasts, were used as whole-cell biocatalysts to reduce substrates with an electron-poor double bond activated by different electron-withdrawing groups. Ketoisophorone, α-methyl-trans-cinnamaldehyde, and trans-β-methyl-β-nitrostyrene were successfully reduced with high rates and selectivity. A series of four alkyl-substituted cyclohex-2-enones was tested to check the versatility and efficiency of the biocatalysts. Reduction of double bond occurred with high rates and enantioselectivity, except for 3,5,5-trimethyl-2-cyclohexenone. DFT (density functional theory) computational studies were performed to investigate whether the steric hindrance and/or the electronic properties of the substrates were crucial for reactivity. The three-dimensional structure of enoate reductases from Kluyveromyces lodderae and Candida castellii, predicted through comparative modeling, resulted similar to that of S. cerevisiae OYE2 and revealed the key role of Trp116 both in substrate specificity and stereocontrol. All the modeling studies indicate that steric hindrance was a major determinant in the enzyme reactivity. Conclusions The OYE biocatalysts, based on recombinant S. cerevisiae expressing OYE genes from non-conventional yeasts, were able to differently reduce the activated double bond of enones, enals and nitro-olefins, exhibiting a wide range of substrate specificity. Moreover whole-cells biocatalysts bypassed the necessity of the cofactor recycling and, tuning reaction parameters, allowed the synthetic exploitation of endogenous carbonyl reductases. Molecular modeling studies highlighted key structural features for further improvement of catalytic properties of OYE enzymes. PMID:24767246

Effects of boron-nitride substrates on Stone-Wales defect formation in graphene: An ab initio molecular dynamics study

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

Jin, K.; Xiao, H. Y.; Zhang, Y.

2014-05-19

Ab initio molecular dynamics simulations are performed to investigate the effects of a boron nitride (BN) substrate on Stone-Wales (SW) defect formation and recovery in graphene. It is found that SW defects can be created by an off-plane recoil atom that interacts with the BN substrate. A mechanism with complete bond breakage for formation of SW defects in suspended graphene is also revealed for recoils at large displacement angles. In addition, further irradiation can result in recovery of the SW defects through a bond rotation mechanism in both graphene and graphene/BN, and the substrate has little effect on the recoverymore » process. This study indicates that the BN substrate enhances the irradiation resistance of graphene.« 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.

Failure Mechanisms of the Coating/Metal Interface in Waterborne Coatings: The Effect of Bonding

PubMed Central

Wan, Hongxia; Song, Dongdong; Li, Xiaogang; Zhang, Dawei; Gao, Jin; Du, Cuiwei

2017-01-01

Waterborne coating is the most popular type of coating, and improving its performance is a key point of research. Cathodic delamination is one of the major modes of failure for organic coatings. It refers to the weakening or loss of adhesion between the coating and substrate. Physical and chemical characteristics of coatings have been studied via scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle measurements, Fourier transform infrared spectroscopy (FTIR), and secondary ion mass spectrometry (SIMS). Early heterogeneous swelling at the metal-coating interface in non-defective coated metals was elucidated using frequency-dependent alternating-current scanning electrochemical microscopy. Two types of coatings (styrene-acrylic coating and terpolymer coating) were compared. The effects of thickness, surface roughness, and chemical bonding on cathodic delamination were investigated. PMID:28772757

Ultraviolet-Visible (UV-Vis) and Fluorescence Spectroscopic Investigation of the Interactions of Ionic Liquids and Catalase.

PubMed

Dong, Xing; Fan, Yunchang; Yang, Peng; Kong, Jichuan; Li, Dandan; Miao, Juan; Hua, Shaofeng; Hu, Chaobing

2016-11-01

The inhibitory effects of nine ionic liquids (ILs) on the catalase activity were investigated using fluorescence, absorption ultraviolet-visible spectroscopy. The interactions of ILs and catalase on the molecular level were studied. The experimental results indicated that ILs could inhibit the catalase activity and their inhibitory abilities depended on their chemical structures. Fluorescence experiments showed that hydrogen bonding played an important role in the interaction process. The inhibitory abilities of ILs on catalase activity could be simply described by their hydrophobicity and hydrogen bonding abilities. Unexpected less inhibitory effects of trifluoromethanesulfonate (TfO - ) might be ascribed to its larger size, which makes it difficult to go through the substrate channel of catalase to the active site. © The Author(s) 2016.

Durable soy-based adhesive dispersions

Treesearch

James M. Wescott; Amy Traska; Charles R. Frihart; Linda Lorenz

2005-01-01

An important aspect of any adhesive bond is that the bond maintains its integrity during its end use. Epoxies form highly durable bonds with many substrates but are usually not considered capable of forming completely durable bonds with wood by standard accelerated tests. However, epoxies are sold for wood boat construction, and some data have indicated that epoxies...

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

Qasim, Mohammad A., E-mail: qasimm@ipfw.edu; Song, Jikui; Markley, John L.

Research highlights: {yields} Large pK shifts in ionizable groups when buried in the protein interior. {yields} Substrate dependent shifts in pH optimum for serine proteases. {yields} Lys side chain is a stronger acid in serine protease S{sub 1} pocket than Asp side chain. -- Abstract: Enzymatic hydrolysis of the synthetic substrate succinyl-Ala-Ala-Pro-Xxx-pNA (where Xxx = Leu, Asp or Lys) catalyzed by bovine chymotrypsin (CHYM) or Streptomyces griseus protease B (SGPB) has been studied at different pH values in the pH range 3-11. The pH optima for substrates having Leu, Asp, and Lys have been found to be 7.5-8.0, 5.5-6.0, andmore » {approx}10, respectively. At the normally reported pH optimum (pH 7-8) of CHYM and SGPB, the substrate with Leu at the reactive site is more than 25,000-fold more reactive than that with Asp. However, when fully protonated, Asp is nearly as good a substrate as Leu. The pK values of the side chains of Asp and Lys in the hydrophobic S{sub 1} pocket of CHYM and SGPB have been calculated from pH-dependent hydrolysis data and have been found to be about 9 for Asp and 7.4 and 9.7 for Lys for CHYM and SGPB, respectively. The results presented in this communication suggest a possible application of CHYM like enzymes in cleaving peptide bonds contributed by acidic amino acids between pH 5 and 6.« less

A dye-decolorizing peroxidase from Bacillus subtilis exhibiting substrate-dependent optimum temperature for dyes and β-ether lignin dimer

PubMed Central

Min, Kyoungseon; Gong, Gyeongtaek; Woo, Han Min; Kim, Yunje; Um, Youngsoon

2015-01-01

In the biorefinery using lignocellulosic biomass as feedstock, pretreatment to breakdown or loosen lignin is important step and various approaches have been conducted. For biological pretreatment, we screened Bacillus subtilis KCTC2023 as a potential lignin-degrading bacterium based on veratryl alcohol (VA) oxidation test and the putative heme-containing dye-decolorizing peroxidase was found in the genome of B. subtilis KCTC2023. The peroxidase from B. subtilis KCTC2023 (BsDyP) was capable of oxidizing various substrates and atypically exhibits substrate-dependent optimum temperature: 30°C for dyes (Reactive Blue19 and Reactive Black5) and 50°C for high redox potential substrates (2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid [ABTS], VA, and veratryl glycerol-β-guaiacyl ether [VGE]) over +1.0 V vs. normal hydrogen electrode. At 50°C, optimum temperature for high redox potential substrates, BsDyP not only showed the highest VA oxidation activity (0.13 Umg−1) among the previously reported bacterial peroxidases but also successfully achieved VGE decomposition by cleaving Cα-Cβ bond in the absence of any oxidative mediator with a specific activity of 0.086 Umg−1 and a conversion rate of 53.5%. Based on our results, BsDyP was identified as the first bacterial peroxidase capable of oxidizing high redox potential lignin-related model compounds, especially VGE, revealing a previously unknown versatility of lignin degrading biocatalyst in nature. PMID:25650125

Plasma spraying of zirconia-reinforced hydroxyapatite composite coatings on titanium: part I: phase, microstructure and bonding strength.

PubMed

Chang, E; Chang, W J; Wang, B C; Yang, C Y

1997-04-01

Plasma-sprayed hydroxyapatite (HA) coatings applied to metal substrates can induce a direct chemical bond with bone and hence achieve biological fixation of the implant. However, the poor bonding strength between HA and substrate has been of concern to orthopaedists. In this study, two submicrometre ZrO2 powders stabilized with both 3 and 8 mol% Y2O3 (TZ3Y and TZ8Y, respectively) were incorporated in a plasma-sprayed HA coating on Ti-6Al-4V substrate to investigate the change in phase, microstructure and bonding strength. The results show that ZrO2 composite coatings contain more unmelted particles and greater porosity. During plasma spraying, ZrO2 reacts with the CaO in HA to form CaZrO3 and accelerates HA decomposition to alpha-TCP and Ca4P2O9. Nevertheless, bonding strength increases with increase of ZrO2 content in the range 0 to 10 wt% studied. The higher Y2O3-containing TZ8Y apparently exerts a greater strengthening effect than the lower Y2O3-containing TZ3Y.

Evaluation of metal bond strength to dentin and enamel using different adhesives and surface treatments.

PubMed

Dundar, Mine; Gungor, Mehmet Ali; Cal, Ebru; Darcan, Alev; Erdem, Adalet

2007-01-01

Because adherence of base metal alloys is important for the long-term clinical success of adhesive fixed partial dentures, it has been necessary to improve adhesion to metal substrate by using different surface treatments. This study used different surface conditioning methods and two different luting resins to evaluate the shear bond strength of base metal alloys to dentin and enamel. Sixty noncarious freshly extracted human teeth were mounted in a plastic holder filled with autopolymerized acrylic resin. After the roots were removed and 30 flat enamel and 30 flat dentin surfaces were exposed, the specimens were divided randomly into two main luting cement groups. Sixty nickel chromium (NiCr) metal specimens were fabricated and subjected to three different surface conditioning procedures: sandblasting with 50 microm aluminum oxide, tribochemical silica coating, and a combination of the two. Scanning electron mircoscopy (SEM) evaluations revealed mainly cohesive failures. Self-cure adhesive resulted in higher bond strengths to dental substrates. Higher bond strengths were achieved through a combination of sandblasting and tribochemical silica coating; however, further clinical research is required. A surface treatment that combines sandblasting with tribochemical silica coating can achieve a more effective bond for adhesive restorations with metal substrates.

Mechanism of papain-catalyzed synthesis of oligo-tyrosine peptides.

PubMed

Mitsuhashi, Jun; Nakayama, Tsutomu; Narai-Kanayama, Asako

2015-01-01

Di-, tri-, and tetra-tyrosine peptides with angiotensin I-converting enzyme inhibitory activity were synthesized by papain-catalyzed polymerization of L-tyrosine ethyl ester in aqueous media at 30 °C. Varying the reaction pH from 6.0 to 7.5 and the initial concentration of the ester substrate from 25 to 100 mM, the highest yield of oligo-tyrosine peptides (79% on a substrate basis) was produced at pH 6.5 and 75 mM, respectively. In the reaction initiated with 100 mM of the substrate, approx. 50% yield of insoluble, highly polymerized peptides accumulated. At less than 15 mM, the reaction proceeded poorly; however, from 30 mM to 120 mM a dose-dependent increase in the consumption rate of the substrate was observed with a sigmoidal curve. Meanwhile, each of the tri- and tetra-tyrosine peptides, even at approx. 5mM, was consumed effectively by papain but was not elongated to insoluble polymers. For deacylation of the acyl-papain intermediate through which a new peptide bond is made, L-tyrosine ethyl ester, even at 5mM, showed higher nucleophilic activity than di- and tri-tyrosine. These results indicate that the mechanism through which papain polymerizes L-tyrosine ethyl ester is as follows: the first interaction between papain and the ester substrate is a rate-limiting step; oligo-tyrosine peptides produced early in the reaction period are preferentially used as acyl donors, while the initial ester substrate strongly contributes as a nucleophile to the elongation of the peptide product; and the balance between hydrolytic fragmentation and further elongation of oligo-tyrosine peptides is dependent on the surrounding concentration of the ester substrate. Copyright © 2015 Elsevier Inc. All rights reserved.

Composite foam structures

NASA Technical Reports Server (NTRS)

Williams, Brian E. (Inventor); Brockmeyer, Jerry (Inventor); Tuffias, Robert H. (Inventor)

2005-01-01

A composite rigid foam structure that has a skin or coating on at least one of its surfaces. The skin is formed in situ by thermal spray techniques. The skin is bonded substantially throughout the surface of the porous substrate to the peripheries of the pores. The skin on the average does not penetrate the surface of the substrate by more than the depth of about 2 to 5 pores. Thus, thermal spraying the skin onto the rigid foam produces a composite that is tightly and uniformly bonded together without unduly increasing the weight of the composite structure. Both thermal conductivity and bonding are excellent.

Transfer of InP epilayers by wafer bonding

NASA Astrophysics Data System (ADS)

Hjort, Klas

2004-08-01

Wafer bonding increases the freedom of design in the integration of dissimilar materials. For example, it is interesting to combine III-V compounds that have direct band gap and high mobility with silicon (Si) that is extensively used in microelectronic applications. The interest to integrate III-V-based materials with Si arises primarily from two types of applications: smart pixels for optical intra- and inter-chip interconnects in the so-called optoelectronic integrated circuits, and optoelectronic devices using some material advantages of combining III-V with Si. Also, in the III-V industry larger substrates are crucial for higher efficiency in high-volume production, and especially so for monolithic microwave integrated circuits (MMIC). For indium phosphide (InP) the development of large-area substrates has not been able to keep up with market demands. One way to circumvent this problem is to use silicon substrates that are large-area, low-cost, and mechanically strong with high thermal conductivity. In addition, silicon is transparent at the emission wavelengths most often used in InP-based optoelectronics. Unfortunately, the large lattice-mismatch, 8.1%, between silicon and InP, has limited the success of heteroepitaxial growth. Hence, one alternative to be reviewed is InP-to-Si wafer bonding. When a direct semiconductor interface is not needed there are several other means of wafer bonding, e.g. adhesive, eutectic, and solid-state. These processes can be used for direct integration of small islets of epitaxially thin InP microelectronics onto other substrates, e.g. by transferring of InP-based epilayers to a Si-based microwave circuit by pick-and-place, BCB resist adhesive bonding and sacrificing of the InP substrate.

Cryogenic Temperature-Gradient Foam/Substrate Tensile Tester

NASA Technical Reports Server (NTRS)

Vailhe, Christophe

2003-01-01

The figure shows a fixture for measuring the tensile strength of the bond between an aluminum substrate and a thermally insulating polymeric foam. The specimen is meant to be representative of insulating foam on an aluminum tank that holds a cryogenic liquid. Prior to the development of this fixture, tensile tests of this type were performed on foam/substrate specimens immersed in cryogenic fluids. Because the specimens were cooled to cryogenic temperatures throughout their thicknesses, they tended to become brittle and to fracture at loads below true bond tensile strengths. The present fixture is equipped to provide a thermal gradient from cryogenic temperature at the foam/substrate interface to room temperature on the opposite foam surface. The fixture includes an upper aluminum block at room temperature and a lower aluminum block cooled to -423 F (approx. -253 C) by use of liquid helium. In preparation for a test, the metal outer surface (the lower surface) of a foam/substrate specimen is bonded to the lower block and the foam outer surface (the upper surface) of the specimen is bonded to the upper block. In comparison with the through-the-thickness cooling of immersion testing, the cryogenic-to-room-temperature thermal gradient that exists during testing on this fixture is a more realistic approximation of the operational thermal condition of sprayed insulating foam on a tank of cryogenic liquid. Hence, tensile tests performed on this fixture provide more accurate indications of operational bond tensile strengths. In addition, the introduction of the present fixture reduces the cost of testing by reducing the amount of cryogenic liquid consumed and the time needed to cool a specimen.

Direct nitration and azidation of aliphatic carbons by an iron-dependent halogenase

PubMed Central

Chang, Wei-chen; Layne, Andrew P; Miles, Linde A; Krebs, Carsten

2014-01-01

Iron-dependent halogenases employ cis-halo-Fe(IV)-oxo (haloferryl) complexes to functionalize unactivated aliphatic carbon centers, a capability elusive to synthetic chemists. Halogenation requires (1) coordination of a halide anion (Cl− or Br−) to the enzyme's Fe(II) cofactor; (2) coupled activation of O2 and decarboxylation of α-ketoglutarate to generate the haloferryl intermediate; (3) abstraction of hydrogen (H•) from the substrate by the ferryl oxo group; and (4) transfer of the cis halogen as Cl• or Br• to the substrate radical. This enzymatic solution to an unsolved chemical challenge is potentially generalizable to installation of other functional groups, provided that the corresponding anions can support the four requisite steps. We show here that the wild-type halogenase SyrB2 can indeed direct aliphatic nitration and azidation reactions by the same chemical logic. The discovery and enhancement by mutagenesis of these previously unknown reaction types suggests unrecognized or untapped versatility in ferryl-mediated enzymatic C–H-bond activation. PMID:24463698

Visualizing the Reaction Cycle in an Iron(II)- and 2-(Oxo)-glutarate-Dependent Hydroxylase.

PubMed

Mitchell, Andrew J; Dunham, Noah P; Martinie, Ryan J; Bergman, Jonathan A; Pollock, Christopher J; Hu, Kai; Allen, Benjamin D; Chang, Wei-Chen; Silakov, Alexey; Bollinger, J Martin; Krebs, Carsten; Boal, Amie K

2017-10-04

Iron(II)- and 2-(oxo)-glutarate-dependent oxygenases catalyze diverse oxidative transformations that are often initiated by abstraction of hydrogen from carbon by iron(IV)-oxo (ferryl) complexes. Control of the relative orientation of the substrate C-H and ferryl Fe-O bonds, primarily by direction of the oxo group into one of two cis-related coordination sites (termed inline and offline), may be generally important for control of the reaction outcome. Neither the ferryl complexes nor their fleeting precursors have been crystallographically characterized, hindering direct experimental validation of the offline hypothesis and elucidation of the means by which the protein might dictate an alternative oxo position. Comparison of high-resolution X-ray crystal structures of the substrate complex, an Fe(II)-peroxysuccinate ferryl precursor, and a vanadium(IV)-oxo mimic of the ferryl intermediate in the l-arginine 3-hydroxylase, VioC, reveals coordinated motions of active site residues that appear to control the intermediate geometries to determine reaction outcome.

Structural Mechanism for the Temperature-Dependent Activation of the Hyperthermophilic Pf2001 Esterase.

PubMed

Varejão, Nathalia; De-Andrade, Rafael A; Almeida, Rodrigo V; Anobom, Cristiane D; Foguel, Debora; Reverter, David

2018-02-06

Lipases and esterases constitute a group of enzymes that catalyze the hydrolysis or synthesis of ester bonds. A major biotechnological interest corresponds to thermophilic esterases, due to their intrinsic stability at high temperatures. The Pf2001 esterase from Pyrococcus furiosus reaches its optimal activity between 70°C and 80°C. The crystal structure of the Pf2001 esterase shows two different conformations: monomer and dimer. The structures reveal important rearrangements in the "cap" subdomain between monomer and dimer, by the formation of an extensive intertwined helical interface. Moreover, the dimer interface is essential for the formation of the hydrophobic channel for substrate selectivity, as confirmed by mutagenesis and kinetic analysis. We also provide evidence for dimer formation at high temperatures, a process that correlates with its enzymatic activation. Thus, we propose a temperature-dependent activation mechanism of the Pf2001 esterase via dimerization that is necessary for the substrate channel formation in the active-site cleft. Copyright © 2017 Elsevier Ltd. All rights reserved.

High voltage photo switch package module

DOEpatents

Sullivan, James S; Sanders, David M; Hawkins, Steven A; Sampayan, Stephen E

2014-02-18

A photo-conductive switch package module having a photo-conductive substrate or wafer with opposing electrode-interface surfaces, and at least one light-input surface. First metallic layers are formed on the electrode-interface surfaces, and one or more optical waveguides having input and output ends are bonded to the substrate so that the output end of each waveguide is bonded to a corresponding one of the light-input surfaces of the photo-conductive substrate. This forms a waveguide-substrate interface for coupling light into the photo-conductive wafer. A dielectric material such as epoxy is then used to encapsulate the photo-conductive substrate and optical waveguide so that only the metallic layers and the input end of the optical waveguide are exposed. Second metallic layers are then formed on the first metallic layers so that the waveguide-substrate interface is positioned under the second metallic layers.

Microshear bond strength of composite resins to enamel and porcelain substrates utilizing unfilled versus filled resins.

PubMed

Najafi-Abrandabadi, Ahmad; Najafi-Abrandabadi, Siamak; Ghasemi, Amir; Kotick, Philip G

2014-11-01

Failures such as marginal discoloration and composite chipping are still the problems of tooth-colored restorations on the substrate of enamel and porcelain, which some of these problems are consequently as a result of failures in the bonding layer. Using filled resin has been recently introduced to increase the bond strength of this layer. The aim of this study was to compare the microshear bond strength (μ-SBS) of composite resins to enamel incubated in periods of 24 h and 9 months and porcelain with unfilled resin and flowable composites (filled resin). In this in vitro study, two groups of 75 enamel samples with different storage times (24 h and 9 months) and a group of 75 porcelain samples were used. They were divided into 5 experimental groups of 15 samples in each. Composite cylinders in tygon tubes were bonded on the surface of acid-etched enamel and pretreated porcelain. Wave, Wave MV, Wave HV, Grandioflow and Margin Bond were used as bonding agents. The μ-SBS was measured at the speed of 1.0 mm/min. The bond strengths were analyzed with one-way analysis of variance (ANOVA) test followed by Tukey test. P < 0.05 was selected as the level of statistical significance in this study. The results showed that for enamel (24 h), the μ-SBS of the Wave MV and Wave HV groups were significantly lower than the Margin Bond group. Tukey test indicated the absence of a significant difference between the μ-SBS of the Wave group and the Margin Bond group. However, the μ-SBS of the Grandioflow group was significantly higher than the one for the Margin Bond as a bonding agent. In enamel (9 months), there was a significant difference between the Grandioflow and Margin Bond groups. Regarding bonding to the porcelain the one-way ANOVA test did not show a significant difference among the groups. This study revealed that flowable composites (filled resins) can be used instead of unfilled resins in bonding composite resins to enamel and porcelain substrates.

Densification of porous refractory substrates. [space shuttle orbiter tiles

NASA Technical Reports Server (NTRS)

Ecord, G. M.; Schomburg, C. (Inventor)

1982-01-01

A hydrolyzed tetraethyl orthosilicate is applied to the surface of a porous refractory substrate following which the substrate is heated to a temperature and for a period of time sufficient to bond the silica released from the tetraethyl orthosilicate to the substrate. The surface is thus densified and strengthened.

Site-selective and stereoselective functionalization of non-activated tertiary C-H bonds

NASA Astrophysics Data System (ADS)

Liao, Kuangbiao; Pickel, Thomas C.; Boyarskikh, Vyacheslav; Bacsa, John; Musaev, Djamaladdin G.; Davies, Huw M. L.

2017-11-01

The synthesis of complex organic compounds usually relies on controlling the reactions of the functional groups. In recent years, it has become possible to carry out reactions directly on the C-H bonds, previously considered to be unreactive. One of the major challenges is to control the site-selectivity because most organic compounds have many similar C-H bonds. The most well developed procedures so far rely on the use of substrate control, in which the substrate has one inherently more reactive C-H bond or contains a directing group or the reaction is conducted intramolecularly so that a specific C-H bond is favoured. A more versatile but more challenging approach is to use catalysts to control which site in the substrate is functionalized. p450 enzymes exhibit C-H oxidation site-selectivity, in which the enzyme scaffold causes a specific C-H bond to be functionalized by placing it close to the iron-oxo haem complex. Several studies have aimed to emulate this enzymatic site-selectivity with designed transition-metal catalysts but it is difficult to achieve exceptionally high levels of site-selectivity. Recently, we reported a dirhodium catalyst for the site-selective functionalization of the most accessible non-activated (that is, not next to a functional group) secondary C-H bonds by means of rhodium-carbene-induced C-H insertion. Here we describe another dirhodium catalyst that has a very different reactivity profile. Instead of the secondary C-H bond, the new catalyst is capable of precise site-selectivity at the most accessible tertiary C-H bonds. Using this catalyst, we modify several natural products, including steroids and a vitamin E derivative, indicating the applicability of this method of synthesis to the late-stage functionalization of complex molecules. These studies show it is possible to achieve site-selectivity at different positions within a substrate simply by selecting the appropriate catalyst. We hope that this work will inspire the design of even more sophisticated catalysts, such that catalyst-controlled C-H functionalization becomes a broadly applied strategy for the synthesis of complex molecules.

Influence of deposition temperature on mechanical properties of plasma-sprayed hydroxyapatite coating on titanium alloy with ZrO2 intermediate layer

NASA Astrophysics Data System (ADS)

Chou, Bang-Yen; Chang, Edward

2003-06-01

Hydroxyapatite coatings were plasma sprayed on the Ti6A14V substrate with and without an intermediate ZrO2 layer; meanwhile the temperatures of substrates were varied at 90, 140, and 200 °C. The coatings were subjected to the standard adhesion test per ASTM C633-79. The purpose of the investigation was to study the effects of those processing variables on the bonding strength and failure behavior of the system. It is found that the bonding strengths of HA/ZrO2 and HA coatings generally decrease with increasing substrate temperature, except for the HA/ZrO2 coating deposited at 200 °C. The rationale of the results is attributed to the residual stress reported in the literature. Introducing ZrO2 bond coat is found to significantly promote the bonding strength of HA coating. The possible strengthening mechanism is the rougher surface of ZrO2 bond coat and the higher toughness of ZrO2, which provide the mechanical strengthening effects. The slightly denser HA in 200 °C deposited HA coating cannot explain the high bonding strength of the HA/ZrO2 coating, nor the mechanical strengthening effect of ZrO2 intermediate layer should apply. It is believed that a stronger diffusion bonding is formed at the interface of HA and ZrO2, which increases the bonding between them chemically. The bonding strengths of HA/ZrO2 and HA coatings are correlated with the area fraction of adhesive failure of the coatings. The correlation explains the findings in this study.

The structures of the horseradish peroxidase C-ferulic acid complex and the ternary complex with cyanide suggest how peroxidases oxidize small phenolic substrates.

PubMed

Henriksen, A; Smith, A T; Gajhede, M

1999-12-03

We have solved the x-ray structures of the binary horseradish peroxidase C-ferulic acid complex and the ternary horseradish peroxidase C-cyanide-ferulic acid complex to 2.0 and 1.45 A, respectively. Ferulic acid is a naturally occurring phenolic compound found in the plant cell wall and is an in vivo substrate for plant peroxidases. The x-ray structures demonstrate the flexibility and dynamic character of the aromatic donor binding site in horseradish peroxidase and emphasize the role of the distal arginine (Arg(38)) in both substrate oxidation and ligand binding. Arg(38) hydrogen bonds to bound cyanide, thereby contributing to the stabilization of the horseradish peroxidase-cyanide complex and suggesting that the distal arginine will be able to contribute with a similar interaction during stabilization of a bound peroxy transition state and subsequent O-O bond cleavage. The catalytic arginine is additionally engaged in an extensive hydrogen bonding network, which also includes the catalytic distal histidine, a water molecule and Pro(139), a proline residue conserved within the plant peroxidase superfamily. Based on the observed hydrogen bonding network and previous spectroscopic and kinetic work, a general mechanism of peroxidase substrate oxidation is proposed.

Formation of Me-O-Si covalent bonds at the interface between polysilazane and stainless steel

NASA Astrophysics Data System (ADS)

Amouzou, Dodji; Fourdrinier, Lionel; Maseri, Fabrizio; Sporken, Robert

2014-11-01

In earlier works, we demonstrated the potential of polysilazane (PSZ) coatings for a use as insulating layers in Cu(In,Ga)Se2 (CIGS) solar cells prepared on steels substrates and showed a good adhesion between PSZ coatings and both AISI316 and AISI430 steels. In the present paper, spectroscopic techniques are used to elucidate the reason of such adhesion. X-ray Photoelectron Spectroscopy (XPS) was used to investigate surfaces for the two steel substrates and showed the presence of metal oxides and metal hydroxides at the top surface. XPS has been also used to probe interfaces between substrates and PSZ, and metallosiloxane (Me-O-Si) covalent bonds have been detected. These results were confirmed by Infra-Red Reflection Absorption Spectroscopy (IRRAS) analyses since vibrations related to Cr-O-Si and Fe-O-Si compounds were detected. Thus, the good adhesion between steel substrates and PSZ coatings was explained by covalent bonding through chemical reactions between PSZ precursors and hydroxide functional groups present on top surface of the two types of steel. Based on these results, an adhesion mechanism between steel substrates and PSZ coatings is proposed.

Rapid kinetics of dehalogenation promoted by iodotyrosine deiodinase from human thyroid.

PubMed

Bobyk, Kostyantyn D; Ballou, David P; Rokita, Steven E

2015-07-28

Reductive dehalogenation such as that catalyzed by iodotyrosine deiodinase (IYD) is highly unusual in aerobic organisms but necessary for iodide salvage from iodotyrosine generated during thyroxine biosynthesis. Equally unusual is the dependence of this process on flavin. Rapid kinetics have now been used to define the basic processes involved in IYD catalysis. Time-dependent quenching of flavin fluorescence was used to monitor halotyrosine association to IYD. The substrates chloro-, bromo-, and iodotyrosine bound with similar rate constants (kon) ranging from 1.3 × 10(6) to 1.9 × 10(6) M(-1) s(-1). Only the inert substrate analogue fluorotyrosine exhibited a significantly (5-fold) slower kon (0.3 × 10(6) M(-1) s(-1)). All data fit a standard two-state model and indicated that no intermediate complex accumulated during closure of the active site lid induced by substrate. Subsequent halide elimination does not appear to limit reactions of bromo- and iodotyrosine since both fully oxidized the reduced enzyme with nearly equivalent second-order rate constants (7.3 × 10(3) and 8.6 × 10(3) M(-1) s(-1), respectively) despite the differing strength of their carbon-halogen bonds. In contrast to these substrates, chlorotyrosine reacted with the reduced enzyme approximately 20-fold more slowly and revealed a spectral intermediate that formed at approximately the same rate as the bromo- and iodotyrosine reactions.

Rapid Kinetics of Dehalogenation Promoted by Iodotyrosine Deiodinase from Human Thyroid

PubMed Central

2015-01-01

Reductive dehalogenation such as that catalyzed by iodotyrosine deiodinase (IYD) is highly unusual in aerobic organisms but necessary for iodide salvage from iodotyrosine generated during thyroxine biosynthesis. Equally unusual is the dependence of this process on flavin. Rapid kinetics have now been used to define the basic processes involved in IYD catalysis. Time-dependent quenching of flavin fluorescence was used to monitor halotyrosine association to IYD. The substrates chloro-, bromo-, and iodotyrosine bound with similar rate constants (kon) ranging from 1.3 × 106 to 1.9 × 106 M–1 s–1. Only the inert substrate analogue fluorotyrosine exhibited a significantly (5-fold) slower kon (0.3 × 106 M–1 s–1). All data fit a standard two-state model and indicated that no intermediate complex accumulated during closure of the active site lid induced by substrate. Subsequent halide elimination does not appear to limit reactions of bromo- and iodotyrosine since both fully oxidized the reduced enzyme with nearly equivalent second-order rate constants (7.3 × 103 and 8.6 × 103 M–1 s–1, respectively) despite the differing strength of their carbon–halogen bonds. In contrast to these substrates, chlorotyrosine reacted with the reduced enzyme approximately 20-fold more slowly and revealed a spectral intermediate that formed at approximately the same rate as the bromo- and iodotyrosine reactions. PMID:26151430

Use of 5'-γ-ferrocenyl adenosine triphosphate (Fc-ATP) bioconjugates having poly(ethylene glycol) spacers in kinase-catalyzed phosphorylations.

PubMed

Martić, Sanela; Rains, Meghan K; Freeman, Daniel; Kraatz, Heinz-Bernhard

2011-08-17

The 5'-γ-ferrocenyl adenosine triphosphate (Fc-ATP) bioconjugates (3 and 4), containing the poly(ethylene glycol) spacers, were synthesized and compared to a hydrophobic analogue as co-substrates for the following protein kinases: sarcoma related kinase (Src), cyclin-dependent kinase (CDK), casein kinase II (CK2α), and protein kinase A (PKA). Electrochemical kinase assays indicate that the hydrophobic Fc-ATP analogue was an optimal co-substrate for which K(M) values were determined to be in the 30-200 μM range, depending on the particular protein kinase. The luminescence kinase assay demonstrated the kinase utility for all Fc-ATP conjugates, which is in line with the electrochemical data. Moreover, Fc-ATP bioconjugates exhibit competitive behavior with respect to ATP. Relatively poor performance of the polar Fc-ATP bioconjugates as co-substrates for protein kinases was presumably due to the additional H-bonding and electrostatic interactions of the poly(ethylene glycol) linkers of Fc-ATP with the kinase catalytic site and the target peptides. Phosphorylation of the full-length protein, His-tagged pro-caspase-3, was demonstrated through Fc-phosphoamide transfer to the Ser residues of the surface-bound protein by electrochemical means. These results suggest that electrochemical detection of the peptide and protein Fc-phosphorylation via tailored Fc-ATP co-substrates may be useful for probing protein-protein interactions.

Method For Improving The Oxidation Resistance Of Metal Substrates Coated With Thermal Barrier Coatings

DOEpatents

Thompson, Anthony Mark; Gray, Dennis Michael; Jackson, Melvin Robert

2003-05-13

A method for providing a protective coating on a metal-based substrate is disclosed. The method involves the application of an aluminum-rich mixture to the substrate to form a discontinuous layer of aluminum-rich particles, followed by the application of a second coating over the discontinuous layer of aluminum-rich particles. Aluminum diffuses from the aluminum-rich layer into the substrate, and into any bond coat layer which is subsequently applied. Related articles are also described. A method for providing a protective coating on a metal-based substrate is disclosed. The method involves the application of an aluminum-rich mixture to the substrate to form a discontinuous layer of aluminum-rich particles, followed by the application of a second coating over the discontinuous layer of aluminum-rich particles. Aluminum diffuses from the aluminum-rich layer into the substrate, and into any bond coat layer which is subsequently applied. Related articles are also described.

Wrinkling of a thin circular sheet bonded to a spherical substrate

PubMed Central

Kohn, Robert V.

2017-01-01

We consider a disc-shaped thin elastic sheet bonded to a compliant sphere. (Our sheet can slip along the sphere; the bonding controls only its normal displacement.) If the bonding is stiff (but not too stiff), the geometry of the sphere makes the sheet wrinkle to avoid azimuthal compression. The total energy of this system is the elastic energy of the sheet plus a (Winkler-type) substrate energy. Treating the thickness of the sheet h as a small parameter, we determine the leading-order behaviour of the energy as h tends to zero, and we give (almost matching) upper and lower bounds for the next-order correction. Our analysis of the leading-order behaviour determines the macroscopic deformation of the sheet; in particular, it determines the extent of the wrinkled region, and predicts the (non-trivial) radial strain of the sheet. The leading-order behaviour also provides insight about the length scale of the wrinkling, showing that it must be approximately independent of the distance r from the centre of the sheet (so that the number of wrinkles must increase with r). Our results on the next-order correction provide insight about how the wrinkling pattern should vary with r. Roughly speaking, they suggest that the length scale of wrinkling should not be exactly constant—rather, it should vary slightly, so that the number of wrinkles at radius r can be approximately piecewise constant in its dependence on r, taking values that are integer multiples of h−a with . This article is part of the themed issue ‘Patterning through instabilities in complex media: theory and applications’. PMID:28373380

Irreversible bonding of polyimide and polydimethylsiloxane (PDMS) based on a thiol-epoxy click reaction

NASA Astrophysics Data System (ADS)

Hoang, Michelle V.; Chung, Hyun-Joong; Elias, Anastasia L.

2016-10-01

Polyimide is one of the most popular substrate materials for the microfabrication of flexible electronics, while polydimethylsiloxane (PDMS) is the most widely used stretchable substrate/encapsulant material. These two polymers are essential in fabricating devices for microfluidics, bioelectronics, and the internet of things; bonding these materials together is a crucial challenge. In this work, we employ click chemistry at room temperature to irreversibly bond polyimide and PDMS through thiol-epoxy bonds using two different methods. In the first method, we functionalize the surfaces of the PDMS and polyimide substrates with mercaptosilanes and epoxysilanes, respectively, for the formation of a thiol-epoxy bond in the click reaction. In the second method, we functionalize one or both surfaces with mercaptosilane and introduce an epoxy adhesive layer between the two surfaces. When the surfaces are bonded using the epoxy adhesive without any surface functionalization, an extremely small peel strength (<0.01 N mm-1) is measured with a peel test, and adhesive failure occurs at the PDMS surface. With surface functionalization, however, remarkably higher peel strengths of ~0.2 N mm-1 (method 1) and  >0.3 N mm-1 (method 2) are observed, and failure occurs by tearing of the PDMS layer. We envision that the novel processing route employing click chemistry can be utilized in various cases of stretchable and flexible device fabrication.

ETV Program Report: Coatings for Wastewater Collection ...

EPA Pesticide Factsheets

The Standard Cement Materials, Inc. Standard Epoxy Coating 4553™ (SEC 4553) epoxy coating used for wastewater collection system rehabilitation was evaluated by EPA’s Environmental Technology Verification Program under laboratory conditions at the Center for Innovative Grouting Material and Technology (CIGMAT) Laboratory at the University of Houston. Testing was conducted over a period of six months to evaluate the coating’s (1) chemical resistance and (2) bonding strength for infrastructure applications. For chemical resistance, coated concrete and clay bricks with holidays (holes created in the coating) were used to evaluate the chemical resistance of the coating/substrate bond under a corrosive environment. Twenty coated concrete (dry and wet) and 20 coated clay brick (dry and wet) specimens were exposed to DI water and sulfuric acid solution (pH=1), and the specimens were visually inspected and weight changes measured. Evaluation of the coating-to-substrate bonding strength was determined using two modified ASTM test methods – one to determine bond strength of the coating with two specimens sandwiched together using the coating, and the second to determine the bond strength by applying a tensile load to the coating applied to specimens of each substrate. Forty-eight bonding tests were performed over the six month evaluation. The tests resulted in the following conclusions about Standard Cement’s SEC 4553 coating: • After the six-month chemi

Thermo-mechanical Fatigue Failure of Thermal Barrier Coated Superalloy Specimen

NASA Astrophysics Data System (ADS)

Subramanian, Rajivgandhi; Mori, Yuzuru; Yamagishi, Satoshi; Okazaki, Masakazu

2015-09-01

Failure behavior of thermal barrier coated (TBC) Ni-based superalloy specimens were studied from the aspect of the effect of bond coat material behavior on low cycle fatigue (LCF) and thermo-mechanical fatigue (TMF) at various temperatures and under various loading conditions. Initially, monotonic tensile tests were carried out on a MCrAlY alloy bond coat material in the temperature range of 298 K to 1273 K (25 °C to 1000 °C). Special attention was paid to understand the ductile to brittle transition temperature (DBTT). Next, LCF and TMF tests were carried out on the thermal barrier coated Ni-based alloy IN738 specimen. After these tests, the specimens were sectioned to understand their failure mechanisms on the basis of DBTT of the bond coat material. Experimental results demonstrated that the LCF and TMF lives of the TBC specimen were closely related to the DBTT of the bond coat material, and also the TMF lives were different from those of LCF tests. It has also been observed that the crack density in the bond coat in the TBC specimen was significantly dependent on the test conditions. More importantly, not only the number of cracks but also the crack penetration probability into substrate were shown to be sensitive to the DBTT.

O-H bond oxidation by a monomeric Mn(III)-OMe complex.

PubMed

Wijeratne, Gayan B; Day, Victor W; Jackson, Timothy A

2015-02-21

Manganese-containing, mid-valent oxidants (Mn(III)-OR) that mediate proton-coupled electron-transfer (PCET) reactions are central to a variety of crucial enzymatic processes. The Mn-dependent enzyme lipoxygenase is such an example, where a Mn(III)-OH unit activates fatty acid substrates for peroxidation by an initial PCET. This present work describes the quantitative generation of the Mn(III)-OMe complex, [Mn(III)(OMe)(dpaq)](+) (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate) via dioxygen activation by [Mn(II)(dpaq)](+) in methanol at 25 °C. The X-ray diffraction structure of [Mn(III)(OMe)(dpaq)](+) exhibits a Mn-OMe group, with a Mn-O distance of 1.825(4) Å, that is trans to the amide functionality of the dpaq ligand. The [Mn(III)(OMe)(dpaq)](+) complex is quite stable in solution, with a half-life of 26 days in MeCN at 25 °C. [Mn(III)(OMe)(dpaq)](+) can activate phenolic O-H bonds with bond dissociation free energies (BDFEs) of less than 79 kcal mol(-1) and reacts with the weak O-H bond of TEMPOH (TEMPOH = 2,2'-6,6'-tetramethylpiperidine-1-ol) with a hydrogen/deuterium kinetic isotope effect (H/D KIE) of 1.8 in MeCN at 25 °C. This isotope effect, together with other experimental evidence, is suggestive of a concerted proton-electron transfer (CPET) mechanism for O-H bond oxidation by [Mn(III)(OMe)(dpaq)](+). A kinetic and thermodynamic comparison of the O-H bond oxidation reactivity of [Mn(III)(OMe)(dpaq)](+) to other M(III)-OR oxidants is presented as an aid to gain more insight into the PCET reactivity of mid-valent oxidants. In contrast to high-valent counterparts, the limited examples of M(III)-OR oxidants exhibit smaller H/D KIEs and show weaker dependence of their oxidation rates on the driving force of the PCET reaction with O-H bonds.

Chemical Constraints Governing the Origin of Metabolism: The Thermodynamic Landscape of Carbon Group Transformations

NASA Technical Reports Server (NTRS)

Weber, Arthur L.; Fonda, Mark (Technical Monitor)

2001-01-01

The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies were estimated for four types reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed that (1) when carbon-carbon bond cleavage involves two different types of functional groups, transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) the energy of carbon-carbon bond transformation is strongly dependent on the type of functional group that donates the shared electron-pair during cleavage, and the group that accepts the shared electron-pair during synthesis, and (3) the energetics of C-C bond transformation is determined primarily by the half-reaction energies of the couples: carbonyl/carboxylic acid, carboxylic acid/carbon dioxide, alcohol/carbonyl, and hydrocarbon/alcohol. The energy of hydrogen-transfer between carbon groups was found to depend on the functional group class of both the hydrogen-donor and hydrogen-acceptor. From these and other observations we concluded that the chemistry of the origin of metabolism (and to a lesser degree modem metabolism) is strongly constrained by the (1) limited disproportionation energy of organic substrates that can be dissipated in a few irreversible reactions, (2) the energy-dominance of few half-reaction couples in carbon-carbon bond transformation that establishes whether a chemical reaction is energetically irreversible, reversible or unfeasible, and (3) the dependence of the transformation-energy on the oxidation state of carbon groups (functional group type) which is contingent on prior reactions in the synthetic pathway.

X-ray structures of uridine phosphorylase from Vibrio cholerae in complexes with uridine, thymidine, uracil, thymine, and phosphate anion: Substrate specificity of bacterial uridine phosphorylases

NASA Astrophysics Data System (ADS)

Prokofev, I. I.; Lashkov, A. A.; Gabdulkhakov, A. G.; Balaev, V. V.; Seregina, T. A.; Mironov, A. S.; Betzel, C.; Mikhailov, A. M.

2016-11-01

In many types of human tumor cells and infectious agents, the demand for pyrimidine nitrogen bases increases during the development of the disease, thus increasing the role of the enzyme uridine phosphorylase in metabolic processes. The rational use of uridine phosphorylase and its ligands in pharmaceutical and biotechnology industries requires knowledge of the structural basis for the substrate specificity of the target enzyme. This paper summarizes the results of the systematic study of the three-dimensional structure of uridine phosphorylase from the pathogenic bacterium Vibrio cholerae in complexes with substrates of enzymatic reactions—uridine, phosphate anion, thymidine, uracil, and thymine. These data, supplemented with the results of molecular modeling, were used to consider in detail the structural basis for the substrate specificity of uridine phosphorylases. It was shown for the first time that the formation of a hydrogen-bond network between the 2'-hydroxy group of uridine and atoms of the active-site residues of uridine phosphorylase leads to conformational changes of the ribose moiety of uridine, resulting in an increase in the reactivity of uridine compared to thymidine. Since the binding of thymidine to residues of uridine phosphorylase causes a smaller local strain of the β-N1-glycosidic bond in this the substrate compared to the uridine molecule, the β-N1-glycosidic bond in thymidine is more stable and less reactive than that in uridine. It was shown for the first time that the phosphate anion, which is the second substrate bound at the active site, interacts simultaneously with the residues of the β5-strand and the β1-strand through hydrogen bonding, thus securing the gate loop in a conformation

X-ray structures of uridine phosphorylase from Vibrio cholerae in complexes with uridine, thymidine, uracil, thymine, and phosphate anion: Substrate specificity of bacterial uridine phosphorylases

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

Prokofev, I. I.; Lashkov, A. A., E-mail: alashkov83@gmail.com; Gabdulkhakov, A. G.

In many types of human tumor cells and infectious agents, the demand for pyrimidine nitrogen bases increases during the development of the disease, thus increasing the role of the enzyme uridine phosphorylase in metabolic processes. The rational use of uridine phosphorylase and its ligands in pharmaceutical and biotechnology industries requires knowledge of the structural basis for the substrate specificity of the target enzyme. This paper summarizes the results of the systematic study of the three-dimensional structure of uridine phosphorylase from the pathogenic bacterium Vibrio cholerae in complexes with substrates of enzymatic reactions—uridine, phosphate anion, thymidine, uracil, and thymine. These data,more » supplemented with the results of molecular modeling, were used to consider in detail the structural basis for the substrate specificity of uridine phosphorylases. It was shown for the first time that the formation of a hydrogen-bond network between the 2′-hydroxy group of uridine and atoms of the active-site residues of uridine phosphorylase leads to conformational changes of the ribose moiety of uridine, resulting in an increase in the reactivity of uridine compared to thymidine. Since the binding of thymidine to residues of uridine phosphorylase causes a smaller local strain of the β-N1-glycosidic bond in this the substrate compared to the uridine molecule, the β-N1-glycosidic bond in thymidine is more stable and less reactive than that in uridine. It was shown for the first time that the phosphate anion, which is the second substrate bound at the active site, interacts simultaneously with the residues of the β5-strand and the β1-strand through hydrogen bonding, thus securing the gate loop in a conformation.« less

Investigation of the flatband voltage (V(FB)) shift of Al2O3 on N2 plasma treated Si substrate.

PubMed

Kim, Hyungchul; Lee, Jaesang; Jeon, Heeyoung; Park, Jingyu; Jeon, Hyeongtag

2013-09-01

The relationships between the physical and electrical characteristics of films treated with N2 plasma followed by forming gas annealing (FGA) were investigated. The Si substrates were treated with various radio frequency (RF) power levels under a N2 ambient. Al2O3 films were then deposited on Si substrates via remote plasma atomic-layer deposition. The plasma characteristics, such as the radical and ion density, were investigated using optical emission spectroscopy. Through X-ray photoelectron spectroscopy, the chemical-bonding configurations of the samples treated with N2 plasma and FGA were examined. The quantity of Si-N bonds increased as the RF power was increased, and Si--O--N bonds were generated after FGA. The flatband voltage (VFB) was shifted in the negative direction with increasing RF power, but the VFB values of the samples after FGA shifted in the positive direction due to the formation of Si--O--N bonds. N2 plasma treatment with various RF power levels slightly increased the leakage current due to the generation of defect sites.

Ligand-accelerated enantioselective methylene C(sp3)-H bond activation.

PubMed

Chen, Gang; Gong, Wei; Zhuang, Zhe; Andrä, Michal S; Chen, Yan-Qiao; Hong, Xin; Yang, Yun-Fang; Liu, Tao; Houk, K N; Yu, Jin-Quan

2016-09-02

Effective differentiation of prochiral carbon-hydrogen (C-H) bonds on a single methylene carbon via asymmetric metal insertion remains a challenge. Here, we report the discovery of chiral acetyl-protected aminoethyl quinoline ligands that enable asymmetric palladium insertion into prochiral C-H bonds on a single methylene carbon center. We apply these palladium complexes to catalytic enantioselective functionalization of β-methylene C-H bonds in aliphatic amides. Using bidentate ligands to accelerate C-H activation of otherwise unreactive monodentate substrates is crucial for outcompeting the background reaction driven by substrate-directed cyclopalladation, thereby avoiding erosion of enantioselectivity. The potential of ligand acceleration in C-H activation is also demonstrated by enantioselective β-C-H arylation of simple carboxylic acids without installing directing groups. Copyright © 2016, American Association for the Advancement of Science.

Bond strength of luting cement to casting and soldering alloy.

PubMed

Kumbuloglu, O; Lassila, L V J; User, A; Toksavul, S; Vallittu, P K

2006-03-01

Adjustment of metal alloy framework of the porcelain-fused-to-metal crown by soldering minor marginal deficiences prior insertion may sometimes be needed. The aim of this study was to compare shear bond strengths of four luting cements to casting metal alloy and soldering metal alloy. A total of 64 flame cast non-precious metal alloy and flame soldered metal alloy samples were used. Durelon, Panavia F, RelyX Unicem Applicap and RelyX ARC stubs were bonded to the alloy substrate surface. After stored in water at 37 degrees C for 1 week, shear bond strength of the cement to the alloy was measured. Differences were analyzed using one way ANOVA (p<0.05). There were no difference between the cast metal alloy and soldering metal alloy substrate.

Use of Vacuum Bagging for Fabricating Thermoplastic Microfluidic Devices

PubMed Central

Cassano, Christopher L.; Simon, Andrew J.; Liu, Wei; Fredrickson, Carl; Fan, Z. Hugh

2014-01-01

In this work we present a novel thermal bonding method for thermoplastic microfluidic devices. This simple method employs a modified vacuum bagging technique, a concept borrowed from the aerospace industry, to produce conventional thick substrate microfluidic devices, as well as multi-layer film devices. The bonds produced using this method are superior to those obtained using conventional thermal bonding methods, including thermal lamination, and are capable of sustaining burst pressures in excess of 550 kPa. To illustrate the utility of this method, thick substrate devices were produced, as well as a six-layer film device that incorporated several complex features. PMID:25329244

CVD aluminiding process for producing a modified platinum aluminide bond coat for improved high temperature performance

NASA Technical Reports Server (NTRS)

Nagaraj, Bangalore A. (Inventor); Williams, Jeffrey L. (Inventor)

2003-01-01

A method of depositing by chemical vapor deposition a modified platinum aluminide diffusion coating onto a superalloy substrate comprising the steps of applying a layer of a platinum group metal to the superalloy substrate; passing an externally generated aluminum halide gas through an internal gas generator which is integral with a retort, the internal gas generator generating a modified halide gas; and co-depositing aluminum and modifier onto the superalloy substrate. In one form, the modified halide gas is hafnium chloride and the modifier is hafnium with the modified platinum aluminum bond coat comprising a single phase additive layer of platinum aluminide with at least about 0.5 percent hafnium by weight percent and about 1 to about 15 weight percent of hafnium in the boundary between a diffusion layer and the additive layer. The bond coat produced by this method is also claimed.

Stretchable electronics based on Ag-PDMS composites

PubMed Central

Larmagnac, Alexandre; Eggenberger, Samuel; Janossy, Hanna; Vörös, Janos

2014-01-01

Patterned structures of flexible, stretchable, electrically conductive materials on soft substrates could lead to novel electronic devices with unique mechanical properties allowing them to bend, fold, stretch or conform to their environment. For the last decade, research on improving the stretchability of circuits on elastomeric substrates has made significant progresses but designing printed circuit assemblies on elastomers remains challenging. Here we present a simple, cost-effective, cleanroom-free process to produce large scale soft electronic hardware where standard surface-mounted electrical components were directly bonded onto all-elastomeric printed circuit boards, or soft PCBs. Ag-PDMS tracks were stencil printed onto a PDMS substrate and soft PCBs were made by bonding the top and bottom layers together and filling punched holes with Ag-PDMS to create vias. Silver epoxy was used to bond commercial electrical components and no mechanical failure was observed after hundreds of stretching cycles. We also demonstrate the fabrication of a stretchable clock generator. PMID:25434843

A Discovery of Strong Metal–Support Bonding in Nanoengineered Au–Fe 3 O 4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy

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

Han, Chang Wan; Choksi, Tej; Milligan, Cory

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous “strong metal-support bonding” between gold nanoparticles and “nano-engineered” Fe 3O 4 substrates by in-situ microscopy. During in-situ vacuum annealing of Au-Fe 3O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3O 4 on Au nanoparticles, the gold nanoparticles transform into the monolayered gold thinfilms and wet the surface of nano-Fe 3O 4, as the surface reduction of nano-Fe 3O 4 proceeds. This phenomenon results frommore » a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3O 4 and the extremely strong adhesion between Au and the reduced Fe 3O 4. This strong-metal support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and, ultimately, for the development of improved catalysts and functional nanostructures.« less

A Discovery of Strong Metal–Support Bonding in Nanoengineered Au–Fe 3 O 4 Dumbbell-like Nanoparticles by in Situ Transmission Electron Microscopy

DOE PAGES

Han, Chang Wan; Choksi, Tej; Milligan, Cory; ...

2017-06-26

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous “strong metal-support bonding” between gold nanoparticles and “nano-engineered” Fe 3O 4 substrates by in-situ microscopy. During in-situ vacuum annealing of Au-Fe 3O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3O 4 on Au nanoparticles, the gold nanoparticles transform into the monolayered gold thinfilms and wet the surface of nano-Fe 3O 4, as the surface reduction of nano-Fe 3O 4 proceeds. This phenomenon results frommore » a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3O 4 and the extremely strong adhesion between Au and the reduced Fe 3O 4. This strong-metal support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and, ultimately, for the development of improved catalysts and functional nanostructures.« less

Synthesis and evaluation of conformationally restricted inhibitors of aspartate semialdehyde dehydrogenase.

PubMed

Evitt, Andrew S; Cox, Russell J

2011-05-01

Inhibitors of the enzyme aspartate semialdehyde dehydrogenase, a key biological target for the generation of a new class of antibiotic compounds, have been developed. To investigate improvements to binding within an inhibitor series, the lowering of the entropic barrier to binding through conformational restriction was investigated. A library of linear and cyclic substrate analogues was generated and computational docking used to aid in structure selection. The cyclic phosphonate inhibitor 18 was thus identified as complimentary to the enzyme active-site. Synthesis and in vitro inhibition assay revealed a K(i) of 3.8 mM against natural substrate, where the linear analogue of 18, compound 15, had previously shown no inhibitory activity. Two further inhibitors, phosphate analogue diastereoisomers 17a and 17b, were synthesised and also found to have low millimolar K(i) values. As a result of the computational docking investigations, a novel substrate binding interaction was discovered: hydrogen bonding between the substrate (phosphate hydroxy-group as the hydrogen bond donor) and the NADPH cofactor (2'-oxygen as the hydrogen bond acceptor).

Computer Simulations Reveal Substrate Specificity of Glycosidic Bond Cleavage in Native and Mutant Human Purine Nucleoside Phosphorylase.

PubMed

Isaksen, Geir Villy; Hopmann, Kathrin Helen; Åqvist, Johan; Brandsdal, Bjørn Olav

2016-04-12

Purine nucleoside phosphorylase (PNP) catalyzes the reversible phosphorolysis of purine ribonucleosides and 2'-deoxyribonucleosides, yielding the purine base and (2'-deoxy)ribose 1-phosphate as products. While this enzyme has been extensively studied, several questions with respect to the catalytic mechanism have remained largely unanswered. The role of the phosphate and key amino acid residues in the catalytic reaction as well as the purine ring protonation state is elucidated using density functional theory calculations and extensive empirical valence bond (EVB) simulations. Free energy surfaces for adenosine, inosine, and guanosine are fitted to ab initio data and yield quantitative agreement with experimental data when the surfaces are used to model the corresponding enzymatic reactions. The cognate substrates 6-aminopurines (inosine and guanosine) interact with PNP through extensive hydrogen bonding, but the substrate specificity is found to be a direct result of the electrostatic preorganization energy along the reaction coordinate. Asn243 has previously been identified as a key residue providing substrate specificity. Mutation of Asn243 to Asp has dramatic effects on the substrate specificity, making 6-amino- and 6-oxopurines equally good as substrates. The principal effect of this particular mutation is the change in the electrostatic preorganization energy between the native enzyme and the Asn243Asp mutant, clearly favoring adenosine over inosine and guanosine. Thus, the EVB simulations show that this particular mutation affects the electrostatic preorganization of the active site, which in turn can explain the substrate specificity.

A new UV-curing elastomeric substrate for rapid prototyping of microfluidic devices

NASA Astrophysics Data System (ADS)

Alvankarian, Jafar; Yeop Majlis, Burhanuddin

2012-03-01

Rapid prototyping in the design cycle of new microfluidic devices is very important for shortening time-to-market. Researchers are facing the challenge to explore new and suitable substrates with simple and efficient microfabrication techniques. In this paper, we introduce and characterize a UV-curing elastomeric polyurethane methacrylate (PUMA) for rapid prototyping of microfluidic devices. The swelling and solubility of PUMA in different chemicals is determined. Time-dependent measurements of water contact angle show that the native PUMA is hydrophilic without surface treatment. The current monitoring method is used for measurement of the electroosmotic flow mobility in the microchannels made from PUMA. The optical, physical, thermal and mechanical properties of PUMA are evaluated. The UV-lithography and molding process is used for making micropillars and deep channel microfluidic structures integrated to the supporting base layer. Spin coating is characterized for producing different layer thicknesses of PUMA resin. A device is fabricated and tested for examining the strength of different bonding techniques such as conformal, corona treating and semi-curing of two PUMA layers in microfluidic application and the results show that the bonding strengths are comparable to that of PDMS. We also report fabrication and testing of a three-layer multi inlet/outlet microfluidic device including a very effective fluidic interconnect for application demonstration of PUMA as a promising new substrate. A simple micro-device is developed and employed for observing the pressure deflection of membrane made from PUMA as a very effective elastomeric valve in microfluidic devices.

Laser Engineered Net Shaping of Nickel-Based Superalloy Inconel 718 Powders onto AISI 4140 Alloy Steel Substrates: Interface Bond and Fracture Failure Mechanism

PubMed Central

Kim, Hoyeol; Cong, Weilong; Zhang, Hong-Chao; Liu, Zhichao

2017-01-01

As a prospective candidate material for surface coating and repair applications, nickel-based superalloy Inconel 718 (IN718) was deposited on American Iron and Steel Institute (AISI) 4140 alloy steel substrate by laser engineered net shaping (LENS) to investigate the compatibility between two dissimilar materials with a focus on interface bonding and fracture behavior of the hybrid specimens. The results show that the interface between the two dissimilar materials exhibits good metallurgical bonding. Through the tensile test, all the fractures occurred in the as-deposited IN718 section rather than the interface or the substrate, implying that the as-deposited interlayer bond strength is weaker than the interfacial bond strength. From the fractography using scanning electron microscopy (SEM) and energy disperse X-ray spectrometry (EDS), three major factors affecting the tensile fracture failure of the as-deposited part are (i) metallurgical defects such as incompletely melted powder particles, lack-of-fusion porosity, and micropores; (ii) elemental segregation and Laves phase, and (iii) oxide formation. The fracture failure mechanism is a combination of all these factors which are detrimental to the mechanical properties and structural integrity by causing premature fracture failure of the as-deposited IN718. PMID:28772702

Evaluation of Oxidation Damage in Thermal Barrier Coating Systems

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Miller, Robert A.

1996-01-01

A method based on the technique of dilatometry has been established to quantitatively evaluate the interfacial damage due to the oxidation in a thermal barrier coating system. Strain isolation and adhesion coefficients have been proposed to characterize the thermal barrier coating (TBC) performance based on its thermal expansion behavior. It has been found that, for a thermal barrier coating system consisting of ZrO2-8%Y2O3/FeCrAlY/4140 steel substrate, the oxidation of the bond coat and substrate significantly reduced the ceramic coating adherence, as inferred from the dilatometry measurements. The in-situ thermal expansion measurements under 30 deg C to 700 deg C thermal cycling in air showed that the adhesion coefficient, A(sub i) decreased by 25% during the first 35 oxidation cycles. Metallography showed that delamination occurred at both the ceramic/bond coat and bond coat/substrate interfaces. In addition, the strain isolation effect has been improved by increasing the FeCrAlY bond coat thickness. The strain isolation coefficient, Si, increased from about 0.04 to 0.25, as the bond coat thickness changed from 0.1 mm to 1.0 mm. It may be possible to design optimum values of strain isolation and interface adhesion coefficients to achieve the best TBC performance.

Laser Engineered Net Shaping of Nickel-Based Superalloy Inconel 718 Powders onto AISI 4140 Alloy Steel Substrates: Interface Bond and Fracture Failure Mechanism.

PubMed

Kim, Hoyeol; Cong, Weilong; Zhang, Hong-Chao; Liu, Zhichao

2017-03-25

As a prospective candidate material for surface coating and repair applications, nickel-based superalloy Inconel 718 (IN718) was deposited on American Iron and Steel Institute (AISI) 4140 alloy steel substrate by laser engineered net shaping (LENS) to investigate the compatibility between two dissimilar materials with a focus on interface bonding and fracture behavior of the hybrid specimens. The results show that the interface between the two dissimilar materials exhibits good metallurgical bonding. Through the tensile test, all the fractures occurred in the as-deposited IN718 section rather than the interface or the substrate, implying that the as-deposited interlayer bond strength is weaker than the interfacial bond strength. From the fractography using scanning electron microscopy (SEM) and energy disperse X-ray spectrometry (EDS), three major factors affecting the tensile fracture failure of the as-deposited part are (i) metallurgical defects such as incompletely melted powder particles, lack-of-fusion porosity, and micropores; (ii) elemental segregation and Laves phase, and (iii) oxide formation. The fracture failure mechanism is a combination of all these factors which are detrimental to the mechanical properties and structural integrity by causing premature fracture failure of the as-deposited IN718.

The microstructure of the surface layer of magnesium laser alloyed with aluminum and silicon

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

Dziadoń, Andrzej

2016-08-15

The surface layer under analysis was formed as a result of diffusion bonding of a thin AlSi20 plate to a magnesium substrate followed by laser melting. Depending on the process parameters, the laser beam melted the AlSi20 plate only or the AlSi20 plate and a layer of the magnesium surface adjacent to it. Two types of microstructure of the remelted layer were thus analyzed. If the melting zone was limited to the AlSi20 plate, the microstructure of the surface layer was typical of a rapidly solidified hypereutectic Al–Si alloy. Since, however, the liquid AlSi20 reacted with the magnesium substrate, themore » following intermetallic phases formed: Al{sub 3}Mg{sub 2}, Mg{sub 17}Al{sub 12} and Mg{sub 2}Si. The microstructure of the modified surface layer of magnesium was examined using optical, scanning electron and transmission electron microscopy. The analysis of the surface properties of the laser modified magnesium revealed that the thin layer has a microstructure of a rapidly solidified Al–Si alloy offering good protection against corrosion. By contrast, the surface layer containing particles of intermetallic phases was more resistant to abrasion but had lower corrosion resistance than the silumin type layer. - Highlights: •A CO{sub 2} laser was used for surface alloying of Mg with AlSi20. •Before alloying, an AlSi20 plate was diffusion bonded with the Mg substrate. •The process parameters affected the alloyed layer microstructure and properties. •With melting limited to AlSi20, the layer had a structure of rapidly solidified AlSi20. •Mg–Al and Mg–Si phases were present when both the substrate and the plate were melted.« less

Mechanistic Studies of Cobalt-Catalyzed C(sp2)-H Borylation of Five-Membered Heteroarenes with Pinacolborane.

PubMed

Obligacion, Jennifer V; Chirik, Paul J

2017-07-07

Studies into the mechanism of cobalt-catalyzed C(sp 2 )-H borylation of five-membered heteroarenes with pinacolborane (HBPin) as the boron source established the catalyst resting state as the trans -cobalt(III) dihydride boryl, ( iPr PNP)Co(H) 2 (BPin) ( iPr PNP = 2,6-( i Pr 2 PCH 2 ) 2 (C 5 H 3 N)), at both low and high substrate conversions. The overall first-order rate law and observation of a normal deuterium kinetic isotope effect on the borylation of benzofuran versus benzofuran-2- d 1 support H 2 reductive elimination from the cobalt(III) dihydride boryl as the turnover-limiting step. These findings stand in contrast to that established previously for the borylation of 2,6-lutidine with the same cobalt precatalyst, where borylation of the 4-position of the pincer occurred faster than the substrate turnover and arene C-H activation by a cobalt(I) boryl is turnover-limiting. Evaluation of the catalytic activity of different cobalt precursors in the C-H borylation of benzofuran with HBPin established that the ligand design principles for C- H borylation depend on the identities of both the arene and the boron reagent used: electron-donating groups improve catalytic activity of the borylation of pyridines and arenes with B 2 Pin 2 , whereas electron-withdrawing groups improve catalytic activity of the borylation of five-membered heteroarenes with HBPin. Catalyst deactivation by P-C bond cleavage from a cobalt(I) hydride was observed in the C-H borylation of arene substrates with C-H bonds that are less acidic than those of five-membered heteroarenes using HBPin and explains the requirement of B 2 Pin 2 to achieve synthetically useful yields with these arene substrates.

AIN-Based Packaging for SiC High-Temperature Electronics

NASA Technical Reports Server (NTRS)

Savrun, Ender

2004-01-01

Packaging made primarily of aluminum nitride has been developed to enclose silicon carbide-based integrated circuits (ICs), including circuits containing SiC-based power diodes, that are capable of operation under conditions more severe than can be withstood by silicon-based integrated circuits. A major objective of this development was to enable packaged SiC electronic circuits to operate continuously at temperatures up to 500 C. AlN-packaged SiC electronic circuits have commercial potential for incorporation into high-power electronic equipment and into sensors that must withstand high temperatures and/or high pressures in diverse applications that include exploration in outer space, well logging, and monitoring of nuclear power systems. This packaging embodies concepts drawn from flip-chip packaging of silicon-based integrated circuits. One or more SiC-based circuit chips are mounted on an aluminum nitride package substrate or sandwiched between two such substrates. Intimate electrical connections between metal conductors on the chip(s) and the metal conductors on external circuits are made by direct bonding to interconnections on the package substrate(s) and/or by use of holes through the package substrate(s). This approach eliminates the need for wire bonds, which have been the most vulnerable links in conventional electronic circuitry in hostile environments. Moreover, the elimination of wire bonds makes it possible to pack chips more densely than was previously possible.

High reliability bond program using small diameter aluminum wire

NASA Technical Reports Server (NTRS)

Macha, M.; Thiel, R. A.

1975-01-01

The program was undertaken to characterize the performance of small diameter aluminum wire ultrasonically bonded to conductors commonly encountered in hybrid assemblies, and to recommend guidelines for improving this performance. Wire, 25.4, 38.1 and 50.8 um (1, 1.5 and 2 mil), was used with bonding metallization consisting of thick film gold, thin film gold and aluminum as well as conventional aluminum pads on semiconductor chips. The chief tool for evaluating the performance was the double bond pull test in conjunction with a 72 hour - 150 C heat soak and -65 C to +150 C thermal cycling. In practice the thermal cycling was found to have relatively little effect compared to the heat soak. Pull strength will decrease after heat soak as a result of annealing of the aluminum wire; when bonded to thick film gold, the pull strength decreased by about 50% (weakening of the bond interface was the major cause of the reduction). Bonds to thin film gold lost about 30 - 40% of their initial pull strenth; weakening of the wire itself at the bond heel was the predominant cause. Bonds to aluminum substrate metallization lost only about 22%. Bonds between thick and thin film gold substrate metallization and semiconductor chips substantiated the previous conclusions but also showed that in about 20 to 25% of the cases, bond interface failure occurred at the semiconductor chip.

Anti-Arrhenius cleavage of covalent bonds in bottlebrush macromolecules on substrate.

PubMed

Lebedeva, Natalia V; Nese, Alper; Sun, Frank C; Matyjaszewski, Krzysztof; Sheiko, Sergei S

2012-06-12

Spontaneous degradation of bottlebrush macromolecules on aqueous substrates was monitored by atomic force microscopy. Scission of C ─ C covalent bonds in the brush backbone occurred due to steric repulsion between the adsorbed side chains, which generated bond tension on the order of several nano-Newtons. Unlike conventional chemical reactions, the rate of bond scission was shown to decrease with temperature. This apparent anti-Arrhenius behavior was caused by a decrease in the surface energy of the underlying substrate upon heating, which results in a corresponding decrease of bond tension in the adsorbed macromolecules. Even though the tension dropped minimally from 2.16 to 1.89 nN, this was sufficient to overpower the increase in the thermal energy (k(B)T) in the Arrhenius equation. The rate constant of the bond-scission reaction was measured as a function of temperature and surface energy. Fitting the experimental data by a perturbed Morse potential V = V(0)(1 - e(-βx))(2) - fx, we determined the depth and width of the potential to be V(0) = 141 ± 19 kJ/mol and β(-1) = 0.18 ± 0.03 Å, respectively. Whereas the V(0) value is in reasonable agreement with the activation energy E(a) = 80-220 kJ/mol of mechanical and thermal degradation of organic polymers, it is significantly lower than the dissociation energy of a C ─ C bond D(e) = 350 kJ/mol. Moreover, the force constant K(x) = 2β(2)V(0) = 1.45 ± 0.36 kN/m of a strained bottlebrush along its backbone is markedly larger than the force constant of a C ─ C bond K(l) = 0.44 kN/m, which is attributed to additional stiffness due to deformation of the side chains.

Water clusters contributed to molecular interactions of ionizable organic pollutants with aromatized biochar via π-PAHB: Sorption experiments and DFT calculations.

PubMed

Zhang, Kun; Chen, Baoliang; Mao, Jiefei; Zhu, Lizhong; Xing, Baoshan

2018-05-08

Molecular interactions between biochars and ionizable organic pollutants (IOPs) are of great concern in natural environments, however the role of water clusters on the biochar surface remain unclear. The pH-dependent adsorption of aniline, phenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 4-methylphenol and 4-nitrophenol onto bamboo wood derived biochar (BW700) as a model was conducted to identify conventional and novel interaction mechanisms between aromatized surface and IOPs. The dissociation constant (pK a,surface ) of surface functional groups of BW700 was characterized by acid-base titration and Zeta potential measurements. The pH-dependent adsorption behavior depended on the pK a,IOP of IOPs and also related to the pK a,surface of biochar surface. An obvious peak of adsorption coefficients (K d ) in the range of solution pH was shaped at pH peak  = (pK a,IOP  + pK a,surface )/2, which cannot be well explained by the conventional mechanisms such as hydrophobic effects, π-π interaction, electrostatic attractions, and hydrogen-binding. The contribution of ice-like adlayer (water clusters) on aromatic surface as H-acceptors is proposed for the first time to the adsorption peak of IOP as H-donors at pH peak . Density functional theory (DFT) calculations provided a possible structure of the complex combined with ice-like adlayer and aromatic substrate of BW700, and indicated that the adsorbing peak resulted from the multiple π-bond and polarization assisted H-bond (π-PAHB) interactions. Three distinct properties of π-PAHB were given, based on multiple π-bond, hydrophobicity-dependence and pH sensitivity. This novel mechanism extends the definition of H-bonds for better understanding the molecular interactions of IOP with carbonaceous materials and their environmental fate. Copyright © 2018 Elsevier Ltd. All rights reserved.

Enamel Bond Strength of New Universal Adhesive Bonding Agents.

PubMed

McLean, D E; Meyers, E J; Guillory, V L; Vandewalle, K S

2015-01-01

Universal bonding agents have been introduced for use as self-etch or etch-and-rinse adhesives depending on the dental substrate and clinician's preference. The purpose of this study was to evaluate the shear bond strength (SBS) of composite to enamel using universal adhesives compared to a self-etch adhesive when applied in self-etch and etch-and-rinse modes over time. Extracted human third molars were used to create 120 enamel specimens. The specimens were ground flat and randomly divided into three groups: two universal adhesives and one self-etch adhesive. Each group was then subdivided, with half the specimens bonded in self-etch mode and half in etch-and-rinse mode. The adhesives were applied as per manufacturers' instructions, and composite was bonded using a standardized mold and cured incrementally. The groups were further divided into two subgroups with 10 specimens each. One subgroup was stored for 24 hours and the second for six months in 37°C distilled water and tested in shear. Failure mode was also determined for each specimen. A three-way analysis of variance (ANOVA) found a significant difference between groups based on bonding agent (p<0.001) and surface treatment (p<0.001) but not on time (p=0.943), with no significant interaction (p>0.05). Clearfil SE in etch-and-rinse and self-etch modes had more mixed fractures than either universal adhesive in either mode. Etching enamel significantly increased the SBS of composite to enamel. Clearfil SE had significantly greater bond strength to enamel than either universal adhesive, which were not significantly different from each other.

Using ALD To Bond CNTs to Substrates and Matrices

NASA Technical Reports Server (NTRS)

Wong, Eric W.; Bronikowski, Michael J.; Kowalczyk, Robert S.

2008-01-01

Atomic-layer deposition (ALD) has been shown to be effective as a means of coating carbon nanotubes (CNTs) with layers of Al2O3 that form strong bonds between the CNTs and the substrates on which the CNTs are grown. ALD is a previously developed vaporphase thin-film-growth technique. ALD differs from conventional chemical vapor deposition, in which material is deposited continually by thermal decomposition of a precursor gas. In ALD, material is deposited one layer of atoms at a time because the deposition process is self-limiting and driven by chemical reactions between the precursor gas and the surface of the substrate or the previously deposited layer.

Transistors using crystalline silicon devices on glass

DOEpatents

McCarthy, Anthony M.

1995-01-01

A method for fabricating transistors using single-crystal silicon devices on glass. This method overcomes the potential damage that may be caused to the device during high voltage bonding and employs a metal layer which may be incorporated as part of the transistor. This is accomplished such that when the bonding of the silicon wafer or substrate to the glass substrate is performed, the voltage and current pass through areas where transistors will not be fabricated. After removal of the silicon substrate, further metal may be deposited to form electrical contact or add functionality to the devices. By this method both single and gate-all-around devices may be formed.

Carbon-fluorine bond activation coupled with carbon-hydrogen bond formation alpha to iridium: kinetics, mechanism, and diastereoselectivity.

PubMed

Garratt, Shaun A; Hughes, Russell P; Kovacik, Ivan; Ward, Antony J; Willemsen, Stefan; Zhang, Donghui

2005-11-09

Reactions of iridium(fluoroalkyl)hydride complexes CpIr(PMe(3))(CF(2)R(F))Y (R(F) = F, CF(3); Y = H, D) with LutHX (Lut = 2,6-dimethylpyridine; X = Cl, I) results in C-F activation coupled with hydride migration to give CpIr(PMe(3))(CYFR(F))X as variable mixtures of diastereomers. Solution conformations and relative diastereomer configurations of the products have been determined by (19)F{(1)H}HOESY NMR to be (S(C), S(Ir))(R(C), R(Ir)) for the kinetic diastereomer and (R(C), S(Ir))(S(C), R(Ir)) for its thermodynamic counterpart. Isotope labeling experiments using LutDCl/CpIr(PMe(3))(CF(2)R(F))H and CpIr(PMe(3))(CF(2)R(F))D/LutHCl) showed that, unlike a previously studied system, H/D exchange is faster than protonation of the alpha-CF bond, giving an identical mixture of product isotopologues from both reaction mixtures. The kinetic rate law shows a first-order dependence on the concentration of iridium substrate, but a half-order dependence on that of LutHCl; this is interpreted to mean that LutHCl dissociates to give HCl as the active protic source for C-F bond activation. Detailed kinetic studies are reported, which demonstrate that lack of complete diastereoselectivity is not a function of the C-F bond activation/H migration steps but that a cationic intermediate plays a double role in loss of diastereoselectivity; the intermediate can undergo epimerization at iridium before being trapped by halide and can also catalyze the epimerization of kinetic diastereomer product to thermodynamic product. A detailed mechanism is proposed and simulations performed to fit the kinetic data.

Structural determinants of enzyme binding affinity: the E1 component of pyruvate dehydrogenase from Escherichia coli in complex with the inhibitor thiamin thiazolone diphosphate.

PubMed

Arjunan, Palaniappa; Chandrasekhar, Krishnamoorthy; Sax, Martin; Brunskill, Andrew; Nemeria, Natalia; Jordan, Frank; Furey, William

2004-03-09

Thiamin thiazolone diphosphate (ThTDP), a potent inhibitor of the E1 component from the Escherichia coli pyruvate dehydrogenase multienzyme complex (PDHc), binds to the enzyme with greater affinity than does the cofactor thiamin diphosphate (ThDP). To identify what determines this difference, the crystal structure of the apo PDHc E1 component complex with ThTDP and Mg(2+) has been determined at 2.1 A and compared to the known structure of the native holoenzyme, PDHc E1-ThDP-Mg(2+) complex. When ThTDP replaces ThDP, reorganization occurs in the protein structure in the vicinity of the active site involving positional and conformational changes in some amino acid residues, a change in the V coenzyme conformation, addition of new hydration sites, and elimination of others. These changes culminate in an increase in the number of hydrogen bonds to the protein, explaining the greater affinity of the apoenzyme for ThTDP. The observed hydrogen bonding pattern is not an invariant feature of ThDP-dependent enzymes but rather specific to this enzyme since the extra hydrogen bonds are made with nonconserved residues. Accordingly, these sequence-related hydrogen bonding differences likewise explain the wide variation in the affinities of different thiamin-dependent enzymes for ThTDP and ThDP. The sequence of each enzyme determines its ability to form hydrogen bonds to the inhibitor or cofactor. Mechanistic roles are suggested for the aforementioned reorganization and its reversal in PDHc E1 catalysis: to promote substrate binding and product release. This study also provides additional insight into the role of water in enzyme inhibition and catalysis.

Ion Beam Sputtered Coatings of Bioglass

NASA Technical Reports Server (NTRS)

Hench, Larry L.; Wilson, J.; Ruzakowski, Patricia Henrietta Anne

1982-01-01

The ion beam sputtering technique available at the NASA-Lewis was used to apply coatings of bioglass to ceramic, metallic, and polymeric substrates. Experiments in vivo and in vitro described investigate these coatings. Some degree of substrate masking was obtained in all samples although stability and reactivity equivalent to bulk bioglass was not observed in all coated samples. Some degree of stability was seen in all coated samples that were reacted in vitro. Both metallic and ceramic substrates coated in this manner failed to show significantly improved coatings over those obtained with existing techniques. Implantation of the coated ceramic substrate samples in bone gave no definite bonding as seen with bulk glass; however, partial and patchy bonding was seen. Polymeric substrates in these studies showed promise of success. The coatings applied were sufficient to mask the underlying reactive test surface and tissue adhesion of collagen to bioglass was seen. Hydrophilic, hydrophobic, charged, and uncharged polymeric surfaces were successfully coated.

Multilayer Article Characterized by Low Coefficient of Thermal Expansion Outer Layer

NASA Technical Reports Server (NTRS)

Lee, Kang N. (Inventor)

2004-01-01

A multilayer article comprises a substrate comprising a ceramic or a silicon-containing metal alloy. The ceramic is a Si-containing ceramic or an oxide ceramic with or without silicon. An outer layer overlies the substrate and at least one intermediate layer is located between the outer layer and thc substrate. An optional bond layer is disposed between thc 1 least one intermediate layer and thc substrate. The at least one intermediate layer may comprise an optional chemical barrier layer adjacent the outer layer, a mullite-containing layer and an optional chemical barrier layer adjacent to the bond layer or substrate. The outer layer comprises a compound having a low coefficient of thermal expansion selected from one of the following systems: rare earth (RE) silicates; at least one of hafnia and hafnia-containing composite oxides; zirconia-containing composite oxides and combinations thereof.

Surface thiolation of silicon for antifouling application.

PubMed

Zhang, Xiaoning; Gao, Pei; Hollimon, Valerie; Brodus, DaShan; Johnson, Arion; Hu, Hongmei

2018-02-07

Thiol groups grafted silicon surface was prepared as previously described. 1H,1H,2H,2H-perfluorodecanethiol (PFDT) molecules were then immobilized on such a surface through disulfide bonds formation. To investigate the contribution of PFDT coating to antifouling, the adhesion behaviors of Botryococcus braunii (B. braunii) and Escherichia coli (E. coli) were studied through biofouling assays in the laboratory. The representative microscope images suggest reduced B. braunii and E. coli accumulation densities on PFDT integrated silicon substrate. However, the antifouling performance of PFDT integrated silicon substrate decreased over time. By incubating the aged substrate in 10 mM TCEP·HCl solution for 1 h, the fouled PFDT coating could be removed as the disulfide bonds were cleaved, resulting in reduced absorption of algal cells and exposure of non-fouled silicon substrate surface. Our results indicate that the thiol-terminated substrate can be potentially useful for restoring the fouled surface, as well as maximizing the effective usage of the substrate.

Laser readable thermoluminescent radiation dosimeters and methods for producing thereof

DOEpatents

Braunlich, Peter F.; Tetzlaff, Wolfgang

1989-01-01

Thin layer thermoluminescent radiation dosimeters for use in laser readable dosimetry systems, and methods of fabricating such thin layer dosimeters. The thin layer thermoluminescent radiation dosimeters include a thin substrate made from glass or other inorganic materials capable of withstanding high temperatures and high heating rates. A thin layer of a thermoluminescent phoshphor material is heat bonded to the substrate using an inorganic binder such as glass. The dosimeters can be mounted in frames and cases for ease in handling. Methods of the invention include mixing a suitable phosphor composition and binder, both being in particulate or granular form. The mixture is then deposited onto a substrate such as by using mask printing techniques. The dosimeters are thereafter heated to fuse and bond the binder and phosphor to the substrate.

Immediate Repair Bond Strength of Fiber-reinforced Composite after Saliva or Water Contamination.

PubMed

Bijelic-Donova, Jasmina; Flett, Andrew; Lassila, Lippo V J; Vallittu, Pekka K

2018-05-31

This in vitro study aimed to evaluate the shear bond strength (SBS) of particulate filler composite (PFC) to saliva- or water-contaminated fiber-reinforced composite (FRC). One type of FRC substrate with semi-interpenetrating polymer matrix (semi-IPN) (everStick C&B) was used in this investigation. A microhybrid PFC (Filtek Z250) substrate served as control. Freshly cured PFC and FRC substrates were first subjected to different contamination and surface cleaning treatments, then the microhybrid PFC restorative material (Filtek Z250) was built up on the substrates in 2-mm increments and light cured. Uncontaminated and saliva- or water-contaminated substrate surfaces were either left untreated or were cleaned via phosphoric acid etching or water spray accompanied with or without adhesive composite application prior applying the adherent PFC material. SBS was evaluated after thermocycling the specimens (6000 cycles, 5°C and 55°C). Three-way ANOVA showed that both the surface contamination and the surface treatment signficantly affected the bond strength (p < 0.05). Saliva contamination reduced the SBS more than did the water contamination. SBS loss after saliva contamination was 73.7% and 31.3% for PFC and FRC, respectively. After water contamination, SBS loss was 17.2% and 13.3% for PFC and FRC, respectively. The type of surface treatment was significant for PFC (p < 0.05), but not for FRC (p = 0.572). Upon contamination of freshly cured PFC or semi-IPN FRC, surfaces should be re-prepared via phosphoric acid etching, water cleaning, drying, and application of adhesive composite in order to recover optimal bond strength.

Laser welding of pre-functionalized glass substrates: a fabrication and chemical stability study

NASA Astrophysics Data System (ADS)

Carvalho, R. R.; Reuvekamp, S.; Zuilhof, H.; Blom, M. T.; Vrouwe, E. X.

2018-01-01

Low-temperature bonding of glass substrates is of great interest in the field of microfluidic-based biosensing, and we study how laser welding could be used for this. This technology allows for the modification of glass channels with temperature-sensitive materials prior to bonding. We study the effects of the welding process by investigation of the thermal degradation of a biotin monolayer and whether it retains the ability to conjugate with fluorescently-labelled streptavidin.

Wafer scale micromachine assembly method

DOEpatents

Christenson, Todd R.

2001-01-01

A method for fusing together, using diffusion bonding, micromachine subassemblies which are separately fabricated is described. A first and second micromachine subassembly are fabricated on a first and second substrate, respectively. The substrates are positioned so that the upper surfaces of the two micromachine subassemblies face each other and are aligned so that the desired assembly results from their fusion. The upper surfaces are then brought into contact, and the assembly is subjected to conditions suited to the desired diffusion bonding.

Stereoselective rhodium-catalysed [2+2+2] cycloaddition of linear allene-ene/yne-allene substrates: reactivity and theoretical mechanistic studies.

PubMed

Haraburda, Ewelina; Torres, Óscar; Parella, Teodor; Solà, Miquel; Pla-Quintana, Anna

2014-04-22

Allene-ene-allene (2 and 5) and allene-yne-allene (3 and 7) N-tosyl and O-linked substrates were satisfactorily synthesised. The [2+2+2] cycloaddition reaction catalysed by the Wilkinson catalyst [RhCl(PPh3 )3 ] was evaluated. Substrates 2 and 5, which bear a double bond in the central position, gave a tricyclic structure in a reaction in which four contiguous stereogenic centres were formed as a single diastereomer. The reaction of substrates 3 and 7, which bear a triple bond in the central position, gave a tricyclic structure with a cyclohexenic ring core, again in a diastereoselective manner. All cycloadducts were formed by a regioselective reaction of the inner allene double bond and, therefore, feature an exocyclic diene motif. A Diels-Alder reaction on N-tosyl linked cycloadducts 8 and 10 allowed pentacyclic scaffolds to be diastereoselectively constructed. The reactivity of the allenes on [2+2+2] cycloaddition reactions was studied for the first time by density functional theory calculations. This mechanistic study rationalizes the order in which the unsaturations take part in the catalytic cycle, the reactivity of the two double bonds of the allene towards the [2+2+2] cycloaddition reaction, and the diastereoselectivity of the reaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermoplastic tape compaction device

DOEpatents

Campbell, Vincent W.

1994-01-01

A device for bonding a thermoplastic tape to a substrate to form a fully consolidated composite. This device has an endless chain associated with a frame so as to rotate in a plane that is perpendicular to a long dimension of the tape, the chain having pivotally connected chain links with each of the links carrying a flexible foot member that extends outwardly from the chain. A selected number of the foot members contact the tape, after the heating thereof, to cause the heated tape to bond to the substrate. The foot members are each a thin band of metal oriented transversely to the chain, with a flexibility and width and length to contact the tape so as to cause the tape to conform to the substrate to achieve consolidation of the tape and the substrate. A biased leaf-type spring within the frame bears against an inner surface of the chain to provide the compliant pressure necessary to bond the tape to the substrate. The chain is supported by sprockets on shafts rotatably supported in the frame and, in one embodiment, one of the shafts has a drive unit to produce rotation such that the foot members in contact with the tape move at the same speed as the tape. Cooling jets are positioned along the frame to cool the resultant consolidated composite.

Specificity and kinetics of haloalkane dehalogenase.

PubMed

Schanstra, J P; Kingma, J; Janssen, D B

1996-06-21

Haloalkane dehalogenase converts halogenated alkanes to their corresponding alcohols. The active site is buried inside the protein and lined with hydrophobic residues. The reaction proceeds via a covalent substrate-enzyme complex. This paper describes a steady-state and pre-steady-state kinetic analysis of the conversion of a number of substrates of the dehalogenase. The kinetic mechanism for the "natural" substrate 1,2-dichloroethane and for the brominated analog and nematocide 1,2-dibromoethane are given. In general, brominated substrates had a lower Km, but a similar kcat than the chlorinated analogs. The rate of C-Br bond cleavage was higher than the rate of C-Cl bond cleavage, which is in agreement with the leaving group abilities of these halogens. The lower Km for brominated compounds therefore originates both from the higher rate of C-Br bond cleavage and from a lower Ks for bromo-compounds. However, the rate-determining step in the conversion (kcat) of 1, 2-dibromoethane and 1,2-dichloroethane was found to be release of the charged halide ion out of the active site cavity, explaining the different Km but similar kcat values for these compounds. The study provides a basis for the analysis of rate-determining steps in the hydrolysis of various environmentally important substrates.

Three-dimensional impedance engineering for mixed-signal system-on-chip applications

NASA Astrophysics Data System (ADS)

Chong, Kyuchul

A novel approach for three-dimensional substrate impedance engineering of p-/p+ epi substrate is proposed for mixed-signal integrated circuit applications. This technology requires minimum intrusion to conventional Si CMOS processing, but offers astounding improvements with regard to RF crosstalk via substrate and RF passive device performance. The engineered substrate consists of conducting as well as semi-insulating regions strategically placed three-dimensionally throughout the volume of the substrate. The p-/p+ epi substrate is used to prevent latch-up at tight design rules in high performance digital CMOS. Metal vias are fabricated from the front side using electroless plating method for Faraday cage isolation structure as well as "true ground" contacts. A self-limiting micro-PS formation process is employed to allow the insertion of semi-insulating regions from the backside of the wafer and RIE etch to remove p- layer is performed from the front side completely eliminating any parasitic pathways for crosstalk. The crosstalk isolation methods in this study are based on the principle of RF noise shielding in addition to insulating. Both the suppression of crosstalk by the metal vias and micro-PS trench isolation are so significant that the crosstalk goes down to the noise floor of the conventional measurement instruments. The use of micro-PS layer effectively can reduce the parasitic substrate effect. These reductions result in higher Q and fr of inductors on micro-PS region. Inductors located on micro-PS are subjected to a much less stringent set of constraints than that on bulk Si substrates, allowing for much higher inductance without severe sacrifice in Q and fr, and much higher Q for with reasonable inductance and fr. The bond pad structure using micro-PS can significantly reduce the parasitic bond pad capacitance and increases the crosstalk isolation characteristic. Reducing the parasitic pad capacitance by using micro-PS results in high bond pad resonant frequency of up to 56.2 GHz. The crosstalk between bond pads becomes much smaller than that of conventional p- bulk substrate by using micro-PS. In addition, the use of micro-PS leads to greatly improved transformer performances including higher Q and fr, mutual reactive coupling coefficients with larger useable band-width and maximum available gain by reducing the substrate effect.

Hybrid Integration of III-V Solar Microcells for High Efficiency Concentrated Photovoltaic Modules

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

Tauke-Pedretti, Anna; Cederberg, Jeffery; Cruz-Campa, Jose Luis

The design, fabrication and performance of InGaAs and InGaP/GaAs microcells are presented. These cells are integrated with a Si wafer providing a path for insertion in hybrid concentrated photovoltaic modules. Comparisons are made between bonded cells and cells fabricated on their native wafer. The bonded cells showed no evidence of degradation in spite of the integration process which involved significant processing including the removal of the III-V substrate. Results from a number of hybrid cell configurations were reported. These cells employed integration techniques including wafer level bonding of processed cells and solder bonding of the cells. Lastly, the cells themselvesmore » showed evidence of degradation in spite of the integration process, which involved significant processing including the removal of the III-V substrate.« less

Hybrid Integration of III-V Solar Microcells for High Efficiency Concentrated Photovoltaic Modules

DOE PAGES

Tauke-Pedretti, Anna; Cederberg, Jeffery; Cruz-Campa, Jose Luis; ...

2018-03-09

The design, fabrication and performance of InGaAs and InGaP/GaAs microcells are presented. These cells are integrated with a Si wafer providing a path for insertion in hybrid concentrated photovoltaic modules. Comparisons are made between bonded cells and cells fabricated on their native wafer. The bonded cells showed no evidence of degradation in spite of the integration process which involved significant processing including the removal of the III-V substrate. Results from a number of hybrid cell configurations were reported. These cells employed integration techniques including wafer level bonding of processed cells and solder bonding of the cells. Lastly, the cells themselvesmore » showed evidence of degradation in spite of the integration process, which involved significant processing including the removal of the III-V substrate.« less

Atomic insight into tribochemical wear mechanism of silicon at the Si/SiO2 interface in aqueous environment: Molecular dynamics simulations using ReaxFF reactive force field

NASA Astrophysics Data System (ADS)

Wen, Jialin; Ma, Tianbao; Zhang, Weiwei; Psofogiannakis, George; van Duin, Adri C. T.; Chen, Lei; Qian, Linmao; Hu, Yuanzhong; Lu, Xinchun

2016-12-01

In this work, the atomic mechanism of tribochemical wear of silicon at the Si/SiO2 interface in aqueous environment was investigated using ReaxFF molecular dynamics (MD) simulations. Two types of Si atom removal pathways were detected in the wear process. The first is caused by the destruction of stretched Si-O-Si bonds on the Si substrate surface and is assisted by the attachment of H atoms on the bridging oxygen atoms of the bonds. The other is caused by the rupture of Si-Si bonds in the stretched Si-Si-O-Si bond chains at the interface. Both pathways effectively remove Si atoms from the silicon surface via interfacial Si-O-Si bridge bonds. Our simulations also demonstrate that higher pressures applied to the silica phase can cause more Si atoms to be removed due to the formation of increased numbers of interfacial Si-O-Si bridge bonds. Besides, water plays a dual role in the wear mechanism, by oxidizing the Si substrate surface as well as by preventing the close contact of the surfaces. This work shows that the removal of Si atoms from the substrate is a result of both chemical reaction and mechanical effects and contributes to the understanding of tribochemical wear behavior in the microelectromechanical systems (MEMS) and Si chemical mechanical polishing (CMP) process.

Shrinkage vectors of a flowable composite in artificial cavity models with different boundary conditions: Ceramic and Teflon.

PubMed

Kaisarly, Dalia; El Gezawi, Moataz; Xu, Xiaohui; Rösch, Peter; Kunzelmann, Karl-Heinz

2018-01-01

Polymerization shrinkage of dental resin composites leads to stress build-up at the tooth-restoration interface that predisposes the restoration to debonding. In contrast to the heterogeneity of enamel and dentin, this study investigated the effect of boundary conditions in artificial cavity models such as ceramic and Teflon. Ceramic serves as a homogenous substrate that provides optimal bonding conditions, which we presented in the form of etched and silanized ceramic in addition to an etched, silanized and bonded ceramic cavity. In contrast, the Teflon cavity presented a non-adhesive boundary condition that provided an exaggerated condition of poor bonding as in the case of contamination during the application procedure or a poor bonding substrate such as sclerotic or deep dentin. The greatest 3D shrinkage vectors and movement in the axial direction were observed in the ceramic cavity with the bonding agent followed by the silanized ceramic cavity, and smallest shrinkage vectors and axial movements were observed in the Teflon cavity. The shrinkage vectors in the ceramic cavities exhibited downward movement toward the cavity bottom with great downward shrinkage of the free surface. The shrinkage vectors in the Teflon cavity pointed towards the center of the restoration with lateral movement greater at one side denoting the site of first detachment from the cavity walls. These results proved that the boundary conditions, in terms of bonding substrates, significantly influenced the shrinkage direction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Learning from oligosaccharide soaks of crystals of an AA13 lytic polysaccharide monooxygenase: crystal packing, ligand binding and active-site disorder.

PubMed

Frandsen, Kristian E H; Poulsen, Jens Christian Navarro; Tovborg, Morten; Johansen, Katja S; Lo Leggio, Leila

2017-01-01

Lytic polysaccharide monooxygenases (LPMOs) are a class of copper-dependent enzymes discovered within the last ten years. They oxidatively cleave polysaccharides (chitin, lignocellulose, hemicellulose and starch-derived), presumably making recalcitrant substrates accessible to glycoside hydrolases. Recently, the first crystal structure of an LPMO-substrate complex was reported, giving insights into the interaction of LPMOs with β-linked substrates (Frandsen et al., 2016). The LPMOs acting on α-linked glycosidic bonds (family AA13) display binding surfaces that are quite different from those of LPMOs that act on β-linked glycosidic bonds (families AA9-AA11), as revealed from the first determined structure (Lo Leggio et al., 2015), and thus presumably the AA13s interact with their substrate in a distinct fashion. Here, several new structures of the same AA13 enzyme, Aspergillus oryzae AA13, are presented. Crystals obtained in the presence of high zinc-ion concentrations were used, as they can be obtained more reproducibly than those used to refine the deposited copper-containing structure. One structure with an ordered zinc-bound active site was solved at 1.65 Å resolution, and three structures from crystals soaked with maltooligosaccharides in solutions devoid of zinc ions were solved at resolutions of up to 1.10 Å. Despite similar unit-cell parameters, small rearrangements in the crystal packing occur when the crystals are depleted of zinc ions, resulting in a more occluded substrate-binding surface. In two of the three structures maltooligosaccharide ligands are bound, but not at the active site. Two of the structures presented show a His-ligand conformation that is incompatible with metal-ion binding. In one of these structures this conformation is the principal one (80% occupancy), giving a rare atomic resolution view of a substantially misfolded enzyme that is presumably rendered inactive.

Rapid-mix and chemical quench studies of ferredoxin-reduced stearoyl-acyl carrier protein desaturase.

PubMed

Lyle, Karen S; Haas, Jeffrey A; Fox, Brian G

2003-05-20

Stearoyl-ACP Delta9 desaturase (Delta9D) catalyzes the NADPH- and O(2)-dependent insertion of a cis double bond between the C9 and C10 positions of stearoyl-ACP (18:0-ACP) to produce oleoyl-ACP (18:1-ACP). This work revealed the ability of reduced [2Fe-2S] ferredoxin (Fd) to act as a catalytically competent electron donor during the rapid conversion of 18:0-ACP into 18:1-ACP. Experiments on the order of addition for substrate and reduced Fd showed high conversion of 18:0-ACP to 18:1-ACP (approximately 95% per Delta9D active site in a single turnover) when 18:0-ACP was added prior to reduced Fd. Reactions of the prereduced enzyme-substrate complex with O(2) and the oxidized enzyme-substrate complex with reduced Fd were studied by rapid-mix and chemical quench methods. For reaction of the prereduced enzyme-substrate complex, an exponential burst phase (k(burst) = 95 s(-1)) of product formation accounted for approximately 90% of the turnover expected for one subunit in the dimeric protein. This rapid phase was followed by a slower phase (k(linear) = 4.0 s(-1)) of product formation corresponding to the turnover expected from the second subunit. For reaction of the oxidized enzyme-substrate complex with excess reduced Fd, a slower, linear rate (k(obsd) = 3.4 s(-1)) of product formation was observed over approximately 1.5 turnovers per Delta9D active site potentially corresponding to a third phase of reaction. An analysis of the deuterium isotope effect on the two rapid-mix reaction sequences revealed only a modest effect on k(burst) ((D)k(burst) approximately 1.5) and k(linear) (D)k(linear) approximately 1.4), indicating C-H bond cleavage does not contribute significantly to the rate-limiting steps of pre-steady-state catalysis. These results were used to assemble and evaluate a minimal kinetic model for Delta9D catalysis.

Laser surface texturing of polypropylene to increase adhesive bonding

NASA Astrophysics Data System (ADS)

Mandolfino, Chiara; Pizzorni, Marco; Lertora, Enrico; Gambaro, Carla

2018-05-01

In this paper, the main parameters of laser surface texturing of polymeric substrates have been studied. The final aim of the texturing is to increase the performance of bonded joints of grey-pigmented polypropylene substrates. The experimental investigation was carried out starting from the identification of the most effective treatment parameters, in order to achieve a good texture without compromising the characteristics of the bulk material. For each of these parameters, three values were individuated and 27 sets of samples were realised. The surface treatment was analysed and related to the mechanical characteristics of the bonded joints performing lap-shear tests. A statistical analysis in order to find the most influential parameter completed the work.

Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: general strategy for amide N-C bond activation.

PubMed

Meng, Guangrong; Szostak, Michal

2016-06-15

The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined ().

Anomalous interface adhesion of graphene membranes

PubMed Central

He, Y.; Chen, W. F.; Yu, W. B.; Ouyang, G.; Yang, G. W.

2013-01-01

In order to understand the anomalous interface adhesion properties between graphene membranes and their substrates, we have developed a theoretical method to calibrate the interface adhesion energy of monolayer and multilayer graphene on substrates based on the bond relaxation consideration. Four kinds of interfaces, including graphene/SiO2, graphene/Cu, graphene/Cu/Ni and Cu/graphene/Ni, were taken into account. It was found that the membrane thickness and the interface confinement condition determine the adhesion energy. The relationship between the critical interface separation and the graphene thickness showed that the interface separation in the self-equilibrium state drops with decreasing membrane thickness. The size-dependent Young's modulus of graphene membrane and the interfacial condition were responsible for the novel interface adhesion energy. The proposed theory was expected to be applied to the design of graphene-based devices. PMID:24036502

Corrosion behaviour of friction-bit-joined and weld-bonded AA7075-T6/galvannealed DP980

DOE PAGES

Lim, Yong Chae; Squires, Lile; Pan, Tsung-Yu; ...

2016-12-22

Joining of aluminium alloys 7075-T6 and galvannealed dual phase 980 steel was achieved by friction bit joining (FBJ) and weld-bonding (FBJ + adhesive) processes. Accelerated laboratory-scale corrosion tests were performed on both FBJ only and weld-bonded specimens to study joint strength under a corrosive environment. Static lap shear tests showed that both FBJ only and weld-bonded cases generally retained more than 80% of the joint strength of non-corroded specimens at the end of corrosion testing. The presence of Zn/Fe coating on the steel substrate resulted in improved corrosion resistance for FBJ specimens, compared to joints produced with bare steel. Finally,more » an optical microscopy was used for cross-sectional analysis of corroded specimens. Some corrosion on the joining bit was observed near the bit head. However, the joining bit was still intact on the steel substrate, indicating that the primary bond was sound.« less

Corrosion behaviour of friction-bit-joined and weld-bonded AA7075-T6/galvannealed DP980

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

Lim, Yong Chae; Squires, Lile; Pan, Tsung-Yu

Joining of aluminium alloys 7075-T6 and galvannealed dual phase 980 steel was achieved by friction bit joining (FBJ) and weld-bonding (FBJ + adhesive) processes. Accelerated laboratory-scale corrosion tests were performed on both FBJ only and weld-bonded specimens to study joint strength under a corrosive environment. Static lap shear tests showed that both FBJ only and weld-bonded cases generally retained more than 80% of the joint strength of non-corroded specimens at the end of corrosion testing. The presence of Zn/Fe coating on the steel substrate resulted in improved corrosion resistance for FBJ specimens, compared to joints produced with bare steel. Finally,more » an optical microscopy was used for cross-sectional analysis of corroded specimens. Some corrosion on the joining bit was observed near the bit head. However, the joining bit was still intact on the steel substrate, indicating that the primary bond was sound.« less

alpha-1,4-Glucan lyase, a new class of starch/glycogen degrading enzyme. III. Substrate specificity, mode of action, and cleavage mechanism.

PubMed

Yu, S; Ahmad, T; Kenne, L; Pedersén, M

1995-05-11

The alpha-1,4-glucan lyase (EC 4.2.2.-), purified from the red alga Gracilariopsis lemaneiformis, is a single polypeptide with a molecular mass of 116,654 Da as determined by matrix-assisted laser-desorption mass spectrometry. It degraded maltose, maltosaccharides, amylose, amylopectin and glycogen, forming 1,5-anhydro-D-fructose from the non-reducing end groups. The substrate specificity, mode of action, and cleavage mechanism of the enzyme were studied by using various naturally occurring and synthesized substrates. This enzyme was highly specific for the alpha-1,4-D-glucosidic bond. When a linear alpha-1,4-glucan was used as substrate, the enzyme split the substrate from the non-reducing end and released 1,5-anhydro-D-fructose successively until only one glucose unit was left. When a branched pentasaccharide of 6(2)-alpha-maltosylmaltotriose, obtained from glycogen by alpha-amylase limitation, was used as substrate, the glucose group in the 4-position of the 4,6-branched residue was not cleaved off. Using maltoheptaose as substrate and following the reaction with HPLC and 1H-NMR spectroscopy, it was found that the action mode of the lyase followed a multichain attack mechanism. 1H- and 13C-NMR spectroscopic studies on unlabelled and labelled amylose (1-2H, 2-2H, 1-13C) as substrates indicated that the lyase cleaved the C-(1')-O(4) bond forming a double bond between C-1' and C-2', thus forming the enol form of 1,5-anhydro-D-fructose. It also indicated that the catalytic process of the lyase involved proton exchanges among C-1, C-2, C-3 and the solvent.

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

NAD(P)H-Independent Asymmetric C=C Bond Reduction Catalyzed by Ene Reductases by Using Artificial Co-substrates as the Hydrogen Donor

PubMed Central

Winkler, Christoph K; Clay, Dorina; Entner, Marcello; Plank, Markus; Faber, Kurt

2014-01-01

To develop a nicotinamide-independent single flavoenzyme system for the asymmetric bioreduction of C=C bonds, four types of hydrogen donor, encompassing more than 50 candidates, were investigated. Six highly potent, cheap, and commercially available co-substrates were identified that (under the optimized conditions) resulted in conversions and enantioselectivities comparable with, or even superior to, those obtained with traditional two-enzyme nicotinamide adenine dinucleotide phosphate (NAD(P)H)-recycling systems. PMID:24382795

Comparison of fatigue crack growth of riveted and bonded aircraft lap joints made of Aluminium alloy 2024-T3 substrates - A numerical study

NASA Astrophysics Data System (ADS)

Pitta, S.; Rojas, J. I.; Crespo, D.

2017-05-01

Aircraft lap joints play an important role in minimizing the operational cost of airlines. Hence, airlines pay more attention to these technologies to improve efficiency. Namely, a major time consuming and costly process is maintenance of aircraft between the flights, for instance, to detect early formation of cracks, monitoring crack growth, and fixing the corresponding parts with joints, if necessary. This work is focused on the study of repairs of cracked aluminium alloy (AA) 2024-T3 plates to regain their original strength; particularly, cracked AA 2024-T3 substrate plates repaired with doublers of AA 2024-T3 with two configurations (riveted and with adhesive bonding) are analysed. The fatigue life of the substrate plates with cracks of 1, 2, 5, 10 and 12.7mm is computed using Fracture Analysis 3D (FRANC3D) tool. The stress intensity factors for the repaired AA 2024-T3 plates are computed for different crack lengths and compared using commercial FEA tool ABAQUS. The results for the bonded repairs showed significantly lower stress intensity factors compared with the riveted repairs. This improves the overall fatigue life of the bonded joint.

Inverting Steric Effects: Using "Attractive" Noncovalent Interactions To Direct Silver-Catalyzed Nitrene Transfer.

PubMed

Huang, Minxue; Yang, Tzuhsiung; Paretsky, Jonathan D; Berry, John F; Schomaker, Jennifer M

2017-12-06

Nitrene transfer (NT) reactions represent powerful and direct methods to convert C-H bonds into amine groups that are prevalent in many commodity chemicals and pharmaceuticals. The importance of the C-N bond has stimulated the development of numerous transition-metal complexes to effect chemo-, regio-, and diastereoselective NT. An ongoing challenge is to understand how subtle interactions between catalyst and substrate influence the site-selectivity of the C-H amination event. In this work, we explore the underlying reasons why Ag(tpa)OTf (tpa = tris(pyridylmethyl)amine) prefers to activate α-conjugated C-H bonds over 3° alkyl C(sp 3 )-H bonds and apply these insights to reaction optimization and catalyst design. Experimental results suggest possible roles of noncovalent interactions (NCIs) in directing the NT; computational studies support the involvement of π···π and Ag···π interactions between catalyst and substrate, primarily by lowering the energy of the directed transition state and reaction conformers. A simple Hess's law relationship can be employed to predict selectivities for new substrates containing competing NCIs. The insights presented herein are poised to inspire the design of other catalyst-controlled C-H functionalization reactions.

Vacuum fusion bonding of glass plates

DOEpatents

Swierkowski, Steve P.; Davidson, James C.; Balch, Joseph W.

2001-01-01

An improved apparatus and method for vacuum fusion bonding of large, patterned glass plates. One or both glass plates are patterned with etched features such as microstructure capillaries and a vacuum pumpout moat, with one plate having at least one hole therethrough for communication with a vacuum pumpout fixture. High accuracy alignment of the plates is accomplished by a temporary clamping fixture until the start of the fusion bonding heat cycle. A complete, void-free fusion bond of seamless, full-strength quality is obtained through the plates; because the glass is heated well into its softening point and because of a large, distributed force that is developed that presses the two plates together from the difference in pressure between the furnace ambient (high pressure) and the channeling and microstructures in the plates (low pressure) due to the vacuum drawn. The apparatus and method may be used to fabricate microcapillary arrays for chemical electrophoresis; for example, any apparatus using a network of microfluidic channels embedded between plates of glass or similar moderate melting point substrates with a gradual softening point curve, or for assembly of glass-based substrates onto larger substrates, such as in flat panel display systems.

Vacuum fusion bonding of glass plates

DOEpatents

Swierkowski, Steve P.; Davidson, James C.; Balch, Joseph W.

2000-01-01

An improved apparatus and method for vacuum fusion bonding of large, patterned glass plates. One or both glass plates are patterned with etched features such as microstructure capillaries and a vacuum pumpout moat, with one plate having at least one hole therethrough for communication with a vacuum pumpout fixture. High accuracy alignment of the plates is accomplished by a temporary clamping fixture until the start of the fusion bonding heat cycle. A complete, void-free fusion bond of seamless, full-strength quality is obtained through the plates; because the glass is heated well into its softening point and because of a large, distributed force that is developed that presses the two plates together from the difference in pressure between the furnace ambient (high pressure) and the channeling and microstructures in the plates (low pressure) due to the vacuum drawn. The apparatus and method may be used to fabricate microcapillary arrays for chemical electrophoresis; for example, any apparatus using a network of microfluidic channels embedded between plates of glass or similar moderate melting point substrates with a gradual softening point curve, or for assembly of glass-based substrates onto larger substrates, such as in flat panel display systems.

Vacuum fusion bonded glass plates having microstructures thereon

DOEpatents

Swierkowski, Steve P.; Davidson, James C.; Balch, Joseph W.

2001-01-01

An improved apparatus and method for vacuum fusion bonding of large, patterned glass plates. One or both glass plates are patterned with etched features such as microstructure capillaries and a vacuum pumpout moat, with one plate having at least one hole therethrough for communication with a vacuum pumpout fixture. High accuracy alignment of the plates is accomplished by a temporary clamping fixture until the start of the fusion bonding heat cycle. A complete, void-free fusion bond of seamless, full-strength quality is obtained through the plates; because the glass is heated well into its softening point and because of a large, distributed force that is developed that presses the two plates together from the difference in pressure between the furnace ambient (high pressure) and the channeling and microstructures in the plates (low pressure) due to the vacuum drawn. The apparatus and method may be used to fabricate microcapillary arrays for chemical electrophoresis; for example, any apparatus using a network of microfluidic channels embedded between plates of glass or similar moderate melting point substrates with a gradual softening point curve, or for assembly of glass-based substrates onto larger substrates, such as in flat panel display systems.

[Preliminary study of bonding strength between diatomite-based dental ceramic and veneering porcelains].

PubMed

Lu, Xiao-li; Gao, Mei-qin; Cheng, Yu-ye; Zhang, Fei-min

2015-04-01

In order to choose the best veneering porcelain for diatomite-based dental ceramic substrate, the bonding strength between diatomite-based dental ceramics and veneering porcelains was measured, and the microstructure and elements distribution of interface were analyzed. The coefficient of thermal expansion (CTE) of diatomite-based dental ceramics was detected by dilatometry. Three veneering porcelain materials were selected with the best CTE matching including alumina veneering porcelain (group A), titanium porcelain veneering porcelain (group B), and E-max veneering porcelain (group C). Shear bonding strength was detected. SEM and EDS were used to observe the interface microstructure and element distribution. Statistical analysis was performed using SPSS 17.0 software package. The CTE of diatomite-based dental ceramics at 25-500 degrees centigrade was 8.85×10-6K-1. The diatomite-based substrate ceramics combined best with group C. Shear bonding strength between group A and C and group B and C both showed significant differences(P<0.05). SEM and EDS showed that the interface of group C sintered tightly and elements permeated on both sides of the interface. The diatomite-based substrate ceramics combines better with E-max porcelain veneer.

Self-regenerating and hybrid irreversible/reversible PDMS microfluidic devices.

PubMed

Shiroma, Letícia S; Piazzetta, Maria H O; Duarte-Junior, Gerson F; Coltro, Wendell K T; Carrilho, Emanuel; Gobbi, Angelo L; Lima, Renato S

2016-05-16

This paper outlines a straightforward, fast, and low-cost method to fabricate polydimethylsiloxane (PDMS) chips. Termed sandwich bonding (SWB), this method requires only a laboratory oven. Initially, SWB relies on the reversible bonding of a coverslip over PDMS channels. The coverslip is smaller than the substrate, leaving a border around the substrate exposed. Subsequently, a liquid composed of PDMS monomers and a curing agent is poured onto the structure. Finally, the cover is cured. We focused on PDMS/glass chips because of their key advantages in microfluidics. Despite its simplicity, this method created high-performance microfluidic channels. Such structures featured self-regeneration after leakages and hybrid irreversible/reversible behavior. The reversible nature was achieved by removing the cover of PDMS with acetone. Thus, the PDMS substrate and glass coverslip could be detached for reuse. These abilities are essential in the stages of research and development. Additionally, SWB avoids the use of surface oxidation, half-cured PDMS as an adhesive, and surface chemical modification. As a consequence, SWB allows surface modifications before the bonding, a long time for alignment, the enclosure of sub-micron channels, and the prototyping of hybrid devices. Here, the technique was successfully applied to bond PDMS to Au and Al.

Self-regenerating and hybrid irreversible/reversible PDMS microfluidic devices

PubMed Central

Shiroma, Letícia S.; Piazzetta, Maria H. O.; Duarte-Junior, Gerson F.; Coltro, Wendell K. T.; Carrilho, Emanuel; Gobbi, Angelo L.; Lima, Renato S.

2016-01-01

This paper outlines a straightforward, fast, and low-cost method to fabricate polydimethylsiloxane (PDMS) chips. Termed sandwich bonding (SWB), this method requires only a laboratory oven. Initially, SWB relies on the reversible bonding of a coverslip over PDMS channels. The coverslip is smaller than the substrate, leaving a border around the substrate exposed. Subsequently, a liquid composed of PDMS monomers and a curing agent is poured onto the structure. Finally, the cover is cured. We focused on PDMS/glass chips because of their key advantages in microfluidics. Despite its simplicity, this method created high-performance microfluidic channels. Such structures featured self-regeneration after leakages and hybrid irreversible/reversible behavior. The reversible nature was achieved by removing the cover of PDMS with acetone. Thus, the PDMS substrate and glass coverslip could be detached for reuse. These abilities are essential in the stages of research and development. Additionally, SWB avoids the use of surface oxidation, half-cured PDMS as an adhesive, and surface chemical modification. As a consequence, SWB allows surface modifications before the bonding, a long time for alignment, the enclosure of sub-micron channels, and the prototyping of hybrid devices. Here, the technique was successfully applied to bond PDMS to Au and Al. PMID:27181918

Molecular dynamics simulation of water at mineral surfaces: Structure, dynamics, energetics and hydrogen bonding

NASA Astrophysics Data System (ADS)

Kalinichev, A. G.; Wang, J.; Kirkpatrick, R.

2006-05-01

Fundamental molecular-level understanding of the properties of aqueous mineral interfaces is of great importance for many geochemical and environmental systems. Interaction between water and mineral surfaces substantially affects the properties of both phases, including the reactivity and functionality of the substrate surface, and the structure, dynamics, and energetics of the near surface aqueous phase. Experimental studies of interfacial water structure and dynamics using surface-sensitive techniques such as sum-frequency vibrational spectroscopy or X-ray and neutron reflectivity are not always possible for many practically important substrates, and their results often require interpretation concerning the atomistic mechanisms responsible for the observed behavior. Molecular computer simulations can provide new insight into the underlying molecular- level relationships between the inorganic substrate structure and composition and the structure, ordering, and dynamics of interfacial water. We have performed a series of molecular dynamics (MD) computer simulations of aqueous interfaces with several silicates (quartz, muscovite, and talc) and hydroxides (brucite, portlandite, gibbsite, Ca/Al and Mg/Al double hydroxides) to quantify the effects of the substrate mineral structure and composition on the structural, transport, and thermodynamic properties of water on these mineral surfaces. Due to the prevalent effects of the development of well-interconnected H-bonding networks across the mineral- water interfaces, all the hydroxide surfaces (including a fully hydroxylated quartz surface) show very similar H2O density profiles perpendicular to the interface. However, the predominant orientations of the interfacial H2O molecules and their detailed 2-dimensional near-surface structure and dynamics parallel to the interface are quite different reflecting the differences in the substrate structural charge distribution and the density and orientations of the surface OH groups. The H2O density profiles and other structural and dynamic characteristics of water at the two siloxane surfaces are very different from each other and from the hydroxide surfaces, since the muscovite surface is negatively charged and hydrophilic, while the talc surface is electrostatically neutral and hydrophobic. In general, at hydrophilic neutral surfaces both donating and accepting H-bonds from the H2O molecules are contributing to the development of the interfacial H-bond network, whereas at hydrophilic but charged surfaces only accepting or donating H-bonds with H2O molecules are possible. At the hydrophobic talc surface H-bonds among H2O molecules dominate the interfacial H-bond network and the water-surface interactions are very weak. The first water layer at all substrates is well ordered parallel to the surface, reflecting substrate crystal structures and indicating the reduced translational and orientational mobility of interfacial H2O molecules. At longer time scale (~100ps) their dynamics can be decomposed into a slow, virtually frozen, regime due to the substrate- bound H2O and a faster regime of almost free water reflecting the dynamics far from the surface. At shorter times (>10ps) the two dynamical regimes are superimposed. The much higher ordering of interfacial water (compared to bulk liquid) can not be adequately described as simply "ice-like". To some extent, it rather resembles the behavior of supercooled water.

Role of hydrogen bonds in the reaction mechanism of chalcone isomerase.

PubMed

Jez, Joseph M; Bowman, Marianne E; Noel, Joseph P

2002-04-23

In flavonoid, isoflavonoid, and anthocyanin biosynthesis, chalcone isomerase (CHI) catalyzes the intramolecular cyclization of chalcones into (S)-flavanones with a second-order rate constant that approaches the diffusion-controlled limit. The three-dimensional structures of alfalfa CHI complexed with different flavanones indicate that two sets of hydrogen bonds may possess critical roles in catalysis. The first set of interactions includes two conserved amino acids (Thr48 and Tyr106) that mediate a hydrogen bond network with two active site water molecules. The second set of hydrogen bonds occurs between the flavanone 7-hydroxyl group and two active site residues (Asn113 and Thr190). Comparison of the steady-state kinetic parameters of wild-type and mutant CHIs demonstrates that efficient cyclization of various chalcones into their respective flavanones requires both sets of contacts. For example, the T48A, T48S, Y106F, N113A, and T190A mutants exhibit 1550-, 3-, 30-, 7-, and 6-fold reductions in k(cat) and 2-3-fold changes in K(m) with 4,2',4'-trihydroxychalcone as a substrate. Kinetic comparisons of the pH-dependence of the reactions catalyzed by wild-type and mutant enzymes indicate that the active site hydrogen bonds contributed by these four residues do not significantly alter the pK(a) of the intramolecular cyclization reaction. Determinations of solvent kinetic isotope and solvent viscosity effects for wild-type and mutant enzymes reveal a change from a diffusion-controlled reaction to one limited by chemistry in the T48A and Y106F mutants. The X-ray crystal structures of the T48A and Y106F mutants support the assertion that the observed kinetic effects result from the loss of key hydrogen bonds at the CHI active site. Our results are consistent with a reaction mechanism for CHI in which Thr48 polarizes the ketone of the substrate and Tyr106 stabilizes a key catalytic water molecule. Hydrogen bonds contributed by Asn113 and Thr190 provide additional stabilization in the transition state. Conservation of these residues in CHIs from other plant species implies a common reaction mechanism for enzyme-catalyzed flavanone formation in all plants.

Machine learnt bond order potential to investigate the low thermal conductivity of stanene nanostructures

NASA Astrophysics Data System (ADS)

Cherukara, Mathew; Narayanan, Badri; Kinaci, Alper; Sasikumar, Kiran; Gray, Stephen; Chan, Maria; Sankaranarayanan, Subramanian

The growth of stanene on a Bi2Te3\\ substrate has engendered a great deal of interest, in part due to stanene's predicted exotic properties. In particular, stanene shows promise in topological insulation, large-gap 2D quantum spin hall states, lossless electrical conduction, enhanced thermoelectricity, and topological superconductivity. However, atomistic investigations of growth mechanisms (needed to guide synthesis), phonon transport (crucial for designing thermoelectrics), and thermo-mechanical behavior of stanene are scarce. This paucity is primarily due to the lack of inter-atomic potentials that can accurately capture atomic interactions in stanene. To address this, we have developed a machine learnt bond-order potential (BOP) based on Tersoff's formalism that can accurately capture bond breaking/formation events, structure, energetics, thermodynamics, thermal conductivity, and mechanical properties of single layer tin, using a training set derived from density functional theory calculations. Finally, we employed our newly developed BOP to study anisotropy in thermal conductivity of stanene sheets, temperature induced rippling, as well as dependence of anharmonicity and thermal conductivity on temperature.

Influence of micro-oxidation on joints of C/C composites and GH3044 for large-size aerospace parts

NASA Astrophysics Data System (ADS)

Shi, Xiaohong; Jin, Xiuxiu; Yan, Ningning; Yang, Li

2017-11-01

To improve the bonding strength of carbon/carbon (C/C) composites and GH3044 nickel-based superalloy, the bonding interlayer with Ti/Ni/Cu/Ni multiple foils were prepared by a two-step technique involving micro-oxidation and partial transient liquid phase (PTLP) process. Interface characteristics and mechanical behavior of joints were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), laser scanning confocal microscope (LSCM) and energy X-ray dispersive spectrometer (EDS). Results show that a porous layer on C/C composites is formed by micro-oxidation for more than 2 min at 1073 K in air, which provides a diffusion path for liquid phase to infiltrate into C/C substrate and generate a wedge interlocking interface. After micro-oxidation for 4 min, the shear strength of joints reaches 32.09 ± 1.98 MPa what is 36.73% higher than that of joints without micro-oxidation (23.47 ± 1.15 MPa). The increase of shear strength remarkably depends on physical interlocking and chemical bonding at porous interface.

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

Han, Chang Wan; Choksi, Tej; Milligan, Cory

The strength of metal-support bonding in heterogeneous catalysts determines their thermal stability, therefore, a tremendous amount of effort has been expended to understand metal-support interactions. Herein, we report the discovery of an anomalous “strong metal-support bonding” between gold nanoparticles and “nano-engineered” Fe 3O 4 substrates by in-situ microscopy. During in-situ vacuum annealing of Au-Fe 3O 4 dumbbell-like nanoparticles, synthesized by the epitaxial growth of nano-Fe 3O 4 on Au nanoparticles, the gold nanoparticles transform into the monolayered gold thinfilms and wet the surface of nano-Fe 3O 4, as the surface reduction of nano-Fe 3O 4 proceeds. This phenomenon results frommore » a unique coupling of the size-and shape-dependent high surface reducibility of nano-Fe 3O 4 and the extremely strong adhesion between Au and the reduced Fe 3O 4. This strong-metal support bonding reveals the significance of controlling the metal oxide support size and morphology for optimizing metal-support bonding and, ultimately, for the development of improved catalysts and functional nanostructures.« less

Transistors using crystalline silicon devices on glass

DOEpatents

McCarthy, A.M.

1995-05-09

A method is disclosed for fabricating transistors using single-crystal silicon devices on glass. This method overcomes the potential damage that may be caused to the device during high voltage bonding and employs a metal layer which may be incorporated as part of the transistor. This is accomplished such that when the bonding of the silicon wafer or substrate to the glass substrate is performed, the voltage and current pass through areas where transistors will not be fabricated. After removal of the silicon substrate, further metal may be deposited to form electrical contact or add functionality to the devices. By this method both single and gate-all-around devices may be formed. 13 figs.

Method for fabricating transistors using crystalline silicon devices on glass

DOEpatents

McCarthy, Anthony M.

1997-01-01

A method for fabricating transistors using single-crystal silicon devices on glass. This method overcomes the potential damage that may be caused to the device during high voltage bonding and employs a metal layer which may be incorporated as part of the transistor. This is accomplished such that when the bonding of the silicon wafer or substrate to the glass substrate is performed, the voltage and current pass through areas where transistors will not be fabricated. After removal of the silicon substrate, further metal may be deposited to form electrical contact or add functionality to the devices. By this method both single and gate-all-around devices may be formed.

Method for fabricating transistors using crystalline silicon devices on glass

DOEpatents

McCarthy, A.M.

1997-09-02

A method for fabricating transistors using single-crystal silicon devices on glass. This method overcomes the potential damage that may be caused to the device during high voltage bonding and employs a metal layer which may be incorporated as part of the transistor. This is accomplished such that when the bonding of the silicon wafer or substrate to the glass substrate is performed, the voltage and current pass through areas where transistors will not be fabricated. After removal of the silicon substrate, further metal may be deposited to form electrical contact or add functionality to the devices. By this method both single and gate-all-around devices may be formed. 13 figs.

Spectroscopic and computational studies of cobalamin species with variable lower axial ligation: implications for the mechanism of Co-C bond activation by class I cobalamin-dependent isomerases.

PubMed

Conrad, Karen S; Jordan, Christopher D; Brown, Kenneth L; Brunold, Thomas C

2015-04-20

5'-deoxyadenosylcobalamin (coenzyme B12, AdoCbl) serves as the cofactor for several enzymes that play important roles in fermentation and catabolism. All of these enzymes initiate catalysis by promoting homolytic cleavage of the cofactor's Co-C bond in response to substrate binding to their active sites. Despite considerable research efforts, the role of the lower axial ligand in facilitating Co-C bond homolysis remains incompletely understood. In the present study, we characterized several derivatives of AdoCbl and its one-electron reduced form, Co(II)Cbl, by using electronic absorption and magnetic circular dichroism spectroscopies. To complement our experimental data, we performed computations on these species, as well as additional Co(II)Cbl analogues. The geometries of all species investigated were optimized using a quantum mechanics/molecular mechanics method, and the optimized geometries were used to compute absorption spectra with time-dependent density functional theory. Collectively, our results indicate that a reduction in the basicity of the lower axial ligand causes changes to the cofactor's electronic structure in the Co(II) state that replicate the effects seen upon binding of Co(II)Cbl to Class I isomerases, which replace the lower axial dimethylbenzimidazole ligand of AdoCbl with a protein-derived histidine (His) residue. Such a reduction of the basicity of the His ligand in the enzyme active site may be achieved through proton uptake by the catalytic triad of conserved residues, DXHXGXK, during Co-C bond homolysis.

Influence of test capacitor features on piezoelectric and dielectric measurement of ferroelectric films.

PubMed

Wang, Zhihong; Lau, Gih Keong; Zhu, Weiguang; Chao, Chen

2006-01-01

This paper presents both theoretical and numerical analyses of the piezoelectric and dielectric responses of a highly idealized film-on-substrate system, namely, a polarized ferroelectric film perfectly bonded to an elastic silicon substrate. It shows that both effective dielectric and piezoelectric properties of the films change with the size and configuration of the test capacitor. There exists a critical electrode size that is smaller than the diameter of the commonly used substrate. The effective film properties converge to their respective constrained values as capacitor size increases to the critical size. If capacitor size is smaller than the critical size, the surface displacement at the top electrode deviates from the net thickness change in response to an applied voltage because the film is deformable at the film/substrate interface. The constrained properties of the films depend only on those of bulk ferroelectrics but are independent of film thickness and substrate properties. The finding of the critical capacitor size together with analytical expressions of the constrained properties makes it possible to realize consistent measurement of piezoelectric and dielectric properties of films. A surface scanning technique is recommended to measure the profile of piezoresponses of the film so that the constrained properties of the film can be identified accurately.

Light-induced V{sub oc} increase and decrease in high-efficiency amorphous silicon solar cells

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

Stuckelberger, M., E-mail: michael.stuckelberger@epfl.ch; Riesen, Y.; Despeisse, M.

High-efficiency amorphous silicon (a-Si:H) solar cells were deposited with different thicknesses of the p-type amorphous silicon carbide layer on substrates of varying roughness. We observed a light-induced open-circuit voltage (V{sub oc}) increase upon light soaking for thin p-layers, but a decrease for thick p-layers. Further, the V{sub oc} increase is enhanced with increasing substrate roughness. After correction of the p-layer thickness for the increased surface area of rough substrates, we can exclude varying the effective p-layer thickness as the cause of the substrate roughness dependence. Instead, we explain the observations by an increase of the dangling-bond density in both themore » p-layer—causing a V{sub oc} increase—and in the intrinsic absorber layer, causing a V{sub oc} decrease. We present a mechanism for the light-induced increase and decrease, justified by the investigation of light-induced changes of the p-layer and supported by Advanced Semiconductor Analysis simulation. We conclude that a shift of the electron quasi-Fermi level towards the conduction band is the reason for the observed V{sub oc} enhancements, and poor amorphous silicon quality on rough substrates enhances this effect.« less

Laser readable thermoluminescent radiation dosimeters and methods for producing thereof

DOEpatents

Braunlich, P.F.; Tetzlaff, W.

1989-04-25

Thin layer thermoluminescent radiation dosimeters for use in laser readable dosimetry systems, and methods of fabricating such thin layer dosimeters are disclosed. The thin layer thermoluminescent radiation dosimeters include a thin substrate made from glass or other inorganic materials capable of withstanding high temperatures and high heating rates. A thin layer of a thermoluminescent phosphor material is heat bonded to the substrate using an inorganic binder such as glass. The dosimeters can be mounted in frames and cases for ease in handling. Methods of the invention include mixing a suitable phosphor composition and binder, both being in particulate or granular form. The mixture is then deposited onto a substrate such as by using mask printing techniques. The dosimeters are thereafter heated to fuse and bond the binder and phosphor to the substrate. 34 figs.

Single-molecule Force Spectroscopy Approach to Enzyme Catalysis*

PubMed Central

Alegre-Cebollada, Jorge; Perez-Jimenez, Raul; Kosuri, Pallav; Fernandez, Julio M.

2010-01-01

Enzyme catalysis has been traditionally studied using a diverse set of techniques such as bulk biochemistry, x-ray crystallography, and NMR. Recently, single-molecule force spectroscopy by atomic force microscopy has been used as a new tool to study the catalytic properties of an enzyme. In this approach, a mechanical force ranging up to hundreds of piconewtons is applied to the substrate of an enzymatic reaction, altering the conformational energy of the substrate-enzyme interactions during catalysis. From these measurements, the force dependence of an enzymatic reaction can be determined. The force dependence provides valuable new information about the dynamics of enzyme catalysis with sub-angstrom resolution, a feat unmatched by any other current technique. To date, single-molecule force spectroscopy has been applied to gain insight into the reduction of disulfide bonds by different enzymes of the thioredoxin family. This minireview aims to present a perspective on this new approach to study enzyme catalysis and to summarize the results that have already been obtained from it. Finally, the specific requirements that must be fulfilled to apply this new methodology to any other enzyme will be discussed. PMID:20382731

Single-molecule force spectroscopy approach to enzyme catalysis.

PubMed

Alegre-Cebollada, Jorge; Perez-Jimenez, Raul; Kosuri, Pallav; Fernandez, Julio M

2010-06-18

Enzyme catalysis has been traditionally studied using a diverse set of techniques such as bulk biochemistry, x-ray crystallography, and NMR. Recently, single-molecule force spectroscopy by atomic force microscopy has been used as a new tool to study the catalytic properties of an enzyme. In this approach, a mechanical force ranging up to hundreds of piconewtons is applied to the substrate of an enzymatic reaction, altering the conformational energy of the substrate-enzyme interactions during catalysis. From these measurements, the force dependence of an enzymatic reaction can be determined. The force dependence provides valuable new information about the dynamics of enzyme catalysis with sub-angstrom resolution, a feat unmatched by any other current technique. To date, single-molecule force spectroscopy has been applied to gain insight into the reduction of disulfide bonds by different enzymes of the thioredoxin family. This minireview aims to present a perspective on this new approach to study enzyme catalysis and to summarize the results that have already been obtained from it. Finally, the specific requirements that must be fulfilled to apply this new methodology to any other enzyme will be discussed.

Characteristics and porcelain bond strength of (Ti,Al)N coating on dental alloys.

PubMed

Chung, Kwok-Hung; Duh, Jeng-Gong; Shin, Daehwan; Cagna, David R; Cronin, Robert J

2002-01-01

The effect of a novel titanium-aluminum nitride film, or (Ti,Al)N film, on the bond strength between a dental porcelain and two nickel-based dental alloy substrates was investigated. A thin layer of (Ti,Al)N film was deposited on flat metal samples using a reactive radio-frequency sputtering method. A uniform thickness of porcelain was applied to the film- coated metal samples. Metal-ceramic specimens were subjected to three-point bending, and failure loads were recorded. Bond strengths between the porcelain and (Ti,Al)N-coated metal alloys ranged from 159.0 +/- 11.7 N to 278.0 +/- 12.3 N. These values were significantly greater (p< 0.05) than bond strengths recorded for control samples that did not incorporate the (Ti,Al)N film. An electron probe microanalyzer with a line profile mode was used to characterize the interface between the (Ti,Al)N film and the porcelain. Results of this investigation suggest that the (Ti,Al)N film (1) increases the flexural bond strength between dental porcelain and nickel-based alloy substrates by permitting elemental diffusion, (2) interferes with the surface oxide formation that characteristically originates from the nickel-based metal alloy substrate, and (3) provides an appropriate oxide layer for porcelain application. Copyright 2002 Wiley Periodicals, Inc. J Biomed Mater Res (Appl Biomater) 63: 516-521, 2002

Adenosylcobinamide methyl phosphate as a pseudocoenzyme for diol dehydrase.

PubMed

Ishida, A; Toraya, T

1993-02-16

Adenosylcobinamide methyl phosphate, a novel analog of adenosylcobalamin lacking the nucleotide loop moiety, was synthesized. It did not show detectable coenzymic activity but behaved as a strong competitive inhibitor against AdoCbl with relatively high affinity (Ki = 2.5 microM). When apoenzyme was incubated at 37 degrees C with this analog in the presence of substrate, the Co-C bond of the analog was almost completely and irreversibly cleaved within 10 min, forming an enzyme-bound Co(II)-containing species. The cleavage was not observed in the absence of substrate. The Co-C bond cleavage in the presence of substrate was not catalytic but stoichiometric, implying that the Co-C bond of the analog undergoes activation when the analog binds to the active site of the enzyme. 5'-Deoxyadenosine was the only product derived from the adenosyl group of the analog upon the Co-C bond cleavage. Apoenzyme did not undergo modification during this process. Therefore, it seems likely that adenosylcobinamide methyl phosphate acts as a pseudocoenzyme or a potent suicide coenzyme. Since adenosylcobinamide neither functions as coenzyme nor binds tightly to apoenzyme, it can be concluded that the phosphodiester moiety of the nucleotide loop of adenosylcobalamin is essential for tight binding to apoenzyme and therefore for subsequent activation of the Co-C bond and catalysis. It is also evident that the nucleotide loop is obligatory for the normal progress of catalytic cycle.

Cements and adhesives for all-ceramic restorations.

PubMed

Manso, Adriana P; Silva, Nelson R F A; Bonfante, Estevam A; Pegoraro, Thiago A; Dias, Renata A; Carvalho, Ricardo M

2011-04-01

Dental cements are designed to retain restorations, prefabricated or cast posts and cores, and appliances in a stable, and long-lasting position in the oral environment. Resin-based cements were developed to overcome drawbacks of nonresinous materials, including low strength, high solubility, and opacity. Successful cementation of esthetic restorations depends on appropriate treatment to the tooth substrate and intaglio surface of the restoration, which in turn, depends on the ceramic characteristics. A reliable resin cementation procedure can only be achieved if the operator is aware of the mechanisms involved to perform the cementation and material properties. This article addresses current knowledge of resin cementation concepts, exploring the bonding mechanisms that influence long-term clinical success of all-ceramic systems. Copyright © 2011 Elsevier Inc. All rights reserved.

An Automatic Braking System That Stabilizes Leukocyte Rolling by an Increase in Selectin Bond Number with Shear

PubMed Central

Chen, Shuqi; Springer, Timothy A.

1999-01-01

Wall shear stress in postcapillary venules varies widely within and between tissues and in response to inflammation and exercise. However, the speed at which leukocytes roll in vivo has been shown to be almost constant within a wide range of wall shear stress, i.e., force on the cell. Similarly, rolling velocities on purified selectins and their ligands in vitro tend to plateau. This may be important to enable rolling leukocytes to be exposed uniformly to activating stimuli on endothelium, independent of local hemodynamic conditions. Wall shear stress increases the rate of dissociation of individual selectin–ligand tether bonds exponentially (1, 4) thereby destabilizing rolling. We find that this is compensated by a shear-dependent increase in the number of bonds per rolling step. We also find an increase in the number of microvillous tethers to the substrate. This explains (a) the lack of firm adhesion through selectins at low shear stress or high ligand density, and (b) the stability of rolling on selectins to wide variation in wall shear stress and ligand density, in contrast to rolling on antibodies (14). Furthermore, our data successfully predict the threshold wall shear stress below which rolling does not occur. This is a special case of the more general regulation by shear of the number of bonds, in which the number of bonds falls below one. PMID:9885254

An automatic braking system that stabilizes leukocyte rolling by an increase in selectin bond number with shear.

PubMed

Chen, S; Springer, T A

1999-01-11

Wall shear stress in postcapillary venules varies widely within and between tissues and in response to inflammation and exercise. However, the speed at which leukocytes roll in vivo has been shown to be almost constant within a wide range of wall shear stress, i.e., force on the cell. Similarly, rolling velocities on purified selectins and their ligands in vitro tend to plateau. This may be important to enable rolling leukocytes to be exposed uniformly to activating stimuli on endothelium, independent of local hemodynamic conditions. Wall shear stress increases the rate of dissociation of individual selectin-ligand tether bonds exponentially (, ) thereby destabilizing rolling. We find that this is compensated by a shear-dependent increase in the number of bonds per rolling step. We also find an increase in the number of microvillous tethers to the substrate. This explains (a) the lack of firm adhesion through selectins at low shear stress or high ligand density, and (b) the stability of rolling on selectins to wide variation in wall shear stress and ligand density, in contrast to rolling on antibodies (). Furthermore, our data successfully predict the threshold wall shear stress below which rolling does not occur. This is a special case of the more general regulation by shear of the number of bonds, in which the number of bonds falls below one.

Hybridization trends for main group elements and expanding the Bent's rule beyond carbon: more than electronegativity.

PubMed

Alabugin, Igor V; Bresch, Stefan; Manoharan, Mariappan

2014-05-22

Trends in hybridization were systematically analyzed through the combination of DFT calculations with NBO analysis for the five elements X (X = B, C, N, O, and F) in 75 HnX-YHm compounds, where Y spans the groups 13-17 of the periods 2-4. This set of substrates probes the flexibility of the hybridization at five atoms X through variations in electronegativity, polarizability, and orbital size of Y. The results illustrate the scope and limitations of the Bent's rule, the classic correlation between electronegativity and hybridization, commonly used in analyzing structural effects in carbon compounds. The rehybridization effects are larger for fluorine- and oxygen-bonds than they are in the similar bonds to carbon. For bonds with the larger elements Y of the lower periods, trends in orbital hybridization depend strongly on both electronegativity and orbital size. For charged species, the effects of substituent orbital size in the more polarizable bonds to heavier elements show a particularly strong response to the charge introduction at the central atom. In the final section, we provide an example of the interplay between hybridization effects with molecular structure and reactivity. In particular, the ability to change hybridization without changes in polarization provides an alternative way to control structure and reactivity, as illustrated by the strong correlation of strain in monosubstituted cyclopropanes with hybridization in the bond to the substituent.

Evaluation of EA-934NA with 2.5 percent Cab-O-Sil

NASA Technical Reports Server (NTRS)

Caldwell, Gordon A.

1990-01-01

Currently, Hysol adhesive EA-934NA is used to bond the Field Joint Protection System on the Shuttle rocket motors at Kennedy Space Center. However, due to processing problems, an adhesive with a higher viscosity is needed to alleviate these difficulties. One possible solution is to add Cab-O-Sil to the current adhesive. The adhesive strength and bond strengths that can be obtained when 2.5 percent Cab-O-Sil is added to adhesive EA-934NA are examined and tested over a range of test temperatures from -20 to 300 F. Tensile adhesion button and lap shear specimens were bonded to D6AC steel and uniaxial tensile specimens (testing for strength, initial tangent modulus, elongation and Poisson's ratio) were prepared using Hysol adhesive EA-934NA with 2.5 percent Cab-O-Sil added. These specimens were tested at -20, 20, 75, 100, 125, 150, 200, 250, and 300 F, respectively. Additional tensile adhesion button specimens bonding Rust-Oleum primed and painted D6AC steel to itself and to cork using adhesive EA-934NA with 2.5 percent Cab-O-Sil added were tested at 20, 75, 125, 200, and 300 F, respectively. Results generally show decreasing strength values with increasing test temperatures. The bond strengths obtained using cork as a substrate were totally dependent on the cohesive strength of the cork.

Repair bond strength of nanohybrid composite resins with a universal adhesive

PubMed Central

Altinci, Pinar; Mutluay, Murat; Tezvergil-Mutluay, Arzu

2018-01-01

Abstract Objective: To investigate the repair bond strength of fresh and aged nanohybrid and hybrid composite resins using a universal adhesive (UA). Materials and methods: Fresh and aged substrates were prepared using two nanohybrid (Venus Pearl, Heraus Kulzer; Filtek Supreme XTE, 3 M ESPE) and one hybrid (Z100, 3 M ESPE) composite resin, and randomly assigned to different surface treatments: (1) no treatment (control), (2) surface roughening with 320-grit (SR), (3) SR + UA (iBOND, Heraus Kulzer), (4) SR + Silane (Signum, Ceramic Bond I, Heraeus Kulzer) + UA, (5) SR + Sandblasting (CoJet, 3 M ESPE) + Silane + UA. After surface treatment, fresh composite resin was added to the substrates at 2 mm layer increments to a height of 5 mm, and light cured. Restored specimens were water-stored for 24 h and sectioned to obtain 1.0 × 1.0 mm beams (n = 12), and were either water-stored for 24 h at 37 °C, or water-stored for 24 h, and then thermocycled for 6000 cycles before microtensile bond strength (µTBS) testing. Data were analyzed with ANOVA and Tukey’s HSD tests (p = .05). Results: Combined treatment of SR, sandblasting, silane and UA provided repair bond strength values comparable to the cohesive strength of each tested resin material (p < .05). Thermocycling significantly reduced the cohesive strength of the composite resins upto 65% (p < .05). Repair bond strengths of UA-treated groups were more stable under thermocycling. Conclusions: Universal adhesive application is a reliable method for composite repair. Sandblasting and silane application slightly increases the repair strength for all substrate types. PMID:29250576

Repair bond strength of nanohybrid composite resins with a universal adhesive.

PubMed

Altinci, Pinar; Mutluay, Murat; Tezvergil-Mutluay, Arzu

2018-01-01

Objective: To investigate the repair bond strength of fresh and aged nanohybrid and hybrid composite resins using a universal adhesive (UA). Materials and methods: Fresh and aged substrates were prepared using two nanohybrid (Venus Pearl, Heraus Kulzer; Filtek Supreme XTE, 3 M ESPE) and one hybrid (Z100, 3 M ESPE) composite resin, and randomly assigned to different surface treatments: (1) no treatment (control), (2) surface roughening with 320-grit (SR), (3) SR + UA (iBOND, Heraus Kulzer), (4) SR + Silane (Signum, Ceramic Bond I, Heraeus Kulzer) + UA, (5) SR + Sandblasting (CoJet, 3 M ESPE) + Silane + UA. After surface treatment, fresh composite resin was added to the substrates at 2 mm layer increments to a height of 5 mm, and light cured. Restored specimens were water-stored for 24 h and sectioned to obtain 1.0 × 1.0 mm beams ( n  = 12), and were either water-stored for 24 h at 37 °C, or water-stored for 24 h, and then thermocycled for 6000 cycles before microtensile bond strength (µTBS) testing. Data were analyzed with ANOVA and Tukey's HSD tests ( p  = .05). Results: Combined treatment of SR, sandblasting, silane and UA provided repair bond strength values comparable to the cohesive strength of each tested resin material ( p  < .05). Thermocycling significantly reduced the cohesive strength of the composite resins upto 65% ( p  < .05). Repair bond strengths of UA-treated groups were more stable under thermocycling. Conclusions: Universal adhesive application is a reliable method for composite repair. Sandblasting and silane application slightly increases the repair strength for all substrate types.

Redirection of the Reaction Specificity of a Thermophilic Acetolactate Synthase toward Acetaldehyde Formation

PubMed Central

Cheng, Maria; Yoshiyasu, Hayato; Okano, Kenji; Ohtake, Hisao; Honda, Kohsuke

2016-01-01

Acetolactate synthase and pyruvate decarboxylase are thiamine pyrophosphate-dependent enzymes that convert pyruvate into acetolactate and acetaldehyde, respectively. Although the former are encoded in the genomes of many thermophiles and hyperthermophiles, the latter has been found only in mesophilic organisms. In this study, the reaction specificity of acetolactate synthase from Thermus thermophilus was redirected to catalyze acetaldehyde formation to develop a thermophilic pyruvate decarboxylase. Error-prone PCR and mutant library screening led to the identification of a quadruple mutant with 3.1-fold higher acetaldehyde-forming activity than the wild-type. Site-directed mutagenesis experiments revealed that the increased activity of the mutant was due to H474R amino acid substitution, which likely generated two new hydrogen bonds near the thiamine pyrophosphate-binding site. These hydrogen bonds might result in the better accessibility of H+ to the substrate-cofactor-enzyme intermediate and a shift in the reaction specificity of the enzyme. PMID:26731734

Porcelain veneer post-bonding crack repair by resin infiltration.

PubMed

Gresnigt, Marco; Magne, Michel; Magne, Pascal

Ceramic laminate veneer restorations are indicated in several clinical situations. Indirect restorations are usually chosen if the less-invasive options - bleaching, resin infiltration, or composite resin restorations - are not possible, or when it is too difficult to achieve an esthetically pleasing result in the long term. Bonded indirect partial restorations are highly dependent on their adhesive interface, as these thin restorations have a relatively low cohesive strength. Therefore, preservation of sound enamel, conditioning of the restorations and of the substrate, and luting procedures are of paramount importance for a successful outcome. Even when utmost care is taken during every step of the procedure, failures such as fractures, chipping, or marginal discoloration and defects sometimes occur. Only very few of these cases of failure are presented or are a subject of interest. In this case presentation, a fracture repair is performed using an infiltration technique with a resin composite material.

Balancing size exclusion and adsorption of polymers in nanopores

NASA Astrophysics Data System (ADS)

Kim, Won; Ryu, Chang Y.

2006-03-01

The liquid chromatography at critical condition (LCCC) presents the condition, at which the size exclusion and adsorption of polymer chains are balanced upon interactions with nanoporous substrates. In this study, we investigate how the polymer interactions with nanopores are affected by the solvent quality and nanopore size. Specifically, we measure the retention times of monodisperse polystyrenes in C18-bonded nanoporous silica column as a function of molecular weight, when a mixed solvent of methylene chloride and acetonitrile are used as elutent. C18-bonded silica particles with 70, 100, and 250 A pore size are used as a stationary phase to study how the transition from SEC-like to IC-like retention behavior depends on the condition of temperature and solvent composition. To locate the LCCC at various nanopore sizes, the temperature and solvent composition have been varied from 0 to 60 C and from 51 to 62 v/v% of methylene chloride, respectively.

Biochemical profiling in silico--predicting substrate specificities of large enzyme families.

PubMed

Tyagi, Sadhna; Pleiss, Juergen

2006-06-25

A general high-throughput method for in silico biochemical profiling of enzyme families has been developed based on covalent docking of potential substrates into the binding sites of target enzymes. The method has been tested by systematically docking transition state--analogous intermediates of 12 substrates into the binding sites of 20 alpha/beta hydrolases from 15 homologous families. To evaluate the effect of side chain orientations to the docking results, 137 crystal structures were included in the analysis. A good substrate must fulfil two criteria: it must bind in a productive geometry with four hydrogen bonds between the substrate and the catalytic histidine and the oxyanion hole, and a high affinity of the enzyme-substrate complex as predicted by a high docking score. The modelling results in general reproduce experimental data on substrate specificity and stereoselectivity: the differences in substrate specificity of cholinesterases toward acetyl- and butyrylcholine, the changes of activity of lipases and esterases upon the size of the acid moieties, activity of lipases and esterases toward tertiary alcohols, and the stereopreference of lipases and esterases toward chiral secondary alcohols. Rigidity of the docking procedure was the major reason for false positive and false negative predictions, as the geometry of the complex and docking score may sensitively depend on the orientation of individual side chains. Therefore, appropriate structures have to be identified. In silico biochemical profiling provides a time efficient and cost saving protocol for virtual screening to identify the potential substrates of the members of large enzyme family from a library of molecules.

Laser welding of fused silica glass with sapphire using a non- stoichiometric, fresnoitic Ba2TiSi2O8·3 SiO2 thin film as an absorber

NASA Astrophysics Data System (ADS)

de Pablos-Martín, A.; Lorenz, M.; Grundmann, M.; Höche, Th.

2017-07-01

Laser welding of dissimilar materials is challenging, due to their difference in coefficients of thermal expansion (CTE). In this work, fused silica-to-sapphire joints were achieved by employment of a ns laser focused in the intermediate Si-enriched fresnoitic glass thin film sealant. The microstructure of the bonded interphase was analyzed down to the nanometer scale and related to the laser parameters used. The crystallization of fresnoite in the glass sealant upon laser process leads to an intense blue emission intensity under UV excitation. This crystallization is favored in the interphase with the silica glass substrate, rather than in the border with the sapphire. The formation of SiO2 particles was confirmed, as well. The bond quality was evaluated by scanning acoustic microscopy (SAM). The substrates remain bonded even after heat treatment at 100 °C for 30 min, despite the large CTE difference between both substrates.

Microwave Induced Direct Bonding of Single Crystal Silicon Wafers

NASA Technical Reports Server (NTRS)

Budraa, N. K.; Jackson, H. W.; Barmatz, M.

1999-01-01

We have heated polished doped single-crystal silicon wafers in a single mode microwave cavity to temperatures where surface to surface bonding occurred. The absorption of microwaves and heating of the wafers is attributed to the inclusion of n-type or p-type impurities into these substrates. A cylindrical cavity TM (sub 010) standing wave mode was used to irradiate samples of various geometry's at positions of high magnetic field. This process was conducted in vacuum to exclude plasma effects. This initial study suggests that the inclusion of impurities in single crystal silicon significantly improved its microwave absorption (loss factor) to a point where heating silicon wafers directly can be accomplished in minimal time. Bonding of these substrates, however, occurs only at points of intimate surface to surface contact. The inclusion of a thin metallic layer on the surfaces enhances the bonding process.

Nanobonding: A key technology for emerging applications in health and environmental sciences

NASA Astrophysics Data System (ADS)

Howlader, Matiar M. R.; Deen, M. Jamal; Suga, Tadatomo

2015-03-01

In this paper, surface-activation-based nanobonding technology and its applications are described. This bonding technology allows for the integration of electronic, photonic, fluidic and mechanical components into small form-factor systems for emerging sensing and imaging applications in health and environmental sciences. Here, we describe four different nanobonding techniques that have been used for the integration of various substrates — silicon, gallium arsenide, glass, and gold. We use these substrates to create electronic (silicon), photonic (silicon and gallium arsenide), microelectromechanical (glass and silicon), and fluidic (silicon and glass) components for biosensing and bioimaging systems being developed. Our nanobonding technologies provide void-free, strong, and nanometer scale bonding at room temperature or at low temperatures (<200 °C), and do not require chemicals, adhesives, or high external pressure. The interfaces of the nanobonded materials in ultra-high vacuum and in air correspond to covalent bonds, and hydrogen or hydroxyl bonds, respectively.

Enantioselective Cyanation of Benzylic C–H Bonds via Copper-Catalyzed Radical Relay

PubMed Central

Zhang, Wen; Wang, Fei; McCann, Scott D.; Wang, Dinghai; Chen, Pinhong; Stahl, Shannon; Liu, Guosheng

2017-01-01

Direct methods for stereoselective functionalization of C(sp3)–H bonds in complex organic molecules could facilitate much more efficient preparation of therapeutics and agrochemicals. Here, we report a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C–H bonds into benzylic nitriles. Hydrogen-atom abstraction affords an achiral benzylic radical that undergoes asymmetric C(sp3)–CN bond upon reaction with a chiral copper catalyst. The reactions proceed efficiently at room temperature with the benzylic substrate as limiting reagent, exhibit broad substrate scope with high enantioselectivity (typically 90-99% enantiomeric excess), and afford products that are key precursors to important bioactive molecules. Mechanistic studies provide evidence for diffusible organic radicals and highlight the difference between these reactions and C–H oxidations mediated by enzymes and other catalysts that operate via radical rebound pathways. PMID:27701109

Lys98 Substitution in Human AP Endonuclease 1 Affects the Kinetic Mechanism of Enzyme Action in Base Excision and Nucleotide Incision Repair Pathways

PubMed Central

Timofeyeva, Nadezhda A.; Koval, Vladimir V.; Ishchenko, Alexander A.; Saparbaev, Murat K.; Fedorova, Olga S.

2011-01-01

Human apurinic/apyrimidinic endonuclease 1 (APE1) is a key enzyme in the base excision repair (BER) and nucleotide incision repair (NIR) pathways. We recently analyzed the conformational dynamics and kinetic mechanism of wild-type (wt) protein, in a stopped-flow fluorescence study. In this study, we investigated the mutant enzyme APE1K98A using the same approach. Lys98 was known to hydrogen bond to the carboxyl group of Asp70, a residue implicated in binding the divalent metal ion. Our data suggested that the conformational selection and induced fit occur during the enzyme action. We expanded upon the evidence that APE1 can pre-exist in two conformations. The isomerization of an enzyme-product complex in the BER process and the additional isomerization stage of enzyme-substrate complex in the NIR process were established for APE1K98A. These stages had not been registered for the wtAPE1. We found that the K98A substitution resulted in a 12-fold reduction of catalytic constant of 5′-phosphodiester bond hydrolysis in (3-hydroxytetrahydrofuran-2-yl)methyl phosphate (F, tetrahydrofuran) containing substrate, and in 200-fold reduction in 5,6-dihydrouridine (DHU) containing substrate. Thus, the K98A substitution influenced NIR more than BER. We demonstrated that the K98A mutation influenced the formation of primary unspecific enzyme-substrate complex in a complicated manner, depending on the Mg2+ concentration and pH. This mutation obstructed the induced fit of enzyme in the complex with undamaged DNA and F-containing DNA and appreciably decreased the stability of primary complex upon interaction of enzyme with DNA, containing the natural apurinic/apyrimidinic (AP) site. Furthermore, it significantly delayed the activation of the less active form of enzyme during NIR and slowed down the conformational conversion of the complex of enzyme with the cleavage product of DHU-substrate. Our data revealed that APE1 uses the same active site to catalyze the cleavage of DHU- and AP-substrates. PMID:21912662

A P-H functionalized Al/P-based frustrated Lewis pair - hydrophosphination of nitriles, ring opening with cyclopropenones and evidence of P[double bond, length as m-dash]C double bond formation.

PubMed

Keweloh, Lukas; Aders, Niklas; Hepp, Alexander; Pleschka, Damian; Würthwein, Ernst-Ulrich; Uhl, Werner

2018-06-12

Hydroalumination of R-P(H)-C[triple bond, length as m-dash]C-tBu with bulky H-Al[CH(SiMe3)2]2 afforded the new P-H functionalized Al/P-based frustrated Lewis pair R-P(H)-C[[double bond, length as m-dash]C(H)-tBu]-AlR2 [R = CH(SiMe3)2; FLP 7]. A weak adduct of 7 with benzonitrile (8) was detected by NMR spectroscopy, but could not be isolated. tert-Butyl isocyanide afforded a similar, but isolable adduct (9), in which the isocyanide C atom was coordinated to aluminium. The unique reactivity of 7 became evident from its reactions with the heteroatom substituted nitriles PhO-C[triple bond, length as m-dash]N, PhCH2S-C[triple bond, length as m-dash]N and H8C4N-C[triple bond, length as m-dash]N. Hydrophosphination of the C[triple bond, length as m-dash]N triple bonds afforded imines at room temperature which were coordinated to the FLP by Al-N and P-C bonds to yield AlCPCN heterocycles (10 to 12). These processes depend on substrate activation by the FLP. Diphenylcyclopropenone and its sulphur derivative reacted with 7 by addition of the P-H bond to a C-C bond of the strained C3 ring and ring opening to afford the fragment (Z)-Ph-C(H)[double bond, length as m-dash]C(Ph)-C-X-Al (X = O, S). The C-O or C-S groups were coordinated to the FLP to yield AlCPCX heterocycles (13 and 14). The thiocarbonyl derived compound 14 contains an internally stabilized phosphenium cation with a localized P[double bond, length as m-dash]C bond, a trigonal planar coordinated P atom and a short P[double bond, length as m-dash]C distance (168.9 pm). Insight into formation mechanisms, the structural and energetic properties of FLP 7 and compounds 13 and 14 was gained by quantum chemical DFT calculations.

Clamping effect on the piezoelectric responses of screen-printed low temperature PZT/Polymer films on flexible substrates

NASA Astrophysics Data System (ADS)

Almusallam, A.; Yang, K.; Zhu, D.; Torah, R. N.; Komolafe, A.; Tudor, J.; Beeby, S. P.

2015-11-01

This paper introduces a new flexible lead zirconate titanate (PZT)/polymer composite material that can be screen-printed onto fabrics and flexible substrates, and investigates the clamping effect of these substrates on the characterization of the piezoelectric material. Experimental results showed that the optimum blend of PZT/polymer binder with a weight ratio of 12:1 provides a dielectric constant of 146. The measured value of the piezoelectric coefficient d33 was found to depend on the substrate used. Measured d33clp values of 70, 40, 36 pC N-1 were obtained from the optimum formulation printed on Polyester-cotton with an interface layer, Kapton and alumina substrates, respectively. The variation in the measured d33clp values occurs because of the effect of the mechanical boundary conditions of the substrate. The piezoelectric film is mechanically bonded to the surface of the substrate and this constrains the film in the plane of the substrate (the 1-direction). This constraint means that the perpendicular forces (applied in the 3-direction) used to measure d33 introduce a strain in the 1-direction that produces a charge of the opposite polarity to that induced by the d33 effect. This is due to the negative sign of the d31 coefficient and has the effect of reducing the measured d33 value. Theoretical and experimental investigations confirm a reduction of 13%, 50% and 55% in the estimated freestanding d33fs values (80 pC N-1) on Polyester-cotton, Kapton and alumina substrates, respectively. These results demonstrate the effect of the boundary conditions of the substrate/PZT interface on the piezoelectric response of the PZT/polymer film and in particular the reduced effect of fabric substrates due to their lowered stiffness.

Fabrication of Robust, Flat, Thinned, UV-Imaging CCDs

NASA Technical Reports Server (NTRS)

Grunthaner, Paula; Elliott, Stythe; Jones, Todd; Nikzad, Shouleh

2004-01-01

An improved process that includes a high-temperature bonding subprocess has been developed to enable the fabrication of robust, flat, silicon-based charge-coupled devices (CCDs) for imaging in ultraviolet (UV) light and/or for detecting low-energy charged particles. The CCDs in question are devices on which CCD circuitry has already been formed and have been thinned for backsurface illumination. These CCDs may be delta doped, and aspects of this type of CCD have been described in several prior articles in NASA Tech Briefs. Unlike prior low-temperature bonding subprocesses based on the use of epoxies or waxes, the high-temperature bonding subprocess is compatible with the deltadoping process as well as with other CCD-fabrication processes. The present improved process and its bonding, thinning, and delta-doping subprocesses, are characterized as postfabrication processes because they are undertaken after the fabrication of CCD circuitry on the front side of a full-thickness silicon substrate. In a typical case, it is necessary to reduce the thickness of the CCD to between 10 and 20 m in order to take advantage of back-side illumination and in order to perform delta doping and/or other back-side treatment to enhance the quantum efficiency. In the prior approach to the fabrication of back-side-illuminated CCDs, the thinning subprocess turned each CCD into a free-standing membrane that was fragile and tended to become wrinkled. In the present improved process, prior to thinning and delta doping, a CCD is bonded on its front side to a silicon substrate that has been prefabricated to include cutouts to accommodate subsequent electrical connections to bonding pads on the CCD circuitry. The substrate provides structural support to increase ruggedness and maintain flatness. At the beginning of this process, the back side of a CCD as fabricated on a full-thickness substrate is polished. Silicon nitride is deposited on the back side, opposite the bonding pads on the front side, in order to define a relatively thick frame. The portion of the CCD not covered by the frame is the portion to be thinned by etching.

Coating Development for GRCop-84 Liners for Reusable Launch Vehicles Aided by Modeling Studies

NASA Technical Reports Server (NTRS)

Raj, Sai V.; Ghosn, Louis J.

2004-01-01

The design of the next generation of reusable launch vehicles calls for using GRCop-84 copper alloy liners based on a composition invented at the NASA Glenn Research Center. Despite its considerable advantage over other copper alloys, it is expected that GRCop-84 will suffer from environmental degradation depending on the type of rocket fuels used and on thermomechanical fatigue. Applying protective coatings on GRCop-84 substrates can minimize or eliminate many of these problems and extend the operational life of the combustion liner. This could increase component reliability, shorten depot maintenance turnaround times, and lower operating costs. Therefore, Glenn is actively pursuing the development of advanced coatings technology for GRCop-84 liners. Technology is being developed in four major areas: (1) new metallic coating compositions, (2) application techniques, (3) test methods, and (4) life prediction design methodology using finite element analysis. The role of finite element analysis in guiding the coating effort is discussed in this report. Thermal analyses were performed at Glenn for different combinations of top- and bondcoat compositions to determine the temperature variation across the coated cross section with the thickness of the top coat. These calculations were conducted for simulated LH2/LO2 booster engine conditions assuming that the bond coat had a constant thickness of 50 m. The preceding graphs show the predicted temperatures at the outer surface of the top coat (hot wall), at the top-coat/bond-coat interface, at the bond-coat/GRCop-84 interface, and at the GRCop-84 cold wall as a function of top-coat thickness for Cu- 26(wt%)Cr top coat (top graph), Ni-17(wt%)Cr-6%Al-0.5%Y top coat and Cu-26%Cr bond coat, and NiAl top coat and Ni bond coat. In all cases, the temperature of the top coat at the hot wall increased with increasing top-coat thickness and with corresponding decreases in the temperatures at the two interfaces and the cold wall. These temperatures are not acutely sensitive to the thermal conductivity of the top coat when it exceeds 25 and 50 W/m/K for low and high heat flux engines. This observation is significant for two reasons. First, several different top-coat compositions can be evaluated as potential protective coatings without loss in the heat-transfer efficiency of the coated system. Second, materials with thermal conductivities less than the critical values of 25 or 50 W/m/K are more likely to act as thermal barrier coatings. The deposition of overlay coatings on GRCop-84 substrates results in the development of residual stresses. The presence of these residual stresses influences the probability of coating spallation, the thermal cycling life, and the fatigue properties of the coated substrate during use. Since it is important to understand how these stresses develop during the vacuum-plasma-spraying coating deposition process, the nature and magnitudes of the cool-down residual stresses were calculated and compared with experimentally determined values across the coated cross section of a disk specimen. The calculations were conducted assuming that the specimen cools down to room temperature from vacuum plasma-spraying temperatures of either 250 or 650 C. The effects of coating the substrate with and without grit blasting were also theoretically examined. The final graph compares the predicted and the experimental results for a GRCop-84 disk coated with about a 50- m-thick Ni bond coat and a 75- to 100- m NiAl top coat, where the curves for NASA-2 assume the presence of a prior residual stress generated by grit blasting under conditions similar to the experimental situation. The predicted cool-down in-plane stresses were compressive in both the NiAl top coat and the Ni bond coat. They were also compressive in the substrate to a depth of about 0.25 mm from the Ni/GRCop-84 interface when the vacuum-plasma-spraying temperature was low. However, using a higher plasma spraying temperaturs likely to leave the substrate under a small tensile stress to counter the compressive stresses in the bond and top coats because of the relaxation of residual stresses generated in the substrate during the grit blasting of its surface prior to spraying. These results suggest that the NiAl and Ni coatings are unlikely to spall after spraying as confirmed by the microstructural observations shown in the following photomicrograph of an as-sprayed specimen. Finally, it is noted that the calculated and experimental results are not in complete agreement, which indicates that both the experimental and modeling techniques need further refinement.

Silicone Disclosing Material used after Ceramic Surface Treatment Reduces Bond Strength.

PubMed

Fraga, Sara; Oliveira, Sara Cioccari; Pereira, Gabriel Kalil Rocha; Beekman, Pieter; Rippe, Marília Pivetta; Kleverlaan, Cornelis J

To evaluate the effect of a silicone disclosing procedure performed at different timepoints on the shear bond strength (SBS) of cements (self-adhesive composite cement, self-etch composite cement, resin-reinforced glass-ionomer cement) to different substrates (zirconia, lithium disilicate, bovine dentin). The substrate/cement combinations were assigned to two groups (n = 15) according to the timepoint, at which the vinyl polyether silicone disclosing agent was applied: after (experimental groups, EXP) or before (control groups, CTRL) specific micromechanical treatments of the substrate surface. To increase standardization, the cements were applied into rubber rings (2.2 mm diameter x 1.0 mm thickness) positioned on the substrate surface. After luting procedures, all specimens were stored in 37°C distilled water for 24 h, then subjected to SBS testing using a wire loop of 0.2 mm diameter at a crosshead speed of 1 mm/min until failure. Failure analysis was performed for all tested specimens. SBS data were submitted to Weibull analysis. The silicone disclosing procedure performed after micromechanical surface treatment reduced the characteristic shear bond strength to zirconia and lithium disilicate when compared to CTRL. However, for dentin specimens, there was no significant difference between CTRL and EXP for any of the cements investigated. Failure analysis showed a predominance of interfacial failures. The silicone disclosing procedure performed after the micromechanical treatment of ceramic surfaces negatively affected the cement bond strength. Therefore, after using it to check the fit of a prosthesis, clinicians should carefully clean the ceramic surface.

Particle Bonding Mechanism in Cold Gas Dynamic Spray: A Three-Dimensional Approach

NASA Astrophysics Data System (ADS)

Zhu, Lin; Jen, Tien-Chien; Pan, Yen-Ting; Chen, Hong-Sheng

2017-12-01

Cold gas dynamic spray (CGDS) is a surface coating process that uses highly accelerated particles to form the surface coating. In the CGDS process, metal particles with a diameter of 1-50 µm are carried by a gas stream at high pressure (typically 20-30 atm) through a de Laval-type nozzle to achieve supersonic velocity upon impact onto the substrate. Typically, the impact velocity ranges between 300 and 1200 m/s in the CGDS process. When the particle is accelerated to its critical velocity, which is defined as the minimum in-flight velocity at which it can deposit on the substrate, adiabatic shear instabilities will occur. Herein, to ascertain the critical velocities of different particle sizes on the bonding efficiency in CGDS process, three-dimensional numerical simulations of single particle deposition process were performed. In the CGDS process, one of the most important parameters which determine the bonding strength with the substrate is particle impact temperature. It is hypothesized that the particle will bond to the substrate when the particle's impacting velocity surpasses the critical velocity, at which the interface can achieve 60% of the melting temperature of the particle material (Ref 1, 2). Therefore, critical velocity should be a main parameter on the coating quality. Note that the particle critical velocity is determined not only by its size, but also by its material properties. This study numerically investigates the critical velocity for the particle deposition process in CGDS. In the present numerical analysis, copper (Cu) was chosen as particle material and aluminum (Al) as substrate material. The impacting velocities were selected between 300 and 800 m/s increasing in steps of 100 m/s. The simulation result reveals temporal and spatial interfacial temperature distribution and deformation between particle(s) and substrate. Finally, a comparison is carried out between the computed results and experimental data.

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

Rodenbeck, Christopher T; Girardi, Michael

Internal nodes of a constituent integrated circuit (IC) package of a multichip module (MCM) are protected from excessive charge during plasma cleaning of the MCM. The protected nodes are coupled to an internal common node of the IC package by respectively associated discharge paths. The common node is connected to a bond pad of the IC package. During MCM assembly, and before plasma cleaning, this bond pad receives a wire bond to a ground bond pad on the MCM substrate.

T. thermophila group I introns that cleave amide bonds

NASA Technical Reports Server (NTRS)

Joyce, Gerald F. (Inventor)

1997-01-01

The present invention relates to nucleic acid enzymes or enzymatic RNA molecules that are capable of cleaving a variety of bonds, including phosphodiester bonds and amide bonds, in a variety of substrates. Thus, the disclosed enzymatic RNA molecules are capable of functioning as nucleases and/or peptidases. The present invention also relates to compositions containing the disclosed enzymatic RNA molecule and to methods of making, selecting, and using such enzymes and compositions.

Fabricating a hybrid imaging device

NASA Technical Reports Server (NTRS)

Wadsworth, Mark (Inventor); Atlas, Gene (Inventor)

2003-01-01

A hybrid detector or imager includes two substrates fabricated under incompatible processes. An array of detectors, such as charged-coupled devices, are formed on the first substrate using a CCD fabrication process, such as a buried channel or peristaltic process. One or more charge-converting amplifiers are formed on a second substrate using a CMOS fabrication process. The two substrates are then bonded together to form a hybrid detector.

Redox Regulation of Methionine Aminopeptidase 2 Activity*

PubMed Central

Chiu, Joyce; Wong, Jason W. H.; Hogg, Philip J.

2014-01-01

Protein translation is initiated with methionine in eukaryotes, and the majority of proteins have their N-terminal methionine removed by methionine aminopeptidases (MetAP1 and MetAP2) prior to action. Methionine removal can be important for protein function, localization, or stability. No mechanism of regulation of MetAP activity has been identified. MetAP2, but not MetAP1, contains a single Cys228-Cys448 disulfide bond that has an −RHStaple configuration and links two β-loop structures, which are hallmarks of allosteric disulfide bonds. From analysis of crystal structures and using mass spectrometry and activity assays, we found that the disulfide bond exists in oxidized and reduced states in the recombinant enzyme. The disulfide has a standard redox potential of −261 mV and is efficiently reduced by the protein reductant, thioredoxin, with a rate constant of 16,180 m−1 s−1. The MetAP2 disulfide bond also exists in oxidized and reduced states in glioblastoma tumor cells, and stressing the cells by oxygen or glucose deprivation results in more oxidized enzyme. The Cys228-Cys448 disulfide is at the rim of the active site and is only three residues distant from the catalytic His231, which suggested that cleavage of the bond would influence substrate hydrolysis. Indeed, oxidized and reduced isoforms have different catalytic efficiencies for hydrolysis of MetAP2 peptide substrates. These findings indicate that MetAP2 is post-translationally regulated by an allosteric disulfide bond, which controls substrate specificity and catalytic efficiency. PMID:24700462

The unique functional role of the C-HS hydrogen bond in the substrate specificity and enzyme catalysis of type 1 methionine aminopeptidase.

PubMed

Reddi, Ravikumar; Singarapu, Kiran Kumar; Pal, Debnath; Addlagatta, Anthony

2016-07-19

It is intriguing how nature attains recognition specificity between molecular interfaces where there is no apparent scope for classical hydrogen bonding or polar interactions. Methionine aminopeptidase (MetAP) is one such enzyme where this fascinating conundrum is at play. In this study, we demonstrate that a unique C-HS hydrogen bond exists between the enzyme methionine aminopeptidase (MetAP) and its N-terminal-methionine polypeptide substrate, which allows specific interaction between apparent apolar interfaces, imposing a strict substrate recognition specificity and efficient catalysis, a feature replicated in Type I MetAPs across all kingdoms of life. We evidence this evolutionarily conserved C-HS hydrogen bond through enzyme assays on wild-type and mutant MetAP proteins from Mycobacterium tuberculosis that show a drastic difference in catalytic efficiency. The X-ray crystallographic structure of the methionine bound protein revealed a conserved water bridge and short contacts involving the Met side-chain, a feature also observed in MetAPs from other organisms. Thermal shift assays showed a remarkable 3.3 °C increase in melting temperature for methionine bound protein compared to its norleucine homolog, where C-HS interaction is absent. The presence of C-HS hydrogen bonding was also corroborated by nuclear magnetic resonance spectroscopy through a change in chemical shift. Computational chemistry studies revealed the unique role of the electrostatic environment in facilitating the C-HS interaction. The significance of this atypical hydrogen bond is underscored by the fact that the function of MetAP is essential for any living cell.

Influence of Impact Conditions on Feedstock Deposition Behavior of Cold-Sprayed Fe-Based Metallic Glass

NASA Astrophysics Data System (ADS)

Ziemian, Constance W.; Wright, Wendelin J.; Cipoletti, David E.

2018-05-01

Cold spray is a promising method by which to deposit dense Fe-based metallic glass coatings on conventional metal substrates. Relatively low process temperatures offer the potential to prevent the crystallization of amorphous feedstock powders while still providing adequate particle softening for bonding and coating formation. In this study, Fe48Mo14Cr15Y2C15B6 powder was sprayed onto a mild steel substrate, using a variety of process conditions, to investigate the feasibility of forming well-bonded amorphous Fe-based coatings. Particle splat adhesion was examined relative to impact conditions, and the limiting values of temperature and velocity associated with successful softening and adhesion were empirically established. Variability of particle sizes, impact temperatures, and impact velocities resulted in splat morphologies ranging from well-adhered deformed particles to substrate craters formed by rebounded particles and a variety of particle/substrate interface conditions. Transmission electron microscopy studies revealed the presence of a thin oxide layer between well-adhered particles and the substrate, suggesting that bonding is feasible even with an increased oxygen content at the interface. Results indicate that the proper optimization of cold spray process parameters supports the formation of Fe-based metallic glass coatings that successfully retain their amorphous structure, as well as the superior corrosion and wear-resistant properties of the feedstock powder.

Thermoplastic tape compaction device

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

Campbell, V.W.

1994-12-27

A device is disclosed for bonding a thermoplastic tape to a substrate to form a fully consolidated composite. This device has an endless chain associated with a frame so as to rotate in a plane that is perpendicular to a long dimension of the tape, the chain having pivotally connected chain links with each of the links carrying a flexible foot member that extends outwardly from the chain. A selected number of the foot members contact the tape, after the heating thereof, to cause the heated tape to bond to the substrate. The foot members are each a thin bandmore » of metal oriented transversely to the chain, with a flexibility and width and length to contact the tape so as to cause the tape to conform to the substrate to achieve consolidation of the tape and the substrate. A biased leaf-type spring within the frame bears against an inner surface of the chain to provide the compliant pressure necessary to bond the tape to the substrate. The chain is supported by sprockets on shafts rotatably supported in the frame and, in one embodiment, one of the shafts has a drive unit to produce rotation such that the foot members in contact with the tape move at the same speed as the tape. Cooling jets are positioned along the frame to cool the resultant consolidated composite. 5 figures.« less

Leaving Group Ability Observably Affects Transition State Structure in a Single Enzyme Active Site.

PubMed

Roston, Daniel; Demapan, Darren; Cui, Qiang

2016-06-15

A reaction's transition state (TS) structure plays a critical role in determining reactivity and has important implications for the design of catalysts, drugs, and other applications. Here, we explore TS structure in the enzyme alkaline phosphatase using hybrid Quantum Mechanics/Molecular Mechanics simulations. We find that minor perturbations to the substrate have major effects on TS structure and the way the enzyme stabilizes the TS. Substrates with good leaving groups (LGs) have little cleavage of the phosphorus-LG bond at the TS, while substrates with poor LGs have substantial cleavage of that bond. The results predict nonlinear free energy relationships for a single rate-determining step, and substantial differences in kinetic isotope effects for different substrates; both trends were observed in previous experimental studies, although the original interpretations differed from the present model. Moreover, due to different degrees of phosphorus-LG bond cleavage at the TS for different substrates, the LG is stabilized by different interactions at the TS: while a poor LG is directly stabilized by an active site zinc ion, a good LG is mainly stabilized by active site water molecules. Our results demonstrate the considerable plasticity of TS structure and stabilization in enzymes. Furthermore, perturbations to reactivity that probe TS structure experimentally (i.e., substituent effects) may substantially perturb the TS they aim to probe, and thus classical experimental approaches such as free energy relations should be interpreted with care.

Thermoplastic tape compaction device

DOEpatents

Campbell, V.W.

1994-12-27

A device is disclosed for bonding a thermoplastic tape to a substrate to form a fully consolidated composite. This device has an endless chain associated with a frame so as to rotate in a plane that is perpendicular to a long dimension of the tape, the chain having pivotally connected chain links with each of the links carrying a flexible foot member that extends outwardly from the chain. A selected number of the foot members contact the tape, after the heating thereof, to cause the heated tape to bond to the substrate. The foot members are each a thin band of metal oriented transversely to the chain, with a flexibility and width and length to contact the tape so as to cause the tape to conform to the substrate to achieve consolidation of the tape and the substrate. A biased leaf-type spring within the frame bears against an inner surface of the chain to provide the compliant pressure necessary to bond the tape to the substrate. The chain is supported by sprockets on shafts rotatably supported in the frame and, in one embodiment, one of the shafts has a drive unit to produce rotation such that the foot members in contact with the tape move at the same speed as the tape. Cooling jets are positioned along the frame to cool the resultant consolidated composite. 5 figures.

The covalently bound diazo group as an infrared probe for hydrogen bonding environments.

PubMed

You, Min; Liu, Liyuan; Zhang, Wenkai

2017-07-26

Covalently bound diazo groups are frequently found in biomolecular substrates. The C[double bond, length as m-dash]N[double bond, length as m-dash]N asymmetric stretching vibration (ν as ) of the diazo group has a large extinction coefficient and appears in an uncongested spectral region. To evaluate the solvatochromism of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band for studying biomolecules, we recorded the infrared (IR) spectra of a diazo model compound, 2-diazo-3-oxo-butyric acid ethyl ester, in different solvents. The width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band was linearly dependent on the Kamlet-Taft solvent parameter, which reflects the polarizability and hydrogen bond accepting ability of the solvent. Therefore, the width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band could be used to probe these properties for a solvent. We found that the position of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band was linearly correlated with the density of hydrogen bond donor groups in the solvent. We studied the relaxation dynamics and spectral diffusion of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band of a natural amino acid, 6-diazo-5-oxo-l-norleucine, in water using nonlinear IR spectroscopy. The relaxation and spectral diffusion time constants of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band were similar to those of the N[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band. We concluded that the position and width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band of the diazo group could be used to probe the hydrogen bond donating and accepting ability of a solvent, respectively. These results suggest that the diazo group could be used as a site-specific IR probe for the local hydration environments.

Ferromagnetic thin films

DOEpatents

Krishnan, K.M.

1994-12-20

A ferromagnetic [delta]-Mn[sub 1[minus]x]Ga[sub x] thin film having perpendicular anisotropy is described which comprises: (a) a GaAs substrate, (b) a layer of undoped GaAs overlying said substrate and bonded thereto having a thickness ranging from about 50 to about 100 nanometers, (c) a layer of [delta]-Mn[sub 1[minus]x]Ga[sub x] overlying said layer of undoped GaAs and bonded thereto having a thickness ranging from about 20 to about 30 nanometers, and (d) a layer of GaAs overlying said layer of [delta]-Mn[sub 1[minus]x]Ga[sub x] and bonded thereto having a thickness ranging from about 2 to about 5 nanometers, wherein x is 0.4[+-]0.05. 7 figures.

Investigation of substrate-mounted thin-film meteoroid sensors for use in large area impact experiments

NASA Technical Reports Server (NTRS)

Carollo, S. F.; Davis, J. M.; Dance, W. E.

1973-01-01

Two types of sensor designs were investigated: (1)a polysulfone dielectric film with vapor-deposited aluminum and gold sensor plates, bonded to a relatively thick aluminum substrate, and (2) an aluminum oxide (A1203) dielectric layer prepared on an aluminum substrate by anodization, with a layer of vapor-deposited aluminum providing one sensor plate and the substrate serving as the other plate. In the first design, specimens were prepared which indicate the state of the art for application of this type of sensor for elements of a meteoroid detection system having an area as large as 10 sq M. Techniques were investigated for casting large-area polysulfone films on the surface of water and for transferring the films from the water. Methods of preparing sensors by layering of films, the deposition of capacitor plates, and sensor film-to-substrate bonding, as well as techniques for making electrical connections to the capacitor plates, were studied.

Detection of thermally grown oxides in thermal barrier coatings by nondestructive evaluation

NASA Astrophysics Data System (ADS)

Fahr, A.; Rogé, B.; Thornton, J.

2006-03-01

The thermal-barrier coatings (TBC) sprayed on hot-section components of aircraft turbine engines commonly consist of a partially stabilized zirconia top-coat and an intermediate bond-coat applied on the metallic substrate. The bond-coat is made of an aluminide alloy that at high engine temperatures forms thermally grown oxides (TGO). Although formation of a thin layer of aluminum oxide at the interface between the ceramic top-coat and the bond-coat has the beneficial effect of protecting the metallic substrate from hot gases, oxide formation at splat boundaries or pores within the bond-coat is a source of weakness. In this study, plasma-sprayed TBC specimens are manufactured from two types of bond-coat powders and exposed to elevated temperatures to form oxides at the ceramic-bond-coat boundary and within the bond-coat. The specimens are then tested using nondestructive evaluation (NDE) and destructive metallography and compared with the as-manufactured samples. The objective is to determine if NDE can identify the oxidation within the bond-coat and give indication of its severity. While ultrasonic testing can provide some indication of the degree of bond-coat oxidation, the eddy current (EC) technique clearly identifies severe oxide formation within the bond-coat. Imaging of the EC signals as the function of probe location provides information on the spatial variations in the degree of oxidation, and thereby identifies which components or areas are prone to premature damage.

PLASMA POLYMER FILMS AS ADHESION PROMOTING PRIMERS FOR ALUMINUM SUBSTRATES. PART I: CHARACTERIZATION OF FILMS AND FILM/SUBSTRATE INTERFACES

EPA Science Inventory

Plasma polymerized hexamethyldisiloxane (HMDSO) films (~800 Å in thickness) were deposited onto aluminum substrates (6111-T4 alloy) in radio frequency (RF) and microwave (MW) powered reactors to be used as primers for structural adhesive bonding. Processing variables such as sub...

Decal transfer microfabrication

DOEpatents

Nuzzo, Ralph G.; Childs, William Robert

2004-10-19

A method of making a microstructure includes forming a pattern in a surface of a silicon-containing elastomer, oxidizing the pattern, contacting the pattern with a substrate; and bonding the oxidized pattern and the substrate such that the pattern and the substrate are irreversibly attached. The silicon-containing elastomer may be removably attached to a transfer pad.

Differential substrate behaviour of phenol and aniline derivatives during oxidation by horseradish peroxidase: kinetic evidence for a two-step mechanism.

PubMed

Gilabert, María Angeles; Hiner, Alexander N P; García-Ruiz, Pedro Antonio; Tudela, José; García-Molina, Francisco; Acosta, Manuel; García-Cánovas, Francisco; Rodríguez-López, José Neptuno

2004-06-01

The catalytic constant (k(cat)) and the second-order association constant of compound II with reducing substrate (k(5)) of horseradish peroxidase C (HRPC) acting on phenols and anilines have been determined from studies of the steady-state reaction velocities (V(0) vs. [S(0)]). Since k(cat)=k(2)k(6)/k(2)+k(6), and k(2) (the first-order rate constant for heterolytic cleavage of the oxygen-oxygen bond of hydrogen peroxide during compound I formation) is known, it has been possible to calculate the first-order rate constant for the transformation of each phenol or aniline by HRPC compound II (k(6)). The values of k(6) are quantitatively correlated to the sigma values (Hammett equation) and can be rationalized by an aromatic substrate oxidation mechanism in which the substrate donates an electron to the oxyferryl group in HRPC compound II, accompanied by two proton additions to the ferryl oxygen atom, one from the substrate and the other the protein or solvent. k(6) is also quantitatively correlated to the experimentally determined (13)C-NMR chemical shifts (delta(1)) and the calculated ionization potentials, E (HOMO), of the substrates. Similar dependencies were observed for k(cat) and k(5). From the kinetic analysis, the absolute values of the Michaelis constants for hydrogen peroxide and the reducing substrates (K(M)(H(2)O(2)) and K(M)(S)), respectively, were obtained.

Synthesis and Evaluation of Chlorinated Substrate Analogues for Farnesyl Diphosphate Synthase

PubMed Central

Heaps, Nicole A.; Poulter, C. Dale

2011-01-01

Substrate analogues for isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP), where the C3 methyl groups were replaced by chlorine, were synthesized and evaluated as substrates for avian farnesyl diphosphate synthase (FPPase). The IPP analogue (3-ClIPP) was a co-substrate when incubated with dimethylallyl diphosphate (DMAPP) or geranyl diphosphate (GPP) to give the corresponding chlorinated analogues of geranyl diphosphate (3-ClGPP) and farnesyl diphosphate (3-ClFPP), respectively. No products were detected in incubations of 3-ClIPP with 3-ClDMAPP. Incubation of IPP with 3-ClDMAPP gave 11-ClFPP as the sole product. Values of KM3-ClIPP (with DMAPP) and KM3-ClDMAPP (with IPP) were similar to those for IPP and DMAPP, however values of kcat for both analogues were substantially lower. These results are consistent with a dissociative electrophilic alkylation mechanism where the rate-limiting step changes from heterolytic cleavage of the carbon-oxygen bond in the allylic substrate to alkylation of the double bond of the homoallylic substrate. PMID:21344952

Method of transferring a thin crystalline semiconductor layer

DOEpatents

Nastasi, Michael A [Sante Fe, NM; Shao, Lin [Los Alamos, NM; Theodore, N David [Mesa, AZ

2006-12-26

A method for transferring a thin semiconductor layer from one substrate to another substrate involves depositing a thin epitaxial monocrystalline semiconductor layer on a substrate having surface contaminants. An interface that includes the contaminants is formed in between the deposited layer and the substrate. Hydrogen atoms are introduced into the structure and allowed to diffuse to the interface. Afterward, the thin semiconductor layer is bonded to a second substrate and the thin layer is separated away at the interface, which results in transferring the thin epitaxial semiconductor layer from one substrate to the other substrate.

Laminated structures and methods and compositions for producing same

DOEpatents

Fumei, Giancarlo J.; Karabedian, James A.

1977-04-05

Methods for bonding two substrates, one of which is polymeric, which comprise coating the surface of at least one substrate with an adhesive composition comprising a major component which is an adhesive for the first substrate and a minor disperse phase which is a solution of a polymer in a solvent for the polymeric substrate and contacting the coated surface of the one substrate with the surface of the other substrate, together with adhesive compositions useful for joining such substrates, laminates so formed, and articles comprised of such laminates.

Catalytic Activity of the Anaerobic Tyrosine Lyase Required for Thiamine Biosynthesis in Escherichia coli*

PubMed Central

Challand, Martin R.; Martins, Filipa T.; Roach, Peter L.

2010-01-01

Thiazole synthase in Escherichia coli is an αβ heterodimer of ThiG and ThiH. ThiH is a tyrosine lyase that cleaves the Cα–Cβ bond of tyrosine, generating p-cresol as a by-product, to form dehydroglycine. This reactive intermediate acts as one of three substrates for the thiazole cyclization reaction catalyzed by ThiG. ThiH is a radical S-adenosylmethionine (AdoMet) enzyme that utilizes a [4Fe-4S]+ cluster to reductively cleave AdoMet, forming methionine and a 5′-deoxyadenosyl radical. Analysis of the time-dependent formation of the reaction products 5′-deoxyadenosine (DOA) and p-cresol has demonstrated catalytic behavior of the tyrosine lyase. The kinetics of product formation showed a pre-steady state burst phase, and the involvement of DOA in product inhibition was identified by the addition of 5′-methylthioadenosine/S-adenosylhomocysteine nucleosidase to activity assays. This hydrolyzed the DOA and changed the rate-determining step but, in addition, substantially increased the uncoupled turnover of AdoMet. Addition of glyoxylate and ammonium inhibited the tyrosine cleavage reaction, but the reductive cleavage of AdoMet continued in an uncoupled manner. Tyrosine analogues were incubated with ThiGH, which showed a strong preference for phenolic substrates. 4-Hydroxyphenylpropionic acid analogues allowed uncoupled AdoMet cleavage but did not result in further reaction (Cα–Cβ bond cleavage). The results of the substrate analogue studies and the product inhibition can be explained by a mechanistic hypothesis involving two reaction pathways, a product-forming pathway and a futile cycle. PMID:19923213

Non-bonded ultrasonic transducer

DOEpatents

Eoff, J.M.

1984-07-06

A mechanically assembled non-bonded ultrasonic transducer includes a substrate, a piezoelectric film, a wetting agent, a thin metal electrode, and a lens held in intimate contact by a mechanical clamp. No epoxy or glue is used in the assembly of this device.

Divergent palladium iodide catalyzed multicomponent carbonylative approaches to functionalized isoindolinone and isobenzofuranimine derivatives.

PubMed

Mancuso, Raffaella; Ziccarelli, Ida; Armentano, Donatella; Marino, Nadia; Giofrè, Salvatore V; Gabriele, Bartolo

2014-04-18

2-Alkynylbenzamides underwent different reaction pathways when allowed to react under PdI2-catalyzed oxidative carbonylation conditions, depending on the nature of the external nucleophile and reaction conditions. Thus, oxidative carbonylation of 2-ethynylbenzamides, bearing a terminal triple bond, carried out in the presence of a secondary amine as external nucleophile, selectively led to the formation of 3-[(dialkylcarbamoyl)methylene]isoindolin-1-ones through the intermediate formation of the corresponding 2-ynamide derivatives followed by intramolecular nucleophilic attack by the nitrogen of the benzamide moiety on the conjugated triple bond. On the other hand, 3-[(alkoxycarbonyl)methylene]isobenzofuran-1(3H)imines were selectively obtained when the oxidative carbonylation of 2-alkynylbenzamides, bearing a terminal or an internal triple bond, was carried out in the presence of an alcohol R'OH (such as methanol or ethanol) as the external nucleophile and HC(OR')3 as a dehydrating agent, necessary to avoid substrate hydrolysis. In this latter case, the reaction pathway leading to the isobenzofuranimine corresponded to the 5-exo-dig intramolecular nucleophilic attack of the oxygen of the benzamide moiety on the triple bond coordinated to the metal center followed by alkoxycarbonylation. The structures of representative products have been confirmed by X-ray crystallographic analysis.

Wetting behaviour of carbon nitride nanostructures grown by plasma enhanced chemical vapour deposition technique

NASA Astrophysics Data System (ADS)

Ahmad Kamal, Shafarina Azlinda; Ritikos, Richard; Abdul Rahman, Saadah

2015-02-01

Tuning the wettability of various coating materials by simply controlling the deposition parameters is essential for various specific applications. In this work, carbon nitride (CNx) films were deposited on silicon (1 1 1) substrates using radio-frequency plasma enhanced chemical vapour deposition employing parallel plate electrode configuration. Effects of varying the electrode distance (DE) on the films' structure and bonding properties were investigated using Field emission scanning electron microscopy, Atomic force microscopy, Fourier transform infrared and X-ray photoemission spectroscopy. The wettability of the films was analyzed using water contact angle measurements. At high DE, the CNx films' surface was smooth and uniform. This changed into fibrous nanostructures when DE was decreased. Surface roughness of the films increased with this morphological transformation. Nitrogen incorporation increased with decrease in DE which manifested the increase in both relative intensities of Cdbnd N to Cdbnd C and Nsbnd H to Osbnd H bonds. sp2-C to sp3-C ratio increased as DE decreased due to greater deformation of sp2 bonded carbon at lower DE. The films' characteristics changed from hydrophilic to super-hydrophobic with the decrease in DE. Roughness ratio, surface porosity and surface energy calculated from contact angle measurements were strongly dependent on the morphology, surface roughness and bonding properties of the films.

OleA Glu117 is key to condensation of two fatty-acyl coenzyme A substrates in long-chain olefin biosynthesis

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

Jensen, Matthew R.; Goblirsch, Brandon R.; Christenson, James K.

In the interest of decreasing dependence on fossil fuels, microbial hydrocarbon biosynthesis pathways are being studied for renewable, tailored production of specialty chemicals and biofuels. One candidate is long-chain olefin biosynthesis, a widespread bacterial pathway that produces waxy hydrocarbons. Found in three- and four-gene clusters, oleABCD encodes the enzymes necessary to produce cis-olefins that differ by alkyl chain length, degree of unsaturation, and alkyl chain branching. The first enzyme in the pathway, OleA, catalyzes the Claisen condensation of two fatty acyl-coenzyme A (CoA) molecules to form a β-keto acid. In this report, the mechanistic role of Xanthomonas campestris OleA Glu117more » is investigated through mutant enzymes. Crystal structures were determined for each mutant as well as their complex with the inhibitor cerulenin. Complemented by substrate modeling, these structures suggest that Glu117 aids in substrate positioning for productive carbon–carbon bond formation. Analysis of acyl-CoA substrate hydrolysis shows diminished activity in all mutants. When the active site lacks an acidic residue in the 117 position, OleA cannot form condensed product, demonstrating that Glu117 has a critical role upstream of the essential condensation reaction. Profiling of pH dependence shows that the apparent pKa for Glu117 is affected by mutagenesis. Taken together, we propose that Glu117 is the general base needed to prime condensation via deprotonation of the second, non-covalently bound substrate during turnover. This is the first example of a member of the thiolase superfamily of condensing enzymes to contain an active site base originating from the second monomer of the dimer.« less

Anti-Arrhenius cleavage of covalent bonds in bottlebrush macromolecules on substrate

PubMed Central

Lebedeva, Natalia V.; Nese, Alper; Sun, Frank C.; Matyjaszewski, Krzysztof; Sheiko, Sergei S.

2012-01-01

Spontaneous degradation of bottlebrush macromolecules on aqueous substrates was monitored by atomic force microscopy. Scission of C─C covalent bonds in the brush backbone occurred due to steric repulsion between the adsorbed side chains, which generated bond tension on the order of several nano-Newtons. Unlike conventional chemical reactions, the rate of bond scission was shown to decrease with temperature. This apparent anti-Arrhenius behavior was caused by a decrease in the surface energy of the underlying substrate upon heating, which results in a corresponding decrease of bond tension in the adsorbed macromolecules. Even though the tension dropped minimally from 2.16 to 1.89 nN, this was sufficient to overpower the increase in the thermal energy (kBT) in the Arrhenius equation. The rate constant of the bond-scission reaction was measured as a function of temperature and surface energy. Fitting the experimental data by a perturbed Morse potential V = V0(1 - e-βx)2 - fx, we determined the depth and width of the potential to be V0 = 141 ± 19 kJ/mol and β-1 = 0.18 ± 0.03 Å, respectively. Whereas the V0 value is in reasonable agreement with the activation energy Ea = 80–220 kJ/mol of mechanical and thermal degradation of organic polymers, it is significantly lower than the dissociation energy of a C─C bond De = 350 kJ/mol. Moreover, the force constant Kx = 2β2V0 = 1.45 ± 0.36 kN/m of a strained bottlebrush along its backbone is markedly larger than the force constant of a C─C bond Kl = 0.44 kN/m, which is attributed to additional stiffness due to deformation of the side chains. PMID:22645366

Adhesion between a rutile surface and a polyimide: a coarse grained molecular dynamics study

NASA Astrophysics Data System (ADS)

Kumar, Arun; Sudarkodi, V.; Parandekar, Priya V.; Sinha, Nishant K.; Prakash, Om; Nair, Nisanth N.; Basu, Sumit

2018-04-01

Titanium, due to its high strength to weight ratio and polyimides, due to their excellent thermal stability are being increasingly used in aerospace applications. We investigate the bonding between a (110) rutile substrate and a popular commercial polyimide, PMR-15, starting from the known atomic structure of the rutile substrate and the architecture of the polymer. First, the long PMR-15 molecule is divided into four fragments and an all-atom non-bonded forcefield governing the interaction between PMR-15 and a rutile substrate is developed. To this end, parameters of Buckingham potential for interaction between each atom in the fragments and the rutile surface are fitted, so as to ensure that the sum of non-bonded and electrostatic interaction energy between the substrate and a large number of configurations of each fragment, calculated by the quantum mechanical route and obtained from the fitted potential, is closely matched. Further, two coarse grained models of PMR-15 are developed—one for interaction between two coarse grained PMR-15 molecules and another for that between a coarse grained PMR-15 and the rutile substrate. Molecular dynamics simulations with the coarse grained models yields a traction separation law—a very useful tool for conducting continuum level finite element simulations of rutile-PMR-15 joints—governing the normal separation of a PMR-15 block from a flat rutile substrate. Moreover, detailed information about the affinity of various fragments to the substrate are also obtained. In fact, though the separation energy between rutile and PMR-15 turns out to be rather low, our analysis—with merely the molecular architecture of the polyimide as the starting point—provides a scheme for in-silico prediction of adhesion energies for new polyimide formulations.

The effect of water storage, elapsed time and contaminants on the bond strength and interfacial polymerization of a nanohybrid composite.

PubMed

Perriard, Jean; Lorente, Maria Cattani; Scherrer, Susanne; Belser, Urs C; Wiskott, H W Anselm

2009-12-01

To systematically characterize the effect of time lapse, water storage, and selected contaminants on the bond strength of a nanofilled dental composite. Half-dumbbell-shaped samples were fabricated out of light-polymerizing composite resin. To function as substrates they were aged for 30 days in water. Prior to bonding, the substrates' surfaces were subjected to the following treatments: 1) Removing a 0.2- to 0.4-mm layer using a fluted carbide bur; 2) grit blasting with 50 microm alumina particles; 3) etching with phosphoric acid gel; 4) grit blasting followed by etching; 5) blasting with tribochemical particles followed by silane application; 6) sanding with 400-grit paper, air aging of the adherent half-sample before bonding; 7) surface contamination with saliva; 8) surface contamination with blood. In each group (n = 30), freshly polymerized (except in group 6) adherent half-samples were bonded to the substrate half-samples by a layer of unfilled adhesive resin. Fifteen full dumbbell-shaped specimens were subjected to tensile testing after 1 h and 15 after 7 days water storage. In a positive control group, freshly cured half-samples were bonded shortly after fabrication. The tensile strength was analyzed using Weibull statistics and presented in terms of the material's characteristic strength and shape parameter. Fractographs of the two weakest and strongest samples of each group were produced. The surfaces were searched to locate hackle, wake hackle and the origin of the fracture. Surface roughness and time lapse increased the bond strength of the repaired specimens. All groups in which surface roughness was produced before bonding increased in repair strength. Post-bonding aging improved strength. Fractographs yielded interpretable data whenever larger surfaces of single phase bonding resin were present. 1) Roughening and etching an aged composite's surface prior to applying a coat of unfilled resin and the filled material increases repair bond strength by up to 100%. 2) The repair bond strength of a roughened aged composite is 25% to 30% inferior to the tensile strength of solid specimens. 3) After 7 days' storage in water, no detrimental effect could be seen from saliva or blood contamination if the surfaces were properly rinsed.

Effect of Substrate Compliance on Measuring Delamination Properties of Elastic Thin Foil

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

Liu, C.

Through the analysis of a model problem, a thin elastic plate bonded to an elastic foundation, we address several issues related to the miniature bulge test for measuring the energy-release rate associated with the interfacial fracture of a bimaterial system, where one of the constituents is a thin foil. These issues include the effect of the substrate compliance on the interpretation of the energy release rate, interfacial strength, and the identification of the boundary of the deforming bulge or the location of the interfacial crack front. The analysis done also suggests a way for measuring the so-called foundation modulus, whichmore » characterizes the property of the substrate. An experimental example, a stainless steel thin foil bonded to an aluminum substrate through hot-isostatic-pressing (HIP), is used to illustrate and highlight some of the conclusions of the model analysis.« less

Effect of Substrate Compliance on Measuring Delamination Properties of Elastic Thin Foil

DOE PAGES

Liu, C.

2018-03-20

Through the analysis of a model problem, a thin elastic plate bonded to an elastic foundation, we address several issues related to the miniature bulge test for measuring the energy-release rate associated with the interfacial fracture of a bimaterial system, where one of the constituents is a thin foil. These issues include the effect of the substrate compliance on the interpretation of the energy release rate, interfacial strength, and the identification of the boundary of the deforming bulge or the location of the interfacial crack front. The analysis done also suggests a way for measuring the so-called foundation modulus, whichmore » characterizes the property of the substrate. An experimental example, a stainless steel thin foil bonded to an aluminum substrate through hot-isostatic-pressing (HIP), is used to illustrate and highlight some of the conclusions of the model analysis.« less

What determines the interfacial configuration of Nb/Al2O3 and Nb/MgO interface

PubMed Central

Du, J. L.; Fang, Y.; Fu, E. G.; Ding, X.; Yu, K. Y.; Wang, Y. G.; Wang, Y. Q.; Baldwin, J. K.; Wang, P. P.; Bai, Q.

2016-01-01

Nb films are deposited on single crystal Al2O3 (110) and MgO(111) substrates by e-beam evaporation technique. Structure of Nb films and orientation relationships (ORs) of Nb/Al2O3 and Nb/MgO interface are studied and compared by the combination of experiments and simulations. The experiments show that the Nb films obtain strong (110) texture, and the Nb film on Al2O3(110) substrate shows a higher crystalline quality than that on MgO(111) substrate. First principle calculations show that both the lattice mismatch and the strength of interface bonding play major roles in determining the crystalline perfection of Nb films and ORs between Nb films and single crystal ceramic substrates. The fundamental mechanisms for forming the interfacial configuration in terms of the lattice mismatch and the strength of interface bonding are discussed. PMID:27698458

RF Sputtering for preparing substantially pure amorphous silicon monohydride

DOEpatents

Jeffrey, Frank R.; Shanks, Howard R.

1982-10-12

A process for controlling the dihydride and monohydride bond densities in hydrogenated amorphous silicon produced by reactive rf sputtering of an amorphous silicon target. There is provided a chamber with an amorphous silicon target and a substrate therein with the substrate and the target positioned such that when rf power is applied to the target the substrate is in contact with the sputtering plasma produced thereby. Hydrogen and argon are fed to the chamber and the pressure is reduced in the chamber to a value sufficient to maintain a sputtering plasma therein, and then rf power is applied to the silicon target to provide a power density in the range of from about 7 watts per square inch to about 22 watts per square inch to sputter an amorphous silicon hydride onto the substrate, the dihydride bond density decreasing with an increase in the rf power density. Substantially pure monohydride films may be produced.

Between Scylla and Charybdis: Hydrophobic Graphene-Guided Water Diffusion on Hydrophilic Substrates

PubMed Central

Kim, Jin-Soo; Choi, Jin Sik; Lee, Mi Jung; Park, Bae Ho; Bukhvalov, Danil; Son, Young-Woo; Yoon, Duhee; Cheong, Hyeonsik; Yun, Jun-Nyeong; Jung, Yousung; Park, Jeong Young; Salmeron, Miquel

2013-01-01

The structure of water confined in nanometer-sized cavities is important because, at this scale, a large fraction of hydrogen bonds can be perturbed by interaction with the confining walls. Unusual fluidity properties can thus be expected in the narrow pores, leading to new phenomena like the enhanced fluidity reported in carbon nanotubes. Crystalline mica and amorphous silicon dioxide are hydrophilic substrates that strongly adsorb water. Graphene, on the other hand, interacts weakly with water. This presents the question as to what determines the structure and diffusivity of water when intercalated between hydrophilic substrates and hydrophobic graphene. Using atomic force microscopy, we have found that while the hydrophilic substrates determine the structure of water near its surface, graphene guides its diffusion, favouring growth of intercalated water domains along the C-C bond zigzag direction. Molecular dynamics and density functional calculations are provided to help understand the highly anisotropic water stripe patterns observed. PMID:23896759

Pressure activated diaphragm bonder

DOEpatents

Evans, L.B.; Malba, V.

1997-05-27

A device is available for bonding one component to another, particularly for bonding electronic components of integrated circuits, such as chips, to a substrate. The bonder device in one embodiment includes a bottom metal block having a machined opening wherein a substrate is located, a template having machined openings which match solder patterns on the substrate, a thin diaphragm placed over the template after the chips have been positioned in the openings therein, and a top metal block positioned over the diaphragm and secured to the bottom block, with the diaphragm retained therebetween. The top block includes a countersink portion which extends over at least the area of the template and an opening through which a high pressure inert gas is supplied to exert uniform pressure distribution over the diaphragm to keep the chips in place during soldering. A heating means is provided to melt the solder patterns on the substrate and thereby solder the chips thereto. 4 figs.

Pressure activated diaphragm bonder

DOEpatents

Evans, Leland B.; Malba, Vincent

1997-01-01

A device is available for bonding one component to another, particularly for bonding electronic components of integrated circuits, such as chips, to a substrate. The bonder device in one embodiment includes a bottom metal block having a machined opening wherein a substrate is located, a template having machined openings which match solder patterns on the substrate, a thin diaphragm placed over the template after the chips have been positioned in the openings therein, and a top metal block positioned over the diaphragm and secured to the bottom block, with the diaphragm retained therebetween. The top block includes a countersink portion which extends over at least the area of the template and an opening through which a high pressure inert gas is supplied to exert uniform pressure distribution over the diaphragm to keep the chips in place during soldering. A heating means is provided to melt the solder patterns on the substrate and thereby solder the chips thereto.

Composition for forming an optically transparent, superhydrophobic coating

DOEpatents

Simpson, John T.; Lewis, Linda A.

2015-12-29

A composition for producing an optically clear, well bonded superhydrophobic coating includes a plurality of hydrophobic particles comprising an average particle size of about 200 nm or less, a binder at a binder concentration of from about 0.1 wt. % to about 0.5 wt. %, and a solvent. The hydrophobic particles may be present in the composition at a particle concentration of from about 0.1 wt. % to about 1 wt. %. An optically transparent, superhydrophobic surface includes a substrate, a plurality of hydrophobic particles having an average particle size of about 200 nm or less dispersed over the substrate, and a discontinuous binder layer bonding the hydrophobic particles to the substrate, where the hydrophobic particles and the binder layer form an optically transparent, superhydrophobic coating.

Durable wood bonding with epoxy adhesives

Treesearch

Charles R. Frihart

2003-01-01

Although wood was one of the earliest materials to be adhesively bonded, the factors that contribute to strong wood bonds are still not well understood. Wood is a very complex substrate in that it is non-uniform in most aspects. On the macro scale, it is a porous structure with different sized and shaped voids for fluid flow. The structural cells contain four different...

Specific adhesion model for bonding hot-melt polyamides to vinyl

Treesearch

Charles R. Frihart

2004-01-01

Hot-melt polyamides are an important market for the dimer acid made from the tall oil fatty acids liberated during the Kraft pulping process. These polyamides bond well to many substrates, but not to polyvinyl chloride (PVC), commonly called vinyl. Dimer-based polyamides made from secondary amines such as piperazine bond well to vinyl. No model for this unique adhesion...

Pseudorotational epitaxy of self-assembled octadecyltrichlorosilane monolayers on sapphire (0001)

DOE PAGES

Steinrück, H. -G.; Magerl, A.; Deutsch, M.; ...

2014-10-06

The structure of octadecyltrichlorosilane self-assembled monolayers (SAMs) on sapphire (0001) was studied by Å-resolution surface-specific x-ray scattering methods. The monolayer was found to consist of three sublayers where the outermost layer corresponds to vertically oriented, closely packed alkyl tails. Laterally, the monolayer is hexagonally packed and exhibits pseudorotational epitaxy to the sapphire, manifested by a broad scattering peak at zero relative azimuthal rotation, with long powderlike tails. The lattice mismatch of ~1% – 3% to the sapphire’s and the different length scale introduced by the lateral Si-O-Si bonding prohibit positional epitaxy. However, the substrate induces an intriguing increase in themore » crystalline coherence length of the SAM’s powderlike crystallites when rotationally aligned with the sapphire’s lattice. As a result, the increase correlates well with the rotational dependence of the separation of corresponding substrate-monolayer lattice sites.« less

Modern reaction-based indicator systems†

PubMed Central

2010-01-01

Traditional analyte-specific synthetic receptors or sensors have been developed on the basis of supramolecular interactions (e.g., hydrogen bonding, electrostatics, weak coordinative bonds). Unfortunately, this approach is often subject to limitations. As a result, increasing attention within the chemical sensor community is turning to the use of analyte-specific molecular indicators, wherein substrate-triggered reactions are used to signal the presence of a given analyte. This tutorial review highlights recent reaction-based indicator systems that have been used to detect selected anions, cations, reactive oxygen species, and neutral substrates. PMID:19587959

Non-bonded piezoelectric ultrasonic transducer

DOEpatents

Eoff, James M.

1985-01-01

A mechanically assembled non-bonded ultrasonic transducer includes a substrate, a piezoelectric film, a wetting agent, a thin metal electrode, and a lens held in intimate contact by a mechanical clamp. No epoxy or glue is used in the assembly of this device.

Clarification of the Mechanism of Acylation Reaction and Origin of Substrate Specificity of the Serine-Carboxyl Peptidase Sedolisin through QM/MM Free Energy Simulations

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

Xu, Qin; Yao, Jianzhuang; Wiodawer, Alexander

2011-01-01

Quantum mechanical/molecular mechanical (QM/MM) free energy simulations are applied for understanding the mechanism of the acylation reaction catalyzed by sedolisin, a representative serine-carboxyl peptidase, leading to the acyl-enzyme (AE) and first product from the enzyme-catalyzed reaction. One of the interesting questions to be addressed in this work is the origin of the substrate specificity of sedolisin that shows a relatively high activity on the substrates with Glu at P1 site. It is shown that the bond making and breaking events of the acylation reaction involving a peptide substrate (LLE*FL) seem to be accompanied by local conformational changes, proton transfers asmore » well as the formation of alternative hydrogen bonds. The results of the simulations indicate that the conformational change of Glu at P1 site and its formation of a low barrier hydrogen bond with Asp-170 (along with the transient proton transfer) during the acylation reaction might play a role in the relatively high specificity for the substrate with Glu at P1 site. The role of some key residues in the catalysis is confirmed through free energy simulations. Glu-80 is found to act as a general base to accept a proton from Ser-287 during the nucleophilic attack and then as a general acid to protonate the leaving group (N H of P1 -Phe) during the cleavage of the scissile peptide bond. Another acidic residue, Asp-170, acts as a general acid catalyst to protonate the carbonyl of P1-Glu during the formation of the tetrahedral intermediate and as a general base for the formation of the acyl-enzyme. The energetic results from the free energy simulations support the importance of proton transfer from Asp-170 to the carbonyl of P1-Glu in the stabilization of the tetrahedral intermediate and the formation of a low-barrier hydrogen bond between the carboxyl group of P1-Glu and Asp-170 in the lowering of the free energy barrier for the cleavage of the peptide bond. Detailed analyses of the proton transfers during acylation are also given.« less

C-C bond forming radical SAM enzymes involved in the construction of carbon skeletons of cofactors and natural products.

PubMed

Yokoyama, Kenichi; Lilla, Edward A

2018-04-10

Covering: up to the end of 2017C-C bond formations are frequently the key steps in cofactor and natural product biosynthesis. Historically, C-C bond formations were thought to proceed by two electron mechanisms, represented by Claisen condensation in fatty acids and polyketide biosynthesis. These types of mechanisms require activated substrates to create a nucleophile and an electrophile. More recently, increasing number of C-C bond formations catalyzed by radical SAM enzymes are being identified. These free radical mediated reactions can proceed between almost any sp3 and sp2 carbon centers, allowing introduction of C-C bonds at unconventional positions in metabolites. Therefore, free radical mediated C-C bond formations are frequently found in the construction of structurally unique and complex metabolites. This review discusses our current understanding of the functions and mechanisms of C-C bond forming radical SAM enzymes and highlights their important roles in the biosynthesis of structurally complex, naturally occurring organic molecules. Mechanistic consideration of C-C bond formation by radical SAM enzymes identifies the significance of three key mechanistic factors: radical initiation, acceptor substrate activation and radical quenching. Understanding the functions and mechanisms of these characteristic enzymes will be important not only in promoting our understanding of radical SAM enzymes, but also for understanding natural product and cofactor biosynthesis.

Fabricating a hybrid imaging device having non-destructive sense nodes

NASA Technical Reports Server (NTRS)

Wadsworth, Mark (Inventor); Atlas, Gene (Inventor)

2001-01-01

A hybrid detector or imager includes two substrates fabricated under incompatible processes. An array of detectors, such as charged-coupled devices, are formed on the first substrate using a CCD fabrication process, such as a buried channel or peristaltic process. One or more charge-converting amplifiers are formed on a second substrate using a CMOS fabrication process. The two substrates are then bonded together to form a hybrid detector.

Amine oxidation by d-arginine dehydrogenase in Pseudomonas aeruginosa.

PubMed

Ouedraogo, Daniel; Ball, Jacob; Iyer, Archana; Reis, Renata A G; Vodovoz, Maria; Gadda, Giovanni

2017-10-15

d-Arginine dehydrogenase from Pseudomonas aeruginosa (PaDADH) is a flavin-dependent oxidoreductase, which is part of a novel two-enzyme racemization system that functions to convert d-arginine to l-arginine. PaDADH contains a noncovalently linked FAD that shows the highest activity with d-arginine. The enzyme exhibits broad substrate specificity towards d-amino acids, particularly with cationic and hydrophobic d-amino acids. Biochemical studies have established the structure and the mechanistic properties of the enzyme. The enzyme is a true dehydrogenase because it displays no reactivity towards molecular oxygen. As established through solvent and multiple kinetic isotope studies, PaDADH catalyzes an asynchronous CH and NH bond cleavage via a hydride transfer mechanism. Steady-state kinetic studies with d-arginine and d-histidine are consistent with the enzyme following a ping-pong bi-bi mechanism. As shown by a combination of crystallography, kinetic and computational data, the shape and flexibility of loop L1 in the active site of PaDADH are important for substrate capture and broad substrate specificity. Copyright © 2017 Elsevier Inc. All rights reserved.

A method to screen and evaluate tissue adhesives for joint repair applications

PubMed Central

2012-01-01

Background Tissue adhesives are useful means for various medical procedures. Since varying requirements cause that a single adhesive cannot meet all needs, bond strength testing remains one of the key applications used to screen for new products and study the influence of experimental variables. This study was conducted to develop an easy to use method to screen and evaluate tissue adhesives for tissue engineering applications. Method Tissue grips were designed to facilitate the reproducible production of substrate tissue and adhesive strength measurements in universal testing machines. Porcine femoral condyles were used to generate osteochondral test tissue cylinders (substrates) of different shapes. Viability of substrates was tested using PI/FDA staining. Self-bonding properties were determined to examine reusability of substrates (n = 3). Serial measurements (n = 5) in different operation modes (OM) were performed to analyze the bonding strength of tissue adhesives in bone (OM-1) and cartilage tissue either in isolation (OM-2) or under specific requirements in joint repair such as filling cartilage defects with clinical applied fibrin/PLGA-cell-transplants (OM-3) or tissues (OM-4). The efficiency of the method was determined on the basis of adhesive properties of fibrin glue for different assembly times (30 s, 60 s). Seven randomly generated collagen formulations were analyzed to examine the potential of method to identify new tissue adhesives. Results Viability analysis of test tissue cylinders revealed vital cells (>80%) in cartilage components even 48 h post preparation. Reuse (n = 10) of test substrate did not significantly change adhesive characteristics. Adhesive strength of fibrin varied in different test settings (OM-1: 7.1 kPa, OM-2: 2.6 kPa, OM-3: 32.7 kPa, OM-4: 30.1 kPa) and was increasing with assembly time on average (2.4-fold). The screening of the different collagen formulations revealed a substance with significant higher adhesive strength on cartilage (14.8 kPa) and bone tissue (11.8 kPa) compared to fibrin and also considerable adhesive properties when filling defects with cartilage tissue (23.2 kPa). Conclusion The method confirmed adhesive properties of fibrin and demonstrated the dependence of adhesive properties and applied settings. Furthermore the method was suitable to screen for potential adhesives and to identify a promising candidate for cartilage and bone applications. The method can offer simple, replicable and efficient evaluation of adhesive properties in ex vivo specimens and may be a useful supplement to existing methods in clinical relevant settings. PMID:22984926

Effect of Suspension Plasma-Sprayed YSZ Columnar Microstructure and Bond Coat Surface Preparation on Thermal Barrier Coating Properties

NASA Astrophysics Data System (ADS)

Bernard, Benjamin; Quet, Aurélie; Bianchi, Luc; Schick, Vincent; Joulia, Aurélien; Malié, André; Rémy, Benjamin

2017-08-01

Suspension plasma spraying (SPS) is identified as promising for the enhancement of thermal barrier coating (TBC) systems used in gas turbines. Particularly, the emerging columnar microstructure enabled by the SPS process is likely to bring about an interesting TBC lifetime. At the same time, the SPS process opens the way to a decrease in thermal conductivity, one of the main issues for the next generation of gas turbines, compared to the state-of-the-art deposition technique, so-called electron beam physical vapor deposition (EB-PVD). In this paper, yttria-stabilized zirconia (YSZ) coatings presenting columnar structures, performed using both SPS and EB-PVD processes, were studied. Depending on the columnar microstructure readily adaptable in the SPS process, low thermal conductivities can be obtained. At 1100 °C, a decrease from 1.3 W m-1 K-1 for EB-PVD YSZ coatings to about 0.7 W m-1 K-1 for SPS coatings was shown. The higher content of porosity in the case of SPS coatings increases the thermal resistance through the thickness and decreases thermal conductivity. The lifetime of SPS YSZ coatings was studied by isothermal cyclic tests, showing equivalent or even higher performances compared to EB-PVD ones. Tests were performed using classical bond coats used for EB-PVD TBC coatings. Thermal cyclic fatigue performance of the best SPS coating reached 1000 cycles to failure on AM1 substrates with a β-(Ni,Pt)Al bond coat. Tests were also performed on AM1 substrates with a Pt-diffused γ-Ni/γ'-Ni3Al bond coat for which more than 2000 cycles to failure were observed for columnar SPS YSZ coatings. The high thermal compliance offered by both the columnar structure and the porosity allowed the reaching of a high lifetime, promising for a TBC application.

Design of fluidic self-assembly bonds for precise component positioning

NASA Astrophysics Data System (ADS)

Ramadoss, Vivek; Crane, Nathan B.

2008-02-01

Self Assembly is a promising alternative to conventional pick and place robotic assembly of micro components. Its benefits include parallel integration of parts with low equipment costs. Various approaches to self assembly have been demonstrated, yet demanding applications like assembly of micro-optical devices require increased positioning accuracy. This paper proposes a new method for design of self assembly bonds that addresses this need. Current methods have zero force at the desired assembly position and low stiffness. This allows small disturbance forces to create significant positioning errors. The proposed method uses a substrate assembly feature to provide a high accuracy alignment guide to the part. The capillary bond region of the part and substrate are then modified to create a non-zero positioning force to maintain the part in the desired assembly position. Capillary force models show that this force aligns the part to the substrate assembly feature and reduces sensitivity of part position to process variation. Thus, the new configuration can substantially improve positioning accuracy of capillary self-assembly. This will result in a dramatic decrease in positioning errors in the micro parts. Various binding site designs are analyzed and guidelines are proposed for the design of an effective assembly bond using this new approach.

Long-Life Self-Renewing Solar Reflector Stack

DOEpatents

Butler, Barry Lynn

1997-07-08

A long-life solar reflector includes a solar collector substrate and a base layer bonded to a solar collector substrate. The first layer includes a first reflective layer and a first acrylic or transparent polymer layer covering the first reflective layer to prevent exposure of the first reflective layer. The reflector also includes at least one upper layer removably bonded to the first acrylic or transparent polymer layer of the base layer. The upper layer includes a second reflective layer and a second acrylic or transparent polymer layer covering the second reflective layer to prevent exposure of the second reflective layer. The upper layer may be removed from the base reflective layer to expose the base layer, thereby lengthening the useful life of the solar reflector. A method of manufacturing a solar reflector includes the steps of bonding a base layer to a solar collector substrate, wherein the base reflective layer includes a first reflective layer and a first transparent polymer or acrylic layer covering the first reflective layer; and removably bonding a first upper layer to the first transparent polymer or acrylic layer of the base layer. The first upper layer includes a second reflective layer and a second transparent polymer or acrylic layer covering the second reflective layer to prevent exposure of the second reflective layer.

Remote site-selective C–H activation directed by a catalytic bifunctional template

PubMed Central

Zhang, Zhipeng; Tanaka, Keita; Yu, Jin-Quan

2017-01-01

Converting C–H bonds directly into carbon-carbon and carbon-heteroatom bonds can significantly improve step-economy in synthesis by providing alternative disconnections to traditional functional group manipulations. In this context, directed C–H activation reactions have been extensively explored for regioselective functionalization1-5. Though applicability can be severely curtailed by distance from the directing group and the shape of the molecule, a number of approaches have been developed to overcome this limitation6-12. For instance, recognition of the distal and geometric relationship between an existing functional group and multiple C–H bonds has recently been exploited to achieve meta-selective C–H activation by use of a covalently attached U-shaped template13-17. However, stoichiometric installation of the template is not feasible in the absence of an appropriate functional group handle. Here we report the design of a catalytic, bifunctional template that binds heterocyclic substrate via reversible coordination instead of covalent linkage, allowing remote site-selective C–H olefination of heterocycles. The two metal centers coordinated to this template play different roles; anchoring substrates to the proximity of catalyst and cleaving the remote C–H bonds respectively. Using this strategy, we demonstrate remote site-selective C–H olefination of heterocyclic substrates which do not have functional group handles for covalently attaching templates. PMID:28273068

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

Friedmann, T.A.; Tallant, D.R.; Barbour, J.C.

Carbon Nitride (CN{sub x}) films have been grown by ion-assisted pulsed-laser deposition (IAPLD). Graphite targets were laser ablated while bombarding the substrate with ions from a broad-beam Kaufman-type ion source. Ion voltage, current density, substrate temperature, and feed gas composition (N{sub 2} in Ar) were varied. Resultant films were characterized by Raman. Fourier transform infrared (FTIR), and Rutherford back scattering (RBS) spectroscopy. Samples with {approximately} 30% N/C ratio have been fabricated. The corresponding Raman and FTIR spectra indicate that nitrogen is incorporated into the samples by insertion into sp{sup 2}-bonded structures. A low level of C{identical_to}N triple bonds is alsomore » found. As the ion current and voltage are increased with a pure Ar ion beam, Raman peaks associated with nanocrystalline graphite appear in the spectra. Adding low levels of nitrogen to the ion beam first reduces the Raman intensity in the vicinity of the graphite disorder peak without adding detectable amounts of nitrogen to the films (as measured by RBS). At higher nitrogen levels in the ion beam, significant amounts of nitrogen are incorporated into the samples, and the magnitude of the ``disorder`` peak increases. By increasing the temperature of the substrate during deposition, the broad peak due mainly to sp{sup 2}-bonded C-N in the FTIR spectra is shifted to lower wavenumber. This could be interpreted as evidence of single-bonded C-N; however, it is more likely that the character of the sp{sup 2} bonding is changing.« less

Substrate and chain length dependencies of the thermal behavior of [CF3(CF2)m(CH2)nCOO]2Cd single monolayers investigated by infrared reflection absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ren, Yanzhi; Asanuma, Morito; Iimura, Ken-ichi; Kato, Teiji

2001-01-01

Temperature-variable grazing incidence reflection absorption (GIR) spectra were recorded for the single monolayer of [CF3(CF2)m(CH2)nCOO)]2Cd [(m,n)=(7,10), (7,16), (7,22), (5,22), and (3,22)], transferred from aqueous Cd2+ subphase to gold- and aluminum-evaporated glass substrates. The spectra reveal that these monolayers have better thermal stability on Al substrates than on Au. An "interaction band" is identified at 1484˜1480 cm-1, due to the νs(COO-) mode of carboxylate headgroups in ionic bonding with the Al surface. It is found that both the van der Waals interaction between the trans zig-zag hydrocarbon chains and the overlapping interaction between the fluorocarbon helixes are responsible for the systematic variation of the monolayer thermal behavior with (m,n). The thermal behavior of a single monolayer of cadmium stearate, serving as a model system, has been investigated to further confirm the spectral interpretation about the partially fluorinated monolayer. In addition, temperature-dependent friction measurements show that the single monolayers of (m,n)=(7,16), (7,22), (5,22), and (3,22) are potential molecular lubricants that can be used in the range of 25˜140 °C.

Vertical integration of array-type miniature interferometers at wafer level by using multistack anodic bonding

NASA Astrophysics Data System (ADS)

Wang, Wei-Shan; Wiemer, Maik; Froemel, Joerg; Enderlein, Tom; Gessner, Thomas; Lullin, Justine; Bargiel, Sylwester; Passilly, Nicolas; Albero, Jorge; Gorecki, Christophe

2016-04-01

In this work, vertical integration of miniaturized array-type Mirau interferometers at wafer level by using multi-stack anodic bonding is presented. Mirau interferometer is suitable for MEMS metrology and for medical imaging according to its vertical-, lateral- resolutions and working distances. Miniaturized Mirau interferometer can be a promising candidate as a key component of an optical coherence tomography (OCT) system. The miniaturized array-type interferometer consists of a microlens doublet, a Si-based MEMS Z scanner, a spacer for focus-adjustment and a beam splitter. Therefore, bonding technologies which are suitable for heterogeneous substrates are of high interest and necessary for the integration of MEMS/MOEMS devices. Multi-stack anodic bonding, which meets the optical and mechanical requirements of the MOEMS device, is adopted to integrate the array-type interferometers. First, the spacer and the beam splitter are bonded, followed by bonding of the MEMS Z scanner. In the meanwhile, two microlenses, which are composed of Si and glass wafers, are anodically bonded to form a microlens doublet. Then, the microlens doublet is aligned and bonded with the scanner/spacer/beam splitter stack. The bonded array-type interferometer is a 7- wafer stack and the thickness is approximately 5mm. To separate such a thick wafer stack with various substrates, 2-step laser cutting is used to dice the bonded stack into Mirau chips. To simplify fabrication process of each component, electrical connections are created at the last step by mounting a Mirau chip onto a flip chip PCB instead of through wafer vias. Stability of Au/Ti films on the MEMS Z scanner after anodic bonding, laser cutting and flip chip bonding are discussed as well.

Microtensile bond strength of contemporary adhesives to primary enamel and dentin.

PubMed

Marquezan, Marcela; da Silveira, Bruno Lopes; Burnett, Luiz Henrique; Rodrigues, Célia Regina Martins Delgado; Kramer, Paulo Floriani

2008-01-01

The purpose of this study was to assess bond strength of three self-etching and two total-etch adhesive systems bonded to primary tooth enamel and dentin. Forty extracted primary human molars were selected and abraded in order to create flat buccal enamel and occlusal dentin surfaces. Teeth were assigned to one of the adhesive systems: Adper Scotch Bond Multi Purpose, Adper Single Bond 2, Adper Prompt L-Pop, Clearfil SE Bond and AdheSE. Immediately to adhesive application, a composite resin (Filtek Z250) block was built up. After 3 months of water storage, each sample was sequentially sectioned in order to obtain sticks with a square cross-sectional area of about 0.72 mm2. The specimens were fixed lengthways to a microtensile device and tested using a universal testing machine with a 50-N load cell at a crosshead speed of 0.5 mm/min. Microtensile bond strength values were recorded in MPa and compared by Analysis of Variance and the post hoc Tukey test (a = 0.05). In enamel, Clearfil SE Bond presented the highest values, followed by Adper Single Bond 2, AdheSE and Adper Scotch Bond Multi Purpose, without significant difference. The highest values in dentin were obtained with Adper Scotch Bond Multi Purpose and all other adhesives did not present significant different values from that, except Adper Prompt L-Pop that achieved the lowest bond strength in both substrates. Adper Scotch Bond Multi Purpose and Adper Single Bond 2 presented significantly lower values in enamel than in dentin although all other adhesives presented similar results in both substrates. contemporary adhesive systems present similar behaviors when bonded to primary teeth, with the exception of the one-step self-etching system; and self-etching systems can achieve bond strength values as good in enamel as in dentin of primary teeth.

Imparting Catalyst-Control upon Classical Palladium-Catalyzed Alkenyl C–H Bond Functionalization Reactions

PubMed Central

Sigman, Matthew S.; Werner, Erik W.

2011-01-01

Conspectus The functional group transformations carried out by the palladium-catalyzed Wacker and Heck reactions are radically different, but they are both alkenyl C-H bond functionalization reactions that have found extensive use in organic synthesis. The synthetic community depends heavily on these important reactions, but selectivity issues arising from control by the substrate, rather than control by the catalyst, have prevented the realization of their full potential. Because of important similarities in the respective selectivity-determining nucleopalladation and β-hydride elimination steps of these processes, we posit that the mechanistic insight garnered through the development of one of these catalytic reactions may be applied to the other. In this Account, we detail our efforts to develop catalyst-controlled variants of both the Wacker oxidation and the Heck reaction to address synthetic limitations and provide mechanistic insight into the underlying organometallic processes of these reactions. In contrast to previous reports, we discovered that electrophilic palladium catalysts with non-coordinating counterions allowed for the use of a Lewis basic ligand to efficiently promote TBHP-mediated Wacker oxidation reactions of styrenes. This discovery led to the mechanistically guided development of a Wacker reaction catalyzed by a palladium complex with a bidentate ligand. This ligation may prohibit coordination of allylic heteroatoms, thereby allowing for the application of the Wacker oxidation to substrates that were poorly behaved under classical conditions. Likewise, we unexpectedly discovered that electrophilic Pd-σ-alkyl intermediates are capable of distinguishing between electronically inequivalent C–H bonds during β-hydride elimination. As a result, we have developed E-styrenyl selective oxidative Heck reactions of previously unsuccessful electronically non-biased alkene substrates using arylboronic acid derivatives. The mechanistic insight gained from the development of this chemistry allowed for the rational design of a similarly E-styrenyl selective classical Heck reaction using aryldiazonium salts and a broad range of alkene substrates. The key mechanistic findings from the development of these reactions provide new insight into how to predictably impart catalyst control in organometallic processes that would otherwise afford complex product mixtures. Given our new understanding, we are optimistic that reactions that introduce increased complexity relative to simple classical processes may now be developed based on our ability to predict the selectivity-determining nucleopalladation and β-hydride elimination steps through catalyst design. PMID:22111756

Tension Amplification in Molecular Brushes in Solutions and on Substrates

PubMed Central

Panyukov, Sergey; Zhulina, Ekaterina B.; Sheiko, Sergei S.; Randall, Greg C.; Brock, James; Rubinstein, Michael

2009-01-01

Molecular bottle-brushes are highly branched macromolecules with side chains densely grafted to a long polymer backbone. The brush-like architecture allows focusing of the side-chain tension to the backbone and its amplification from the picoNewton to nanoNewton range. The backbone tension depends on the overall molecular conformation and the surrounding environment. Here we study the relation between the tension and conformation of the molecular brushes in solutions, melts, and on substrates. In solutions, we find that the backbone tension in dense brushes with side chains attached to every backbone monomer is on the order of f0N3/8 in athermal solvents, f0N1/3 in θ-solvents, and f0 in poor solvents and melts, where N is the degree of polymerization of side chains, f0≃ kBT/b is the maximum tension in side chains, b is the Kuhn length, kB is Boltzmann constant, and T is absolute temperature. Depending on the side chain length and solvent quality, molecular brushes in solutions develop tension on the order of 10–100 picoNewtons, which is sufficient to break hydrogen bonds. Significant amplification of tension occurs upon adsorption of brushes onto a substrate. On a strongly attractive substrate, maximum tension in the brush backbone is ~ f0N, reaching values on the order of several nanoNewtons which exceed the strength of a typical covalent bond. At low grafting density and high spreading parameter the cross-sectional profile of adsorbed molecular brush is approximately rectangular with thicknes ~bA/S, where A is the Hamaker constant and S is the spreading parameter. At a very high spreading parameter (S > A), the brush thickness saturates at monolayer ~ b. At a low spreading parameter, the cross-sectional profile of adsorbed molecular brush has triangular tent-like shape. In the cross-over between these two opposite cases, covering a wide range of parameter space, the adsorbed molecular brush consists of two layers. Side chains in the lower layer gain surface energy due to the direct interaction with the substrate, while the second layer spreads on the top of the first layer. Scaling theory predicts that this second layer has a triangular cross-section with width R ~ N3/5 and height h ~ N2/5. Using self-consistent field theory we calculate the cap profile y (x) = h (1 − x2/R2)2, where x is the transverse distance from the backbone. The predicted cap shape is in excellent agreement with both computer simulation and experiment. PMID:19673133

Stereoselectivity of Mucorales lipases toward triradylglycerols--a simple solution to a complex problem.

PubMed Central

Scheib, H.; Pleiss, J.; Kovac, A.; Paltauf, F.; Schmid, R. D.

1999-01-01

The lipases from Rhizopus and Rhizomucor are members of the family of Mucorales lipases. Although they display high sequence homology, their stereoselectivity toward triradylglycerols (sn-2 substituted triacylglycerols) varies. Four different triradylglycerols were investigated, which were classified into two groups: flexible substrates with rotatable O'-C1' ether or ester bonds adjacent to C2 of glycerol and rigid substrates with a rigid N'-C1' amide bond or a phenyl ring in sn-2. Although Rhizopus lipase shows opposite stereopreference for flexible and rigid substrates (hydrolysis in sn-1 and sn-3, respectively), Rhizomucor lipase hydrolyzes both groups of triradylglycerols preferably in sn-1. To explain these experimental observations, computer-aided molecular modeling was applied to study the molecular basis of stereoselectivity. A generalized model for both lipases of the Mucorales family highlights the residues mediating stereoselectivity: (1) L258, the C-terminal neighbor of the catalytic histidine, and (2) G266, which is located in a loop contacting the glycerol backbone of a bound substrate. Interactions with triradylglycerol substrates are dominated by van der Waals contacts. Stereoselectivity can be predicted by analyzing the value of a single substrate torsion angle that discriminates between sn-1 and sn-3 stereopreference for all substrates and lipases investigated here. This simple model can be easily applied in enzyme and substrate engineering to predict Mucorales lipase variants and synthetic substrates with desired stereoselectivity. PMID:10210199

Optical fingerprints of solid-liquid interfaces: a joint ATR-IR and first principles investigation

NASA Astrophysics Data System (ADS)

Yang, L.; Niu, F.; Tecklenburg, S.; Pander, M.; Nayak, S.; Erbe, A.; Wippermann, S.; Gygi, F.; Galli, G.

Despite the importance of understanding the structural and bonding properties of solid-liquid interfaces for a wide range of (photo-)electrochemical applications, there are presently no experimental techniques available to directly probe the microscopic structure of solid-liquid interfaces. To develop robust strategies to interpret experiments and validate theory, we carried out attenuated total internal reflection (ATR-IR) spectroscopy measurements and ab initio molecular dynamics (AIMD) simulations of the vibrational properties of interfaces between liquid water and well-controlled prototypical semiconductor substrates. We show the Ge(100)/H2O interface to feature a reversible potential-dependent surface phase transition between Ge-H and Ge-OH termination. The Si(100)/H2O interface is proposed as a model system for corrosion and oxidation processes. We performed AIMD calculations under finite electric fields, revealing different pathways for initial oxidation. These pathways are predicted to exhibit unique spectral signatures. A significant increase in surface specificity can be achieved utilizing an angle-dependent ATR-IR experiment, which allows to detect such signatures at the interfacial layer and consequently changes in the hydrogen bond network. Funding from DOE-BES Grant No. DE-SS0008939 and the Deutsche Forschungsgemeinschaft (RESOLV, EXC 1069) are gratefully acknowledged.

Surface force and vibrational spectroscopic analyses of interfacial water molecules in the vicinity of methoxy-tri(ethylene glycol)-terminated monolayers: mechanisms underlying the effect of lateral packing density on bioinertness.

PubMed

Sekine, Taito; Asatyas, Syifa; Sato, Chikako; Morita, Shigeaki; Tanaka, Masaru; Hayashi, Tomohiro

Unequivocal dependence of bioinertness of self-assembled monolayers of methoxy-tri(ethylene glycol)-terminated alkanethiol (EG3-OMe SAMs) on their packing density has been a mystery for more than two decades. We tackled this long-standing question by performing surface force and surface-enhanced infrared absorption (SEIRA) spectroscopic measurements. Our surface force measurements revealed a physical barrier of interfacial water in the vicinity of the Au-supported EG3-OMe SAM (low packing density), whereas the Ag-supported one (high packing density) did not possess such interfacial water. In addition, the results of SEIRA measurements clearly exhibited that hydrogen bonding states of the interfacial water differ depending on the substrates. We also characterized the bioinertness of these SAMs by protein adsorption tests and adhesion assays of platelet and human umbilical vein endothelial cells. The hydrogen bonding states of the interfacial water and water-induced interaction clearly correlated with the bioinertness of the SAMs, suggesting that the interfacial water plays an important role determining the interaction of the SAMs with biomolecules and cells.

S-Glutathionyl-(chloro)hydroquinone reductases: a novel class of glutathione transferases

PubMed Central

XUN, Luying; BELCHIK, Sara M.; XUN, Randy; HUANG, Yan; ZHOU, Huina; SANCHEZ, Emiliano; KANG, ChulHee; BOARD, Philip G.

2010-01-01

Sphingobium chlorophenolicum completely mineralizes PCP (pentachlorophenol). Two GSTs (glutathione transferases), PcpC and PcpF, are involved in the degradation. PcpC uses GSH to reduce TeCH (tetrachloro-p-hydroquinone) to TriCH (trichloro-p-hydroquinone) and then to DiCH (dichloro-p-hydroquinone) during PCP degradation. However, oxidatively damaged PcpC produces GS-TriCH (S-glutathionyl-TriCH) and GS-DiCH (S-glutathionyl-TriCH) conjugates. PcpF converts the conjugates into TriCH and DiCH, re-entering the degradation pathway. PcpF was further characterized in the present study. It catalysed GSH-dependent reduction of GS-TriCH via a Ping Pong mechanism. First, PcpF reacted with GS-TriCH to release TriCH and formed disulfide bond between its Cys53 residue and the GS moiety. Then, a GSH came in to regenerate PcpF and release GS–SG. A TBLASTN search revealed that PcpF homologues were widely distributed in bacteria, halobacteria (archaea), fungi and plants, and they belonged to ECM4 (extracellular mutant 4) group COG0435 in the conserved domain database. Phylogenetic analysis grouped PcpF and homologues into a distinct group, separated from Omega class GSTs. The two groups shared conserved amino acid residues, for GSH binding, but had different residues for the binding of the second substrate. Several recombinant PcpF homologues and two human Omega class GSTs were produced in Escherichia coli and purified. They had zero or low activities for transferring GSH to standard substrates, but all had reasonable activities for GSH-dependent reduction of disulfide bond (thiol transfer), dehydroascorbate and dimethylarsinate. All the tested PcpF homologues reduced GS-TriCH, but the two Omega class GSTs did not. Thus PcpF homologues were tentatively named S-glutathionyl-(chloro)hydroquinone reductases for catalysing the GSH-dependent reduction of GS-TriCH. PMID:20388120

Acoustic emission and fatigue damage induced in plasma-sprayed hydroxyapatite coating layers.

PubMed

Laonapakul, Teerawat; Otsuka, Yuichi; Nimkerdphol, Achariya Rakngarm; Mutoh, Yoshiharu

2012-04-01

In order to improve the adhesive strength of hydroxyapatite (HAp) coatings, grit blasting with Al(2)O(3) powder and then wet blasting with HAp/Ti mixed powders was carried out on a commercially pure Ti (cp-Ti) substrate. Subsequently, an HAp/Ti bond coat layer and HAp top coat layer were deposited by plasma spraying. Fatigue tests of the HAp-coated specimens were carried out under four-point bending. Acoustic emission (AE) signals during the entire fatigue test were monitored to investigate the fatigue cracking behavior of the HAp-coated specimens. The HAp-coated specimens could survive up to 10(7) cycles without spallation of the HAp coating layers at the stress amplitude of 120 MPa. The HAp-coated specimens without HAp/Ti bond coat layer showed shorter fatigue life and easy crack nucleation compared to the HAp-coated specimens with HAp/Ti bond coat layer. The delamination and spallation of the HAp top coat with HAp/Ti bond coat on cp-Ti was not observed until the crack propagated into the cp-Ti during the final fracture stage of the fatigue cycle. Therefore, the HAp/Ti bond coat layer was found to greatly improve the fatigue damage resistance of the HAp coating layer. Three stages of the fatigue failure behavior of the HAp top coat with HAp/Ti bond coat on a cp-Ti substrate can be clearly estimated by the AE monitoring technique. These stages are cracks nucleating and propagating in the coating layer, cracks propagating in the substrate, and cracks propagating unstably to final fracture. Copyright © 2011 Elsevier Ltd. All rights reserved.

Composite-composite repair bond strength: effect of different adhesion primers.

PubMed

Tezvergil, A; Lassila, L V J; Vallittu, P K

2003-11-01

Recently, new products have been introduced to repair composite restorations that may be used as 'one-step' primers or monomers and silane compounds which are used separately as 'multi-step' primers. The aim of this study was to compare the shear bond strength of the new composite resin to aged composite, by using different adhesion primers. The substrates were particulate filler composite (Z250, 3M-ESPE), which was aged by boiling for 8 h and storing at 37 degrees C in water for 3 weeks. The aged substrate surfaces were wet-ground flat with 320-grit silicon carbide paper and subjected randomly (n=8) to either one-step adhesion primer: Compoconnect (CC) (Heraus Kulzer), or multi-step: Clearfil Repair (CF) (Kuraray) or an intermediate resin: Scothchbond Multi-purpose adhesive resin (3M-ESPE) according to the manufacturers' recommendations. Specimens with no surface treatment were used as control (C). New composite resin (Z250) was added to the substrate using 2 mm layer increments and light cured. The specimens were either water stored for 48 h or water stored for 24 h and then thermocycled for 6000 cycles. The shear bond strengths were measured with a crosshead speed of 1.0 mm/min using a universal testing machine. Data were analysed by two-way ANOVA and Tukey's post-hoc tests (p=0.05). All surface treatment methods showed significant difference compared to control (p<0.05). CF showed higher bond strength than CC and MP (p<0.05). Storage condition did not show a significant difference (p>0.05) in bond strength values. It was concluded that multi-step adhesion primer yielded higher bond strength compared to one-step primer or intermediate resin.

Driving force analysis of proton tunnelling across a reactivity series for an enzyme-substrate complex.

PubMed

Hothi, Parvinder; Hay, Sam; Roujeinikova, Anna; Sutcliffe, Michael J; Lee, Michael; Leys, David; Cullis, Paul M; Scrutton, Nigel S

2008-11-24

Quantitative structure-activity relationships are widely used to probe C-H bond breakage by quinoprotein enzymes. However, we showed recently that p-substituted benzylamines are poor reactivity probes for the quinoprotein aromatic amine dehydrogenase (AADH) because of a requirement for structural change in the enzyme-substrate complex prior to C-H bond breakage. This rearrangement is partially rate limiting, which leads to deflated kinetic isotope effects for p-substituted benzylamines. Here we report reactivity (driving force) studies of AADH with p-substituted phenylethylamines for which the kinetic isotope effect (approximately 16) accompanying C-H/C-(2)H bond breakage is elevated above the semi-classical limit. We show bond breakage occurs by quantum tunnelling and that within the context of the environmentally coupled framework for H-tunnelling the presence of the p-substituent places greater demand on the apparent need for fast promoting motions. The crystal structure of AADH soaked with phenylethylamine or methoxyphenylethylamine indicates that the structural change identified with p-substituted benzylamines should not limit the reaction with p-substituted phenylethylamines. This is consistent with the elevated kinetic isotope effects measured with p-substituted phenylethylamines. We find a good correlation in the rate constant for proton transfer with bond dissociation energy for the reactive C-H bond, consistent with a rate that is limited by a Marcus-like tunnelling mechanism. As the driving force becomes larger, the rate of proton transfer increases while the Marcus activation energy becomes smaller. This is the first experimental report of the driving force perturbation of H-tunnelling in enzymes using a series of related substrates. Our study provides further support for proton tunnelling in AADH.

Factors affecting hydrogen-tunneling contribution in hydroxylation reactions promoted by oxoiron(IV) porphyrin π-cation radical complexes.

PubMed

Cong, Zhiqi; Kinemuchi, Haruki; Kurahashi, Takuya; Fujii, Hiroshi

2014-10-06

Hydrogen atom transfer with a tunneling effect (H-tunneling) has been proposed to be involved in aliphatic hydroxylation reactions catalyzed by cytochrome P450 and synthetic heme complexes as a result of the observation of large hydrogen/deuterium kinetic isotope effects (KIEs). In the present work, we investigate the factors controlling the H-tunneling contribution to the H-transfer process in hydroxylation reaction by examining the kinetics of hydroxylation reactions at the benzylic positions of xanthene and 1,2,3,4-tetrahydronaphthalene by oxoiron(IV) 5,10,15,20-tetramesitylporphyrin π-cation radical complexes ((TMP(+•))Fe(IV)O(L)) under single-turnover conditions. The Arrhenius plots for these hydroxylation reactions of H-isotopomers have upwardly concave profiles. The Arrhenius plots of D-isotopomers, clear isosbestic points, and product analysis rule out the participation of thermally dependent other reaction processes in the concave profiles. These results provide evidence for the involvement of H-tunneling in the rate-limiting H-transfer process. These profiles are simulated using an equation derived from Bell's tunneling model. The temperature dependence of the KIE values (k(H)/k(D)) determined for these reactions indicates that the KIE value increases as the reaction temperature becomes lower, the bond dissociation energy (BDE) of the C-H bond of a substrate becomes higher, and the reactivity of (TMP(+•))Fe(IV)O(L) decreases. In addition, we found correlation of the slope of the ln(k(H)/k(D)) - 1/T plot and the bond strengths of the Fe═O bond of (TMP(+•))Fe(IV)O(L) estimated from resonance Raman spectroscopy. These observations indicate that these factors modulate the extent of the H-tunneling contribution by modulating the ratio of the height and thickness of the reaction barrier.

Noncovalent Organocatalysis Based on Hydrogen Bonding: Elucidation of Reaction Paths by Computational Methods

NASA Astrophysics Data System (ADS)

Etzenbach-Effers, Kerstin; Berkessel, Albrecht

In this article, the functions of hydrogen bonds in organocatalytic reactions are discussed on atomic level by presenting DFT studies of selected examples. Theoretical investigation provides a detailed insight in the mechanism of substrate activation and orientation, and the stabilization of transition states and intermediates by hydrogen bonding (e.g. oxyanion hole). The examples selected comprise stereoselective catalysis by bifunctional thioureas, solvent catalysis by fluorinated alcohols in epoxidation by hydrogen peroxide, and intramolecular cooperative hydrogen bonding in TADDOL-type catalysts.

Inhibition of polygylcine hydrolases by substrate analog peptides

USDA-ARS?s Scientific Manuscript database

Polyglycine hydrolases are proteases secreted by fungal pathogens that target corn defense chitinases. They cleave interdomain glycine-glycine bonds within a polyglycine linker, separating substrate chitinases into two single domain proteins. Polyglycine hydrolases consist of 640 amino acids with a ...

Method and apparatus for preparing multiconductor cable with flat conductors

NASA Technical Reports Server (NTRS)

Marcell, G. V. (Inventor)

1969-01-01

A method and apparatus for preparing flat conductor cable having a plurality of ribbon-like conductors disposed upon and adhesively bonded to the surface of a substrate is described. The conductors are brought into contact with the substrate surface, and while maintained in axial tension on said substrate, the combination is seated on a yieldably compressible layer to permit the conductor to become embedded into the surface of the substrate film.

Reduction of α,β-Unsaturated Ketones by Old Yellow Enzymes: Mechanistic Insights from Quantum Mechanics/Molecular Mechanics Calculations.

PubMed

Lonsdale, Richard; Reetz, Manfred T

2015-11-25

Enoate reductases catalyze the reduction of activated C═C bonds with high enantioselectivity. The oxidative half-reaction, which involves the addition of a hydride and a proton to opposite faces of the C═C bond, has been studied for the first time by hybrid quantum mechanics/molecular mechanics (QM/MM). The reduction of 2-cyclohexen-1-one by YqjM from Bacillus subtilis was selected as the model system. Two-dimensional QM/MM (B3LYP-D/OPLS2005) reaction pathways suggest that the hydride and proton are added as distinct steps, with the former step preceding the latter. Furthermore, we present interesting insights into the reactivity of this enzyme, including the weak binding of the substrate in the active site, the role of the two active site histidine residues for polarization of the substrate C═O bond, structural details of the transition states to hydride and proton transfer, and the role of Tyr196 as proton donor. The information presented here will be useful for the future design of enantioselective YqjM mutants for other substrates.

Interaction Mode and Regioselectivity in Vitamin B12-Dependent Dehalogenation of Aryl Halides by Dehalococcoides mccartyi Strain CBDB1.

PubMed

Zhang, Shangwei; Adrian, Lorenz; Schüürmann, Gerrit

2018-02-20

The bacterium Dehalococcoides, strain CBDB1, transforms aromatic halides through reductive dehalogenation. So far, however, the structures of its vitamin B 12 -containing dehalogenases are unknown, hampering clarification of the catalytic mechanism and substrate specificity as basis for targeted remediation strategies. This study employs a quantum chemical donor-acceptor approach for the Co(I)-substrate electron transfer. Computational characterization of the substrate electron affinity at carbon-halogen bonds enables discriminating aromatic halides ready for dehalogenation by strain CBDB1 (active substrates) from nondehalogenated (inactive) counterparts with 92% accuracy, covering 86 of 93 bromobenzenes, chlorobenzenes, chlorophenols, chloroanilines, polychlorinated biphenyls, and dibenzo-p-dioxins. Moreover, experimental regioselectivity is predicted with 78% accuracy by a site-specific parameter encoding the overlap potential between the Co(I) HOMO (highest occupied molecular orbital) and the lowest-energy unoccupied sigma-symmetry substrate MO (σ*), and the observed dehalogenation pathways are rationalized with a success rate of 81%. Molecular orbital analysis reveals that the most reactive unoccupied sigma-symmetry orbital of carbon-attached halogen X (σ C-X * ) mediates its reductive cleavage. The discussion includes predictions for untested substrates, thus providing opportunities for targeted experimental investigations. Overall, the presently introduced orbital interaction model supports the view that with bacterial strain CBDB1, an inner-sphere electron transfer from the supernucleophile B 12 Co(I) to the halogen substituent of the aromatic halide is likely to represent the rate-determining step of the reductive dehalogenation.

An Assessment of the Residual Stresses in Low Pressure Plasma Sprayed Coatings on an Advanced Copper Alloy

NASA Technical Reports Server (NTRS)

Raj, S. V.; Ghosn, L. J.; Agarwal, A.; Lachtrupp, T. P.

2002-01-01

Modeling studies were conducted on low pressure plasma sprayed (LPPS) NiAl top coat applied to an advanced Cu-8(at.%)Cr-4%Nb alloy (GRCop-84) substrate using Ni as a bond coat. A thermal analysis suggested that the NiAl and Ni top and bond coats, respectively, would provide adequate thermal protection to the GRCop-84 substrate in a rocket engine operating under high heat flux conditions. Residual stress measurements were conducted at different depths from the free surface on coated and uncoated GRCop-84 specimens by x-ray diffraction. These data are compared with theoretically estimated values assessed by a finite element analysis simulating the development of these stresses as the coated substrate cools down from the plasma spraying temperature to room temperature.

Peptide Bond Synthesis by a Mechanism Involving an Enzymatic Reaction and a Subsequent Chemical Reaction*

PubMed Central

Abe, Tomoko; Hashimoto, Yoshiteru; Zhuang, Ye; Ge, Yin; Kumano, Takuto; Kobayashi, Michihiko

2016-01-01

We recently reported that an amide bond is unexpectedly formed by an acyl-CoA synthetase (which catalyzes the formation of a carbon-sulfur bond) when a suitable acid and l-cysteine are used as substrates. DltA, which is homologous to the adenylation domain of nonribosomal peptide synthetase, belongs to the same superfamily of adenylate-forming enzymes, which includes many kinds of enzymes, including the acyl-CoA synthetases. Here, we demonstrate that DltA synthesizes not only N-(d-alanyl)-l-cysteine (a dipeptide) but also various oligopeptides. We propose that this enzyme catalyzes peptide synthesis by the following unprecedented mechanism: (i) the formation of S-acyl-l-cysteine as an intermediate via its “enzymatic activity” and (ii) subsequent “chemical” S → N acyl transfer in the intermediate, resulting in peptide formation. Step ii is identical to the corresponding reaction in native chemical ligation, a method of chemical peptide synthesis, whereas step i is not. To the best of our knowledge, our discovery of this peptide synthesis mechanism involving an enzymatic reaction and a subsequent chemical reaction is the first such one to be reported. This new process yields peptides without the use of a thioesterified fragment, which is required in native chemical ligation. Together with these findings, the same mechanism-dependent formation of N-acyl compounds by other members of the above-mentioned superfamily demonstrated that all members most likely form peptide/amide compounds by using this novel mechanism. Each member enzyme acts on a specific substrate; thus, not only the corresponding peptides but also new types of amide compounds can be formed. PMID:26586916

Formation of Au nano-patterns on various substrates using simplified nano-transfer printing method

NASA Astrophysics Data System (ADS)

Kim, Jong-Woo; Yang, Ki-Yeon; Hong, Sung-Hoon; Lee, Heon

2008-06-01

For future device applications, fabrication of the metal nano-patterns on various substrates, such as Si wafer, non-planar glass lens and flexible plastic films become important. Among various nano-patterning technologies, nano-transfer print method is one of the simplest techniques to fabricate metal nano-patterns. In nano-transfer printing process, thin Au layer is deposited on flexible PDMS mold, containing surface protrusion patterns, and the Au layer is transferred from PDMS mold to various substrates due to the difference of bonding strength of Au layer to PDMS mold and to the substrate. For effective transfer of Au layer, self-assembled monolayer, which has strong bonding to Au, is deposited on the substrate as a glue layer. In this study, complicated SAM layer coating process was replaced to simple UV/ozone treatment, which can activates the surface and form the -OH radicals. Using simple UV/ozone treatments on both Au and substrate, Au nano-pattern can be successfully transferred to as large as 6 in. diameter Si wafer, without SAM coating process. High fidelity transfer of Au nano-patterns to non-planar glass lens and flexible PET film was also demonstrated.

Purification and Characterization of Allophanate Hydrolase (AtzF) from Pseudomonas sp. Strain ADP

PubMed Central

Shapir, Nir; Sadowsky, Michael J.; Wackett, Lawrence P.

2005-01-01

AtzF, allophanate hydrolase, is a recently discovered member of the amidase signature family that catalyzes the terminal reaction during metabolism of s-triazine ring compounds by bacteria. In the present study, the atzF gene from Pseudomonas sp. strain ADP was cloned and expressed as a His-tagged protein, and the protein was purified and characterized. AtzF had a deduced subunit molecular mass of 66,223, based on the gene sequence, and an estimated holoenzyme molecular mass of 260,000. The active protein did not contain detectable metals or organic cofactors. Purified AtzF hydrolyzed allophanate with a kcat/Km of 1.1 × 104 s−1 M−1, and 2 mol of ammonia was released per mol allophanate. The substrate range of AtzF was very narrow. Urea, biuret, hydroxyurea, methylcarbamate, and other structurally analogous compounds were not substrates for AtzF. Only malonamate, which strongly inhibited allophanate hydrolysis, was an alternative substrate, with a greatly reduced kcat/Km of 21 s−1 M−1. Data suggested that the AtzF catalytic cycle proceeds through a covalent substrate-enzyme intermediate. AtzF reacts with malonamate and hydroxylamine to generate malonohydroxamate, potentially derived from hydroxylamine capture of an enzyme-tethered acyl group. Three putative catalytically important residues, one lysine and two serines, were altered by site-directed mutagenesis, each with complete loss of enzyme activity. The identity of a putative serine nucleophile was probed using phenyl phosphorodiamidate that was shown to be a time-dependent inhibitor of AtzF. Inhibition was due to phosphoroamidation of Ser189 as shown by liquid chromatography/matrix-assisted laser desorption ionization mass spectrometry. The modified residue corresponds in sequence alignments to the nucleophilic serine previously identified in other members of the amidase signature family. Thus, AtzF affects the cleavage of three carbon-to-nitrogen bonds via a mechanism similar to that of enzymes catalyzing single-amide-bond cleavage reactions. AtzF orthologs appear to be widespread among bacteria. PMID:15901697

RF magnetron sputtering of a hydroxyapatite target: A comparison study on polytetrafluorethylene and titanium substrates

NASA Astrophysics Data System (ADS)

Surmenev, Roman A.; Surmeneva, Maria A.; Grubova, Irina Yu.; Chernozem, Roman V.; Krause, Bärbel; Baumbach, Tilo; Loza, Kateryna; Epple, Matthias

2017-08-01

A pure hydroxyapatite (HA) target was used to prepare the biocompatible coating of HA on the surface of a polytetrafluorethylene (PTFE) substrate, which was placed on the same substrate holder with technically pure titanium (Ti) in the single deposition runs by radio-frequency (RF) magnetron sputtering. The XPS, XRD and FTIR analyses of the obtained surfaces showed that for all substrates, instead of the HA coating deposition, the coating of a mixture of calcium carbonate and calcium fluoride was grown. According to SEM investigations, the surface of PTFE was etched, and the surface topography of uncoated Ti was preserved after the depositions. The FTIR results reveal no phosphate bonds; only calcium tracks were observed in the EDX-spectra on the surface of the coated PTFE substrates. Phosphate oxide (V), which originated from the target, could be removed using a vacuum pump system, or no phosphate-containing bonds could be formed on the substrate surface because of the severe substrate bombardment process, which prevented the HA coating deposition. The observed results may be connected with the surface re-sputtering effect of the growing film by high-energy negatively charged ions (most probably oxygen or fluorine), which are accelerated in the cathode dark sheath.

A Palladium-Catalyzed Carbonylation Approach to Eight-Membered Lactam Derivatives with Antitumor Activity.

PubMed

Mancuso, Raffaella; Raut, Dnyaneshwar S; Marino, Nadia; De Luca, Giorgio; Giordano, Cinzia; Catalano, Stefania; Barone, Ines; Andò, Sebastiano; Gabriele, Bartolo

2016-02-24

The reactivity of 2-(2-alkynylphenoxy)anilines under PdI2 /KI-catalyzed oxidative carbonylation conditions has been studied. Although a different reaction pathway could have been operating, N-palladation followed by CO insertion was the favored pathway with all substrates tested, including those containing an internal or terminal triple bond. This led to the formation of a carbamoylpalladium species, the fate of which, as predicted by theoretical calculations, strongly depended on the nature of the substituent on the triple bond. In particular, 8-endo-dig cyclization preferentially occurred when the triple bond was terminal, leading to the formation of carbonylated ζ-lactam derivatives, the structures of which have been confirmed by XRD analysis. These novel medium-sized heterocyclic compounds showed antitumor activity against both estrogen receptor-positive (MCF-7) and triple negative (MDA-MB-231) breast cancer cell lines. In particular, ζ-lactam 3 j' may represent a novel and promising antitumor agent because biological tests clearly demonstrate that this compound significantly reduces cell viability and motility in both MCF-7 and MDA-MB-231 breast cancer cell lines, without affecting normal breast epithelial cell viability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Diamond Electron Tunneling Micro-Electromechanical Sensor

NASA Technical Reports Server (NTRS)

Albin, Sacharia

2000-01-01

A new pressure sensing device using field emission from diamond coated silicon tips has been developed. A high electric field applied between a nano-tip array and a diaphragm configured as electrodes produces electron emission governed by the Fowler Nordheim equation. The electron emission is very sensitive to the separation between the diaphragm and the tips, which is fixed at an initial spacing and bonded such that a cavity is created between them. Pressure applied to the diaphragm decreases the spacing between the electrodes, thereby increasing the number of electrons emitted. Silicon has been used as a substrate on which arrays of diamond coated sharp tips have been fabricated for electron emission. Also, a diaphragm has been made using wet orientation dependent etching. These two structures were bonded together using epoxy and tested. Current - voltage measurements were made at varying pressures for 1-5 V biasing conditions. The sensitivity was found to be 2.13 mV/V/psi for a 20 x 20 array, which is comparable to that of silicon piezoresistive transducers. Thinner diaphragms as well as alternative methods of bonding are expected to improve the electrical characteristics of the device. This transducer will find applications in many engineering fields for pressure measurement.

Solid state direct bonding of polymers by vacuum ultraviolet light below 160 nm

NASA Astrophysics Data System (ADS)

Hashimoto, Yuki; Yamamoto, Takatoki

2017-10-01

This work investigated the application of vacuum ultraviolet (VUV) irradiation to the bonding of various substrates, including glass, polycarbonate (PC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS) and polymethyl methacrylate (PMMA). This method has the advantage of being able to bond various substrates without the application of heat or adhesives, and therefore may be very useful in the fabrication of micro/nanoscale structures composed of polymers. In contrast to previous applications of this technique, the present study used VUV radiation at wavelengths at and below 160 nm so as to take advantage of the higher energy in this range. Bonding was assessed based on measuring the shear stress of various test specimens subjected to VUV irradiation and then pressed together, and a number of analytical methods were also employed to examine the irradiated surfaces in order to elucidate the morphological and chemical changes following VUV treatment. These analyses included water contact angle measurements, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), time of flight secondary ion mass spectrometry (TOF-SIMS) and atomic force microscopy (AFM). Poor bonding was identified between combinations consisting of PMMA/PC, PMMA/COP, PMMA/PMMA, PMMA/glass, and PC/COP, whereas all other combinations resulted in successful bonding with the bonding stress values such as PC/PC = 2.0 MPa, PC/glass = 10.7 MPa and COP/COP = 1.7 MPa, respectively.

Orientation-dependent structural and photocatalytic properties of LaCoO3 epitaxial nano-thin films

NASA Astrophysics Data System (ADS)

Zhang, Yan-ping; Liu, Hai-feng; Hu, Hai-long; Xie, Rui-shi; Ma, Guo-hua; Huo, Ji-chuan; Wang, Hai-bin

2018-02-01

LaCoO3 epitaxial films were grown on (100), (110) and (111) oriented LaAlO3 substrates by the polymer-assisted deposition method. Crystal structure measurement and cross-section observation indicate that all the LaCoO3 films are epitaxially grown in accordance with the orientation of LaAlO3 substrates, with biaxial compressive strain in the ab plane. Owing to the different strain directions of CoO6 octahedron, the mean Co-O bond length increases by different amounts in (100), (110) and (111) oriented films compared with that of bulk LaCoO3, and the (100) oriented LaCoO3 has the largest increase. Photocatalytic degradation of methyl orange indicates that the order of photocatalytic activity of the three oriented films is (100) > (111) > (110). Combined with analysis of electronic nature and band structure for LaCoO3 films, it is found that the change of the photocatalytic activity is closely related to the crystal field splitting energy of Co3+ and Co-O binding energy. The increase in the mean Co-O bond length will decrease the crystal field splitting energy of Co3+ and Co-O binding energy and further reduce the value of band gap energy, thus improving the photocatalytic activity. This may also provide a clue for expanding the visible-light-induced photocatalytic application of LaCoO3.

Structure of conjugated polyketone reductase from Candida parapsilosis IFO 0708 reveals conformational changes for substrate recognition upon NADPH binding.

PubMed

Qin, Hui-Min; Yamamura, Akihiro; Miyakawa, Takuya; Kataoka, Michihiko; Nagai, Takahiro; Kitamura, Nahoko; Urano, Nobuyuki; Maruoka, Shintaro; Ohtsuka, Jun; Nagata, Koji; Shimizu, Sakayu; Tanokura, Masaru

2014-01-01

Conjugated polyketone reductase C2 (CPR-C2) from Candida parapsilosis IFO 0708, identified as a nicotinamide adenine dinucleotide phosphate (NADPH)-dependent ketopantoyl lactone reductase, belongs to the aldo-keto reductase superfamily. This enzyme reduces ketopantoyl lactone to D-pantoyl lactone in a strictly stereospecific manner. To elucidate the structural basis of the substrate specificity, we determined the crystal structures of the apo CPR-C2 and CPR-C2/NADPH complex at 1.70 and 1.80 Å resolutions, respectively. CPR-C2 adopted a triose-phosphate isomerase barrel fold at the core of the structure. Binding with the cofactor NADPH induced conformational changes in which Thr27 and Lys28 moved 15 and 5.0 Å, respectively, in the close vicinity of the adenosine 2'-phosphate group of NADPH to form hydrogen bonds. Based on the comparison of the CPR-C2/NADPH structure with 3-α-hydroxysteroid dehydrogenase and mutation analyses, we constructed substrate binding models with ketopantoyl lactone, which provided insight into the substrate specificity by the cofactor-induced structure. The results will be useful for the rational design of CPR-C2 mutants targeted for use in the industrial manufacture of ketopantoyl lactone.

Unraveling the stereochemical and dynamic aspects of the catalytic site of bacterial peptidyl-tRNA hydrolase

PubMed Central

Kabra, Ashish; Shahid, Salman; Pal, Ravi Kant; Yadav, Rahul; Pulavarti, S.V.S. Rama Krishna; Jain, Anupam; Tripathi, Sarita; Arora, Ashish

2017-01-01

Bacterial peptidyl-tRNA hydrolase (Pth; EC 3.1.1.29) hydrolyzes the peptidyl-tRNAs accumulated in the cytoplasm and thereby prevents cell death by alleviating tRNA starvation. X-ray and NMR studies of Vibrio cholerae Pth (VcPth) and mutants of its key residues involved in catalysis show that the activity and selectivity of the protein depends on the stereochemistry and dynamics of residues H24, D97, N118, and N14. D97-H24 interaction is critical for activity because it increases the nucleophilicity of H24. The N118 and N14 have orthogonally competing interactions with H24, both of which reduce the nucleophilicity of H24 and are likely to be offset by positioning of a peptidyl-tRNA substrate. The region proximal to H24 and the lid region exhibit slow motions that may assist in accommodating the substrate. Helix α3 exhibits a slow wobble with intermediate time scale motions of its N-cap residue N118, which may work as a flypaper to position the scissile ester bond of the substrate. Overall, the dynamics of interactions between the side chains of N14, H24, D97, and N118, control the catalysis of substrate by this enzyme. PMID:28096445

Why do receptor–ligand bonds in cell adhesion cluster into discrete focal-adhesion sites?

DOE PAGES

Gao, Zhiwen; Gao, Yanfei

2016-05-14

We report that cell adhesion often exhibits the clustering of the receptor–ligand bonds into discrete focal-adhesion sites near the contact edge, thus resembling a rosette shape or a contracting membrane anchored by a small number of peripheral forces. The ligands on the extracellular matrix are immobile, and the receptors in the cell plasma membrane consist of two types: high-affinity integrins (that bond to the substrate ligands and are immobile) and low-affinity integrins (that are mobile and not bonded to the ligands). Thus the adhesion energy density is proportional to the high-affinity integrin density. This paper provides a mechanistic explanation formore » the clustering/assembling of the receptor–ligand bonds from two main points: (1) the cellular contractile force leads to the density evolution of these two types of integrins, and results into a large high-affinity integrin density near the contact edge and (2) the front of a propagating crack into a decreasing toughness field will be unstable and wavy. From this fracture mechanics perspective, the chemomechanical equilibrium is reached when a small number of patches with large receptor–ligand bond density are anticipated to form at the cell periphery, as opposed to a uniform distribution of bonds on the entire interface. Finally, cohesive fracture simulations show that the de-adhesion force can be significantly enhanced by this nonuniform bond density field, but the de-adhesion force anisotropy due to the substrate elastic anisotropy is significantly reduced.« less

Why do receptor–ligand bonds in cell adhesion cluster into discrete focal-adhesion sites?

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

Gao, Zhiwen; Gao, Yanfei

We report that cell adhesion often exhibits the clustering of the receptor–ligand bonds into discrete focal-adhesion sites near the contact edge, thus resembling a rosette shape or a contracting membrane anchored by a small number of peripheral forces. The ligands on the extracellular matrix are immobile, and the receptors in the cell plasma membrane consist of two types: high-affinity integrins (that bond to the substrate ligands and are immobile) and low-affinity integrins (that are mobile and not bonded to the ligands). Thus the adhesion energy density is proportional to the high-affinity integrin density. This paper provides a mechanistic explanation formore » the clustering/assembling of the receptor–ligand bonds from two main points: (1) the cellular contractile force leads to the density evolution of these two types of integrins, and results into a large high-affinity integrin density near the contact edge and (2) the front of a propagating crack into a decreasing toughness field will be unstable and wavy. From this fracture mechanics perspective, the chemomechanical equilibrium is reached when a small number of patches with large receptor–ligand bond density are anticipated to form at the cell periphery, as opposed to a uniform distribution of bonds on the entire interface. Finally, cohesive fracture simulations show that the de-adhesion force can be significantly enhanced by this nonuniform bond density field, but the de-adhesion force anisotropy due to the substrate elastic anisotropy is significantly reduced.« less