Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

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

Colby, Denise; Bergman, Robert; Ellman, Jonathan

2010-05-13

Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the areamore » of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach that has seen widespread success involves the use of a proximal heteroatom that serves as a directing group for the selective functionalization of a specific C-H bond. In a survey of examples of heteroatom-directed Rh catalysis, two mechanistically distinct reaction pathways are revealed. In one case, the heteroatom acts as a chelator to bind the Rh catalyst, facilitating reactivity at a proximal site. In this case, the formation of a five-membered metallacycle provides a favorable driving force in inducing reactivity at the desired location. In the other case, the heteroatom initially coordinates the Rh catalyst and then acts to stabilize the formation of a metal-carbon bond at a proximal site. A true test of the utility of a synthetic method is in its application to the synthesis of natural products or complex molecules. Several groups have demonstrated the applicability of C-H bond functionalization reactions towards complex molecule synthesis. Target-oriented synthesis provides a platform to test the effectiveness of a method in unique chemical and steric environments. In this respect, Rh-catalyzed methods for C-H bond functionalization stand out, with several syntheses being described in the literature that utilize C-H bond functionalization in a key step. These syntheses are highlighted following the discussion of the method they employ.« less

Direct mounted photovoltaic device with improved adhesion and method thereof

DOEpatents

Boven, Michelle L; Keenihan, James R; Lickly, Stan; Brown, Jr., Claude; Cleereman, Robert J; Plum, Timothy C

2014-12-23

The present invention is premised upon a photovoltaic device suitable for directly mounting on a structure. The device includes an active portion including a photovoltaic cell assembly having a top surface portion that allows transmission of light energy to a photoactive portion of the photovoltaic device for conversion into electrical energy and a bottom surface having a bottom bonding zone; and an inactive portion immediately adjacent to and connected to the active portion, the inactive portion having a region for receiving a fastener to connect the device to the structure and having on a top surface, a top bonding zone; wherein one of the top and bottom bonding zones comprises a first bonding element and the other comprises a second bonding element, the second bonding element designed to interact with the first bonding element on a vertically overlapped adjacent photovoltaic device to bond the device to such adjacent device or to the structure.

Amide-Directed Photoredox Catalyzed C-C Bond Formation at Unactivated sp3 C-H Bonds

PubMed Central

Chu, John C. K.; Rovis, Tomislav

2017-01-01

Carbon-carbon (C-C) bond formation is paramount in the synthesis of biologically relevant molecules, modern synthetic materials and commodity chemicals such as fuels and lubricants. Traditionally, the presence of a functional group is required at the site of C-C bond formation. Strategies that allow C-C bond formation at inert carbon-hydrogen (C-H) bonds allow scientists to access molecules which would otherwise be inaccessible and to develop more efficient syntheses of complex molecules.1,2 Herein we report a method for the formation of C-C bonds by directed cleavage of traditionally non-reactive C-H bonds and their subsequent coupling with readily available alkenes. Our methodology allows for the selective C-C bond formation at single C-H bonds in molecules that contain a multitude of seemingly indifferentiable such bonds. Selectivity arises through a relayed photoredox catalyzed oxidation of an N-H bond. We anticipate our findings to serve as a starting point for functionalization at inert C-H bonds through a hydrogen atom transfer strategy. PMID:27732580

Modeling of direct wafer bonding: Effect of wafer bow and etch patterns

NASA Astrophysics Data System (ADS)

Turner, K. T.; Spearing, S. M.

2002-12-01

Direct wafer bonding is an important technology for the manufacture of silicon-on-insulator substrates and microelectromechanical systems. As devices become more complex and require the bonding of multiple patterned wafers, there is a need to understand the mechanics of the bonding process. A general bonding criterion based on the competition between the strain energy accumulated in the wafers and the surface energy that is dissipated as the bond front advances is developed. The bonding criterion is used to examine the case of bonding bowed wafers. An analytical expression for the strain energy accumulation rate, which is the quantity that controls bonding, and the final curvature of a bonded stack is developed. It is demonstrated that the thickness of the wafers plays a large role and bonding success is independent of wafer diameter. The analytical results are verified through a finite element model and a general method for implementing the bonding criterion numerically is presented. The bonding criterion developed permits the effect of etched features to be assessed. Shallow etched patterns are shown to make bonding more difficult, while it is demonstrated that deep etched features can facilitate bonding. Model results and their process design implications are discussed in detail.

Low-temperature poly(oxymethylene) direct bonding via self-assembled monolayer

NASA Astrophysics Data System (ADS)

Fu, Weixin; Ma, Bo; Kuwae, Hiroyuki; Shoji, Shuichi; Mizuno, Jun

2018-02-01

A direct bonding of poly(oxymethylene) (POM) was feasible at 100 °C by using self-assembled monolayer (SAM) as a surface modification method. (3-aminopropyl)triethoxysilane (APTES) and (3-glycidyloxypropyl)trimethoxysilane (GOPTS) were used in our work. X-ray photoelectron spectroscopy showed that both APTES and GOPTS modified the POM surface successfully. Bonding strength evaluation revealed that surface modification was affected by pretreatment (VUV/O3) process time. In addition, the bonding condition with highest strength had an average strength of 372 kPa. This technology is expected to be used in packaging for micro-/nano-electromechanical systems, such as biomedical devices.

Transition metal catalyzed manipulation of non-polar carbon–hydrogen bonds for synthetic purpose

PubMed Central

MURAI, Shinji

2011-01-01

The direct addition of ortho C–H bonds in various aromatic compounds such as ketones, esters, imines, imidates, nitriles, and aldehydes to olefins and acetylenes can be achieved with the aid of transition metal catalysts. The ruthenium catalyzed reaction is usually highly efficient and useful as a general synthetic method. The coordination to the metal center by a heteroatom in a directing group such as carbonyl and imino groups in aromatic compounds is the key step in this process. Mechanistically, the reductive elimination to form a C–C bond is the rate-determining step, while the C–H bond cleavage step is not. PMID:21558759

Directed amination of non-acidic arene C-H bonds by a copper-silver catalytic system.

PubMed

Tran, Ly Dieu; Roane, James; Daugulis, Olafs

2013-06-03

Amine meets arene: A method for direct amination of β-C(sp(2))-H bonds of benzoic acid derivatives and γ-C(sp(2))-H bonds of benzylamine derivatives has been developed. The reaction is catalyzed by Cu(OAc)2 and a Ag2CO3 cocatalyst, and shows high generality and functional-group tolerance, as well as providing a straightforward means for the preparation of ortho-aminobenzoic acid derivatives. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reducing the anisotropy of a Brazilian disc generated in a bonded-particle model

NASA Astrophysics Data System (ADS)

Zhang, Q.; Zhang, X. P.; Ji, P. Q.

2018-03-01

The Brazilian test is a widely used method for determining the tensile strength of rocks and for calibrating parameters in bonded-particle models (BPMs). In previous studies, the Brazilian disc has typically been trimmed from a compacted rectangular specimen. The present study shows that different tensile strength values are obtained depending on the compressive loading direction. Several measures are proposed to reduce the anisotropy of the disc. The results reveal that the anisotropy of the disc is significantly influenced by the compactibility of the specimen from which it is trimmed. A new method is proposed in which the Brazilian disc is directly generated with a particle boundary, effectively reducing the anisotropy. The stiffness (particle and bond) and strength (bond) of the boundary are set at less than and greater than those of the disc assembly, respectively, which significantly decreases the stress concentration at the boundary contacts and prevents breakage of the boundary particle bonds. This leads to a significant reduction in the anisotropy of the disc and the discreteness of the tensile strength. This method is more suitable for carrying out a realistic Brazilian test for homogeneous rock-like material in the BPM.

Heat exchanger and method of making. [bonding rocket chambers with a porous metal matrix

NASA Technical Reports Server (NTRS)

Fortini, A.; Kazaroff, J. M. (Inventor)

1978-01-01

A heat exchanger of increased effectiveness is disclosed. A porous metal matrix is disposed in a metal chamber or between walls through which a heat-transfer fluid is directed. The porous metal matrix has internal bonds and is bonded to the chamber in order to remove all thermal contact resistance within the composite structure. Utilization of the invention in a rocket chamber is disclosed as a specific use. Also disclosed is a method of constructing the heat exchanger.

31 CFR 363.125 - How is payment made on a book-entry savings bond?

Code of Federal Regulations, 2012 CFR

2012-07-01

... 31 Money and Finance:Treasury 2 2012-07-01 2012-07-01 false How is payment made on a book-entry... GOVERNING SECURITIES HELD IN TREASURYDIRECT Book-Entry Savings Bonds Purchased Through TreasuryDirect Payment § 363.125 How is payment made on a book-entry savings bond? We will make payment by the ACH method...

31 CFR 363.125 - How is payment made on a book-entry savings bond?

Code of Federal Regulations, 2013 CFR

2013-07-01

... 31 Money and Finance:Treasury 2 2013-07-01 2013-07-01 false How is payment made on a book-entry... GOVERNING SECURITIES HELD IN TREASURYDIRECT Book-Entry Savings Bonds Purchased Through TreasuryDirect Payment § 363.125 How is payment made on a book-entry savings bond? We will make payment by the ACH method...

31 CFR 363.125 - How is payment made on a book-entry savings bond?

Code of Federal Regulations, 2010 CFR

2010-07-01

... 31 Money and Finance: Treasury 2 2010-07-01 2010-07-01 false How is payment made on a book-entry... GOVERNING SECURITIES HELD IN TREASURYDIRECT Book-Entry Savings Bonds Purchased Through TreasuryDirect Payment § 363.125 How is payment made on a book-entry savings bond? We will make payment by the ACH method...

31 CFR 363.125 - How is payment made on a book-entry savings bond?

Code of Federal Regulations, 2014 CFR

2014-07-01

... 31 Money and Finance: Treasury 2 2014-07-01 2014-07-01 false How is payment made on a book-entry... GOVERNING SECURITIES HELD IN TREASURYDIRECT Book-Entry Savings Bonds Purchased Through TreasuryDirect Payment § 363.125 How is payment made on a book-entry savings bond? We will make payment by the ACH method...

31 CFR 363.125 - How is payment made on a book-entry savings bond?

Code of Federal Regulations, 2011 CFR

2011-07-01

... 31 Money and Finance:Treasury 2 2011-07-01 2011-07-01 false How is payment made on a book-entry... GOVERNING SECURITIES HELD IN TREASURYDIRECT Book-Entry Savings Bonds Purchased Through TreasuryDirect Payment § 363.125 How is payment made on a book-entry savings bond? We will make payment by the ACH method...

Correlation of bond strength with surface roughness using a new roughness measurement technique.

PubMed

Winkler, M M; Moore, B K

1994-07-01

The correlation between shear bond strength and surface roughness was investigated using new surface measurement methods. Bonding agents and associated resin composites were applied to set amalgam after mechanically roughening its surface. Surface treatments were noe (as set against glass), 80 grit, and 600 grit abrasive paper. Surface roughness (R(a) as measured parallel and perpendicular (+) to the direction of the polishing scratches and true profile length were measured. A knife-edge was applied (rate = 2.54 mm/min) at the bonding agent/amalgam interface of each sample until failure. Coefficients of determination for mean bond strength vs either roughness (R(a), of profile length were significantly higher for measurements in parallel directions than for those measurements in (+) directions. The shear bond strength to set amalgam for a PENTA-containing adhesives system (L.D. Caulk Division) was not significantly different from that of a PENTA-free adhesive (3M Dental Products Division), even though PENTA has been reported to increase bond strength to nonprecious metals. The shear bond strength of resin composite to amalgam is correlated to surface roughness when it is measured parallel to the polishing scratches. This correlation is significantly lower when surface roughness is measured in the typical manner, perpendicular to the polishing scratches.

Direct observation and control of hydrogen-bond dynamics using low-temperature scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Kumagai, Takashi

2015-08-01

Hydrogen(H)-bond dynamics are involved in many elementary processes in chemistry and biology. Because of its fundamental importance, a variety of experimental and theoretical approaches have been employed to study the dynamics in gas, liquid, solid phases, and their interfaces. This review describes the recent progress of direct observation and control of H-bond dynamics in several model systems on a metal surface by using low-temperature scanning tunneling microscopy (STM). General aspects of H-bond dynamics and the experimental methods are briefly described in chapter 1 and 2. In the subsequent four chapters, I present direct observation of an H-bond exchange reaction within a single water dimer (chapter 3), a symmetric H bond (chapter 4) and H-atom relay reactions (chapter 5) within water-hydroxyl complexes, and an intramolecular H-atom transfer reaction (tautomerization) within a single porphycene molecule (chapter 6). These results provide novel microscopic insights into H-bond dynamics at the single-molecule level, and highlight significant impact on the process from quantum effects, namely tunneling and zero-point vibration, resulting from the small mass of H atom. Additionally, local environmental effect on H-bond dynamics is also examined by using atom/molecule manipulation with the STM.

Method for Surface Texturing Titanium Products

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor)

1998-01-01

The present invention teaches a method of producing a textured surface upon an arbitrarily configured titanium or titanium alloy object for the purpose of improving bonding between the object and other materials such as polymer matrix composites and/or human bone for the direct in-growth of orthopaedic implants. The titanium or titanium alloy object is placed in an electrolytic cell having an ultrasonically agitated solution of sodium chloride therein whereby a pattern of uniform "pock mark" like pores or cavities are produced upon the object's surface. The process is very cost effective compared to other methods of producing rough surfaces on titanium and titanium alloy components. The surface textures produced by the present invention are etched directly into the parent metal at discrete sites separated by areas unaffected by the etching process. Bonding materials to such surface textures on titanium or titanium alloy can thus support a shear load even if adhesion of the bonding material is poor.

Irreversible, direct bonding of nanoporous polymer membranes to PDMS or glass microdevices.

PubMed

Aran, Kiana; Sasso, Lawrence A; Kamdar, Neal; Zahn, Jeffrey D

2010-03-07

A method for integrating porous polymer membranes such as polycarbonate, polyethersulfone and polyethylene terephthalate to microfluidic devices is described. The use of 3-aminopropyltriethoxysilane as a chemical crosslinking agent was extended to integrate membranes with PDMS and glass microfluidic channels. A strong, irreversible bond between the membranes and microfluidic structure was achieved. The bonding strength in the APTES treated devices was significantly greater than in devices fabricated using either a PDMS "glue" or two-part epoxy bonding method. Evaluation of a filtering microdevice and the pore structure via SEM indicates the APTES conjugation does not significantly alter the membrane transport function and pore morphology.

Method for joining metal by solid-state bonding

DOEpatents

Burkhart, L. Elkin; Fultz, Chester R.; Maulden, Kerry A.

1979-01-01

The present development is directed to a method for joining metal at relatively low temperatures by solid-state bonding. Planar surfaces of the metal workpieces are placed in a parallel abutting relationship with one another. A load is applied to at least one of the workpieces for forcing the workpieces together while one of the workpieces is relatively slowly oscillated in a rotary motion over a distance of about 1.degree.. After a preselected number of oscillations, the rotary motion is terminated and the bond between the abutting surfaces is effected. An additional load may be applied to facilitate the bond after terminating the rotary motion.

Method of making cascaded die mountings with springs-loaded contact-bond options

DOEpatents

Hsu, John S [Oak Ridge, TN; Adams, Donald J [Knoxville, TN; Su, Gui-Jia [Knoxville, TN; Marlino, Laura D [Oak Ridge, TN; Ayers, Curtis W [Kingston, TN; Coomer, Chester [Knoxville, TN

2007-06-19

A cascaded die mounting device and method using spring contacts for die attachment, with or without metallic bonds between the contacts and the dies, is disclosed. One embodiment is for the direct refrigerant cooling of an inverter/converter carrying higher power levels than most of the low power circuits previously taught, and does not require using a heat sink.

Combined surface activated bonding using H-containing HCOOH vapor treatment for Cu/Adhesive hybrid bonding at below 200 °C

NASA Astrophysics Data System (ADS)

He, Ran; Fujino, Masahisa; Akaike, Masatake; Sakai, Taiji; Sakuyama, Seiki; Suga, Tadatomo

2017-08-01

Cu/adhesive hybrid bonding is an attractive approach to three-dimensional (3D) integration because it provides direct Cusbnd Cu vertical interconnects and high mechanical stability. However, Cu/adhesive hybrid bonding at below 200 °C is still challenging because of bonding temperature mismatch between Cusbnd Cu and polymer adhesives and lacking of effective adhesive-compatible Cu surface activation methods. In this paper, we investigate and demonstrate a ;Cu-first; hybrid bonding technique by using hydrogen(H)-containing formic acid (HCOOH) vapor prebonding surface treatment for the first time. In this technique, high-quality Cusbnd Cu bonding is obtained at 180-200 °C that is close to or even lower than the temperature of subsequent adhesive curing. We experimentally investigate the effects of the H-containing HCOOH vapor treatment for Cusbnd Cu bonding and cyclo-olefin polymer adhesive-adhesive bonding. This technique enables Cu/adhesive hybrid bonding at below 200 °C, promising smaller thermal stress, higher throughput, and lower cost comparing to the existing ;adhesive-first; hybrid bonding method.

Selective Hydrogen Atom Abstraction through Induced Bond Polarization: Direct α-Arylation of Alcohols through Photoredox, HAT, and Nickel Catalysis.

PubMed

Twilton, Jack; Christensen, Melodie; DiRocco, Daniel A; Ruck, Rebecca T; Davies, Ian W; MacMillan, David W C

2018-05-04

The combination of nickel metallaphotoredox catalysis, hydrogen atom transfer catalysis, and a Lewis acid activation mode, has led to the development of an arylation method for the selective functionalization of alcohol α-hydroxy C-H bonds. This approach employs zinc-mediated alcohol deprotonation to activate α-hydroxy C-H bonds while simultaneously suppressing C-O bond formation by inhibiting the formation of nickel alkoxide species. The use of Zn-based Lewis acids also deactivates other hydridic bonds such as α-amino and α-oxy C-H bonds. This approach facilitates rapid access to benzylic alcohols, an important motif in drug discovery. A 3-step synthesis of the drug Prozac exemplifies the utility of this new method. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

31 CFR 351.67 - What happens if any person purchases book-entry Series EE savings bonds in excess of the maximum...

Code of Federal Regulations, 2010 CFR

2010-07-01

... bonds in excess of the maximum annual amount? We reserve the right to take any action we deem necessary to adjust the excess, including the right to remove the excess bonds from your New Treasury Direct account and refund the payment price to your bank account of record using the ACH method of payment. ...

Gold-based electrical interconnections for microelectronic devices

DOEpatents

Peterson, Kenneth A.; Garrett, Stephen E.; Reber, Cathleen A.; Watson, Robert D.

2002-01-01

A method of making an electrical interconnection from a microelectronic device to a package, comprising ball or wedge compression bonding a gold-based conductor directly to a silicon surface, such as a polysilicon bonding pad in a MEMS or IMEMS device, without using layers of aluminum or titanium disposed in-between the conductor and the silicon surface. After compression bonding, optional heating of the bond above 363 C. allows formation of a liquid gold-silicon eutectic phase containing approximately 3% (by weight) silicon, which significantly improves the bond strength by reforming and enhancing the initial compression bond. The same process can be used for improving the bond strength of Au--Ge bonds by forming a liquid Au-12Ge eutectic phase.

Two‐Dimensional Fluorinated Graphene: Synthesis, Structures, Properties and Applications

PubMed Central

Long, Peng; Feng, Yiyu; Li, Yu

2016-01-01

Fluorinated graphene, an up‐rising member of the graphene family, combines a two‐dimensional layer‐structure, a wide bandgap, and high stability and attracts significant attention because of its unique nanostructure and carbon–fluorine bonds. Here, we give an extensive review of recent progress on synthetic methods and C–F bonding; additionally, we present the optical, electrical and electronic properties of fluorinated graphene and its electrochemical/biological applications. Fluorinated graphene exhibits various types of C–F bonds (covalent, semi‐ionic, and ionic bonds), tunable F/C ratios, and different configurations controlled by synthetic methods including direct fluorination and exfoliation methods. The relationship between the types/amounts of C–F bonds and specific properties, such as opened bandgap, high thermal and chemical stability, dispersibility, semiconducting/insulating nature, magnetic, self‐lubricating and mechanical properties and thermal conductivity, is discussed comprehensively. By optimizing the C–F bonding character and F/C ratios, fluorinated graphene can be utilized for energy conversion and storage devices, bioapplications, electrochemical sensors and amphiphobicity. Based on current progress, we propose potential problems of fluorinated graphene as well as the future challenge on the synthetic methods and C‐F bonding character. This review will provide guidance for controlling C–F bonds, developing fluorine‐related effects and promoting the application of fluorinated graphene. PMID:27981018

LAMMPS framework for dynamic bonding and an application modeling DNA

NASA Astrophysics Data System (ADS)

Svaneborg, Carsten

2012-08-01

We have extended the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) to support directional bonds and dynamic bonding. The framework supports stochastic formation of new bonds, breakage of existing bonds, and conversion between bond types. Bond formation can be controlled to limit the maximal functionality of a bead with respect to various bond types. Concomitant with the bond dynamics, angular and dihedral interactions are dynamically introduced between newly connected triplets and quartets of beads, where the interaction type is determined from the local pattern of bead and bond types. When breaking bonds, all angular and dihedral interactions involving broken bonds are removed. The framework allows chemical reactions to be modeled, and use it to simulate a simplistic, coarse-grained DNA model. The resulting DNA dynamics illustrates the power of the present framework. Catalogue identifier: AEME_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEME_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public Licence No. of lines in distributed program, including test data, etc.: 2 243 491 No. of bytes in distributed program, including test data, etc.: 771 Distribution format: tar.gz Programming language: C++ Computer: Single and multiple core servers Operating system: Linux/Unix/Windows Has the code been vectorized or parallelized?: Yes. The code has been parallelized by the use of MPI directives. RAM: 1 Gb Classification: 16.11, 16.12 Nature of problem: Simulating coarse-grain models capable of chemistry e.g. DNA hybridization dynamics. Solution method: Extending LAMMPS to handle dynamic bonding and directional bonds. Unusual features: Allows bonds to be created and broken while angular and dihedral interactions are kept consistent. Additional comments: The distribution file for this program is approximately 36 Mbytes and therefore is not delivered directly when download or E-mail is requested. Instead an html file giving details of how the program can be obtained is sent. Running time: Hours to days. The examples provided in the distribution take just seconds to run.

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer

NASA Astrophysics Data System (ADS)

Choi, Gilbert J.; Zhu, Qilei; Miller, David C.; Gu, Carol J.; Knowles, Robert R.

2016-11-01

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process—a subset of the classical Hofmann-Löffler-Freytag reaction—amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using traditional HAT-based approaches.

Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.

PubMed

Choi, Gilbert J; Zhu, Qilei; Miller, David C; Gu, Carol J; Knowles, Robert R

2016-11-10

Despite advances in hydrogen atom transfer (HAT) catalysis, there are currently no molecular HAT catalysts that are capable of homolysing the strong nitrogen-hydrogen (N-H) bonds of N-alkyl amides. The motivation to develop amide homolysis protocols stems from the utility of the resultant amidyl radicals, which are involved in various synthetically useful transformations, including olefin amination and directed carbon-hydrogen (C-H) bond functionalization. In the latter process-a subset of the classical Hofmann-Löffler-Freytag reaction-amidyl radicals remove hydrogen atoms from unactivated aliphatic C-H bonds. Although powerful, these transformations typically require oxidative N-prefunctionalization of the amide starting materials to achieve efficient amidyl generation. Moreover, because these N-activating groups are often incorporated into the final products, these methods are generally not amenable to the direct construction of carbon-carbon (C-C) bonds. Here we report an approach that overcomes these limitations by homolysing the N-H bonds of N-alkyl amides via proton-coupled electron transfer. In this protocol, an excited-state iridium photocatalyst and a weak phosphate base cooperatively serve to remove both a proton and an electron from an amide substrate in a concerted elementary step. The resultant amidyl radical intermediates are shown to promote subsequent C-H abstraction and radical alkylation steps. This C-H alkylation represents a catalytic variant of the Hofmann-Löffler-Freytag reaction, using simple, unfunctionalized amides to direct the formation of new C-C bonds. Given the prevalence of amides in pharmaceuticals and natural products, we anticipate that this method will simplify the synthesis and structural elaboration of amine-containing targets. Moreover, this study demonstrates that concerted proton-coupled electron transfer can enable homolytic activation of common organic functional groups that are energetically inaccessible using traditional HAT-based approaches.

Highly selective rhodium catalyzed domino C-H activation/cyclizations.

PubMed

Trans, Duc N; Cramer, Nicolai

2011-01-01

The direct functionalization of carbon-hydrogen bonds is an emerging tool to establish more sustainable and efficient synthetic methods. We present its implementation in a cascade reaction that provides a rapid assembly of functionalized indanylamines from simple and readily available starting materials. Careful choice of the ancillary ligand---an electron-rich bidentate phosphine ligand--enables highly diastereoselective rhodium(i)-catalyzed intramolecular allylations of unsubstituted ketimines induced by a directed C-H bond activation and allene carbo-metalation sequence.

Direct bonding of gallium nitride to silicon carbide: Physical, and electrical characterization

NASA Astrophysics Data System (ADS)

Lee, Jaeseob

The direct bonding method is applied to the GaN/SiC system, and the processing conditions for successful direct bonding are clarified. Direct bonding of GaN/SiC is achieved at 900°C. The direct bonding of GaN to Si-face SiC is very dependent on the choice of chemical treatments, but the bonding of GaN to C-face SiC is less dependent on surface preparation. If a native oxide is present when the bonded interface is prepared, the current through the interface is decreased, which is attributed to an energy barrier due to the presence of charged interface states. TEM images indicate 10nm spaced dislocations at the interface for the GaN/SiC (Si-face), and ˜6nm for the GaN/SiC (C-face), which form to accommodate the lattice mismatch (3.4%) and twist (1˜2°) and tilt misfit (0.2° for Si-face SiC and 3° for C-face SiC). In some regions (˜30%) an amorphous oxide layer forms at the interface, which is attributed to inadequate surface preparation prior to bonding. The strain of the GaN film with a Ga/C interface was ˜0.1%, tensile strain, and that of GaN with a Ga/Si interface was ˜0.2%, tensile strain. Our analysis indicates that the GaN/SiC thermal misfit dominates the strain of the GaN after bonding. The electrical characteristics of n-p GaN/SiC heterojunctions display diode ideality factors, saturation currents, energy barrier heights, and band offsets of 1.5 +/- 0.1, 10-13 A/cm 2, 0.75 +/- 0.10 eV, and DeltaEC = 0.87 +/- 0.10 eV for the Ga/Si interface and 1.2 +/- 0.1, 10 -16 A/cm2, 0.56 +/- 0.10 eV, and Delta EC = 0.46 +/- 0.10 eV for the Ga/C interface.

Luting of CAD/CAM ceramic inlays: direct composite versus dual-cure luting cement.

PubMed

Kameyama, Atsushi; Bonroy, Kim; Elsen, Caroline; Lührs, Anne-Katrin; Suyama, Yuji; Peumans, Marleen; Van Meerbeek, Bart; De Munck, Jan

2015-01-01

The aim of this study was to investigate bonding effectiveness in direct restorations. A two-step self-etch adhesive and a light-cure resin composite was compared with luting with a conventional dual-cure resin cement and a two-step etch and rinse adhesive. Class-I box-type cavities were prepared. Identical ceramic inlays were designed and fabricated with a computer-aided design/computer-aided manufacturing (CAD/CAM) device. The inlays were seated with Clearfil SE Bond/Clearfil AP-X (Kuraray Medical) or ExciTE F DSC/Variolink II (Ivoclar Vivadent), each by two operators (five teeth per group). The inlays were stored in water for one week at 37°C, whereafter micro-tensile bond strength testing was conducted. The micro-tensile bond strength of the direct composite was significantly higher than that from conventional luting, and was independent of the operator (P<0.0001). Pre-testing failures were only observed with the conventional method. High-power light-curing of a direct composite may be a viable alternative to luting lithium disilicate glass-ceramic CAD/CAM restorations.

31 CFR 360.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2011 CFR

2011-07-01

... book-entry bonds in New Treasury Direct. 360.3 Section 360.3 Money and Finance: Treasury Regulations... Converting definitive savings bonds to book-entry bonds in New Treasury Direct. Series I savings bonds that were originally issued as definitive bonds may be converted to book-entry bonds through New Treasury...

31 CFR 353.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2011 CFR

2011-07-01

... book-entry bonds in New Treasury Direct. 353.3 Section 353.3 Money and Finance: Treasury Regulations... § 353.3 Converting definitive savings bonds to book-entry bonds in New Treasury Direct. Series EE savings bonds that were originally issued as definitive bonds may be converted to book-entry bonds through...

Palladium-catalyzed stereoretentive olefination of unactivated C(sp3)-H bonds with vinyl iodides at room temperature: synthesis of β-vinyl α-amino acids.

PubMed

Wang, Bo; Lu, Chengxi; Zhang, Shu-Yu; He, Gang; Nack, William A; Chen, Gong

2014-12-05

A method is reported for palladium-catalyzed N-quinolyl carboxamide-directed olefination of the unactivated C(sp(3))-H bonds of phthaloyl alanine with a broad range of vinyl iodides at room temperature. This reaction represents the first example of the stereoretentive installation of multisubstituted terminal and internal olefins onto unactivated C(sp(3))-H bonds. These methods enable access to a wide range of challenging β-vinyl α-amino acid products in a streamlined and controllable fashion, beginning from simple precursors.

Comparison of the Effect of Dentin Bonding, Dentin Sealing Agents on the Microleakage of Provisional Crowns Fabricated with Direct and Indirect Technique-An Invitro Study

PubMed Central

Muthukumar, B; Kumar, M Vasantha

2015-01-01

Background Postoperative sensitivity after temporization is a common complaint in Fixed Partial Denture patients. It is caused by weak and ill fitting temporary restorations which results in microleakage. This can be controlled by providing good temporary restorations and by coating the exposed dentinal tubules of the prepared tooth with dentin bonding agent or dental varnish. Aim The purpose of the study was to determine the effect of dentin-bonding, dentin sealing agents on the microleakage of temporary crowns made by tooth colored auto polymerizing resin fabricated with direct and indirect technique. Materials and Methods Thirty premolar and molar human teeth were collected which were extracted recently was used for the study. The teeth were marked and divided into 3 groups each containing 10 nos. They were individually mounted with self-cure acrylic resin. It was then mounted on a milling machine and crown preparations done. Temporary crowns were fabricated by direct and indirect method with two types of materials. In group A (Control group), the temporary crowns fabricated with both direct and indirect method were cemented directly with temporary luting cement. In group B dentine-bonding agent (solobond M) was applied once to the prepared surface of each tooth specimen before the cementation of temporary crowns where as in case of group C a single layer of dental varnish is applied prior to crown cementation. The entire specimens were immersed in 1% methylene blue and allowed to undergo thermal treatment. It was then sectioned in a hard tissue microtome. Each section was evaluated for dye penetration into the dentin tubules by comparing it with a visual scale. Statistical Analysis SPSS Version 13 software was used for non-parametric data analysis by a qualified statistician. P-values less than 0.05 (p-value<0.05) were considered to be statistically significant. Results Group B (Dentin Bonding Agent) specimens cemented with crowns fabricated in direct technique showed the least amount of microleakage when compared with group A and group C. Group C (Dental Varnish) specimen showed comparatively more amount of microleakage than that of group B. Group A (control group) specimens showed the maximum amount of microleakage. Conclusion The application of a single layer of Dental varnish appears to be of no significant benefit when compared to crowns cemented with the application of Dentin bonding agent on the tooth surface. The application of a single layer of Dentin bonding agent (Solobond M) and temporary crowns fabricated with direct technique may be of some benefit for crown preparations as an interim measure prior to the luting of final crown. PMID:26266219

Simulation of water flow in fractured porous medium by using discretized virtual internal bond

NASA Astrophysics Data System (ADS)

Peng, Shujun; Zhang, Zhennan; Li, Chunfang; He, Guofu; Miao, Guoqing

2017-12-01

The discretized virtual internal bond (DVIB) is adopted to simulate the water flow in fractured porous medium. The intact porous medium is permeable because it contains numerous micro cracks and pores. These micro discontinuities construct a fluid channel network. The representative volume of this fluid channel network is modeled as a lattice bond cell with finite number of bonds in statistical sense. Each bond serves as a fluid channel. In fractured porous medium, many bond cells are cut by macro fractures. The conductivity of the fracture facet in a bond cell is taken over by the bonds parallel to the flow direction. The equivalent permeability and volumetric storage coefficient of a micro bond are calibrated based on the ideal bond cell conception, which makes it unnecessary to consider the detailed geometry of a specific element. Such parameter calibration method is flexible and applicable to any type of element. The accuracy check results suggest this method has a satisfying accuracy in both the steady and transient flow simulation. To simulate the massive fractures in rockmass, the bond cells intersected by fracture are assigned aperture values, which are assumed random numbers following a certain distribution law. By this method, any number of fractures can be implicitly incorporated into the background mesh, avoiding the setup of fracture element and mesh modification. The fracture aperture heterogeneity is well represented by this means. The simulation examples suggest that the present method is a feasible, simple and efficient approach to the numerical simulation of water flow in fractured porous medium.

Understanding Nitrogen Fixation

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

Paul J. Chirik

The purpose of our program is to explore fundamental chemistry relevant to the discovery of energy efficient methods for the conversion of atmospheric nitrogen (N{sub 2}) into more value-added nitrogen-containing organic molecules. Such transformations are key for domestic energy security and the reduction of fossil fuel dependencies. With DOE support, we have synthesized families of zirconium and hafnium dinitrogen complexes with elongated and activated N-N bonds that exhibit rich N{sub 2} functionalization chemistry. Having elucidated new methods for N-H bond formation from dihydrogen, C-H bonds and Broensted acids, we have since turned our attention to N-C bond construction. These reactionsmore » are particularly important for the synthesis of amines, heterocycles and hydrazines with a range of applications in the fine and commodity chemicals industries and as fuels. One recent highlight was the discovery of a new N{sub 2} cleavage reaction upon addition of carbon monoxide which resulted in the synthesis of an important fertilizer, oxamide, from the diatomics with the two strongest bonds in chemistry. Nitrogen-carbon bonds form the backbone of many important organic molecules, especially those used in the fertilizer and pharamaceutical industries. During the past year, we have continued our work in the synthesis of hydrazines of various substitution patterns, many of which are important precursors for heterocycles. In most instances, the direct functionalization of N{sub 2} offers a more efficient synthetic route than traditional organic methods. In addition, we have also discovered a unique CO-induced N{sub 2} bond cleavage reaction that simultaneously cleaves the N-N bond of the metal dinitrogen compound and assembles new C-C bond and two new N-C bonds. Treatment of the CO-functionalized core with weak Broensted acids liberated oxamide, H{sub 2}NC(O)C(O)NH{sub 2}, an important slow release fertilizer that is of interest to replace urea in many applications. The synthesis of ammonia, NH{sub 3}, from its elements, H{sub 2} and N{sub 2}, via the venerable Haber-Bosch process is one of the most significant technological achievements of the past century. Our research program seeks to discover new transition metal reagents and catalysts to disrupt the strong N {triple_bond} N bond in N{sub 2} and create new, fundamental chemical linkages for the construction of molecules with application as fuels, fertilizers and fine chemicals. With DOE support, our group has discovered a mild method for ammonia synthesis in solution as well as new methods for the construction of nitrogen-carbon bonds directly from N{sub 2}. Ideally these achievements will evolve into more efficient nitrogen fixation schemes that circumvent the high energy demands of industrial ammonia synthesis. Industrially, atmospheric nitrogen enters the synthetic cycle by the well-established Haber-Bosch process whereby N{sub 2} is hydrogenated to ammonia at high temperature and pressure. The commercialization of this reaction represents one of the greatest technological achievements of the 20th century as Haber-Bosch ammonia is responsible for supporting approximately 50% of the world's population and serves as the source of half of the nitrogen in the human body. The extreme reaction conditions required for an economical process have significant energy consequences, consuming 1% of the world's energy supply mostly in the form of pollution-intensive coal. Moreover, industrial H{sub 2} synthesis via the water gas shift reaction and the steam reforming of methane is fossil fuel intensive and produces CO{sub 2} as a byproduct. New synthetic methods that promote this thermodynamically favored transformation ({Delta}G{sup o} = -4.1 kcal/mol) under milder conditions or completely obviate it are therefore desirable. Most nitrogen-containing organic molecules are derived from ammonia (and hence rely on the Haber-Bosch and H{sub 2} synthesis processes) and direct synthesis from atmospheric nitrogen could, in principle, be more energy-efficient. This is particularly attractive given the interest in direct hydrazine fuel cells.« less

A Unique Bonding Technique for Immediate Orthognathic Surgery

PubMed Central

Ayinipully, Hariprasad; Paul, Rosaline Tina; Ponnambathayil, Shaji Aboobacker; Rasheed, Althaf Thanimoottil

2015-01-01

Introduction A challenge in orthodontics is achieving ideal bracket position which determines treatment results and finishing. A new bonding method is done indirectly on the cast and bonded directly on the teeth, but it does not require conventional trays to carry the brackets to the teeth. Materials and Methods Heavy sized archwires like 0.019″x0.025″ or 0.018″ SS are bent to the malocclusion to generate a template which comprises of an Bracket -Archwire Assembly (BAA). This assembly is transferred onto the teeth using the molar bands with tubes which serves as a jig for proper orientation of the BAA, then the adhesive is cured at one shot to complete the bonding procedure. Results Two surgical cases successfully bonded with this technique is presented in this article. Conclusion This bonding method finds specific advantages in surgical orthodontics – when the surgeon decides on a surgery-first treatment objective, management of single or a couple of periodontally extruded teeth, management of impacted teeth and in patients needing fixed functional appliance immediately before the completion of growth spurt. PMID:26266212

Mechanical Attachment of Reusable Surface Insulation to Space Shuttle Primary Structure

NASA Technical Reports Server (NTRS)

Fleck, R. W.; Lehman, J. K.

1973-01-01

Three methods of attaching surface insulation tiles to shuttle primary structure have been proposed: direct bond, mechanical attachment, and subpanels with standoffs. The direct bond approach is lightweight but is difficult to refurbish and inspect. The subpanel approach is heavier but allows for easy refurbishment since subpanels are easily removed and replaced. The mechanical attachment approach allows easy refurbishment and inspection and is lightweight when an efficient insulator is used between surface insulation tiles and primary structure.

Effects of three drying methods of post space dentin bonding used in a direct resin composite core build-up method.

PubMed

Iwashita, Taichi; Mine, Atsushi; Matsumoto, Mariko; Nakatani, Hayaki; Higashi, Mami; Kawaguchi-Uemura, Asuka; Kabetani, Tomoshige; Tajiri, Yuko; Imai, Dai; Hagino, Ryosuke; Miura, Jiro; Minamino, Takuya; Yatani, Hirofumi

2018-06-14

The purpose of this study was to evaluate drying methods for post space dentin bonding in a direct resin composite core build-up method. Experiment 1: Four root canal plastic models, having diameters of 1.0 or 1.8mm and parallel or tapered shapes, were prepared. After drying each post space using three drying methods (air drying, paper-point drying, or ethanol drying, which involves filling the space with 99.5 vol% ethanol followed by air drying), the residual liquid in the models was weighed. Experiment 2: Thirty endodontically treated single-root teeth were dried using the above-described drying methods and filled with dual-cure resin composite. The bonded specimens were sectioned into square beams of approximately 1mm 2 for microtensile bond strength (μTBS) testing. Nine teeth were observed through transmission electron microscopy (TEM) and micro computed tomography (μCT). The weight of residual liquid and μTBS were analyzed using Scheffé multiple comparison. Experiment 1: The results of air drying were significantly different from those of paper-point drying (p<0.001) and ethanol drying (p<0.001), and no significant difference was observed between paper-point drying and ethanol drying. Experiment 2: The μTBS significantly decreased in the order of ethanol drying, paper-point drying, and air drying (air drying/ethanol drying: p<0.001, air drying/paper-point drying: p=0.048, ethanol drying/paper-point drying: p=0.032). TEM and μCT observation revealed a sufficient dentin/adhesive interface in the ethanol drying group. Ethanol drying was found to be more effective for post space dentin bonding, as compared with air drying and paper-point drying. Copyright © 2018 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Bond Management - Higher Education.

ERIC Educational Resources Information Center

Washington State Legislature, Olympia. Joint Committee on Higher Education.

In this instance, the Joint Committee on Higher Education in Washington State was directed to review capital funding methods at the 4-year institutions of higher education in the state. The major finding of the study, which emerged after an intensive survey of bond practices, was that some means should be found to enhance management effectiveness…

A quality quantitative method of silicon direct bonding based on wavelet image analysis

NASA Astrophysics Data System (ADS)

Tan, Xiao; Tao, Zhi; Li, Haiwang; Xu, Tiantong; Yu, Mingxing

2018-04-01

The rapid development of MEMS (micro-electro-mechanical systems) has received significant attention from researchers in various fields and subjects. In particular, the MEMS fabrication process is elaborate and, as such, has been the focus of extensive research inquiries. However, in MEMS fabrication, component bonding is difficult to achieve and requires a complex approach. Thus, improvements in bonding quality are relatively important objectives. A higher quality bond can only be achieved with improved measurement and testing capabilities. In particular, the traditional testing methods mainly include infrared testing, tensile testing, and strength testing, despite the fact that using these methods to measure bond quality often results in low efficiency or destructive analysis. Therefore, this paper focuses on the development of a precise, nondestructive visual testing method based on wavelet image analysis that is shown to be highly effective in practice. The process of wavelet image analysis includes wavelet image denoising, wavelet image enhancement, and contrast enhancement, and as an end result, can display an image with low background noise. In addition, because the wavelet analysis software was developed with MATLAB, it can reveal the bonding boundaries and bonding rates to precisely indicate the bond quality at all locations on the wafer. This work also presents a set of orthogonal experiments that consist of three prebonding factors, the prebonding temperature, the positive pressure value and the prebonding time, which are used to analyze the prebonding quality. This method was used to quantify the quality of silicon-to-silicon wafer bonding, yielding standard treatment quantities that could be practical for large-scale use.

The effect of grinding and/or airborne-particle abrasion on the bond strength between zirconia and veneering porcelain: a systematic review

PubMed Central

Lundberg, Karin; Wu, Lindsey; Papia, Evaggelia

2017-01-01

Abstract Objective: The aim of the study was to make an inventory of current literature on the bond strength between zirconia and veneering porcelain after surface treatment of zirconia by grinding with diamond bur and/or with airborne-particle abrasion. Material and methods: The literature search for the present review was made following recommended guidelines using acknowledged methodology on how to do a systematic review. The electronic databases PubMed, Cochrane Library, and Science Direct were used in the present study. Results: Twelve studies were selected. Test methods used in the original studies included shear bond strength (SBS) test, tensile bond strength test, and micro-tensile bond strength test. The majority of studies used SBS. Results showed a large variation within each surface treatment of zirconia, using different grain size, blasting time, and pressure. Conclusions: Airborne-particle abrasion might improve the bond strength and can therefore be considered a feasible surface treatment for zirconia that is to be bonded. Grinding has been recommended as a surface treatment for zirconia to improve the bond strength; however, this recommendation cannot be verified. A standardized test method and surface treatment are required to be able to compare the results from different studies and draw further conclusions. PMID:28642927

Comparison of porcelain bond strength of different metal frameworks prepared by using conventional and recently introduced fabrication methods.

PubMed

Kaleli, Necati; Saraç, Duygu

2017-07-01

Most studies evaluating dental laser sintering systems have focused on the marginal accuracy of the restorations. However, the bond strength at the metal-ceramic interface is another important factor that affects the survival of restorations, and currently, few studies focus on this aspect. The purpose of this in vitro study was to compare the porcelain bond strength of cobalt-chromium (Co-Cr) metal frameworks prepared by using the conventional lost-wax technique, milling, direct metal laser sintering (DMLS), and laser cusing, a direct process powder-bed system. A total of 96 metal frameworks (n=24 in each group) were prepared by using conventional lost-wax (group C), milling (group M), DMLS (group LS), and direct process powder-bed (group LC) methods according to International Organization for Standardization standard ISO 9693-1. After porcelain application, a 3-point bend test was applied to each specimen by using a universal testing machine. Data were statistically analyzed using 1-way ANOVA and Tukey honest significant difference tests (α=.05). Failure types at the metal-ceramic interfaces were examined using stereomicroscopy. Additionally, 1 specimen from each group was prepared for scanning electron microscopy analysis to evaluate the surface topography of metal frameworks. The mean bond strength was 38.08 ±3.82 MPa for group C, 39.29 ±3.51 MPa for group M, 40.73 ±3.58 MPa for group LS, and 41.24 ±3.75 MPa for group LC. Statistically significant differences were observed among the 4 groups (P=.016). All groups, except for LS, exhibited adhesive and mixed type bond failure. Both of the laser sintering methods were found to be successful in terms of metal-ceramic bond strength. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Theoretical study of optical activity of 1:1 hydrogen bond complexes of water with S-warfarin

NASA Astrophysics Data System (ADS)

Dadsetani, Mehrdad; Abdolmaleki, Ahmad; Zabardasti, Abedin

2016-11-01

The molecular interaction between S-warfarin (SW) and a single water molecule was investigated using the B3LYP method at 6-311 ++G(d,p) basis set. The vibrational spectra of the optimized complexes have been investigated for stabilization checking. Quantum theories of atoms in molecules, natural bond orbitals, molecular electrostatic potentials and energy decomposition analysis methods have been applied to analyze the intermolecular interactions. The intermolecular charge transfer in the most stable complex is in the opposite direction from those in the other complexes. The optical spectra and the hyperpolarizabilities of SW-water hydrogen bond complexes have been computed.

31 CFR 315.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2011 CFR

2011-07-01

... book-entry bonds in New Treasury Direct. 315.3 Section 315.3 Money and Finance: Treasury Regulations.... SAVINGS NOTES General Information § 315.3 Converting definitive savings bonds to book-entry bonds in New... book-entry bonds through New Treasury Direct, an online system for holding Treasury securities. The Web...

31 CFR 315.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2010 CFR

2010-07-01

... to book-entry bonds in New Treasury Direct. 315.3 Section 315.3 Money and Finance: Treasury.... SAVINGS NOTES General Information § 315.3 Converting definitive savings bonds to book-entry bonds in New... book-entry bonds through New Treasury Direct, an online system for holding Treasury securities. The Web...

Heat exchanger and method of making. [rocket lining

NASA Technical Reports Server (NTRS)

Fortini, A.; Kazaroff, J. M. (Inventor)

1980-01-01

A heat exchange of increased effectiveness is disclosed. A porous metal matrix is disposed in a metal chamber or between walls through which a heat-transfer fluid is directed. The porous metal matrix has internal bonds and is bonded to the chamber in order to remove all thermal contact resistance within the composite structure. Utilization of the invention in a rocket chamber is disclosed as a specific use. Also disclosed is a method of constructing the heat exchanger.

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.

Methods and system for controlled laser-driven explosive bonding

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

Rubenchik, Alexander M.; Farmer, Joseph C.; Hackel, Lloyd

A technique for bonding two dissimilar materials includes positioning a second material over a first material at an oblique angle and applying a tamping layer over the second martial. A laser beam is directed at the second material that generates a plasma at the location of impact on the second material. The plasma generates pressure that accelerates a portion of the second material to a very high velocity and towards the first material. The second material impacts the first material causing bonding of the two materials.

Effect of adding Te to layered GaSe crystals to increase the van der Waals bonding force

NASA Astrophysics Data System (ADS)

Tanabe, Tadao; Zhao, Shu; Sato, Yohei; Oyama, Yutaka

2017-10-01

The interplanar binding strength of layered GaSe1-xTex crystals was directly measured using a tensile testing machine. The GaSe1-xTex crystals were grown by a low temperature liquid phase solution method under a controlled Se vapor pressure. The stoichiometry-controlled GaSe1-xTex crystal has the ɛ-polytype structure of GaSe, where the Te atoms are substituted for some of the Se atoms in the GaSe crystal. The effect of adding Te on the bonding strength between the GaSe layers was determined from direct measurements of the van der Waals bonding energy. The bonding energy was increased from 0.023 × 106 N/m2 for GaSe to 0.16 × 106 N/m2 for GaSe1-xTex (x = 0.106).

Bent Bonds and Multiple Bonds.

ERIC Educational Resources Information Center

Robinson, Edward A.; Gillespie, Ronald J.

1980-01-01

Considers carbon-carbon multiple bonds in terms of Pauling's bent bond model, which allows direct calculation of double and triple bonds from the length of a CC single bond. Lengths of these multiple bonds are estimated from direct measurements on "bent-bond" models constructed of plastic tubing and standard kits. (CS)

Direct arylation/alkylation/magnesiation of benzyl alcohols in the presence of Grignard reagents via Ni-, Fe-, or Co-catalyzed sp3 C-O bond activation.

PubMed

Yu, Da-Gang; Wang, Xin; Zhu, Ru-Yi; Luo, Shuang; Zhang, Xiao-Bo; Wang, Bi-Qin; Wang, Lei; Shi, Zhang-Jie

2012-09-12

Direct application of benzyl alcohols (or their magnesium salts) as electrophiles in various reactions with Grignard reagents has been developed via transition metal-catalyzed sp(3) C-O bond activation. Ni complex was found to be an efficient catalyst for the first direct cross coupling of benzyl alcohols with aryl/alkyl Grignard reagents, while Fe, Co, or Ni catalysts could promote the unprecedented conversion of benzyl alcohols to benzyl Grignard reagents in the presence of (n)hexylMgCl. These methods offer straightforward pathways to transform benzyl alcohols into a variety of functionalities.

Regioselective synthesis of C3 alkylated and arylated benzothiophenes

NASA Astrophysics Data System (ADS)

Shrives, Harry J.; Fernández-Salas, José A.; Hedtke, Christin; Pulis, Alexander P.; Procter, David J.

2017-03-01

Benzothiophenes are heterocyclic constituents of important molecules relevant to society, including those with the potential to meet modern medical challenges. The construction of molecules would be vastly more efficient if carbon-hydrogen bonds, found in all organic molecules, can be directly converted into carbon-carbon bonds. In the case of elaborating benzothiophenes, functionalization of carbon-hydrogen bonds at carbon-number 3 (C3) is markedly more demanding than at C2 due to issues of regioselectivity (C3 versus C2), and the requirement of high temperatures, precious metals and the installation of superfluous directing groups. Herein, we demonstrate that synthetically unexplored but readily accessible benzothiophene S-oxides serve as novel precursors for C3-functionalized benzothiophenes. Employing an interrupted Pummerer reaction to capture and then deliver phenol and silane coupling partners, we have discovered a directing group-free method that delivers C3-arylated and -alkylated benzothiophenes with complete regioselectivity, under metal-free and mild conditions.

[Effects of different resin removal methods on shear bond strength of rebonded orthodontic brackets].

PubMed

Wu, Hai-miao; Zhao, Bin-jiao; Chen, Dong

2015-06-01

To compare the shear bond strength (SBS) of rebonded orthodontic metal brackets with different resin removal methods. Forty extracted premolars were chosen as samples and divided into 4 experimental groups. The teeth were bonded with brackets. The brackets from 3 groups were debonded while adhesive remnants were removed from bracket bases by methods of grinding, sandblasting, and direct flaming, respectively and then rebonded. The SBS values of all rebonded brackets were determined after pH cycling experiment for 30 days. Some rebonded bracket bases were selected and observed under scanning electron microscope (SEM). The data was analyzed by one-way ANOVA test using SPSS 13.0 software package. Statistical analysis revealed a significant difference of SBS values among the 4 experimental groups (P<0.05). The SBS values of the group by direct flaming was significantly lower compared to the other groups (P<0.05). There was no significant difference of SBS values among the other groups. The rebonded brackets after resin removal by grinding and sandblasting have a similar SBS compared to the initial brackets adhesive.

Direct Carboxylation of the Diazo Group ipso-C(sp2)-H bond with Carbon Dioxide: Access to Unsymmetrical Diazomalonates and Derivatives.

PubMed

Liu, Qianyi; Li, Man; Xiong, Rui; Mo, Fanyang

2017-12-15

The direct carboxylation of the ipso-C(sp 2 )-H bond of a diazo compound with carbon dioxide under mild reaction conditions is described. This method is transition-metal-free, uses a weak base, and proceeds at ambient temperature under atmospheric pressure in carbon dioxide. The carboxylation exhibits high reactivity and is amenable to subsequent diversification. A series of unsymmetrical 1,3-diester/keto/amide diazo compounds are obtained with moderate to excellent yields (up to 99%) with good functional group compatibility.

Etching of enamel for direct bonding with a thulium fiber laser

NASA Astrophysics Data System (ADS)

Kabaş Sarp, Ayşe S.; Gülsoy, Murat

2011-03-01

Background: Laser etching of enamel for direct bonding can decrease the risk of surface enamel loss and demineralization which are the adverse effects of acid etching technique. However, in excess of +5.5°C can cause irreversible pulpal responses. In this study, a 1940- nm Thulium Fiber Laser in CW mode was used for laser etching. Aim: Determination of the suitable Laser parameters of enamel surface etching for direct bonding of ceramic brackets and keeping that intrapulpal temperature changes below the threshold value. Material and Method: Polycrystalline ceramic orthodontic brackets were bonded on bovine teeth by using 2 different kinds of etching techniques: Acid and Laser Etching. In addition to these 3 etched groups, there was also a group which was bonded without etching. Brackets were debonded with a material testing machine. Breaking time and the load at the breaking point were measured. Intrapulpal temperature changes were recorded by a K-type Thermocouple. For all laser groups, intrapulpal temperature rise was below the threshold value of 5.5°C. Results and Conclusion: Acid-etched group ( 11.73 MPa) significantly required more debonding force than 3- second- irradiated ( 5.03 MPa) and non-etched groups ( 3.4 MPa) but the results of acid etched group and 4- second- irradiated group (7.5 MPa) showed no significant difference. Moreover, 4- second irradiated group was over the minimum acceptable value for clinical use. Also, 3- second lasing caused a significant reduction in time according to acid-etch group. As a result, 1940- nm laser irradiation is a promising method for laser etching.

Thermally robust and biomolecule-friendly room-temperature bonding for the fabrication of elastomer-plastic hybrid microdevices.

PubMed

Nguyen, T P O; Tran, B M; Lee, N Y

2016-08-16

Here, we introduce a simple and fast method for bonding a poly(dimethylsiloxane) (PDMS) silicone elastomer to different plastics. In this technique, surface modification and subsequent bonding processes are performed at room temperature. Furthermore, only one chemical is needed, and no surface oxidation step is necessary prior to bonding. This bonding method is particularly suitable for encapsulating biomolecules that are sensitive to external stimuli, such as heat or plasma treatment, and for embedding fracturable materials prior to the bonding step. Microchannel-fabricated PDMS was first oxidized by plasma treatment and reacted with aminosilane by forming strong siloxane bonds (Si-O-Si) at room temperature. Without the surface oxidation of the amine-terminated PDMS and plastic, the two heterogeneous substrates were brought into intimate physical contact and left at room temperature. Subsequently, aminolysis occurred, leading to the generation of a permanent seal via the formation of robust urethane bonds after only 5 min of assembling. Using this method, large-area (10 × 10 cm) bonding was successfully realized. The surface was characterized by contact angle measurements and X-ray photoelectron spectroscopy (XPS) analyses, and the bonding strength was analyzed by performing peel, delamination, leak, and burst tests. The bond strength of the PDMS-polycarbonate (PC) assembly was approximately 409 ± 6.6 kPa, and the assembly withstood the injection of a tremendous amount of liquid with the per-minute injection volume exceeding 2000 times its total internal volume. The thermal stability of the bonded microdevice was confirmed by performing a chamber-type multiplex polymerase chain reaction (PCR) of two major foodborne pathogens - Escherichia coli O157:H7 and Salmonella typhimurium - and assessing the possibility for on-site direct detection of PCR amplicons. This bonding method demonstrated high potential for the stable construction of closed microfluidic systems socketed with biomolecule-immobilized surfaces such as DNA, antibody, enzyme, peptide, and protein microarrays.

31 CFR 360.3 - Converting definitive savings bonds to book-entry bonds in TreasuryDirect®.

Code of Federal Regulations, 2014 CFR

2014-07-01

... originally issued as definitive bonds may be converted to book-entry bonds through TreasuryDirect®, an online.... Bond owners who wish to convert their definitive savings bonds should follow online instructions for...

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

31 CFR 360.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Direct, an online system for holding Treasury securities. The Web address for New Treasury Direct is www.treasurydirect.gov. Bond owners who wish to convert their definitive savings bonds should follow online...

31 CFR 360.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Direct, an online system for holding Treasury securities. The Web address for New Treasury Direct is www.treasurydirect.gov. Bond owners who wish to convert their definitive savings bonds should follow online...

Cascaded die mountings with spring-loaded contact-bond options

DOEpatents

Hsu, John S.; Adams, Donald J.; Su, Gui-Jia; Marlino, Laura D.; Ayers, Curtis W.; Coomer, Chester

2005-08-16

A cascaded die mounting device and method using spring contacts for die attachment, with or without metallic bonds between the contacts and the dies, is disclosed. One embodiment is for the direct refrigerant cooling of an inverter/converter carrying higher power levels than most of the low power circuits previously taught, and does not require using a heat sink.

Transition Metal Free C-N Bond Forming Dearomatizations and Aryl C-H Aminations by in Situ Release of a Hydroxylamine-Based Aminating Agent.

PubMed

Farndon, Joshua J; Ma, Xiaofeng; Bower, John F

2017-10-11

We outline a simple protocol that accesses directly unprotected secondary amines by intramolecular C-N bond forming dearomatization or aryl C-H amination. The method is dependent on the generation of a potent electrophilic aminating agent released by in situ deprotection of O-Ts activated N-Boc hydroxylamines.

31 CFR 359.52 - What happens if any person purchases book-entry Series I savings bonds in excess of the maximum...

Code of Federal Regulations, 2010 CFR

2010-07-01

... the maximum amount? We reserve the right to take any action we deem necessary to adjust the excess, including the right to remove the excess bonds from your New Treasury Direct account and refund the payment price to your bank account of record using the ACH method of payment. ...

Comparison of shear test methods for evaluating the bond strength of resin cement to zirconia ceramic.

PubMed

Kim, Jae-Hoon; Chae, Soyeon; Lee, Yunhee; Han, Geum-Jun; Cho, Byeong-Hoon

2014-11-01

This study compared the sensitivity of three shear test methods for measuring the shear bond strength (SBS) of resin cement to zirconia ceramic and evaluated the effects of surface treatment methods on the bonding. Polished zirconia ceramic (Cercon base, DeguDent) discs were randomly divided into four surface treatment groups: no treatment (C), airborne-particle abrasion (A), conditioning with Alloy primer (Kuraray Medical Co.) (P) and conditioning with Alloy primer after airborne-particle abrasion (AP). The bond strengths of the resin cement (Multilink N, Ivoclar Vivadent) to the zirconia specimens of each surface treatment group were determined by three SBS test methods: the conventional SBS test with direct filling of the mold (Ø 4 mm × 3 mm) with resin cement (Method 1), the conventional SBS test with cementation of composite cylinders (Ø 4 mm × 3 mm) using resin cement (Method 2) and the microshear bond strength (μSBS) test with cementation of composite cylinders (Ø 0.8 mm × 1 mm) using resin cement (Method 3). Both the test method and the surface treatment significantly influenced the SBS values. In Method 3, as the SBS values increased, the coefficients of variation decreased and the Weibull parameters increased. The AP groups showed the highest SBS in all of the test methods. Only in Method 3 did the P group show a higher SBS than the A group. The μSBS test was more sensitive to differentiating the effects of surface treatment methods than the conventional SBS tests. Primer conditioning was a stronger contributing factor for the resin bond to zirconia ceramic than was airborne-particle abrasion.

Direct quantitative measurement of the C═O⋅⋅⋅H–C bond by atomic force microscopy

PubMed Central

Kawai, Shigeki; Nishiuchi, Tomohiko; Kodama, Takuya; Spijker, Peter; Pawlak, Rémy; Meier, Tobias; Tracey, John; Kubo, Takashi; Meyer, Ernst; Foster, Adam S.

2017-01-01

The hydrogen atom—the smallest and most abundant atom—is of utmost importance in physics and chemistry. Although many analysis methods have been applied to its study, direct observation of hydrogen atoms in a single molecule remains largely unexplored. We use atomic force microscopy (AFM) to resolve the outermost hydrogen atoms of propellane molecules via very weak C═O⋅⋅⋅H–C hydrogen bonding just before the onset of Pauli repulsion. The direct measurement of the interaction with a hydrogen atom paves the way for the identification of three-dimensional molecules such as DNAs and polymers, building the capabilities of AFM toward quantitative probing of local chemical reactivity. PMID:28508080

Atomic bonding effects in annular dark field scanning transmission electron microscopy. I. Computational predictions

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

Odlyzko, Michael L.; Mkhoyan, K. Andre, E-mail: mkhoyan@umn.edu; Himmetoglu, Burak

2016-07-15

Annular dark field scanning transmission electron microscopy (ADF-STEM) image simulations were performed for zone-axis-oriented light-element single crystals, using a multislice method adapted to include charge redistribution due to chemical bonding. Examination of these image simulations alongside calculations of the propagation of the focused electron probe reveal that the evolution of the probe intensity with thickness exhibits significant sensitivity to interatomic charge transfer, accounting for observed thickness-dependent bonding sensitivity of contrast in all ADF-STEM imaging conditions. Because changes in image contrast relative to conventional neutral atom simulations scale directly with the net interatomic charge transfer, the strongest effects are seen inmore » crystals with highly polar bonding, while no effects are seen for nonpolar bonding. Although the bonding dependence of ADF-STEM image contrast varies with detector geometry, imaging parameters, and material temperature, these simulations predict the bonding effects to be experimentally measureable.« less

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.

Low-temperature direct bonding of glass nanofluidic chips using a two-step plasma surface activation process.

PubMed

Xu, Yan; Wang, Chenxi; Dong, Yiyang; Li, Lixiao; Jang, Kihoon; Mawatari, Kazuma; Suga, Tadatomo; Kitamori, Takehiko

2012-01-01

Owing to the well-established nanochannel fabrication technology in 2D nanoscales with high resolution, reproducibility, and flexibility, glass is the leading, ideal, and unsubstitutable material for the fabrication of nanofluidic chips. However, high temperature (~1,000 °C) and a vacuum condition are usually required in the conventional fusion bonding process, unfortunately impeding the nanofluidic applications and even the development of the whole field of nanofluidics. We present a direct bonding of fused silica glass nanofluidic chips at low temperature, around 200 °C in ambient air, through a two-step plasma surface activation process which consists of an O(2) reactive ion etching plasma treatment followed by a nitrogen microwave radical activation. The low-temperature bonded glass nanofluidic chips not only had high bonding strength but also could work continuously without leakage during liquid introduction driven by air pressure even at 450 kPa, a very high pressure which can meet the requirements of most nanofluidic operations. Owing to the mild conditions required in the bonding process, the method has the potential to allow the integration of a range of functional elements into nanofluidic chips during manufacture, which is nearly impossible in the conventional high-temperature fusion bonding process. Therefore, we believe that the developed low-temperature bonding would be very useful and contribute to the field of nanofluidics.

Palladium-catalysed transannular C-H functionalization of alicyclic amines

NASA Astrophysics Data System (ADS)

Topczewski, Joseph J.; Cabrera, Pablo J.; Saper, Noam I.; Sanford, Melanie S.

2016-03-01

Discovering pharmaceutical candidates is a resource-intensive enterprise that frequently requires the parallel synthesis of hundreds or even thousands of molecules. C-H bonds are present in almost all pharmaceutical agents. Consequently, the development of selective, rapid and efficient methods for converting these bonds into new chemical entities has the potential to streamline pharmaceutical development. Saturated nitrogen-containing heterocycles (alicyclic amines) feature prominently in pharmaceuticals, such as treatments for depression (paroxetine, amitifadine), diabetes (gliclazide), leukaemia (alvocidib), schizophrenia (risperidone, belaperidone), malaria (mefloquine) and nicotine addiction (cytisine, varenicline). However, existing methods for the C-H functionalization of saturated nitrogen heterocycles, particularly at sites remote to nitrogen, remain extremely limited. Here we report a transannular approach to selectively manipulate the C-H bonds of alicyclic amines at sites remote to nitrogen. Our reaction uses the boat conformation of the substrates to achieve palladium-catalysed amine-directed conversion of C-H bonds to C-C bonds on various alicyclic amine scaffolds. We demonstrate this approach by synthesizing new derivatives of several bioactive molecules, including varenicline.

Methods for measuring exchangeable protons in glycosaminoglycans.

PubMed

Beecher, Consuelo N; Larive, Cynthia K

2015-01-01

Recent NMR studies of the exchangeable protons of GAGs in aqueous solution, including those of the amide, sulfamate, and hydroxyl moieties, have demonstrated potential for the detection of intramolecular hydrogen bonds, providing insights into secondary structure preferences. GAG amide protons are observable by NMR over wide pH and temperature ranges; however, specific solution conditions are required to reduce the exchange rate of the sulfamate and hydroxyl protons and allow their detection by NMR. Building on the vast body of knowledge on detection of hydrogen bonds in peptides and proteins, a variety of methods can be used to identify hydrogen bonds in GAGs including temperature coefficient measurements, evaluation of chemical shift differences between oligo- and monosaccharides, and relative exchange rates measured through line shape analysis and EXSY spectra. Emerging strategies to allow direct detection of hydrogen bonds through heteronuclear couplings offer promise for the future. Molecular dynamic simulations are important in this effort both to predict and confirm hydrogen bond donors and acceptors.

Reliable four-point flexion test and model for die-to-wafer direct bonding

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

Tabata, T., E-mail: toshiyuki.tabata@cea.fr; Sanchez, L.; Fournel, F.

2015-07-07

For many years, wafer-to-wafer (W2W) direct bonding has been very developed particularly in terms of bonding energy measurement and bonding mechanism comprehension. Nowadays, die-to-wafer (D2W) direct bonding has gained significant attention, for instance, in photonics and microelectro-mechanics, which supposes controlled and reliable fabrication processes. So, whatever the stuck materials may be, it is not obvious whether bonded D2W structures have the same bonding strength as bonded W2W ones, because of possible edge effects of dies. For that reason, it has been strongly required to develop a bonding energy measurement technique which is suitable for D2W structures. In this paper, bothmore » D2W- and W2W-type standard SiO{sub 2}-to-SiO{sub 2} direct bonding samples are fabricated from the same full-wafer bonding. Modifications of the four-point flexion test (4PT) technique and applications for measuring D2W direct bonding energies are reported. Thus, the comparison between the modified 4PT and the double-cantilever beam techniques is drawn, also considering possible impacts of the conditions of measures such as the water stress corrosion at the debonding interface and the friction error at the loading contact points. Finally, reliability of a modified technique and a new model established for measuring D2W direct bonding energies is demonstrated.« less

Functionalization of P4 through Direct P-C Bond Formation.

PubMed

Borger, Jaap E; Ehlers, Andreas W; Slootweg, J Chris; Lammertsma, Koop

2017-09-04

Research on chlorine-free conversions of P 4 into organophosphorus compounds (OPCs) has a long track record, but methods that allow desirable, direct P-C bond formations have only recently emerged. These include the use of metal organyls, carbenes, carboradicals, and photochemical approaches. The versatile product scope enables the preparation of both industrially relevant organophosphorus compounds, as well as a broad range of intriguing new compound classes. Herein we provide a concise overview of recent breakthroughs and outline the acquired fundamental insights to aid future developments. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relevance of Micro-leakage to Orthodontic Bonding - a Review

PubMed Central

M, Karandish

2016-01-01

As it is seen, by passing the evolutionary process of banding of orthodontic attachments to the bonding ones, orthodontics have witnessed many developments, such as application of new adhesives, optimized base designs, new bracket materials, curing methods and more efficient primers. The studies often address the morphological, micro-leakage, and shear bond tests to evaluate bond efficacy. Among studies endeavored to develop the bond strength of brackets, some observed the reduction of micro-leakage of bracket-adhesive and enamel-adhesive interfaces. Owing to the importance of micro-leakage in orthodontics, this study aimed at reviewing the micro-leakage values directly relevant to the enamel decay and debonding of the brackets. To reach the best bond strength, the researchers tried to design different studies to evaluate the effect of variables and prevent any possible side effects in clinical situations. It is noticed that most studies have mainly focused on adhesives, enamel preparation and methods of curing which are discussed in this review. The literature was reviewed by searching databases, using micro-leakage and orthodontic bonding as the keywords . Having found the relevant studies, the researchers entered them into the database. After reviewing numerous studies conducted in this field, the type of adhesive or curing method was not found to have determinative role in the value of micro-leakage although more standardized studies are needed. PMID:28959751

Method and apparatus for an insulating glazing unit and compliant seal for an insulating glazing unit

DOEpatents

Francis, IV, William H.; Freebury, Gregg E.; Beidleman, Neal J.; Hulse, Michael

2016-05-03

A Vacuum Insulating Glazing Unit (VIGU) comprises two or more glass lites (panes) spaced apart from one another and hermetically bonded to an edge seal assembly therebetween. The resulting cavity between the lites is evacuated to create at least one insulating vacuum cavity within which are disposed a plurality of stand-off members to maintain separation between the lites. The edge seal assembly is preferably compliant in the longitudinal (i.e., edgewise) direction to allow longitudinal relative motion between the two lites (e.g., from thermal expansion). The longitudinal compliance may be obtained by imprinting a three-dimensional pattern into the edge seal material. The edge seal assembly is preferably bonded to the lites with a first bond portion that is hermetic and a second bond portion that is load-resistant. Methods for producing VIGUs and/or compliant edge seal assemblies and VIGU and edge seal apparatus are disclosed.

Cleanliness evaluation of rough surfaces with diffuse IR reflectance

NASA Technical Reports Server (NTRS)

Pearson, L. H.

1995-01-01

Contamination on bonding surfaces has been determined to be a primary cause for degraded bond strength in certain solid rocket motor bondlines. Hydrocarbon and silicone based organic contaminants that are airborne or directly introduced to a surface are a significant source of contamination. Diffuse infrared (IR) reflectance has historically been used as an effective technique for detection of organic contaminants, however, common laboratory methods involving the use of a Fourier transform IR spectrometer (FTIR) are impractical for inspecting the large bonding surface areas found on solid rocket motors. Optical methods involving the use of acousto-optic tunable filters and fixed bandpass optical filters are recommended for increased data acquisition speed. Testing and signal analysis methods are presented which provide for simultaneous measurement of contamination concentration and roughness level on rough metal surfaces contaminated with hydrocarbons.

Development and Demonstration of a Multiplexed Magnetic Tweezers Assay

NASA Astrophysics Data System (ADS)

Johnson, Keith Charles

This dissertation is concerned with the methods and applications of single molecule force spectroscopy. In the introduction, the traditional single molecule force spectroscopy instruments are introduced and the advantages and drawbacks of each are discussed. The first chapter is a review of methods to ensure that biomolecular bond lifetime parameter estimations are not contaminated by multiple bond data. This review culminates in an examination of the literature on the strength of the bond between biotin and streptavidin and finds that by filtering the numerous publications for those that clearly demonstrate specific single bond behavior, there is a consensus of the bond strength and kinetic parameters. The second chapter of the dissertation discusses the capabilities of a magnetic tweezer assay, which combines massive multiplexing, precision bead tracking, and bi-directional force control into a flexible and stabile platform for examining single molecule behavior. Using a novel method for increasing the precision of force estimations on heterogeneous paramagnetic beads, I demonstrate the instrument by examining the force dependence of uncoiling and recoiling velocity of type 1 fimbriae from Eschericia coli (E. coli) bacteria, and see similar results to previous studies. Chapter 3 is a study of the lifetime of the activated FimH-mannose bond under various force conditions using the previously described magnetic tweezer. The bond is found to be extremely long-lived at forces less than 30 pN, with an average lifetime > 1000 times longer than the biotin-streptavidin bond, making it one of the strongest non-covalent interactions known in nature. Furthermore, the average lifetime of the bond is similar between 9 and 30 pN of force, suggesting a force range at which the lifetime is force-independent, demonstrating ideal bond behavior for the first time in a natural system. It is hypothesized that the long lifetime and ideal behavior is due to a gateway that locks mannose into the binding pocket and opens at a rate independent of force. This study elucidates a mechanism for very strong biological binding, and provides insight into approaches for developing novel antiadhesive therapies. This dissertation is concluded with a review of the body of work in chapters 1-3 and a discussion of the future directions for this research.

Natural chemical shielding analysis of nuclear magnetic resonance shielding tensors from gauge-including atomic orbital calculations

NASA Astrophysics Data System (ADS)

Bohmann, Jonathan A.; Weinhold, Frank; Farrar, Thomas C.

1997-07-01

Nuclear magnetic shielding tensors computed by the gauge including atomic orbital (GIAO) method in the Hartree-Fock self-consistent-field (HF-SCF) framework are partitioned into magnetic contributions from chemical bonds and lone pairs by means of natural chemical shielding (NCS) analysis, an extension of natural bond orbital (NBO) analysis. NCS analysis complements the description provided by alternative localized orbital methods by directly calculating chemical shieldings due to delocalized features in the electronic structure, such as bond conjugation and hyperconjugation. Examples of NCS tensor decomposition are reported for CH4, CO, and H2CO, for which a graphical mnemonic due to Cornwell is used to illustrate the effect of hyperconjugative delocalization on the carbon shielding.

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

Wang, Hong; Wang, Jy-An John; Ren, Fei

Integration of smart patches into full-tension splice connectors in overhead power transmission lines was investigated. Lead zirconate titanate (PZT) -5A was used as a smart material and an aluminum beam was used as a host structure. Negative electrode termination was examined by using copper adhesive tape and direct bonding methods. Various commercial adhesives were studied for PZT integration onto the host structure. Aluminum beam specimens with integrated PZT smart patches were tested under thermal cycling at a temperature of 125 C, which is the higher-end temperature experienced by in-service aluminum conductor steel-reinforced cables. Electromechanical impedance (EMI) measurements were conducted atmore » room temperature, and the root mean square deviation (RMSD) of the conductance signals was used to analyze the EMI data. It has been shown that the negative electrode method has an important effect on the performance of the integrated PZT. The PZT displayed more susceptibility to cracking when copper tape was used than when direct bonding was used. The reliability of PZT in direct bonding depended on the adhesives used in bonding layers. Although a hard alumina based adhesive can lead to cracking of the PZT, a high-temperature epoxy with adequate flexibility, such as Duralco 4538D, can provide the desired performance under target thermal cycling conditions. The RMSD parameter can characterize conductance signatures effectively. It also was demonstrated that RMSD can be used to quantify the fatigue of the PZT integration system, although RMSD is used primarily as a damage index in monitoring structural health.« less

Performance and Reliability of Bonded Interfaces for High-temperature Packaging: Annual Progress Report

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

DeVoto, Douglas J.

2017-10-19

As maximum device temperatures approach 200 °Celsius, continuous operation, sintered silver materials promise to maintain bonds at these high temperatures without excessive degradation rates. A detailed characterization of the thermal performance and reliability of sintered silver materials and processes has been initiated for the next year. Future steps in crack modeling include efforts to simulate crack propagation directly using the extended finite element method (X-FEM), a numerical technique that uses the partition of unity method for modeling discontinuities such as cracks in a system.

Influence of laboratory degradation methods and bonding application parameters on microTBS of self-etch adhesives to dentin.

PubMed

Erhardt, Maria Carolina G; Pisani-Proença, Jatyr; Osorio, Estrella; Aguilera, Fátima S; Toledano, Manuel; Osorio, Raquel

2011-04-01

To evaluate the laboratory resistance to degradation and the use of different bonding treatments on resin-dentin bonds formed with three self-etching adhesive systems. Flat, mid-coronal dentin surfaces from extracted human molars were bonded according to manufacturer's directions and submitted to two challenging regimens: (A) chemical degradation with 10% NaOC1 immersion for 5 hours; and (B) fatigue loading at 90 N using 50,000 cycles at 3.0 Hz. Additional dentin surfaces were bonded following four different bonding application protocols: (1) according to manufacturer's directions; (2) acid-etched with 36% phosphoric acid (H3PO4) for 15 seconds; (3) 10% sodium hypochlorite (NaOClaq) treated for 2 minutes, after H3PO4-etching; and (4) doubling the application time of the adhesives. Two one-step self-etch adhesives (an acetone-based: Futurabond/FUT and an ethanol-based: Futurabond NR/FNR) and a two-step self-etch primer system (Clearfil SE Bond/CSE) were examined. Specimens were sectioned into beams and tested for microtensile bond strength (microTBS). Selected debonded specimens were observed under scanning electron microscopy (SEM). Data (MPa) were analyzed by ANOVA and multiple comparisons tests (alpha= 0.05). microTBS significantly decreased after chemical and mechanical challenges (P< 0.05). CSE showed higher microTBS than the other adhesive systems, regardless the bonding protocol. FUT attained the highest microTBS after doubling the application time. H3PO4 and H3PO4 + NaOCl pretreatments significantly decreased bonding efficacy of the adhesives.

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.

Theoretical studies on the unimolecular decomposition of ethylene glycol.

PubMed

Ye, Lili; Zhao, Long; Zhang, Lidong; Qi, Fei

2012-01-12

The unimolecular decomposition processes of ethylene glycol have been investigated with the QCISD(T) method with geometries optimized at the B3LYP/6-311++G(d,p) level. Among the decomposition channels identified, the H(2)O-elimination channels have the lowest barriers, and the C-C bond dissociation is the lowest-energy dissociation channel among the barrierless reactions (the direct bond cleavage reactions). The temperature and pressure dependent rate constant calculations show that the H(2)O-elimination reactions are predominant at low temperature, whereas at high temperature, the direct C-C bond dissociation reaction is dominant. At 1 atm, in the temperature range 500-2000 K, the calculated rate constant is expressed to be 7.63 × 10(47)T(-10.38) exp(-42262/T) for the channel CH(2)OHCH(2)OH → CH(2)CHOH + H(2)O, and 2.48 × 10(51)T(-11.58) exp(-43593/T) for the channel CH(2)OHCH(2)OH → CH(3)CHO + H(2)O, whereas for the direct bond dissociation reaction CH(2)OHCH(2)OH → CH(2)OH + CH(2)OH the rate constant expression is 1.04 × 10(71)T(-16.16) exp(-52414/T).

Regioselective synthesis of C3 alkylated and arylated benzothiophenes

PubMed Central

Shrives, Harry J.; Fernández-Salas, José A.; Hedtke, Christin; Pulis, Alexander P.; Procter, David J.

2017-01-01

Benzothiophenes are heterocyclic constituents of important molecules relevant to society, including those with the potential to meet modern medical challenges. The construction of molecules would be vastly more efficient if carbon–hydrogen bonds, found in all organic molecules, can be directly converted into carbon–carbon bonds. In the case of elaborating benzothiophenes, functionalization of carbon–hydrogen bonds at carbon-number 3 (C3) is markedly more demanding than at C2 due to issues of regioselectivity (C3 versus C2), and the requirement of high temperatures, precious metals and the installation of superfluous directing groups. Herein, we demonstrate that synthetically unexplored but readily accessible benzothiophene S-oxides serve as novel precursors for C3-functionalized benzothiophenes. Employing an interrupted Pummerer reaction to capture and then deliver phenol and silane coupling partners, we have discovered a directing group-free method that delivers C3-arylated and -alkylated benzothiophenes with complete regioselectivity, under metal-free and mild conditions. PMID:28317882

31 CFR 359.1 - What regulations govern Series I savings bonds?

Code of Federal Regulations, 2010 CFR

2010-07-01

... been converted to book-entry bonds through New Treasury Direct. (b) The regulations in 31 CFR part 363 apply to: (1) book-entry Series I savings bonds that were originally issued as book-entry bonds in New Treasury Direct; and (2) definitive Series I savings bonds that have been converted to book-entry bonds...

31 CFR 351.1 - What regulations govern Series EE savings bonds?

Code of Federal Regulations, 2010 CFR

2010-07-01

... been converted to book-entry bonds through New Treasury Direct. (b) The regulations in 31 CFR part 363 apply to: (1) book-entry Series EE savings bonds that were originally issued as book-entry bonds in New Treasury Direct; and (2) definitive Series EE savings bonds that have been converted to book-entry bonds...

A single molecule assay to probe monovalent and multivalent bonds between hyaluronan and its key leukocyte receptor CD44 under force

NASA Astrophysics Data System (ADS)

Bano, Fouzia; Banerji, Suneale; Howarth, Mark; Jackson, David G.; Richter, Ralf P.

2016-09-01

Glycosaminoglycans (GAGs), a category of linear, anionic polysaccharides, are ubiquitous in the extracellular space, and important extrinsic regulators of cell function. Despite the recognized significance of mechanical stimuli in cellular communication, however, only few single molecule methods are currently available to study how monovalent and multivalent GAG·protein bonds respond to directed mechanical forces. Here, we have devised such a method, by combining purpose-designed surfaces that afford immobilization of GAGs and receptors at controlled nanoscale organizations with single molecule force spectroscopy (SMFS). We apply the method to study the interaction of the GAG polymer hyaluronan (HA) with CD44, its receptor in vascular endothelium. Individual bonds between HA and CD44 are remarkably resistant to rupture under force in comparison to their low binding affinity. Multiple bonds along a single HA chain rupture sequentially and independently under load. We also demonstrate how strong non-covalent bonds, which are versatile for controlled protein and GAG immobilization, can be effectively used as molecular anchors in SMFS. We thus establish a versatile method for analyzing the nanomechanics of GAG·protein interactions at the level of single GAG chains, which provides new molecular-level insight into the role of mechanical forces in the assembly and function of GAG-rich extracellular matrices.

Palladium-Catalyzed Transannular C–H Functionalization of Alicyclic Amines

PubMed Central

Saper, Noam I.; Sanford, Melanie S.

2016-01-01

The discovery of pharmaceutical candidates is a resource-intensive enterprise that frequently requires the parallel synthesis of hundreds or even thousands of molecules. Carbon-hydrogen bonds are present in almost all pharmaceutical agents. As such, the development of selective, rapid, and efficient methods for converting carbon-hydrogen bonds into new chemical entities has the potential to dramatically streamline pharmaceutical development1,2,3,4. Saturated nitrogen-containing heterocycles (alicyclic amines) feature prominently in pharmaceuticals, including treatments for depression (paroxetine, amitifadine), diabetes (gliclazide), leukemia (alvocidib), schizophrenia (risperidone, belaperidone), and nicotine addiction (cytisine and varenicline)5. However, existing methods for the C–H functionalization of saturated nitrogen heterocycles, particularly at sites remote to nitrogen, remain extremely limited 6,7. Here we report a new approach to selectively manipulate the carbon–hydrogen bonds of alicyclic amines at sites remote to nitrogen. Our reaction leverages the boat conformation of the substrates to achieve the palladium-catalyzed amine-directed conversion of C–H bonds to C–C bonds on various alicyclic amine scaffolds. This approach is applied to the synthesis of novel derivatives of several bioactive molecules, including the top-selling smoking cessation drug varenicline (Chantix®). We anticipate that this method should prove broadly useful in medicinal chemistry. PMID:26886789

31 CFR 315.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2013 CFR

2013-07-01

... book-entry bonds through New Treasury Direct, an online system for holding Treasury securities. The Web... definitive savings bonds should follow online instructions for conversion. Regulations governing converted...

31 CFR 315.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2012 CFR

2012-07-01

... book-entry bonds through New Treasury Direct, an online system for holding Treasury securities. The Web... definitive savings bonds should follow online instructions for conversion. Regulations governing converted...

31 CFR 315.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2014 CFR

2014-07-01

... book-entry bonds through New Treasury Direct, an online system for holding Treasury securities. The Web... definitive savings bonds should follow online instructions for conversion. Regulations governing converted...

31 CFR 353.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2012 CFR

2012-07-01

... New Treasury Direct, an online system for holding Treasury securities. The Web address for New... bonds should follow online instructions for conversion. Regulations governing converted bonds are found...

31 CFR 353.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2010 CFR

2010-07-01

... New Treasury Direct, an online system for holding Treasury securities. The Web address for New... bonds should follow online instructions for conversion. Regulations governing converted bonds are found...

31 CFR 353.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2013 CFR

2013-07-01

... New Treasury Direct, an online system for holding Treasury securities. The Web address for New... bonds should follow online instructions for conversion. Regulations governing converted bonds are found...

Influence of surface treatment on shear bond strength of orthodontic brackets.

PubMed

Brunharo, Ione Helena Vieira Portella; Fernandes, Daniel Jogaib; de Miranda, Mauro Sayão; Artese, Flavia

2013-01-01

The shear bond strength of orthodontic brackets bonded to micro-hybrid and micro-particulate resins under different surface treatment methods was assessed. Two hundred and eighty test samples were divided into 28 groups (n = 10), where 140 specimens were filled with Durafill micro-particulate resin and 140 with Charisma composite. In 140 samples, a coupling agent (silane) was applied. The surface treatment methods were: Phosphoric and hydrofluoric acid etching, sodium bicarbonate and aluminum oxide blasting, stone and burs. A Universal Instron Machine was used to apply an occlusal shear force directly to the resin composite bracket surface at a speed of 0.5 mm/min. The means were compared using analysis of variance and multivariate regression to assess the interaction between composites and surface treatment methods. Means and standard deviations for the groups were: Sodium bicarbonate jet 11.27 ± 2.78; burs 9.26 ± 3.01; stone 7.95 ± 3.67; aluminum oxide blasting 7.04 ± 3.21; phosphoric acid 5.82 ± 1.90; hydrofluoric acid 4.54 ± 2.87, and without treatment 2.75 ± 1.49. An increase of 1.94 MPa in shear bond strength was seen in Charisma groups. Silane agent application reduced the Charisma shear bond strength by 0.68 Mpa, but increased Durafill means for bicarbonate blasting (0.83), burs (0.98) and stone drilling (0.46). The sodium bicarbonate blasting, burs and stone drilling methods produced adequate shear bond strength and may be suitable for clinical use. The Charisma micro hybrid resin composite showed higher shear bond means than Durafill micro particle composite.

Experimental Exploration of Metal Cable as Reinforcement in 3D Printed Concrete.

PubMed

Bos, Freek P; Ahmed, Zeeshan Y; Jutinov, Evgeniy R; Salet, Theo A M

2017-11-16

The Material Deposition Method (MDM) is enjoying increasing attention as an additive method to create concrete mortar structures characterised by a high degree of form-freedom, a lack of geometrical repetition, and automated construction. Several small-scale structures have been realised around the world, or are under preparation. However, the nature of this construction method is unsuitable for conventional reinforcement methods to achieve ductile failure behaviour. Sometimes, this is solved by combining printing with conventional casting and reinforcing techniques. This study, however, explores an alternative strategy, namely to directly entrain a metal cable in the concrete filament during printing to serve as reinforcement. A device is introduced to apply the reinforcement. Several options for online reinforcement media are compared for printability. Considerations specific to the manufacturing process are discussed. Subsequently, pull-out tests on cast and printed specimens provide an initial characterisation of bond behaviour. Bending tests furthermore show the potential of this reinforcement method. The bond stress of cables in printed concrete was comparable to values reported for smooth rebar but lower than that of the same cables in cast concrete. The scatter in experimental results was high. When sufficient bond length is available, ductile failure behaviour for tension parallel to the filament direction can be achieved, even though cable slip occurs. Further improvements to the process should pave the way to achieve better post-crack resistance, as the concept in itself is feasible.

Effect of annealing procedure on the bonding of ceramic to cobalt-chromium alloys fabricated by rapid prototyping.

PubMed

Tulga, Ayca

2018-04-01

An annealing procedure is a heat treatment process to improve the mechanical properties of cobalt-chromium (Co-Cr) alloys. However, information is lacking about the effect of the annealing process on the bonding ability of ceramic to Co-Cr alloys fabricated by rapid prototyping. The purpose of this in vitro study was to evaluate the effects of the fabrication techniques and the annealing procedure on the shear bond strength of ceramic to Co-Cr alloys fabricated by different techniques. Ninety-six cylindrical specimens (10-mm diameter, 10-mm height) made of Co-Cr alloy were prepared by casting (C), milling (M), direct process powder-bed (LaserCUSING) with and without annealing (CL+, CL), and direct metal laser sintering (DMLS) with annealing (EL+) and without annealing (EL). After the application of ceramic to the metal specimens, the metal-ceramic bond strength was assessed using a shear force test at a crosshead speed of 0.5 mm/min. Shear bond strength values were statistically analyzed by 1-way ANOVA and Tukey multiple comparison tests (α=.05). Although statistically significant differences were found among the 3 groups (M, 29.87 ±2.06; EL, 38.92 ±2.04; and CL+, 40.93 ±2.21; P=.002), no significant differences were found among the others (P>.05). The debonding surfaces of all specimens exhibited mixed failure mode. These results showed that the direct process powder-bed method is promising in terms of metal-ceramic bonding ability. The manufacturing technique of Co-Cr alloys and the annealing process influence metal-ceramic bonding. Copyright © 2017 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Bidentate, monoanionic auxiliary-directed functionalization of carbon-hydrogen bonds.

PubMed

Daugulis, Olafs; Roane, James; Tran, Ly Dieu

2015-04-21

In recent years, carbon-hydrogen bond functionalization has evolved from an organometallic curiosity to a tool used in mainstream applications in the synthesis of complex natural products and drugs. The use of C-H bonds as a transformable functional group is advantageous because these bonds are the most abundant functionality in organic molecules. One-step conversion of these bonds to the desired functionality shortens synthetic pathways, saving reagents, solvents, and labor. Less chemical waste is generated as well, showing that this chemistry is environmentally beneficial. This Account describes the development and use of bidentate, monoanionic auxiliaries for transition-metal-catalyzed C-H bond functionalization reactions. The chemistry was initially developed to overcome the limitations with palladium-catalyzed C-H bond functionalization assisted by monodentate directing groups. By the use of electron-rich bidentate directing groups, functionalization of unactivated sp(3) C-H bonds under palladium catalysis has been developed. Furthermore, a number of abundant base-metal complexes catalyze functionalization of sp(2) C-H bonds. At this point, aminoquinoline, picolinic acid, and related compounds are among the most used and versatile directing moieties in C-H bond functionalization chemistry. These groups facilitate catalytic functionalization of sp(2) and sp(3) C-H bonds by iron, cobalt, nickel, copper, ruthenium, rhodium, and palladium complexes. Exceptionally general reactivity is observed, enabling, among other transformations, direct arylation, alkylation, fluorination, sulfenylation, amination, etherification, carbonylation, and alkenylation of carbon-hydrogen bonds. The versatility of these auxilaries can be attributed to the following factors. First, they are capable of stabilizing high oxidation states of transition metals, thereby facilitating the C-H bond functionalization step. Second, the directing groups can be removed, enabling their use in synthesis and functionalization of natural products and medicinally relevant substances. While the development of these directing groups presents a significant advance, several limitations of this methodology are apparent. The use of expensive second-row transition metal catalysts is still required for efficient sp(3) C-H bond functionalization. Furthermore, the need to install and subsequently remove the relatively expensive directing group is a disadvantage.

Bidentate, Monoanionic Auxiliary-Directed Functionalization of Carbon–Hydrogen Bonds

PubMed Central

Daugulis, Olafs; Roane, James; Tran, Ly Dieu

2015-01-01

CONSPECTUS In recent years, carbon–hydrogen bond functionalization has evolved from an organometallic curiosity to mainstream applications in the synthesis of complex natural products and drugs. The use of C–H bonds as a transformable functional group is advantageous because these bonds are the most abundant functionality in organic molecules. One-step conversion of these bonds to the desired functionality shortens synthetic pathways, saving reagents, solvents, and labor. Less chemical waste is generated as well, showing that this chemistry is environmentally beneficial. This Account describes the development and use of bidentate, monoanionic auxiliaries for transition-metal-catalyzed C–H bond functionalization reactions. The chemistry was initially developed to overcome the limitations with palladium-catalyzed C–H bond functionalization assisted by monodentate directing groups. By the use of electron-rich bidentate directing groups, functionalization of unactivated sp3 C–H bonds under palladium catalysis has been developed. Furthermore, a number of abundant base-metal complexes catalyze functionalization of sp2 C–H bonds. At this point, aminoquinoline, picolinic acid, and related compounds are among the most used and versatile directing moieties in C–H bond functionalization chemistry. These groups facilitate catalytic functionalization of sp2 and sp3 C–H bonds by iron, cobalt, nickel, copper, ruthenium, rhodium, and palladium complexes. Exceptionally general reactivity is observed, enabling, among other transformations, direct arylation, alkylation, fluorination, sulfenylation, amination, etherification, carbonylation, and alkenylation of carbon–hydrogen bonds. The versatility of these auxilaries can be attributed to the following factors. First, they are capable of stabilizing high oxidation states of transition metals, thereby facilitating the C–H bond functionalization step. Second, the directing groups can be removed, enabling their use in synthesis and functionalization of natural products and medicinally relevant substances. While the development of these directing groups presents a significant advance, several limitations of this methodology are apparent. The use of expensive second-row transition metal catalysts is still required for efficient sp3 C–H bond functionalization. Furthermore, a disadvantage is the need to install and subsequently remove the relatively expensive directing group. PMID:25756616

31 CFR 360.3 - Converting definitive savings bonds to book-entry bonds in New Treasury Direct.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Treasury Direct, an online system for holding Treasury securities. The Web address for New Treasury Direct... follow online instructions for conversion. Regulations governing converted bonds are found at 31 CFR part...

The ReaxFF reactive force-field: Development, applications, and future directions

DOE PAGES

Senftle, Thomas; Hong, Sungwook; Islam, Md Mahbubul; ...

2016-03-04

The reactive force-field (ReaxFF) interatomic potential is a powerful computational tool for exploring, developing and optimizing material properties. Methods based on the principles of quantum mechanics (QM), while offering valuable theoretical guidance at the electronic level, are often too computationally intense for simulations that consider the full dynamic evolution of a system. Alternatively, empirical interatomic potentials that are based on classical principles require significantly fewer computational resources, which enables simulations to better describe dynamic processes over longer timeframes and on larger scales. Such methods, however, typically require a predefined connectivity between atoms, precluding simulations that involve reactive events. The ReaxFFmore » method was developed to help bridge this gap. Approaching the gap from the classical side, ReaxFF casts the empirical interatomic potential within a bond-order formalism, thus implicitly describing chemical bonding without expensive QM calculations. As a result, this article provides an overview of the development, application, and future directions of the ReaxFF method.« less

Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments.

PubMed

Zhu, Tianyu; de Silva, Piotr; Van Voorhis, Troy

2018-01-09

Chemical bonding plays a central role in the description and understanding of chemistry. Many methods have been proposed to extract information about bonding from quantum chemical calculations, the majority of them resorting to molecular orbitals as basic descriptors. Here, we present a method called self-attractive Hartree (SAH) decomposition to unravel pairs of electrons directly from the electron density, which unlike molecular orbitals is a well-defined observable that can be accessed experimentally. The key idea is to partition the density into a sum of one-electron fragments that simultaneously maximize the self-repulsion and maintain regular shapes. This leads to a set of rather unusual equations in which every electron experiences self-attractive Hartree potential in addition to an external potential common for all the electrons. The resulting symmetry breaking and localization are surprisingly consistent with chemical intuition. SAH decomposition is also shown to be effective in visualization of single/multiple bonds, lone pairs, and unusual bonds due to the smooth nature of fragment densities. Furthermore, we demonstrate that it can be used to identify specific chemical bonds in molecular complexes and provides a simple and accurate electrostatic model of hydrogen bonding.

31 CFR 353.3 - Converting definitive savings bonds to book-entry bonds in TreasuryDirect®.

Code of Federal Regulations, 2014 CFR

2014-07-01

... TreasuryDirect®, an online system for holding Treasury securities. The Web address for TreasuryDirect® is... follow online instructions for conversion. Regulations governing converted bonds are found at 31 CFR part...

Bond Strength of Composite CFRP Reinforcing Bars in Timber

PubMed Central

Corradi, Marco; Righetti, Luca; Borri, Antonio

2015-01-01

The use of near-surface mounted (NSM) fibre-reinforced polymer (FRP) bars is an interesting method for increasing the shear and flexural strength of existing timber members. This article examines the behaviour of carbon FRP (CFRP) bars in timber under direct pull-out conditions. The objective of this experimental program is to investigate the bond strength between composite bars and timber: bars were epoxied into small notches made into chestnut and fir wood members using a commercially-available epoxy system. Bonded lengths varied from 150 to 300 mm. Failure modes, stress and strain distributions and the bond strength of CFRP bars have been evaluated and discussed. The pull-out capacity in NSM CFRP bars at the onset of debonding increased with bonded length up to a length of 250 mm. While CFRP bar’s pull-out was achieved only for specimens with bonded lengths of 150 and 200 mm, bar tensile failure was mainly recorded for bonded lengths of 250 and 300 mm. PMID:28793423

Solid-phase materials for chelating metal ions and methods of making and using same

DOEpatents

Harrup, Mason K.; Wey, John E.; Peterson, Eric S.

2003-06-10

A solid material for recovering metal ions from aqueous streams, and methods of making and using the solid material, are disclosed. The solid material is made by covalently bonding a chelating agent to a silica-based solid, or in-situ condensing ceramic precursors along with the chelating agent to accomplish the covalent bonding. The chelating agent preferably comprises a oxime type chelating head, preferably a salicylaldoxime-type molecule, with an organic tail covalently bonded to the head. The hydrocarbon tail includes a carbon-carbon double bond, which is instrumental in the step of covalently bonding the tail to the silica-based solid or the in-situ condensation. The invented solid material may be contacted directly with aqueous streams containing metal ions, and is selective to ions such as copper (II) even in the presence of such ions as iron (III) and other materials that are present in earthen materials. The solid material with high selectivity to copper may be used to recover copper from mining and plating industry streams, to replace the costly and toxic solvent extraction steps of conventional copper processing.

The direct arylation of allylic sp3 C-H bonds via organic and photoredox catalysis

NASA Astrophysics Data System (ADS)

Cuthbertson, James D.; MacMillan, David W. C.

2015-03-01

The direct functionalization of unactivated sp3 C-H bonds is still one of the most challenging problems facing synthetic organic chemists. The appeal of such transformations derives from their capacity to facilitate the construction of complex organic molecules via the coupling of simple and otherwise inert building blocks, without introducing extraneous functional groups. Despite notable recent efforts, the establishment of general and mild strategies for the engagement of sp3 C-H bonds in C-C bond forming reactions has proved difficult. Within this context, the discovery of chemical transformations that are able to directly functionalize allylic methyl, methylene and methine carbons in a catalytic manner is a priority. Although protocols for direct oxidation and amination of allylic C-H bonds (that is, C-H bonds where an adjacent carbon is involved in a C = C bond) have become widely established, the engagement of allylic substrates in C-C bond forming reactions has thus far required the use of pre-functionalized coupling partners. In particular, the direct arylation of non-functionalized allylic systems would enable access to a series of known pharmacophores (molecular features responsible for a drug's action), though a general solution to this long-standing challenge remains elusive. Here we report the use of both photoredox and organic catalysis to accomplish a mild, broadly effective direct allylic C-H arylation. This C-C bond forming reaction readily accommodates a broad range of alkene and electron-deficient arene reactants, and has been used in the direct arylation of benzylic C-H bonds.

The direct arylation of allylic sp(3) C-H bonds via organic and photoredox catalysis.

PubMed

Cuthbertson, James D; MacMillan, David W C

2015-03-05

The direct functionalization of unactivated sp(3) C-H bonds is still one of the most challenging problems facing synthetic organic chemists. The appeal of such transformations derives from their capacity to facilitate the construction of complex organic molecules via the coupling of simple and otherwise inert building blocks, without introducing extraneous functional groups. Despite notable recent efforts, the establishment of general and mild strategies for the engagement of sp(3) C-H bonds in C-C bond forming reactions has proved difficult. Within this context, the discovery of chemical transformations that are able to directly functionalize allylic methyl, methylene and methine carbons in a catalytic manner is a priority. Although protocols for direct oxidation and amination of allylic C-H bonds (that is, C-H bonds where an adjacent carbon is involved in a C = C bond) have become widely established, the engagement of allylic substrates in C-C bond forming reactions has thus far required the use of pre-functionalized coupling partners. In particular, the direct arylation of non-functionalized allylic systems would enable access to a series of known pharmacophores (molecular features responsible for a drug's action), though a general solution to this long-standing challenge remains elusive. Here we report the use of both photoredox and organic catalysis to accomplish a mild, broadly effective direct allylic C-H arylation. This C-C bond forming reaction readily accommodates a broad range of alkene and electron-deficient arene reactants, and has been used in the direct arylation of benzylic C-H bonds.

Reactive polymer fused deposition manufacturing

DOEpatents

Kunc, Vlastimil; Rios, Orlando; Love, Lonnie J.; Duty, Chad E.; Johs, Alexander

2017-05-16

Methods and compositions for additive manufacturing that include reactive or thermosetting polymers, such as urethanes and epoxies. The polymers are melted, partially cross-linked prior to the depositing, deposited to form a component object, solidified, and fully cross-linked. These polymers form networks of chemical bonds that span the deposited layers. Application of a directional electromagnetic field can be applied to aromatic polymers after deposition to align the polymers for improved bonding between the deposited layers.

Repulsive tip tilting as the dominant mechanism for hydrogen bond-like features in atomic force microscopy imaging

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

Lee, Alex J.; Sakai, Yuki; Kim, Minjung

2016-05-09

Experimental atomic force microscopy (AFM) studies have reported distinct features in regions with little electron density for various organic systems. These unexpected features have been proposed to be a direct visualization of intermolecular hydrogen bonding. Here, we apply a computational method using ab initio real-space pseudopotentials along with a scheme to account for tip tilting to simulate AFM images of the 8-hydroxyquinoline dimer and related systems to develop an understanding of the imaging mechanism for hydrogen bonds. We find that contrast for the observed “hydrogen bond” feature comes not from the electrostatic character of the bonds themselves but rather frommore » repulsive tip tilting induced by neighboring electron-rich atoms.« less

Method for fabricating laminated uranium composites

DOEpatents

Chapman, L.R.

1983-08-03

The present invention is directed to a process for fabricating laminated composites of uranium or uranium alloys and at least one other metal or alloy. The laminated composites are fabricated by forming a casting of the molten uranium with the other metal or alloy which is selectively positioned in the casting and then hot-rolling the casting into a laminated plate in or around which the casting components are metallurgically bonded to one another to form the composite. The process of the present invention provides strong metallurgical bonds between the laminate components primarily since the bond disrupting surface oxides on the uranium or uranium alloy float to the surface of the casting to effectively remove the oxides from the bonding surfaces of the components.

Smart patch integration development of compression connector structural health monitoring in overhead transmission lines

NASA Astrophysics Data System (ADS)

Wang, Hong; Wang, Jy-An J.; Ren, Fei; Chan, John

2016-04-01

Integration of smart patches into full-tension splice connectors in overhead power transmission lines was investigated. Lead zirconate titanate (PZT) -5A was used as a smart material and an aluminum beam was used as a host structure. Negative electrode termination was examined by using copper adhesive tape and direct bonding methods. Various commercial adhesives were studied for PZT integration onto the host structure. Aluminum beam specimens with integrated PZT smart patches were tested under thermal cycling at a temperature of 125°C, which is the higher-end temperature experienced by in-service aluminum conductor steel-reinforced cables. Electromechanical impedance (EMI) measurements were conducted at room temperature, and the root mean square deviation (RMSD) of the conductance signals was used to analyze the EMI data. It has been shown that the negative electrode method has an important effect on the performance of the integrated PZT. The PZT displayed more susceptibility to cracking when copper tape was used than when direct bonding was used. The reliability of PZT in direct bonding depended on the adhesives used in bonding layers. Although a hard alumina-based adhesive can lead to cracking of the PZT, a high-temperature epoxy with adequate flexibility, such as Duralco 4538D, can provide the desired performance under target thermal cycling conditions. The RMSD parameter can characterize conductance signatures effectively. It also was demonstrated that RMSD can be used to quantify the fatigue of the PZT integration system, although RMSD is used primarily as a damage index in monitoring structural health.

Direct-write 3D printing of NdFeB bonded magnets

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

Compton, Brett Gibson; Kemp, James William; Novikov, Timofei V.

We report a method to fabricate Nd-Fe-B bonded magnets of complex shape via extrusion-based additive manufacturing (AM), also known as 3D-printing. We have successfully formulated a 3D-printable epoxy-based ink for direct-write AM with anisotropic MQA NdFeB magnet particles that can be deposited at room temperature. The new feedstocks contain up to 40 vol.% MQA anisotropic Nd-Fe-B magnet particles, and they are shown to remain uniformly dispersed in the thermoset matrix throughout the deposition process. Ring, bar, and horseshoe-type 3D magnet structures were printed and cured in air at 100°C without degrading the magnetic properties. Lastly, this study provides a newmore » pathway for fabricating Nd-Fe-B bonded magnets with complex geometry at low temperature, and presents new opportunities for fabricating multifunctional hybrid structures and devices.« less

Direct-write 3D printing of NdFeB bonded magnets

DOE PAGES

Compton, Brett Gibson; Kemp, James William; Novikov, Timofei V.; ...

2016-08-17

We report a method to fabricate Nd-Fe-B bonded magnets of complex shape via extrusion-based additive manufacturing (AM), also known as 3D-printing. We have successfully formulated a 3D-printable epoxy-based ink for direct-write AM with anisotropic MQA NdFeB magnet particles that can be deposited at room temperature. The new feedstocks contain up to 40 vol.% MQA anisotropic Nd-Fe-B magnet particles, and they are shown to remain uniformly dispersed in the thermoset matrix throughout the deposition process. Ring, bar, and horseshoe-type 3D magnet structures were printed and cured in air at 100°C without degrading the magnetic properties. Lastly, this study provides a newmore » pathway for fabricating Nd-Fe-B bonded magnets with complex geometry at low temperature, and presents new opportunities for fabricating multifunctional hybrid structures and devices.« less

3D simulation of friction stir welding based on movable cellular automaton method

NASA Astrophysics Data System (ADS)

Eremina, Galina M.

2017-12-01

The paper is devoted to a 3D computer simulation of the peculiarities of material flow taking place in friction stir welding (FSW). The simulation was performed by the movable cellular automaton (MCA) method, which is a representative of particle methods in mechanics. Commonly, the flow of material in FSW is simulated based on computational fluid mechanics, assuming the material as continuum and ignoring its structure. The MCA method considers a material as an ensemble of bonded particles. The rupture of interparticle bonds and the formation of new bonds enable simulations of crack nucleation and healing as well as mas mixing and microwelding. The simulation results showed that using pins of simple shape (cylinder, cone, and pyramid) without a shoulder results in small displacements of plasticized material in workpiece thickness directions. Nevertheless, the optimal ratio of longitudinal velocity to rotational speed makes it possible to transport the welded material around the pin several times and to produce a joint of good quality.

Chemical bond activation observed with an x-ray laser

DOE PAGES

Beye, Martin; Öberg, Henrik; Xin, Hongliang; ...

2016-09-01

The concept of bonding and anti-bonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Lastly, we apply time-resolved soft X-ray spectroscopy at a free-electron laser to directly observe the decreased bonding–anti-bonding splitting following bond-activation using an ultra short optical laser pulse.

An Ultrasonic Guided Wave Method to Estimate Applied Biaxial Loads (Preprint)

DTIC Science & Technology

2011-11-01

VALIDATION A fatigue test was performed with an array of six surface-bonded PZT transducers on a 6061 aluminum plate as shown in Figure 4. The specimen...direct paths of propagation are oriented at different angles. This method is applied to experimental sparse array data recorded during a fatigue test...and the additional complication of the resulting fatigue cracks interfering with some of the direct arrivals is addressed via proper selection of

A Unified Theory for the Blue- and Red-Shifting Phenomena in Hydrogen and Halogen Bonds.

PubMed

Wang, Changwei; Danovich, David; Shaik, Sason; Mo, Yirong

2017-04-11

Typical hydrogen and halogen bonds exhibit red-shifts of their vibrational frequencies upon the formation of hydrogen and halogen bonding complexes (denoted as D···Y-A, Y = H and X). The finding of blue-shifts in certain complexes is of significant interest, which has led to numerous studies of the origins of the phenomenon. Because charge transfer mixing (i.e., hyperconjugation in bonding systems) has been regarded as one of the key forces, it would be illuminating to compare the structures and vibrational frequencies in bonding complexes with the charge transfer effect "turned on" and "turned off". Turning off the charge transfer mixing can be achieved by employing the block-localized wave function (BLW) method, which is an ab initio valence bond (VB) method. Further, with the BLW method, the overall stability gained in the formation of a complex can be analyzed in terms of a few physically meaningful terms. Thus, the BLW method provides a unified and physically lucid way to explore the nature of red- and blue-shifting phenomena in both hydrogen and halogen bonding complexes. In this study, a direct correlation between the total stability and the variation of the Y-A bond length is established based on our BLW computations, and the consistent roles of all energy components are clarified. The n(D) → σ*(Y-A) electron transfer stretches the Y-A bond, while the polarization due to the approach of interacting moieties reduces the HOMO-LUMO gap and results in a stronger orbital mixing within the YA monomer. As a consequence, both the charge transfer and polarization stabilize bonding systems with the Y-A bond stretched and red-shift the vibrational frequency of the Y-A bond. Notably, the energy of the frozen wave function is the only energy component which prefers the shrinking of the Y-A bond and thus is responsible for the associated blue-shifting. The total variations of the Y-A bond length and the corresponding stretching vibrational frequency are thus determined by the competition between the frozen-energy term and the sum of polarization and charge transfer energy terms. Because the frozen energy is composed of electrostatic and Pauli exchange interactions and frequency shifting is a long-range phenomenon, we conclude that long-range electrostatic interaction is the driving force behind the frozen energy term.

Direct Acylation of C(sp(3))-H Bonds Enabled by Nickel and Photoredox Catalysis.

PubMed

Joe, Candice L; Doyle, Abigail G

2016-03-14

Using nickel and photoredox catalysis, the direct functionalization of C(sp(3))-H bonds of N-aryl amines by acyl electrophiles is described. The method affords a diverse range of α-amino ketones at room temperature and is amenable to late-stage coupling of complex and biologically relevant groups. C(sp(3))-H activation occurs by photoredox-mediated oxidation to generate α-amino radicals which are intercepted by nickel in catalytic C(sp(3))-C coupling. The merger of these two modes of catalysis leverages nickel's unique properties in alkyl cross-coupling while avoiding limitations commonly associated with transition-metal-mediated C(sp(3))-H activation, including requirements for chelating directing groups and high reaction temperatures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence against Stable Protein S-Nitrosylation as a Widespread Mechanism of Post-translational Regulation.

PubMed

Wolhuter, Kathryn; Whitwell, Harry J; Switzer, Christopher H; Burgoyne, Joseph R; Timms, John F; Eaton, Philip

2018-02-01

S-nitrosation, commonly referred to as S-nitrosylation, is widely regarded as a ubiquitous, stable post-translational modification that directly regulates many proteins. Such a widespread role would appear to be incompatible with the inherent lability of the S-nitroso bond, especially its propensity to rapidly react with thiols to generate disulfide bonds. As anticipated, we observed robust and widespread protein S-nitrosation after exposing cells to nitrosocysteine or lipopolysaccharide. Proteins detected using the ascorbate-dependent biotin switch method are typically interpreted to be directly regulated by S-nitrosation. However, these S-nitrosated proteins are shown to predominantly comprise transient intermediates leading to disulfide bond formation. These disulfides are likely to be the dominant end effectors resulting from elevations in nitrosating cellular nitric oxide species. We propose that S-nitrosation primarily serves as a transient intermediate leading to disulfide formation. Overall, we conclude that the current widely held perception that stable S-nitrosation directly regulates the function of many proteins is significantly incorrect. Copyright © 2017 The Author(s). Published by Elsevier Inc. All rights reserved.

Effect of ultrasonic agitation on push-out bond strength and adaptation of root-end filling materials

PubMed Central

2018-01-01

Objectives This study evaluated the effect of ultrasonic agitation of mineral trioxide aggregate (MTA), calcium silicate-based cement (CSC), and Sealer 26 (S26) on adaptation at the cement/dentin interface and push-out bond strength. Materials and Methods Sixty maxillary canines were divided into 6 groups (n = 10): MTA, S26, and CSC, with or without ultrasonic activation (US). After obturation, the apical portions of the teeth were sectioned, and retrograde cavities were prepared and filled with cement by hand condensation. In the US groups, the cement was activated for 60 seconds: 30 seconds in the mesio-distal direction and 30 seconds in the buccal-lingual direction, using a mini Irrisonic insert coupled with the ultrasound transducer. After the materials set, 1.5-mm thick sections were obtained from the apexes. The presence of gaps and the bond between cement and dentin were analyzed using low-vacuum scanning electron microscopy. Push-out bond strength was measured using a universal testing machine. Results Ultrasonic agitation increased the interfacial adaptation of the cements. The S26 US group showed a higher adaptation value than MTA (p < 0.05). US improved the push-out bond strength for all the cements (p < 0.05). Conclusions The US of retrograde filling cements enhanced the bond to the dentin wall of the root-end filling materials tested. PMID:29765903

Methods of measurement for semiconductor materials, process control, and devices

NASA Technical Reports Server (NTRS)

Bullis, W. M. (Editor)

1972-01-01

Activities directed toward the development of methods of measurement for semiconductor materials, process control, and devices are described. Accomplishments include the determination of the reasons for differences in measurements of transistor delay time, identification of an energy level model for gold-doped silicon, and the finding of evidence that it does not appear to be necessary for an ultrasonic bonding tool to grip the wire and move it across the substrate metallization to make the bond. Work is continuing on measurement of resistivity of semiconductor crystals; study of gold-doped silicon; development of the infrared response technique; evaluation of wire bonds and die attachment; measurement of thermal properties of semiconductor devices, delay time, and related carrier transport properties in junction devices, and noise properties of microwave diodes; and characterization of silicon nuclear radiation detectors.

Anisotropic electrical conduction and reduction in dangling-bond density for polycrystalline Si films prepared by catalytic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Niikura, Chisato; Masuda, Atsushi; Matsumura, Hideki

1999-07-01

Polycrystalline Si (poly-Si) films with high crystalline fraction and low dangling-bond density were prepared by catalytic chemical vapor deposition (Cat-CVD), often called hot-wire CVD. Directional anisotropy in electrical conduction, probably due to structural anisotropy, was observed for Cat-CVD poly-Si films. A novel method to separately characterize both crystalline and amorphous phases in poly-Si films using anisotropic electrical conduction was proposed. On the basis of results obtained by the proposed method and electron spin resonance measurements, reduction in dangling-bond density for Cat-CVD poly-Si films was achieved using the condition to make the quality of the included amorphous phase high. The properties of Cat-CVD poly-Si films are found to be promising in solar-cell applications.

Experimental Exploration of Metal Cable as Reinforcement in 3D Printed Concrete

PubMed Central

Ahmed, Zeeshan Y.; Jutinov, Evgeniy R.; Salet, Theo A. M.

2017-01-01

The Material Deposition Method (MDM) is enjoying increasing attention as an additive method to create concrete mortar structures characterised by a high degree of form-freedom, a lack of geometrical repetition, and automated construction. Several small-scale structures have been realised around the world, or are under preparation. However, the nature of this construction method is unsuitable for conventional reinforcement methods to achieve ductile failure behaviour. Sometimes, this is solved by combining printing with conventional casting and reinforcing techniques. This study, however, explores an alternative strategy, namely to directly entrain a metal cable in the concrete filament during printing to serve as reinforcement. A device is introduced to apply the reinforcement. Several options for online reinforcement media are compared for printability. Considerations specific to the manufacturing process are discussed. Subsequently, pull-out tests on cast and printed specimens provide an initial characterisation of bond behaviour. Bending tests furthermore show the potential of this reinforcement method. The bond stress of cables in printed concrete was comparable to values reported for smooth rebar but lower than that of the same cables in cast concrete. The scatter in experimental results was high. When sufficient bond length is available, ductile failure behaviour for tension parallel to the filament direction can be achieved, even though cable slip occurs. Further improvements to the process should pave the way to achieve better post-crack resistance, as the concept in itself is feasible. PMID:29144426

Comparison of the push-out shear bond strength of four types of glass ionomers when used to bond amalgam: An in vitro study

PubMed Central

Mathew, Vinod Babu; Ramachandran, S; Indira, R; Shankar, P

2011-01-01

Background: Dental amalgam is the primary direct posterior restorative material used worldwide, but it have certain shortcomings due to the lack of adhesiveness to the cavity. The introduction of the concept of bonded amalgam helped improve the use of amalgam as a restorative material. Aim: Evaluation of the comparative push-out shear bond strength of four types of conventional glass ionomers used to bond amalgam to tooth in simulated class I situations. Materials and Methods: Four chemical cure glass ionomers are used: GC Fuji I, GC Fuji II, GC Fuji III and GC Fuji VII, and are compared with unbonded amalgam. The push-out bond strength was tested using the Instron Universal Testing Machine at a crosshead speed of 0.5 mm/min. Statistical Analysis: One-way ANOVA and post hoc Bonferroni tests were used to analyze the data. Results: The results showed that the use of glass ionomer to bond amalgam resulted in an increase in the bond strength of amalgam. The Type VII glass ionomer showed the highest bond strength in comparison with the other glass ionomers. Conclusions: Conventional glass ionomer bonds to amalgam and shows a beneficial increase in the bond strength of the restoration in comparison with unbonded amalgam. PMID:22144798

A novel dentin bond strength measurement technique using a composite disk in diametral compression.

PubMed

Huang, Shih-Hao; Lin, Lian-Shan; Rudney, Joel; Jones, Rob; Aparicio, Conrado; Lin, Chun-Pin; Fok, Alex

2012-04-01

New methods are needed that can predict the clinical failure of dental restorations that primarily rely on dentin bonding. Existing methods have shortcomings, e.g. severe deviation in the actual stress distribution from theory and a large standard deviation in the measured bond strength. We introduce here a novel test specimen by examining an endodontic model for dentin bonding. Specifically, we evaluated the feasibility of using the modified Brazilian disk test to measure the post-dentin interfacial bond strength. Four groups of resin composite disks which contained a slice of dentin with or without an intracanal post in the center were tested under diametral compression until fracture. Advanced nondestructive examination and imaging techniques in the form of acoustic emission (AE) and digital image correlation (DIC) were used innovatively to capture the fracture process in real time. DIC showed strain concentration first appearing at one of the lateral sides of the post-dentin interface. The appearance of the interfacial strain concentration also coincided with the first AE signal detected. Utilizing both the experimental data and finite-element analysis, the bond/tensile strengths were calculated to be: 11.2 MPa (fiber posts), 12.9 MPa (metal posts), 8.9 MPa (direct resin fillings) and 82.6 MPa for dentin. We have thus established the feasibility of using the composite disk in diametral compression to measure the bond strength between intracanal posts and dentin. The new method has the advantages of simpler specimen preparation, no premature failure, more consistent failure mode and smaller variations in the calculated bond strength. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Palladium- and Copper-Catalyzed Arylation of Carbon-Hydrogen Bonds

PubMed Central

Daugulis, Olafs; Do, Hien-Quang; Shabashov, Dmitry

2010-01-01

The transition-metal-catalyzed functionalization of C-H bonds is a powerful method for generating carbon-carbon bonds. Although significant advances to this field have been reported during the last decade, many challenges remain. First, most of the methods are substrate-specific and thus cannot be generalized. Second, conversions of unactivated (i.e. not benzylic or alpha to heteroatom) sp3 C–H bonds to C–C bonds are rare, with most examples limited to t-butyl groups—a conversion that is inherently simple because there are no β-hydrogens that can be eliminated. Finally, the palladium, rhodium, and ruthenium catalysts routinely used for the conversion of C–H bonds to C–C bonds are expensive. Catalytically active metals that are cheaper and less exotic (e.g. copper, iron, and manganese) are rarely used. This Account describes our attempts to provide solutions to these three problems. We have developed a general method for directing-group-containing arene arylation by aryl iodides. Using palladium acetate as the catalyst, we arylated anilides, benzamides, benzoic acids, benzylamines, and 2-substituted pyridine derivatives under nearly identical conditions. We have also developed a method for the palladium-catalyzed auxiliary-assisted arylation of unactivated sp3 C–H bonds. This procedure allows for the β-arylation of carboxylic acid derivatives and the γ-arylation of amine derivatives. Furthermore, copper catalysis can be used to mediate the arylation of acidic arene C–H bonds (i.e. those with pKa values <35 in DMSO). Using a copper iodide catalyst in combination with a base and a phenanthroline ligand, we successfully arylated electron-rich and electron-deficient heterocycles and electron-poor arenes possessing at least two electron-withdrawing groups. The reaction exhibits unusual regioselectivity: arylation occurs at the most hindered position. This copper-catalyzed method supplements the well-known C–H activation/borylation methodology, in which functionalization usually occurs at the least hindered position. We also describe preliminary investigations to determine the mechanisms of these transformations. We anticipate that other transition metals, including iron, nickel, cobalt, and silver, will also be able to facilitate deprotonation/arylation reaction sequences. PMID:19552413

Palladium- and copper-catalyzed arylation of carbon-hydrogen bonds.

PubMed

Daugulis, Olafs; Do, Hien-Quang; Shabashov, Dmitry

2009-08-18

The transition-metal-catalyzed functionalization of C-H bonds is a powerful method for generating carbon-carbon bonds. Although significant advances to this field have been reported during the past decade, many challenges remain. First, most of the methods are substrate-specific and thus cannot be generalized. Second, conversions of unactivated (i.e., not benzylic or alpha to heteroatom) sp(3) C-H bonds to C-C bonds are rare, with most examples limited to t-butyl groups, a conversion that is inherently simple because there are no beta-hydrogens that can be eliminated. Finally, the palladium, rhodium, and ruthenium catalysts routinely used for the conversion of C-H bonds to C-C bonds are expensive. Catalytically active metals that are cheaper and less exotic (e.g., copper, iron, and manganese) are rarely used. This Account describes our attempts to provide solutions to these three problems. We have developed a general method for directing-group-containing arene arylation by aryl iodides. Using palladium acetate as the catalyst, we arylated anilides, benzamides, benzoic acids, benzylamines, and 2-substituted pyridine derivatives under nearly identical conditions. We have also developed a method for the palladium-catalyzed auxiliary-assisted arylation of unactivated sp(3) C-H bonds. This procedure allows for the beta-arylation of carboxylic acid derivatives and the gamma-arylation of amine derivatives. Furthermore, copper catalysis can be used to mediate the arylation of acidic arene C-H bonds (i.e., those with pK(a) values <35 in DMSO). Using a copper iodide catalyst in combination with a base and a phenanthroline ligand, we successfully arylated electron-rich and electron-deficient heterocycles and electron-poor arenes possessing at least two electron-withdrawing groups. The reaction exhibits unusual regioselectivity: arylation occurs at the most hindered position. This copper-catalyzed method supplements the well-known C-H activation/borylation methodology, in which functionalization usually occurs at the least hindered position. We also describe preliminary investigations to determine the mechanisms of these transformations. We anticipate that other transition metals, including iron, nickel, cobalt, and silver, will also be able to facilitate deprotonation/arylation reaction sequences.

Hydrolytic degradation of the resin-dentine interface induced by the simulated pulpal pressure, direct and indirect water ageing.

PubMed

Feitosa, Victor P; Leme, Ariene A; Sauro, Salvatore; Correr-Sobrinho, Lourenço; Watson, Timothy F; Sinhoreti, Mário A; Correr, Américo B

2012-12-01

The aim of this study was to compare the hydrolytic effects induced by simulated pulpal pressure, direct or indirect water exposure within the resin-dentine interfaces created with three "simplified" resin bonding systems (RBSs). A two-step/self-etching (CSE: Clearfil SE Bond), one-step/self-etching (S3: Clearfil S3) and etch-and-rinse/self-priming (SB: Single-bond 2) adhesives were applied onto dentine and submitted to three different prolonged (6 or 12 months) ageing strategies: (i) Simulated Pulpal Pressure (SPP); (ii) Indirect Water Exposure (IWE: intact bonded-teeth); (iii) Direct Water Exposure (DWE: resin-dentine sticks). Control and aged specimens were submitted to microtensile bond strength (μTBS) and nanoleakage evaluation. Water sorption (WS) survey was also performed on resin disks. Results were analysed with two-way ANOVA and Tukey's test (p < 0.05). The μTBS of CS3 and SB dropped significantly (p < 0.05) after 6 months of SPP and DWE. CSE showed a significant μTBS reduction only after 12 months of DWE (p = 0.038). IWE promoted no statistical change in μTBS (p > 0.05) and no evident change in nanoleakage. Conversely, SPP induced a clear formation of "water-trees" in CS3 and SB. WS outcomes were CS3 > SB = CSE. The hydrolytic degradation of resin-dentine interfaces depend upon the type of the in vitro ageing strategy employed in the experimental design. Direct water exposure remains the quickest method to age the resin-dentine bonds. However, the use of SPP may better simulate the in vivo scenario. However, the application of a separate hydrophobic solvent-free adhesive layer may reduce the hydrolytic degradation and increase the longevity of resin-dentine interfaces created with simplified adhesives. Copyright © 2012 Elsevier Ltd. All rights reserved.

Interstellar hydrogen bonding

NASA Astrophysics Data System (ADS)

Etim, Emmanuel E.; Gorai, Prasanta; Das, Ankan; Chakrabarti, Sandip K.; Arunan, Elangannan

2018-06-01

This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.

In situ measurement of the bonded film thickness of Z-Tetraol lubricant on magnetic recording media

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

Zhu Lei; Li Feng

2010-10-15

Currently, the bonded film thickness of perfluoropolyether lubricant on top of magnetic recording media is measured by a two-step process. First, the media disk has to be rinsed thoroughly using a fluorocarbon solvent (for instance, Vetrel) to remove the mobile lubricant. Second, the thickness of the remaining lubricant on the media surface which is regarded as the bonded lubricant thickness is then measured either by Fourier transform infrared spectroscopy (FTIR) or electron spectroscopy for chemical analysis. As the total lubricant thickness approaches single molecular dimension ({approx}10 A), current methods face tremendous challenge on the accuracy and sensitivity of the measurement.more » We studied the spectral characteristics responding to the lubricant bonding with the carbon overcoat by the time-of-flight secondary ion mass spectra and proposed to use the peak area ratio (C{sub 3}H{sub 2}F/C{sub 3}H{sub 5}O and C{sub 4}H{sub 10}O/C{sub 3}H{sub 6}O{sub 2}) to characterize the bonded Z-Tetraol lubricant that produces a direct bonded lubricant thickness measurement without the need to remove the mobile lubricant with a solvent. After taking the background signal of disks prior to bonding by UV irradiation into account, this method becomes independent of the total lubricant thickness as well as shows good correlation linearity (R{sup 2{approx}}87%) with the current FTIR method for the ratio of C{sub 4}H{sub 10}O/C{sub 3}H{sub 6}O{sub 2}.« less

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.

In vitro laser nerve repair: protein solder strip irradiation or irradiation alone?

PubMed

Trickett, I; Dawes, J M; Knowles, D S; Lanzetta, M; Owen, E R

1997-01-01

This study investigated the potential of sutureless nerve repair using two promising laser fusion methods: direct 2 microns irradiation of the epineurium, and protein solder assisted epineurial fusion using a 800 nm laser. Laser anastomosis of the rat sciatic nerve was performed in vitro without stay sutures in two groups of six animals. In the first group, direct laser fusion used a pulsed Cr, Tm: YAG laser. In the second group an albumin-based fluid solder containing the dye indocyanine green was applied to the epineurium, then irradiated with a diode laser. These two techniques were compared with regards to coaptation success and axonal damage. Direct laser welding produced weak bonds despite microscopic investigation of the irradiated nerves showing fusion of the epineurium. The unsatisfactory bonding can be attributed to poor tissue overlap and insufficient protein in the thin epineurium denaturation of underlying axons was also observed. In contrast, the laser solder method produced successful welds with greatly reduced axonal damage, and significantly improved the tensile strength. This study confirmed the technical possibilities of sutureless nerve anastomosis. Laser activated solders enable stronger bonds, by the addition of protein to the anastomosis site, and less thermal damage to underlying tissue through selective absorption of laser energy by dye in the solder. Further in vivo studies are required before drawing final conclusions.

Evaluation of an alternative technique to optimize direct bonding of orthodontic brackets to temporary crowns.

PubMed

Dias, Francilena Maria Campos Santos; Pinzan-Vercelino, Célia Regina Maio; Tavares, Rudys Rodolfo de Jesus; Gurgel, Júlio de Araújo; Bramante, Fausto Silva; Fialho, Melissa Nogueira Proença

2015-01-01

To compare shear bond strength of different direct bonding techniques of orthodontic brackets to acrylic resin surfaces. The sample comprised 64 discs of chemically activated acrylic resin (CAAR) randomly divided into four groups: discs in group 1 were bonded by means of light-cured composite resin (conventional adhesive); discs in group 2 had surfaces roughened with a diamond bur followed by conventional direct bonding by means of light-cured composite resin; discs in group 3 were bonded by means of CAAR (alternative adhesive); and discs in group 4 had surfaces roughened with a diamond bur followed by direct bonding by means of CAAR. Shear bond strength values were determined after 24 hours by means of a universal testing machine at a speed of 0.5 mm/min, and compared by analysis of variance followed by post-hoc Tukey test. Adhesive remnant index (ARI) was measured and compared among groups by means of Kruskal-Wallis and Dunn tests. Groups 3 and 4 had significantly greater shear bond strength values in comparison to groups 1 and 2. Groups 3 and 4 yielded similar results. Group 2 showed better results when compared to group 1. In ARI analyses, groups 1 and 2 predominantly exhibited a score equal to 0, whereas groups 3 and 4 predominantly exhibited a score equal to 3. Direct bonding of brackets to acrylic resin surfaces using CAAR yielded better results than light-cured composite resin. Surface preparation with diamond bur only increased shear bond strength in group 2.

Synthesis of antiviral tetrahydrocarbazole derivatives by photochemical and acid-catalyzed C-H functionalization via intermediate peroxides (CHIPS).

PubMed

Gulzar, Naeem; Klussmann, Martin

2014-06-20

The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order to streamline synthesis by saving steps, time and material compared to conventional methods that require the introduction and removal of activating or directing groups. Therefore, the functionalization of C-H bonds is also attractive for green chemistry. Under oxidative conditions, two C-H bonds or one C-H and one heteroatom-H bond can be transformed to C-C and C-heteroatom bonds, respectively. Often these oxidative coupling reactions require synthetic oxidants, expensive catalysts or high temperatures. Here, we describe a two-step procedure to functionalize indole derivatives, more specifically tetrahydrocarbazoles, by C-H amination using only elemental oxygen as oxidant. The reaction uses the principle of C-H functionalization via Intermediate PeroxideS (CHIPS). In the first step, a hydroperoxide is generated oxidatively using visible light, a photosensitizer and elemental oxygen. In the second step, the N-nucleophile, an aniline, is introduced by Brønsted-acid catalyzed activation of the hydroperoxide leaving group. The products of the first and second step often precipitate and can be conveniently filtered off. The synthesis of a biologically active compound is shown.

Direct computation of general chemical energy differences: Application to ionization potentials, excitation, and bond energies.

PubMed

Beste, A; Harrison, R J; Yanai, T

2006-08-21

Chemists are mainly interested in energy differences. In contrast, most quantum chemical methods yield the total energy which is a large number compared to the difference and has therefore to be computed to a higher relative precision than would be necessary for the difference alone. Hence, it is desirable to compute energy differences directly, thereby avoiding the precision problem. Whenever it is possible to find a parameter which transforms smoothly from an initial to a final state, the energy difference can be obtained by integrating the energy derivative with respect to that parameter (cf. thermodynamic integration or adiabatic connection methods). If the dependence on the parameter is predominantly linear, accurate results can be obtained by single-point integration. In density functional theory and Hartree-Fock, we applied the formalism to ionization potentials, excitation energies, and chemical bond breaking. Example calculations for ionization potentials and excitation energies showed that accurate results could be obtained with a linear estimate. For breaking bonds, we introduce a nongeometrical parameter which gradually turns the interaction between two fragments of a molecule on. The interaction changes the potentials used to determine the orbitals as well as the constraint on the orbitals to be orthogonal.

Nonlinear Analysis of Bonded Composite Tubular Lap Joints

NASA Technical Reports Server (NTRS)

Oterkus, E.; Madenci, E.; Smeltzer, S. S., III; Ambur, D. R.

2005-01-01

The present study describes a semi-analytical solution method for predicting the geometrically nonlinear response of a bonded composite tubular single-lap joint subjected to general loading conditions. The transverse shear and normal stresses in the adhesive as well as membrane stress resultants and bending moments in the adherends are determined using this method. The method utilizes the principle of virtual work in conjunction with nonlinear thin-shell theory to model the adherends and a cylindrical shear lag model to represent the kinematics of the thin adhesive layer between the adherends. The kinematic boundary conditions are imposed by employing the Lagrange multiplier method. In the solution procedure, the displacement components for the tubular joint are approximated in terms of non-periodic and periodic B-Spline functions in the longitudinal and circumferential directions, respectively. The approach presented herein represents a rapid-solution alternative to the finite element method. The solution method was validated by comparison against a previously considered tubular single-lap joint. The steep variation of both peeling and shearing stresses near the adhesive edges was successfully captured. The applicability of the present method was also demonstrated by considering tubular bonded lap-joints subjected to pure bending and torsion.

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.

High-speed liquid chromatographic determination of pilocarpine in pharmaceutical dosage forms.

PubMed

Khalil, S K

1977-11-01

A specific method for the direct determination of pilocarpine in aqueous pharmaceuticals in the presence of decomposition products, methylcellulose, and other ingredients usually present in pharmaceuticals is described. The method involves separation by high-speed liquid chromatography using, in series, octadecylsilane bonded to silica and cyanopropylsilane bonded to silica columns and a tetrahydrofuran-pH 9.2 borate buffer (3:7) eluant. Quantitation is achieved by monitoring the absorbance of the effluent at 254 nm and using a pyridine internal standard and a calibration curve prepared from known concentrations of pilocarpine nitrate. The reproducibility of the retention time and peak area was better than 2.0%.

Enzymatic Functionalization of Carbon-Hydrogen Bonds1

PubMed Central

Lewis, Jared C.; Coelho, Pedro S.

2010-01-01

The development of new catalytic methods to functionalize carbon-hydrogen (C-H) bonds continues to progress at a rapid pace due to the significant economic and environmental benefits of these transformations over traditional synthetic methods. In nature, enzymes catalyze regio- and stereoselective C-H bond functionalization using transformations ranging from hydroxylation to hydroalkylation under ambient reaction conditions. The efficiency of these enzymes relative to analogous chemical processes has led to their increased use as biocatalysts in preparative and industrial applications. Furthermore, unlike small molecule catalysts, enzymes can be systematically optimized via directed evolution for a particular application and can be expressed in vivo to augment the biosynthetic capability of living organisms. While a variety of technical challenges must still be overcome for practical application of many enzymes for C-H bond functionalization, continued research on natural enzymes and on novel artificial metalloenzymes will lead to improved synthetic processes for efficient synthesis of complex molecules. In this critical review, we discuss the most prevalent mechanistic strategies used by enzymes to functionalize non-acidic C-H bonds, the application and evolution of these enzymes for chemical synthesis, and a number of potential biosynthetic capabilities uniquely enabled by these powerful catalysts. PMID:21079862

Neutron Crystallography for the Study of Hydrogen Bonds in Macromolecules.

PubMed

Oksanen, Esko; Chen, Julian C-H; Fisher, Suzanne Zoë

2017-04-07

Abstract : The hydrogen bond (H bond) is one of the most important interactions that form the foundation of secondary and tertiary protein structure. Beyond holding protein structures together, H bonds are also intimately involved in solvent coordination, ligand binding, and enzyme catalysis. The H bond by definition involves the light atom, H, and it is very difficult to study directly, especially with X-ray crystallographic techniques, due to the poor scattering power of H atoms. Neutron protein crystallography provides a powerful, complementary tool that can give unambiguous information to structural biologists on solvent organization and coordination, the electrostatics of ligand binding, the protonation states of amino acid side chains and catalytic water species. The method is complementary to X-ray crystallography and the dynamic data obtainable with NMR spectroscopy. Also, as it gives explicit H atom positions, it can be very valuable to computational chemistry where exact knowledge of protonation and solvent orientation can make a large difference in modeling. This article gives general information about neutron crystallography and shows specific examples of how the method has contributed to structural biology, structure-based drug design; and the understanding of fundamental questions of reaction mechanisms.

Neutron crystallography for the study of hydrogen bonds in macromolecules

DOE PAGES

Oksanen, Esko; Chen, Julian C.; Fisher, Zoe

2017-04-07

The hydrogen bond (H bond) is one of the most important interactions that form the foundation of secondary and tertiary protein structure. Beyond holding protein structures together, H bonds are also intimately involved in solvent coordination, ligand binding, and enzyme catalysis. The H bond by definition involves the light atom, H, and it is very difficult to study directly, especially with X-ray crystallographic techniques, due to the poor scattering power of H atoms. Neutron protein crystallography provides a powerful, complementary tool that can give unambiguous information to structural biologists on solvent organization and coordination, the electrostatics of ligand binding, themore » protonation states of amino acid side chains and catalytic water species. The method is complementary to X-ray crystallography and the dynamic data obtainable with NMR spectroscopy. Also, as it gives explicit H atom positions, it can be very valuable to computational chemistry where exact knowledge of protonation and solvent orientation can make a large difference in modeling. Finally, this article gives general information about neutron crystallography and shows specific examples of how the method has contributed to structural biology, structure-based drug design; and the understanding of fundamental questions of reaction mechanisms.« less

Neutron crystallography for the study of hydrogen bonds in macromolecules

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

Oksanen, Esko; Chen, Julian C.; Fisher, Zoe

The hydrogen bond (H bond) is one of the most important interactions that form the foundation of secondary and tertiary protein structure. Beyond holding protein structures together, H bonds are also intimately involved in solvent coordination, ligand binding, and enzyme catalysis. The H bond by definition involves the light atom, H, and it is very difficult to study directly, especially with X-ray crystallographic techniques, due to the poor scattering power of H atoms. Neutron protein crystallography provides a powerful, complementary tool that can give unambiguous information to structural biologists on solvent organization and coordination, the electrostatics of ligand binding, themore » protonation states of amino acid side chains and catalytic water species. The method is complementary to X-ray crystallography and the dynamic data obtainable with NMR spectroscopy. Also, as it gives explicit H atom positions, it can be very valuable to computational chemistry where exact knowledge of protonation and solvent orientation can make a large difference in modeling. Finally, this article gives general information about neutron crystallography and shows specific examples of how the method has contributed to structural biology, structure-based drug design; and the understanding of fundamental questions of reaction mechanisms.« less

Direct evidence for dominant bond-directional interactions in a honeycomb lattice iridate Na 2IrO 3

DOE PAGES

Hwan Chun, Sae; Kim, Jong-Woo; Kim, Jungho; ...

2015-05-11

We show that heisenberg interactions are ubiquitous in magnetic materials and play a central role in modelling and designing quantum magnets. Bond-directional interactions offer a novel alternative to Heisenberg exchange and provide the building blocks of the Kitaev model, which has a quantum spin liquid as its exact ground state. Honeycomb iridates, A 2IrO 3 (A = Na, Li), offer potential realizations of the Kitaev magnetic exchange coupling, and their reported magnetic behaviour may be interpreted within the Kitaev framework. However, the extent of their relevance to the Kitaev model remains unclear, as evidence for bond-directional interactions has so farmore » been indirect. Here we present direct evidence for dominant bond-directional interactions in antiferromagnetic Na 2IrO 3 and show that they lead to strong magnetic frustration. Diffuse magnetic X-ray scattering reveals broken spin-rotational symmetry even above the Néel temperature, with the three spin components exhibiting short-range correlations along distinct crystallographic directions. Lastly, this spin- and real-space entanglement directly uncovers the bond-directional nature of these interactions, thus providing a direct connection between honeycomb iridates and Kitaev physics.« less

Innovations in bonding to zirconia based ceramics: Part III. Phosphate monomer resin cements.

PubMed

Mirmohammadi, Hesam; Aboushelib, Moustafa N M; Salameh, Ziad; Feilzer, Albert J; Kleverlaan, Cornelis J

2010-08-01

To compare the bond strength values and the ranking order of three phosphate monomer containing resin cements using microtensile (microTBS) and microshear (microSBS) bond strength tests. Zirconia discs (Procera Zirconia) were bonded to resin composite discs (Filtek Z250) using three different cements (Panavia F 2.0, RelyX UniCem, and Multilink). Two bond strength tests were used to determine zirconia resin bond strength; microtensile bond strength test (microTBS) and microshear bond strength test (microSBS). Ten specimens were tested for each group (n=10). Two-way analysis of variance (ANOVA) was used to analyze the data (alpha=0.05). There were statistical significant differences in bond strength values and in the ranking order obtained using the two test methods. microTBS reported significant differences in bond strength values, whereas microSBS failed to detect such effect. Both Multilink and Panavia demonstrated basically cohesive failure in the resin cement while RelyX UniCem demonstrated interfacial failure. Based on the findings of this study, the data obtained using either microTBS or microSBS could not be directly compared. microTBS was more sensitive to material differences compared to microSBS which failed to detect such differences. Copyright 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Method of processing materials using an inductively coupled plasma

DOEpatents

Hull, D.E.; Bieniewski, T.M.

1987-04-13

A method of processing materials. The invention enables ultrafine, ultrapure powders to be formed from solid ingots in a gas free environment. A plasma is formed directly from an ingot which insures purity. The vaporized material is expanded through a nozzle and the resultant powder settles on a cold surface. An inductively coupled plasma may also be used to process waste chemicals. Noxious chemicals are directed through a series of plasma tubes, breaking molecular bonds and resulting in relatively harmless atomic constituents. 3 figs.

Direct Enantioselective Conjugate Addition of Carboxylic Acids with Chiral Lithium Amides as Traceless Auxiliaries

PubMed Central

2016-01-01

Michael addition is a premier synthetic method for carbon–carbon and carbon–heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B. PMID:25562717

Direct enantioselective conjugate addition of carboxylic acids with chiral lithium amides as traceless auxiliaries.

PubMed

Lu, Ping; Jackson, Jeffrey J; Eickhoff, John A; Zakarian, Armen

2015-01-21

Michael addition is a premier synthetic method for carbon-carbon and carbon-heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B.

High-κ Al2O3 material in low temperature wafer-level bonding for 3D integration application

NASA Astrophysics Data System (ADS)

Fan, J.; Tu, L. C.; Tan, C. S.

2014-03-01

This work systematically investigated a high-κ Al2O3 material for low temperature wafer-level bonding for potential applications in 3D microsystems. A clean Si wafer with an Al2O3 layer thickness of 50 nm was applied as our experimental approach. Bonding was initiated in a clean room ambient after surface activation, followed by annealing under inert ambient conditions at 300 °C for 3 h. The investigation consisted of three parts: a mechanical support study using the four-point bending method, hermeticity measurements using the helium bomb test, and thermal conductivity analysis for potential heterogeneous bonding. Compared with samples bonded using a conventional oxide bonding material (SiO2), a higher interfacial adhesion energy (˜11.93 J/m2) and a lower helium leak rate (˜6.84 × 10-10 atm.cm3/sec) were detected for samples bonded using Al2O3. More importantly, due to the excellent thermal conductivity performance of Al2O3, this technology can be used in heterogeneous direct bonding, which has potential applications for enhancing the performance of Si photonic integrated devices.

DNA-nanoparticle superlattices formed from anisotropic building blocks

NASA Astrophysics Data System (ADS)

Jones, Matthew R.; Macfarlane, Robert J.; Lee, Byeongdu; Zhang, Jian; Young, Kaylie L.; Senesi, Andrew J.; Mirkin, Chad A.

2010-11-01

Directional bonding interactions in solid-state atomic lattices dictate the unique symmetries of atomic crystals, resulting in a diverse and complex assortment of three-dimensional structures that exhibit a wide variety of material properties. Methods to create analogous nanoparticle superlattices are beginning to be realized, but the concept of anisotropy is still largely underdeveloped in most particle assembly schemes. Some examples provide interesting methods to take advantage of anisotropic effects, but most are able to make only small clusters or lattices that are limited in crystallinity and especially in lattice parameter programmability. Anisotropic nanoparticles can be used to impart directional bonding interactions on the nanoscale, both through face-selective functionalization of the particle with recognition elements to introduce the concept of valency, and through anisotropic interactions resulting from particle shape. In this work, we examine the concept of inherent shape-directed crystallization in the context of DNA-mediated nanoparticle assembly. Importantly, we show how the anisotropy of these particles can be used to synthesize one-, two- and three-dimensional structures that cannot be made through the assembly of spherical particles.

31 CFR 363.101 - Can an account owner transfer a book-entry savings bond to a minor?

Code of Federal Regulations, 2010 CFR

2010-07-01

... REGULATIONS GOVERNING SECURITIES HELD IN TREASURYDIRECT Book-Entry Savings Bonds Purchased Through TreasuryDirect Gifts § 363.101 Can an account owner transfer a book-entry savings bond to a minor? An account owner can transfer a book-entry savings bond held in TreasuryDirect ® to a minor as a gift or pursuant...

Conformation-induced remote meta-C-H activation of amines

NASA Astrophysics Data System (ADS)

Tang, Ri-Yuan; Li, Gang; Yu, Jin-Quan

2014-03-01

Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a long-standing challenge in organic chemistry. The small differences in intrinsic reactivity of C-H bonds in any given organic molecule can lead to the activation of undesired C-H bonds by a non-selective catalyst. One solution to this problem is to distinguish C-H bonds on the basis of their location in the molecule relative to a specific functional group. In this context, the activation of C-H bonds five or six bonds away from a functional group by cyclometallation has been extensively studied. However, the directed activation of C-H bonds that are distal to (more than six bonds away) functional groups has remained challenging, especially when the target C-H bond is geometrically inaccessible to directed metallation owing to the ring strain encountered in cyclometallation. Here we report a recyclable template that directs the olefination and acetoxylation of distal meta-C-H bonds--as far as 11 bonds away--of anilines and benzylic amines. This template is able to direct the meta-selective C-H functionalization of bicyclic heterocycles via a highly strained, tricyclic-cyclophane-like palladated intermediate. X-ray and nuclear magnetic resonance studies reveal that the conformational biases induced by a single fluorine substitution in the template can be enhanced by using a ligand to switch from ortho- to meta-selectivity.

Conformation-induced remote meta-C-H activation of amines.

PubMed

Tang, Ri-Yuan; Li, Gang; Yu, Jin-Quan

2014-03-13

Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a long-standing challenge in organic chemistry. The small differences in intrinsic reactivity of C-H bonds in any given organic molecule can lead to the activation of undesired C-H bonds by a non-selective catalyst. One solution to this problem is to distinguish C-H bonds on the basis of their location in the molecule relative to a specific functional group. In this context, the activation of C-H bonds five or six bonds away from a functional group by cyclometallation has been extensively studied. However, the directed activation of C-H bonds that are distal to (more than six bonds away) functional groups has remained challenging, especially when the target C-H bond is geometrically inaccessible to directed metallation owing to the ring strain encountered in cyclometallation. Here we report a recyclable template that directs the olefination and acetoxylation of distal meta-C-H bonds--as far as 11 bonds away--of anilines and benzylic amines. This template is able to direct the meta-selective C-H functionalization of bicyclic heterocycles via a highly strained, tricyclic-cyclophane-like palladated intermediate. X-ray and nuclear magnetic resonance studies reveal that the conformational biases induced by a single fluorine substitution in the template can be enhanced by using a ligand to switch from ortho- to meta-selectivity.

Alkali metal mediated C-C bond coupling reaction

NASA Astrophysics Data System (ADS)

Tachikawa, Hiroto

2015-02-01

Metal catalyzed carbon-carbon (C-C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz)2, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz)2, the structure of [Li(Bz)2]- was drastically changed: Bz-Bz parallel form was rapidly fluctuated as a function of time, and a new C-C single bond was formed in the C1-C1' position of Bz-Bz interaction system. In the hole capture, the intermolecular vibration between Bz-Bz rings was only enhanced. The mechanism of C-C bond formation in the electron capture was discussed on the basis of theoretical results.

X-ray targeted bond or compound destruction

DOEpatents

Pravica, Sr., Michael G.

2016-11-01

This document provides methods, systems, and devices for inducing a decomposition reaction by directing x-rays towards a location including a particular compound. The x-rays can have an irradiation energy that corresponds to a bond distance of a bond in the particular compound in order to break that bond and induce a decomposition of that particular compound. In some cases, the particular compound is a hazardous substance or part of a hazardous substance. In some cases, the particular compound is delivered to a desired location in an organism and x-rays induce a decomposition reaction that creates a therapeutic substance (e.g., a toxin that kills cancer cells) in the location of the organism. In some cases, the particular compound decomposes to produce a reactant in a reactor apparatus (e.g., fuel cell or semiconductor fabricator).

Cross-Dehydrogenative Coupling Reactions Between P(O)-H and X-H (X = S, N, O, P) Bonds.

PubMed

Hosseinian, Akram; Farshbaf, Sepideh; Fekri, Leila Zare; Nikpassand, Mohammad; Vessally, Esmail

2018-05-26

P(O)-X (X = S, N, O, P) bond-containing compounds have extensive application in medicinal chemistry, agrochemistry, and material chemistry. These useful organophosphorus compounds also have many applications in organic synthesis. In light of the importance of titled compounds, there is continuing interest in the development of synthetic methods for P(O)-X bonds construction. In the last 4 years, the direct coupling reaction of P(O)-H compounds with thiols, alcohols, and amines/amides has received much attention because of the atom-economic character. This review aims to give an overview of new developments in cross-dehydrogenative coupling reactions between P(O)-H and X-H (X = S, N, O, P) bonds, with special emphasis on the mechanistic aspects of the reactions.

Multicomponent DFT study of geometrical H/D isotope effect on hydrogen-bonded organic conductor, κ-H3(Cat EDT-ST)2

NASA Astrophysics Data System (ADS)

Yamamoto, Kaichi; Kanematsu, Yusuke; Nagashima, Umpei; Ueda, Akira; Mori, Hatsumi; Tachikawa, Masanori

2017-04-01

We theoretically investigated a significant contraction of the hydrogen-bonding O⋯O distance upon H/D substitution in our recently developed purely organic crystals, κ-H3(Cat-EDT-ST)2 (H-ST) and its isotopologue κ-D3(Cat-EDT-ST)2 (D-ST), having π-electron systems coupled with hydrogen-bonding fluctuation. The origin of this geometrical H/D isotope effect was elucidated by using the multicomponent DFT method, which takes the H/D nuclear quantum effect into account. The optimized O⋯O distance in H-ST was found to be longer than that in D-ST due to the anharmonicity of the potential energy curve along the Osbnd H bond direction, which was in reasonable agreement with the experimental trend.

An energetic scale for equilibrium H/D fractionation factors illuminates hydrogen bond free energies in proteins

PubMed Central

Cao, Zheng; Bowie, James U

2014-01-01

Equilibrium H/D fractionation factors have been extensively employed to qualitatively assess hydrogen bond strengths in protein structure, enzyme active sites, and DNA. It remains unclear how fractionation factors correlate with hydrogen bond free energies, however. Here we develop an empirical relationship between fractionation factors and free energy, allowing for the simple and quantitative measurement of hydrogen bond free energies. Applying our empirical relationship to prior fractionation factor studies in proteins, we find: [1] Within the folded state, backbone hydrogen bonds are only marginally stronger on average in α-helices compared to β-sheets by ∼0.2 kcal/mol. [2] Charge-stabilized hydrogen bonds are stronger than neutral hydrogen bonds by ∼2 kcal/mol on average, and can be as strong as –7 kcal/mol. [3] Changes in a few hydrogen bonds during an enzyme catalytic cycle can stabilize an intermediate state by –4.2 kcal/mol. [4] Backbone hydrogen bonds can make a large overall contribution to the energetics of conformational changes, possibly playing an important role in directing conformational changes. [5] Backbone hydrogen bonding becomes more uniform overall upon ligand binding, which may facilitate participation of the entire protein structure in events at the active site. Our energetic scale provides a simple method for further exploration of hydrogen bond free energies. PMID:24501090

Reactive Molecular Dynamics Simulations to Understand Mechanical Response of Thaumasite under Temperature and Strain Rate Effects.

PubMed

Hajilar, Shahin; Shafei, Behrouz; Cheng, Tao; Jaramillo-Botero, Andres

2017-06-22

Understanding the structural, thermal, and mechanical properties of thaumasite is of great interest to the cement industry, mainly because it is the phase responsible for the aging and deterioration of civil infrastructures made of cementitious materials attacked by external sources of sulfate. Despite the importance, effects of temperature and strain rate on the mechanical response of thaumasite had remained unexplored prior to the current study, in which the mechanical properties of thaumasite are fully characterized using the reactive molecular dynamics (RMD) method. With employing a first-principles based reactive force field, the RMD simulations enable the description of bond dissociation and formation under realistic conditions. From the stress-strain curves of thaumasite generated in the x, y, and z directions, the tensile strength, Young's modulus, and fracture strain are determined for the three orthogonal directions. During the course of each simulation, the chemical bonds undergoing tensile deformations are monitored to reveal the bonds responsible for the mechanical strength of thaumasite. The temperature increase is found to accelerate the bond breaking rate and consequently the degradation of mechanical properties of thaumasite, while the strain rate only leads to a slight enhancement of them for the ranges considered in this study.

The direct arylation of allylic sp3 C–H bonds via organocatalysis and photoredox catalysis

PubMed Central

Cuthbertson, James D.; MacMillan, David W. C.

2015-01-01

The direct functionalization of unactivated sp3 C–H bonds is still one of the most challenging problems facing synthetic organic chemists. The appeal of such transformations derives from their capacity to facilitate the construction of complex organic molecules via the coupling of simple and otherwise inert building blocks, without introducing extraneous functional groups. Despite notable recent efforts,1 the establishment of general and mild strategies for the engagement of sp3 C–H bonds in carbon–carbon bond forming reactions has proven difficult. Within this context, the discovery of chemical transformations that are able to directly functionalize allylic methyl, methylene, and methine carbons in a catalytic manner is a priority. While protocols for direct allylic C–H oxidation and amination have become widely established,2,3 the engagement of allylic substrates in carbon–carbon bond-forming reactions has thus far required the use of pre-functionalized coupling partners.4 In particular, the direct arylation of non-functionalized allylic systems would enable chemists to rapidly access a series of known pharmacophores, though a general solution to this longstanding challenge remains elusive. We describe herein the use of both photoredox and organic catalysis to accomplish the first mild, broadly effective direct allylic C–H arylation. This new C–C bond-forming reaction readily accommodates a broad range of alkene and electron-deficient arene reactants and has been used in the direct arylation of benzylic C–H bonds. PMID:25739630

The US Stock Market Leads the Federal Funds Rate and Treasury Bond Yields

PubMed Central

Guo, Kun; Zhou, Wei-Xing; Cheng, Si-Wei; Sornette, Didier

2011-01-01

Using a recently introduced method to quantify the time-varying lead-lag dependencies between pairs of economic time series (the thermal optimal path method), we test two fundamental tenets of the theory of fixed income: (i) the stock market variations and the yield changes should be anti-correlated; (ii) the change in central bank rates, as a proxy of the monetary policy of the central bank, should be a predictor of the future stock market direction. Using both monthly and weekly data, we found very similar lead-lag dependence between the S&P 500 stock market index and the yields of bonds inside two groups: bond yields of short-term maturities (Federal funds rate (FFR), 3M, 6M, 1Y, 2Y, and 3Y) and bond yields of long-term maturities (5Y, 7Y, 10Y, and 20Y). In all cases, we observe the opposite of (i) and (ii). First, the stock market and yields move in the same direction. Second, the stock market leads the yields, including especially the FFR. Moreover, we find that the short-term yields in the first group lead the long-term yields in the second group before the financial crisis that started in mid-2007 and the inverse relationship holds afterwards. These results suggest that the Federal Reserve is increasingly mindful of the stock market behavior, seen as key to the recovery and health of the economy. Long-term investors seem also to have been more reactive and mindful of the signals provided by the financial stock markets than the Federal Reserve itself after the start of the financial crisis. The lead of the S&P 500 stock market index over the bond yields of all maturities is confirmed by the traditional lagged cross-correlation analysis. PMID:21857954

The US stock market leads the federal funds rate and treasury bond yields.

PubMed

Guo, Kun; Zhou, Wei-Xing; Cheng, Si-Wei; Sornette, Didier

2011-01-01

Using a recently introduced method to quantify the time-varying lead-lag dependencies between pairs of economic time series (the thermal optimal path method), we test two fundamental tenets of the theory of fixed income: (i) the stock market variations and the yield changes should be anti-correlated; (ii) the change in central bank rates, as a proxy of the monetary policy of the central bank, should be a predictor of the future stock market direction. Using both monthly and weekly data, we found very similar lead-lag dependence between the S&P 500 stock market index and the yields of bonds inside two groups: bond yields of short-term maturities (Federal funds rate (FFR), 3M, 6M, 1Y, 2Y, and 3Y) and bond yields of long-term maturities (5Y, 7Y, 10Y, and 20Y). In all cases, we observe the opposite of (i) and (ii). First, the stock market and yields move in the same direction. Second, the stock market leads the yields, including especially the FFR. Moreover, we find that the short-term yields in the first group lead the long-term yields in the second group before the financial crisis that started in mid-2007 and the inverse relationship holds afterwards. These results suggest that the Federal Reserve is increasingly mindful of the stock market behavior, seen as key to the recovery and health of the economy. Long-term investors seem also to have been more reactive and mindful of the signals provided by the financial stock markets than the Federal Reserve itself after the start of the financial crisis. The lead of the S&P 500 stock market index over the bond yields of all maturities is confirmed by the traditional lagged cross-correlation analysis.

Bonding temperature dependence of GaInAsP/InP laser diode grown on hydrophilically directly bonded InP/Si substrate

NASA Astrophysics Data System (ADS)

Aikawa, Masaki; Onuki, Yuya; Hayasaka, Natsuki; Nishiyama, Tetsuo; Kamada, Naoki; Han, Xu; Kallarasan Periyanayagam, Gandhi; Uchida, Kazuki; Sugiyama, Hirokazu; Shimomura, Kazuhiko

2018-02-01

The bonding-temperature-dependent lasing characteristics of 1.5 a µm GaInAsP laser diode (LD) grown on a directly bonded InP/Si substrate were successfully obtained. We have fabricated the InP/Si substrate using a direct hydrophilic wafer bonding technique at bonding temperatures of 350, 400, and 450 °C, and deposited GaInAsP/InP double heterostructure layers on this InP/Si substrate. The surface conditions, X-ray diffraction (XRD) analysis, photoluminescence (PL) spectra, and electrical characteristics after the growth were compared at these bonding temperatures. No significant differences were confirmed in X-ray diffraction analysis and PL spectra at these bonding temperatures. We realized the room-temperature lasing of the GaInAsP LD on the InP/Si substrate bonded at 350 and 400 °C. The threshold current densities were 4.65 kA/cm2 at 350 °C and 4.38 kA/cm2 at 400 °C. The electrical resistance was found to increase with annealing temperature.

Correlation of nonorthogonality of best hybrid bond orbitals with bond strength of orthogonal orbitals

PubMed Central

Pauling, Linus

1976-01-01

An expression is derived for the bond length of two spd orbitals with maximum values in two directions forming a given bond angle by consideration of the nonorthogonality integral of two best orbitals in these directions. This equation is equivalent to the expression derived by formulating the pair of orthogonal orbitals. Similar expressions are derived for spdf orbitals. Applications are made to icosahedral and cuboctahedral bonds and to the packing of nucleons in atomic nuclei. PMID:16578736

Correlation of nonorthogonality of best hybrid bond orbitals with bond strength of orthogonal orbitals.

PubMed

Pauling, L

1976-02-01

An expression is derived for the bond length of two spd orbitals with maximum values in two directions forming a given bond angle by consideration of the nonorthogonality integral of two best orbitals in these directions. This equation is equivalent to the expression derived by formulating the pair of orthogonal orbitals. Similar expressions are derived for spdf orbitals. Applications are made to icosahedral and cuboctahedral bonds and to the packing of nucleons in atomic nuclei.

Synthesis of 2H- and 13C-substituted dithanes

DOEpatents

Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

2003-01-01

The present invention is directed to labeled compounds, [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

Synthesis Of 2h- And 13c-Substituted Dithanes

DOEpatents

Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

2004-05-04

The present invention is directed to labeled compounds, [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

31 CFR 363.55 - May I transfer my book-entry savings bonds to another person?

Code of Federal Regulations, 2013 CFR

2013-07-01

... 31 Money and Finance:Treasury 2 2013-07-01 2013-07-01 false May I transfer my book-entry savings...Direct General § 363.55 May I transfer my book-entry savings bonds to another person? (a) You may transfer a savings bond or a portion of a savings bond to the TreasuryDirect ® account of another person in...

31 CFR 363.55 - May I transfer my book-entry savings bonds to another person?

Code of Federal Regulations, 2014 CFR

2014-07-01

... 31 Money and Finance: Treasury 2 2014-07-01 2014-07-01 false May I transfer my book-entry savings...Direct General § 363.55 May I transfer my book-entry savings bonds to another person? (a) You may transfer a savings bond or a portion of a savings bond to the TreasuryDirect ® account of another person in...

31 CFR 363.55 - May I transfer my book-entry savings bonds to another person?

Code of Federal Regulations, 2011 CFR

2011-07-01

... 31 Money and Finance:Treasury 2 2011-07-01 2011-07-01 false May I transfer my book-entry savings...Direct General § 363.55 May I transfer my book-entry savings bonds to another person? (a) You may transfer a savings bond or a portion of a savings bond to the TreasuryDirect® account of another person in...

Bond strength evaluation in adhesive joints using NDE and DIC methods

NASA Astrophysics Data System (ADS)

Poudel, Anish

Adhesive bonding of graphite epoxy composite laminates to itself or traditional metal alloys in modern aerospace and aircraft structural applications offers an excellent opportunity to use the most efficient and intelligent combination of materials available thus providing an attractive package for efficient structural designs. However, one of the major issues of adhesive bonding is the occasional formation of interfacial defects such as kissing or weak bonds in the bondline interface. Also, there are shortcomings of existing non-destructive evaluation (NDE) methods to non-destructively detect/characterize these interfacial defects and reliably predicting the bond shear strength. As a result, adhesive bonding technology is still not solely implemented in primary structures of an aircraft. Therefore, there is a greater demand for a novel NDE tool that can meet the existing aerospace requirement for adhesive bondline characterization. This research implemented a novel Acoustography ultrasonic imaging and digital image correlation (DIC) technique to detect and characterize interfacial defects in the bondline and determine bond shear strength in adhesively bonded composite-metal joints. Adhesively bonded Carbon Fiber Reinforced Plastic (CFRP) laminate and 2024-T3 Aluminum single lap shear panels subjected to various implanted kissing/weak bond defects were the primary focus of this study. Kissing/weak bonds were prepared by controlled surface contamination in the composite bonding surface and also by improperly mixing the adhesive constituent. SEM analyses were also conducted to understand the surface morphology of substrates and their interaction with the contaminants. Morphological changes were observed in the microscopic scale and the chemical analysis confirmed the stability of the contaminant at or very close to the interface. In addition, it was also demonstrated that contaminants migrated during the curing of the adhesive from CFRP substrate which caused a decrease of bond shear strength in single lap shear test samples. Through-transmission ultrasonics (TTU) Acoustography at 3.8 MHz showed promising results on the detectability of bondline defects in adhesively bonded CFRP-Al lap shear test samples. A correlation between Acoustography ultrasonic attenuation and average bond shear strength in CFRP-Al lap shear panels demonstrated that differential attenuation increased with the reduction of the bond shear strength. Similarly, optical DIC tests were conducted to identify and quantify kissing bond defects in CFRP-Al single lap shear joints. DIC results demonstrated changes in the normal strain (epsilonyy) contour map of the contaminated specimens at relatively lower load levels (15% ~ 30% of failure loads). Kissing bond regions were characterized by negative strains, and these were attributed to high compressive bending strains and the localized disbonding taking placed at the bondline interface as a result of the load application. It was also observed that contaminated samples suffered from more compressive strains (epsilonyy) compared to the baseline sample along the loading direction and they suffered from less compressive strains (epsilonxx) compared to the baseline sample perpendicular to the loading direction. This demonstrated the adverse effect of the kissing bond on the adhesive joint integrity. This was a very significant finding for the reason that hybrid ultrasonic DIC is being developed as a faster, more efficient, and more reliable NDE technique for determining bond quality and predicting bond shear strength in adhesively bonded structures.

The Tension-Stiffening Contribution of NSM CFRP to the Behavior of Strengthened RC Beams

PubMed Central

Shukri, Ahmad Azim; Darain, Kh Mahfuz ud; Jumaat, Mohd Zamin

2015-01-01

Tension stiffening is a characteristic behavior of reinforced concrete (RC) beams which is directly affected by the bond-slip property of steel bar and concrete interfaces. A beam strengthened with a near-surface mounted (NSM) technique would be even more affected by tension stiffening, as the NSM reinforcement also possess a bond-slip property. Yet assessing how much the tension stiffening of NSM contributes to the behavior of RC beams is difficult due to the fact that bond-slip effects cannot be directly incorporated into a strain-based moment-curvature analysis. As such, the tension stiffening is typically incorporated through various empirical formulations, which can require a great deal of testing and calibrations to be done. In this paper a relatively new method, which can be called the mechanics-based segmental approach, is used to directly simulate the tension stiffening effect of NSM reinforcements on RC beams, without the need for empirical formulations to indirectly simulate the tension stiffening. Analysis shows that the tension stiffening of NSM fiber reinforced polymer (FRP) contributes a significant portion to the stiffness and strength of the strengthened RC beam not only during serviceability, but at all load levels. PMID:28793429

The Tension-Stiffening Contribution of NSM CFRP to the Behavior of Strengthened RC Beams.

PubMed

Shukri, Ahmad Azim; Darain, Kh Mahfuz Ud; Jumaat, Mohd Zamin

2015-07-08

Tension stiffening is a characteristic behavior of reinforced concrete (RC) beams which is directly affected by the bond-slip property of steel bar and concrete interfaces. A beam strengthened with a near-surface mounted (NSM) technique would be even more affected by tension stiffening, as the NSM reinforcement also possess a bond-slip property. Yet assessing how much the tension stiffening of NSM contributes to the behavior of RC beams is difficult due to the fact that bond-slip effects cannot be directly incorporated into a strain-based moment-curvature analysis. As such, the tension stiffening is typically incorporated through various empirical formulations, which can require a great deal of testing and calibrations to be done. In this paper a relatively new method, which can be called the mechanics-based segmental approach, is used to directly simulate the tension stiffening effect of NSM reinforcements on RC beams, without the need for empirical formulations to indirectly simulate the tension stiffening. Analysis shows that the tension stiffening of NSM fiber reinforced polymer (FRP) contributes a significant portion to the stiffness and strength of the strengthened RC beam not only during serviceability, but at all load levels.

Covalent intermolecular interaction of the nitric oxide dimer (NO)2

NASA Astrophysics Data System (ADS)

Zhang, Hui; Zheng, Gui-Li; Lv, Gang; Geng, Yi-Zhao; Ji, Qing

2015-09-01

Covalent bonds arise from the overlap of the electronic clouds in the internucleus region, which is a pure quantum effect and cannot be obtained in any classical way. If the intermolecular interaction is of covalent character, the result from direct applications of classical simulation methods to the molecular system would be questionable. Here, we analyze the special intermolecular interaction between two NO molecules based on quantum chemical calculation. This weak intermolecular interaction, which is of covalent character, is responsible for the formation of the NO dimer, (NO)2, in its most stable conformation, a cis conformation. The natural bond orbital (NBO) analysis gives an intuitive illustration of the formation of the dimer bonding and antibonding orbitals concomitant with the breaking of the π bonds with bond order 0.5 of the monomers. The dimer bonding is counteracted by partially filling the antibonding dimer orbital and the repulsion between those fully or nearly fully occupied nonbonding dimer orbitals that make the dimer binding rather weak. The direct molecular mechanics (MM) calculation with the UFF force fields predicts a trans conformation as the most stable state, which contradicts the result of quantum mechanics (QM). The lesson from the investigation of this special system is that for the case where intermolecular interaction is of covalent character, a specific modification of the force fields of the molecular simulation method is necessary. Project supported by the National Natural Science Foundation of China (Grant Nos. 90403007 and 10975044), the Key Subject Construction Project of Hebei Provincial Universities, China, the Research Project of Hebei Education Department, China (Grant Nos. Z2012067 and Z2011133), the National Natural Science Foundation of China (Grant No. 11147103), and the Open Project Program of State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Sciences, China (Grant No. Y5KF211CJ1).

Directed-Backbone Dissociation Following Bond-Specific Carbon-Sulfur UVPD at 213 nm

NASA Astrophysics Data System (ADS)

Talbert, Lance E.; Julian, Ryan R.

2018-04-01

Ultraviolet photodissociation or UVPD is an increasingly popular option for tandem-mass spectrometry experiments. UVPD can be carried out at many wavelengths, and it is important to understand how the results will be impacted by this choice. Here, we explore the utility of 213 nm photons for initiating bond-selective fragmentation. It is found that bonds previously determined to be labile at 266 nm, including carbon-iodine and sulfur-sulfur bonds, can also be cleaved with high selectivity at 213 nm. In addition, many carbon-sulfur bonds that are not subject to direct dissociation at 266 nm can be selectively fragmented at 213 nm. This capability can be used to site-specifically create alaninyl radicals that direct backbone dissociation at the radical site, creating diagnostic d-ions. Furthermore, the additional carbon-sulfur bond fragmentation capability leads to signature triplets for fragmentation of disulfide bonds. Absorption of amide bonds can enhance dissociation of nearby labile carbon-sulfur bonds and can be used for stochastic backbone fragmentation typical of UVPD experiments at shorter wavelengths. Several potential applications of the bond-selective fragmentation chemistry observed at 213 nm are discussed. [Figure not available: see fulltext.

[Methods Used for Monitoring Cure Reactions in Real-time in an Autoclave

NASA Technical Reports Server (NTRS)

Cooper, John B.; Wise, Kent L.; Jensen, Brian J. (Technical Monitor)

2000-01-01

The goal of the research was to investigate methods for monitoring cure reactions in real-time in an autoclave. This is of particular importance to NASA Langley Research Center because polyimides were proposed for use in the High Speed Civil Transport (HSCT) program. Understanding the cure chemistry behind the polyimides would allow for intelligent processing of the composites made from their use. This work has led to two publications in peer-reviewed journals and a patent. The journal articles are listed as Appendix A which is on the instrument design of the research and Appendix B which is on the cure chemistry. Also, a patent has been awarded for the instrumental design developed under this grant which is given as Appendix C. There has been a significant amount of research directed at developing methods for monitoring cure reactions in real-time within the autoclave. The various research efforts can be categorized as methods providing either direct chemical bonding information or methods that provide indirect chemical bonding information. Methods falling into the latter category are fluorescence, dielectric loss, ultrasonic and similar type methods. Correlation of such measurements with the underlying chemistry is often quite difficult since these techniques do not allow monitoring of the curing chemistry which is ultimately responsible for material properties. Direct methods such as vibrational spectroscopy, however, can often be easily correlated with the underlying chemistry of a reaction. Such methods include Raman spectroscopy, mid-IR absorbance, and near-IR absorbance. With the recent advances in fiber-optics, these spectroscopic techniques can be applied to remote on-line monitoring.

Interfacial structure, bonding and composition of InAs and GaSb thin films determined using coherent Bragg rod analysis.

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

Cionca, C.; Walko, D. A.; Yacoby, Y.

2007-01-01

We have used Bragg rod x-ray diffraction combined with a direct method of phase retrieval to extract atomic resolution electron-density maps of a complementary series of heteroepitaxial III-V semiconductor samples. From the three-dimensional electron-density maps we derive the monolayer spacings, the chemical compositions, and the characteristics of the bonding for all atomic planes in the film and across the film-substrate interface. InAs films grown on GaSb(001) under two different As conditions (using dimer or tetramer forms) both showed conformal roughness and mixed GaAs/InSb interfacial bonding character. The As tetramer conditions favored InSb bonding at the interface while, in the casemore » of the dimer, the percentages corresponding to GaAs and InSb bonding were equal within the experimental error. The GaSb film grown on InAs(001) displayed significant In and As interdiffusion and had a relatively large fraction of GaAs-like bonds at the interface.« less

31 CFR 363.100 - What are the rules for purchasing and delivering gift savings bonds to minors?

Code of Federal Regulations, 2010 CFR

2010-07-01

... TreasuryDirect Gifts § 363.100 What are the rules for purchasing and delivering gift savings bonds to minors? (a) A TreasuryDirect ® account owner can purchase a savings bond as a gift with a minor as the recipient. (b) An account owner can deliver a bond purchased as a gift to a minor. The account owner must...

Chemoselective Aliphatic C–H Bond Oxidation Enabled by Polarity Reversal

PubMed Central

2017-01-01

Methods for selective oxidation of aliphatic C–H bonds are called on to revolutionize organic synthesis by providing novel and more efficient paths. Realization of this goal requires the discovery of mechanisms that can alter in a predictable manner the innate reactivity of these bonds. Ideally, these mechanisms need to make oxidation of aliphatic C–H bonds, which are recognized as relatively inert, compatible with the presence of electron rich functional groups that are highly susceptible to oxidation. Furthermore, predictable modification of the relative reactivity of different C–H bonds within a molecule would enable rapid diversification of the resulting oxidation products. Herein we show that by engaging in hydrogen bonding, fluorinated alcohols exert a polarity reversal on electron rich functional groups, directing iron and manganese catalyzed oxidation toward a priori stronger and unactivated C–H bonds. As a result, selective hydroxylation of methylenic sites in hydrocarbons and remote aliphatic C–H oxidation of otherwise sensitive alcohol, ether, amide, and amine substrates is achieved employing aqueous hydrogen peroxide as oxidant. Oxidations occur in a predictable manner, with outstanding levels of product chemoselectivity, preserving the first-formed hydroxylation product, thus representing an extremely valuable tool for synthetic planning and development. PMID:29296677

Chemoselective Aliphatic C-H Bond Oxidation Enabled by Polarity Reversal.

PubMed

Dantignana, Valeria; Milan, Michela; Cussó, Olaf; Company, Anna; Bietti, Massimo; Costas, Miquel

2017-12-27

Methods for selective oxidation of aliphatic C-H bonds are called on to revolutionize organic synthesis by providing novel and more efficient paths. Realization of this goal requires the discovery of mechanisms that can alter in a predictable manner the innate reactivity of these bonds. Ideally, these mechanisms need to make oxidation of aliphatic C-H bonds, which are recognized as relatively inert, compatible with the presence of electron rich functional groups that are highly susceptible to oxidation. Furthermore, predictable modification of the relative reactivity of different C-H bonds within a molecule would enable rapid diversification of the resulting oxidation products. Herein we show that by engaging in hydrogen bonding, fluorinated alcohols exert a polarity reversal on electron rich functional groups, directing iron and manganese catalyzed oxidation toward a priori stronger and unactivated C-H bonds. As a result, selective hydroxylation of methylenic sites in hydrocarbons and remote aliphatic C-H oxidation of otherwise sensitive alcohol, ether, amide, and amine substrates is achieved employing aqueous hydrogen peroxide as oxidant. Oxidations occur in a predictable manner, with outstanding levels of product chemoselectivity, preserving the first-formed hydroxylation product, thus representing an extremely valuable tool for synthetic planning and development.

Enantioselective Copper-Catalyzed Carboetherification of Unactivated Alkenes**

PubMed Central

Bovino, Michael T.; Liwosz, Timothy W.; Kendel, Nicole E.; Miller, Yan; Tyminska, Nina

2014-01-01

Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein is reported a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols that terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition state calculations support a cis-oxycupration stereochemistry-determining step. PMID:24798697

[Comparative study of three bonding methods in attaching removable thermoplastic appliances].

PubMed

Chu, Kejia; Wang, Haihui; Zheng, Zhijun; Li, Qi

2015-10-01

To evaluate the operation time and clinical effect of three types of materials (i.e., total-etching adhesive, self-etching adhesive, resin-modified glass ionomer cement) that are used to bond removable thermoplastic appliances. Thirty malocclusion patients (156 attachments) with removable thermoplastic appliances were randomly divided into three groups, with 10 individuals each. Attachments of groups A and B were bonded using 3M Adper Single Bond 2 and 3M Adper Easy One, respectively; both adhesives utilized 3M Z350 nano composite resin. Attachments of group C was directly bonded using GC Fuji Ortho LC. The operation time of each attachment was recorded. Failure rates of adhesion were evaluated during adhesion, 1 month after treatment, and 6 months after treatment. The operation time of group C was shorter than those of groups A and B (P<0.01). Significant difference of adhesion failure rates was not found among the three groups (P>0.05). No significant difference of adhesion failure rates was also observed in different times of the same group (P>0.05). The attachment stability of the three types of materials achieved satisfactory effects. However, the operation method of resin-modified glass ionomer cement is more concise and suitable for clinical promotion.

Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.

PubMed

Sharma, Ankit; Hartwig, John F

2013-11-27

We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by the catalytic diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S, or C-C bond at the allylic position in good yield with a high branched-to-linear selectivity and excellent enantioselectivity (ee ≤97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

Dynamic Responses and Initial Decomposition under Shock Loading: A DFTB Calculation Combined with MSST Method for β-HMX with Molecular Vacancy.

PubMed

He, Zheng-Hua; Chen, Jun; Ji, Guang-Fu; Liu, Li-Min; Zhu, Wen-Jun; Wu, Qiang

2015-08-20

Despite extensive efforts on studying the decomposition mechanism of HMX under extreme condition, an intrinsic understanding of mechanical and chemical response processes, inducing the initial chemical reaction, is not yet achieved. In this work, the microscopic dynamic response and initial decomposition of β-HMX with (1 0 0) surface and molecular vacancy under shock condition, were explored by means of the self-consistent-charge density-functional tight-binding method (SCC-DFTB) in conjunction with multiscale shock technique (MSST). The evolutions of various bond lengths and charge transfers were analyzed to explore and understand the initial reaction mechanism of HMX. Our results discovered that the C-N bond close to major axes had less compression sensitivity and higher stretch activity. The charge was transferred mainly from the N-NO2 group along the minor axes and H atom to C atom during the early compression process. The first reaction of HMX primarily initiated with the fission of the molecular ring at the site of the C-N bond close to major axes. Further breaking of the molecular ring enhanced intermolecular interactions and promoted the cleavage of C-H and N-NO2 bonds. More significantly, the dynamic response behavior clearly depended on the angle between chemical bond and shock direction.

Direct Characterization of a Reactive Lattice-Confined Ru 2 Nitride by Photocrystallography

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

Das, Anuvab; Reibenspies, Joseph H.; Chen, Yu-Sheng

2017-02-16

Reactive metal–ligand (M–L) multiply bonded complexes are ubiquitous intermediates in redox catalysis and have thus been long-standing targets of synthetic chemistry. The intrinsic reactivity of mid-to-late M–L multiply bonded complexes renders these structures challenging to isolate and structurally characterize. Although synthetic tuning of the ancillary ligand field can stabilize M–L multiply bonded complexes and result in isolable complexes, these efforts inevitably attenuate the reactivity of the M–L multiple bond. Here, we report the first direct characterization of a reactive Ru2 nitride intermediate by photocrystallography. Photogeneration of reactive M–L multiple bonds within crystalline matrices supports direct characterization of these critical intermediatesmore » without synthetic derivatization.« less

Comparative Evaluation of Effects of Laser Modalities on Shear Bond Strengths of Veneering Porcelains to Laser Sintered Substructures: An In Vitro Study.

PubMed

Gorler, Oguzhan; Saygin, Aysegul Goze

2017-06-01

Laser modalities and direct metal laser sintering (DMLS) have a potential to enhance micromechanical bonding between dental super- and infrastructures. However, the effect of different manufacturing methods on the metal-ceramic bond strength needs further evaluation. We investigated the effect of surface treatment with Er:YAG, Nd:YAG, and Ho:YAG lasers on the shear bond strength (SBS) of high-fusion dental porcelains (Vita and G-Ceram) to infrastructures prepared with DMLS in vitro settings. Study specimens (n = 128) were randomly divided into study subsets (n = 8), considering treatment types applied on the surface of infrastructures, including sandblasting and selected laser modalities; infrastructure types as direct laser sintered (DLS) and Ni-Cr based; and superstructure porcelains as Vita and G-Ceram. The SBS test was performed to assess the effectiveness of surface modifications that were also examined with a stereo microscope. Considering laser procedure types, the highest SBS values were obtained by Er:YAG laser, followed by, with a decreasing efficiency, Ho:YAG laser and sandblasting procedures, and Nd:YAG laser procedure (p < 0.05). Nd:YAG laser decreases the bonding of Vita and G-Ceram in all the infrastructures compared with sandblasting. Considering porcelains, the highest SBS values were obtained by Vita (p < 0.05). Considering infrastructures, the highest SBS values were obtained by DMLS procedure (p < 0.05). The laser procedures caused surface irregularities as revealed by the stereo microscopic examination. In current experimental settings, Er:YAG laser applied to DLS infrastructure veneered with Vita porcelain increases bonding strength more distinctly, and Nd:YAG laser applied to Ni-Cr-based infrastructure veneered with G-Ceram porcelain alters bonding strength unfavorably.

Alkali metal mediated C–C bond coupling reaction

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

Tachikawa, Hiroto, E-mail: hiroto@eng.hokudai.ac.jp

2015-02-14

Metal catalyzed carbon-carbon (C–C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz){sub 2}, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz){sub 2}, the structure of [Li(Bz){sub 2}]{sup −} was drastically changed: Bz–Bz parallel form was rapidly fluctuated as a function of time, and a new C–C single bond was formed in the C{sub 1}–C{sub 1}′ position of Bz–Bz interaction system. In the hole capture, the intermolecular vibrationmore » between Bz–Bz rings was only enhanced. The mechanism of C–C bond formation in the electron capture was discussed on the basis of theoretical results.« less

Oxidative 1,2-carboamination of alkenes with alkyl nitriles and amines toward γ-amino alkyl nitriles

NASA Astrophysics Data System (ADS)

Liu, Yan-Yun; Yang, Xu-Heng; Song, Ren-Jie; Luo, Shenglian; Li, Jin-Heng

2017-04-01

Difunctionalization of alkenes has become a powerful tool for quickly increasing molecular complexity in synthesis. Despite significant progress in the area of alkene difunctionalization involving the incorporation of a nitrogen atom across the C-C double bonds, approaches for the direct 1,2-carboamination of alkenes to produce linear N-containing molecules are scarce and remain a formidable challenge. Here we describe a radical-mediated oxidative intermolecular 1,2-alkylamination of alkenes with alkyl nitriles and amines involving C(sp3)-H oxidative functionalization catalysed by a combination of Ag2CO3 with iron Lewis acids. This three-component alkene 1,2-alkylamination method is initiated by the C(sp3)-H oxidative radical functionalization, which enables one-step formation of two new chemical bonds, a C-C bond and a C-N bond, to selectively produce γ-amino alkyl nitriles.

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

Length-dependence of intramolecular electron transfer in σ-bonded rigid molecular rods: an ab initio molecular orbital study

NASA Astrophysics Data System (ADS)

Pati, Ranjit; Karna, Shashi P.

2002-01-01

The dependence of electron transfer (ET) coupling element, VAB, on the length of rigid-rod-like systems consisting of bicyclo[1.1.1]pentane (BCP), cubane (CUB), and bicyclo[2.2.2]octane (BCO) monomers, has been investigated with the use of ab initio Hartree-Fock (HF) method employing Marcus-Hush two-state (TS) model. The value of VAB decreases exponentially with increase in the number of the cage units of the σ-bonded molecules. The calculated decay constant, β, shows good agreement with previously reported data. For molecular length⩾15 Å, the value of VAB becomes negligibly small, suggesting complete suppression of the through bond direct tunneling contribution to ET process.

Development of gas-pressure bonding process for air-cooled turbine blades

NASA Technical Reports Server (NTRS)

Meiners, K. E.

1972-01-01

An investigation was conducted on the application of gas-pressure bonding to the joining of components for convectively cooled turbine blades and vanes. A processing procedure was established for joining the fins of Udimet 700 and TD NiCr sheet metal airfoil shells to cast B1900 struts without the use of internal support tooling. Alternative methods employing support tooling were investigated. Testing procedures were developed and employed to determine shear strengths and internal burst pressures of flat and cylindrical bonded finned shell configurations at room temperature and 1750 F. Strength values were determined parallel and transverse to the cooling fin direction. The effect of thermal cycles from 1750 F to room temperature on strength was also investigated.

Quantum mechanical electronic structure calculation reveals orientation dependence of hydrogen bond energy in proteins.

PubMed

Mondal, Abhisek; Datta, Saumen

2017-06-01

Hydrogen bond plays a unique role in governing macromolecular interactions with exquisite specificity. These interactions govern the fundamental biological processes like protein folding, enzymatic catalysis, molecular recognition. Despite extensive research work, till date there is no proper report available about the hydrogen bond's energy surface with respect to its geometric parameters, directly derived from proteins. Herein, we have deciphered the potential energy landscape of hydrogen bond directly from the macromolecular coordinates obtained from Protein Data Bank using quantum mechanical electronic structure calculations. The findings unravel the hydrogen bonding energies of proteins in parametric space. These data can be used to understand the energies of such directional interactions involved in biological molecules. Quantitative characterization has also been performed using Shannon entropic calculations for atoms participating in hydrogen bond. Collectively, our results constitute an improved way of understanding hydrogen bond energies in case of proteins and complement the knowledge-based potential. Proteins 2017; 85:1046-1055. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Metal-Free Oxidative C-C Bond Formation through C-H Bond Functionalization.

PubMed

Narayan, Rishikesh; Matcha, Kiran; Antonchick, Andrey P

2015-10-12

The formation of C-C bonds embodies the core of organic chemistry because of its fundamental application in generation of molecular diversity and complexity. C-C bond-forming reactions are well-known challenges. To achieve this goal through direct functionalization of C-H bonds in both of the coupling partners represents the state-of-the-art in organic synthesis. Oxidative C-C bond formation obviates the need for prefunctionalization of both substrates. This Minireview is dedicated to the field of C-C bond-forming reactions through direct C-H bond functionalization under completely metal-free oxidative conditions. Selected important developments in this area have been summarized with representative examples and discussions on their reaction mechanisms. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterogeneous integration based on low-temperature bonding for advanced optoelectronic devices

NASA Astrophysics Data System (ADS)

Higurashi, Eiji

2018-04-01

Heterogeneous integration is an attractive approach to manufacturing future optoelectronic devices. Recent progress in low-temperature bonding techniques such as plasma activation bonding (PAB) and surface-activated bonding (SAB) enables a new approach to integrating dissimilar materials for a wide range of photonics applications. In this paper, low-temperature direct bonding and intermediate layer bonding techniques are focused, and their state-of-the-art applications in optoelectronic devices are reviewed. First, we describe the room-temperature direct bonding of Ge/Ge and Ge/Si wafers for photodetectors and of GaAs/SiC wafers for high-power semiconductor lasers. Then, we describe low-temperature intermediate layer bonding using Au and lead-free Sn-3.0Ag-0.5Cu solders for optical sensors and MEMS packaging.

Resonant inelastic X-ray scattering on ferrous and ferric bis-imidazole porphyrin and cytochrome c: Nature and role of the axial methionine-Fe bond

DOE PAGES

Kroll, Thomas; Hadt, Ryan G.; Wilson, Samuel A.; ...

2014-12-04

Axial Cu–S(Met) bonds in electron transfer (ET) active sites are generally found to lower their reduction potentials. An axial S(Met) bond is also present in cytochrome c (cyt c) and is generally thought to increase the reduction potential. The highly covalent nature of the porphyrin environment in heme proteins precludes using many spectroscopic approaches to directly study the Fe site to experimentally quantify this bond. Alternatively, L-edge X-ray absorption spectroscopy (XAS) enables one to directly focus on the 3d-orbitals in a highly covalent environment and has previously been successfully applied to porphyrin model complexes. However, this technique cannot be extendedmore » to metalloproteins in solution. Here, we use metal K-edge XAS to obtain L-edge like data through 1s2p resonance inelastic X-ray scattering (RIXS). It has been applied here to a bis-imidazole porphyrin model complex and cyt c. The RIXS data on the model complex are directly correlated to L-edge XAS data to develop the complementary nature of these two spectroscopic methods. Comparison between the bis-imidazole model complex and cyt c in ferrous and ferric oxidation states show quantitative differences that reflect differences in axial ligand covalency. The data reveal an increased covalency for the S(Met) relative to N(His) axial ligand and a higher degree of covalency for the ferric states relative to the ferrous states. These results are reproduced by DFT calculations, which are used to evaluate the thermodynamics of the Fe–S(Met) bond and its dependence on redox state. Furthermore, these results provide insight into a number of previous chemical and physical results on cyt c.« less

The Halogen Bond in the Design of Functional Supramolecular Materials: Recent Advances

PubMed Central

2013-01-01

Halogen bonding is an emerging noncovalent interaction for constructing supramolecular assemblies. Though similar to the more familiar hydrogen bonding, four primary differences between these two interactions make halogen bonding a unique tool for molecular recognition and the design of functional materials. First, halogen bonds tend to be much more directional than (single) hydrogen bonds. Second, the interaction strength scales with the polarizability of the bond-donor atom, a feature that researchers can tune through single-atom mutation. In addition, halogen bonds are hydrophobic whereas hydrogen bonds are hydrophilic. Lastly, the size of the bond-donor atom (halogen) is significantly larger than hydrogen. As a result, halogen bonding provides supramolecular chemists with design tools that cannot be easily met with other types of noncovalent interactions and opens up unprecedented possibilities in the design of smart functional materials. This Account highlights the recent advances in the design of halogen-bond-based functional materials. Each of the unique features of halogen bonding, directionality, tunable interaction strength, hydrophobicity, and large donor atom size, makes a difference. Taking advantage of the hydrophobicity, researchers have designed small-size ion transporters. The large halogen atom size provided a platform for constructing all-organic light-emitting crystals that efficiently generate triplet electrons and have a high phosphorescence quantum yield. The tunable interaction strengths provide tools for understanding light-induced macroscopic motions in photoresponsive azobenzene-containing polymers, and the directionality renders halogen bonding useful in the design on functional supramolecular liquid crystals and gel-phase materials. Although halogen bond based functional materials design is still in its infancy, we foresee a bright future for this field. We expect that materials designed based on halogen bonding could lead to applications in biomimetics, optics/photonics, functional surfaces, and photoswitchable supramolecules. PMID:23805801

Cu-catalyzed C(sp³)-H bond activation reaction for direct preparation of cycloallyl esters from cycloalkanes and aromatic aldehydes.

PubMed

Zhao, Jincan; Fang, Hong; Han, Jianlin; Pan, Yi

2014-05-02

Cu-catalyzed dehydrogenation-olefination and esterification of C(sp(3))-H bonds of cycloalkanes with TBHP as an oxidant has been developed. The reaction involves four C-H bond activations and gives cycloallyl ester products directly from cycloalkanes and aromatic aldehydes.

Directional Dependence of Hydrogen Bonds: a Density-based Energy Decomposition Analysis and Its Implications on Force Field Development

PubMed Central

Lu, Zhenyu; Zhou, Nengjie; Wu, Qin; Zhang, Yingkai

2011-01-01

One well-known shortcoming of widely-used biomolecular force fields is the description of the directional dependence of hydrogen bonding (HB). Here we aim to better understand the origin of this difficulty and thus provide some guidance for further force field development. Our theoretical approaches center on a novel density-based energy decomposition analysis (DEDA) method [J. Chem. Phys., 131, 164112 (2009)], in which the frozen density energy is variationally determined through constrained search. This unique and most significant feature of DEDA enables us to find that the frozen density interaction term is the key factor in determining the HB orientation, while the sum of polarization and charge-transfer components shows very little HB directional dependence. This new insight suggests that the difficulty for current non-polarizable force fields to describe the HB directional dependence is not due to the lack of explicit polarization or charge-transfer terms. Using the DEDA results as reference, we further demonstrate that the main failure coming from the atomic point charge model can be overcome largely by introducing extra charge sites or higher order multipole moments. Among all the electrostatic models explored, the smeared charge distributed multipole model (up to quadrupole), which also takes account of charge penetration effects, gives the best agreement with the corresponding DEDA results. Meanwhile, our results indicate that the van der Waals interaction term needs to be further improved to better model directional hydrogen bonding. PMID:22267958

Effect of smear layer deproteinization on bonding of self-etch adhesives to dentin: a systematic review and meta-analysis

PubMed Central

Alshaikh, Khaldoan H.; Mahmoud, Salah H.

2018-01-01

Objectives The aim of this systematic review was to critically analyze previously published studies of the effects of dentin surface pretreatment with deproteinizing agents on the bonding of self-etch (SE) adhesives to dentin. Additionally, a meta-analysis was conducted to quantify the effects of the above-mentioned surface pretreatment methods on the bonding of SE adhesives to dentin. Materials and Methods An electronic search was performed using the following databases: Scopus, PubMed and ScienceDirect. The online search was performed using the following keywords: ‘dentin’ or ‘hypochlorous acid’ or ‘sodium hypochlorite’ and ‘self-etch adhesive.’ The following categories were excluded during the assessment process: non-English articles, randomized clinical trials, case reports, animal studies, and review articles. The reviewed studies were subjected to meta-analysis to quantify the effect of the application time and concentration of sodium hypochlorite (NaOCl) and hypochlorous acid (HOCl) deproteinizing agents on bonding to dentin. Results Only 9 laboratory studies fit the inclusion criteria of this systematic review. The results of the meta-analysis revealed that the pooled average microtensile bond strength values to dentin pre-treated with deproteinizing agents (15.71 MPa) was significantly lower than those of the non-treated control group (20.94 MPa). Conclusions In light of the currently available scientific evidence, dentin surface pretreatment with deproteinizing agents does not enhance the bonding of SE adhesives to dentin. The HOCl deproteinizing agent exhibited minimal adverse effects on bonding to dentin in comparison with NaOCl solutions. PMID:29765895

Chemoselective phototransformation of C-H bonds on a polymer surface through a photoinduced cerium recycling redox reaction.

PubMed

Huang, Zhenhua; Wu, Zhengfang; Yang, Peng; Yang, Wantai

2014-09-01

It is generally accepted that Ce(4+) is unable to directly oxidize unreactive alkyl C-H bonds without the assistance of adjacent polar groups. Herein, we demonstrate in our newly developed confined photochemical reaction system that this recognized issue may be challenged. As we found, when a thin layer of a CeCl(3)/HCl aqueous solution was applied to a polymeric substrate and the substrate subjected to UV irradiation, Ce(3+) was first photooxidized to form Ce(4+) in the presence of H(+), and the in situ formed Ce(4+) then performs an oxidation reaction on the C-H bonds of the polymer surface to form surface-carbon radicals for radical graft polymerization reactions and functional-group transformations, while reducing to Ce(3+) and releasing H(+) in the process. This photoinduced cerium recycling redox (PCRR) reaction behaved as a biomimetic system in an artificial recycling reaction, leading to a sustainable chemical modification strategy for directly transforming alkyl C-H bonds on polymer surfaces into small-molecule groups and polymer brushes. This method is expected to provide a green and economical tool for industrial applications of polymer-surface modification. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The 2D Selfassembly of Benzimidazole and its Co-crystallization

NASA Astrophysics Data System (ADS)

Costa, Paulo; Teeter, Jacob; Kunkel, Donna; Sinitskii, Alexander; Enders, Axel

Benzimidazoles (BI) are organic molecules that form ferroelectric crystals. Key to their ferroelectric behavior are the switchable N . . . HN type bonds and how they couple to the electron system of the molecules. We attempted to crystallize BI on various metal surfaces and studied them using STM. We observed that on Au and Ag, BI joins into zipper chains characteristic of its bulk structure that can pack into a continuous 2D layer. Because the dipole of BI lies in the direction of its switchable hydrogen bond, these zippers should in principle have reversible polarizations that point along the direction they run. BI's crystallization is reminiscent to how croconic acid (CA) crystallizes in 2D using O . . . HO bonding, suggesting that these molecules may be able to co-crystallize through OH . . . N bonds. This would present the opportunity to modify BI's properties, such as the energy needed to switch a hydrogen from a donor to acceptor site. When co-deposited, CA and BI successfully combine into a co-crystal formed by building blocks consisting of 2 CA and 2 BI molecules. These findings demonstrate the usefulness of using STM as a preliminary check to verify if two molecules are compatible with each other without having to attempt crystallization with multiple solvents and mixing methods.

Copper and liquid crystal polymer bonding towards lead sensing

NASA Astrophysics Data System (ADS)

Redhwan, Taufique Z.; Alam, Arif U.; Haddara, Yaser M.; Howlader, Matiar M. R.

2018-02-01

Lead (Pb) is a highly toxic and carcinogenic heavy metal causing adverse impacts on environment and human health, thus requiring its careful monitoring. In this work, we demonstrate the integration of copper (Cu) film-based electrodes toward Pb sensing. For this, we developed a direct bonding method for Cu thin film and liquid crystal polymer (LCP) substrate using oxygen plasma treatment followed by contact and heat at 230 °C. The oxygen plasma activation forms hydroxyl groups (OH-) on Cu and LCP. The activated surfaces further adsorb water molecules when exposed to clean room air during contact. After contact, hydrogen bonds are formed between the OH- groups. The interfacial water is removed when the contacted films are heated, leading to shrinkage of OH- chain. This results in an intermediate oxide layer linking the Cu and C sites of Cu and LCP respectively. A strong adhesion (670 N·m-1) is obtained between Cu/LCP that may offer prolonged use of the electrode without delamination in wet sensing applications. Anodic stripping voltammetry of Pb using Cu thin film electrode shows a stronger current peak than sputtered Cu electrode, which implies the significance of the direct bonding approach to integrate thin films. We also studied the electrochemical impedance that will enable modeling of integrated environmental sensors for on-site monitoring of heavy metals.

Convenient Relations for the Estimation of Bond Ionicity in A-B Type Compounds.

ERIC Educational Resources Information Center

Barbe, Jacques

1983-01-01

Bond character is directly conditioned by the peculiar capacity of bonded atoms to exchange electrons; such a capacity is clearly illustrated by electronegativity. The determination of bond character using the electronegativity difference between the bonded atoms is discussed and an equation focusing on relationships between bonds is provided. (JN)

A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation

NASA Astrophysics Data System (ADS)

Garrison Kinney, R.; Tjutrins, Jevgenijs; Torres, Gerardo M.; Liu, Nina Jiabao; Kulkarni, Omkar; Arndtsen, Bruce A.

2018-02-01

The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.

31 CFR 363.161 - What definitive savings bonds are eligible to be converted to book-entry bonds?

Code of Federal Regulations, 2010 CFR

2010-07-01

... Bond § 363.161 What definitive savings bonds are eligible to be converted to book-entry bonds? Series E... eligible to be converted to book-entry bonds? 363.161 Section 363.161 Money and Finance: Treasury... conversion to book-entry bonds in TreasuryDirect®. [74 FR 19420, Apr. 29, 2009] ...

Method of Fabricating a Composite Apparatus

NASA Technical Reports Server (NTRS)

Wilkie, W. Keats (Inventor); Bryant, Robert G. (Inventor); Fox, Robert L. (Inventor); Hellbaum, Richard F. (Inventor); High, James W. (Inventor); Jalink, Antony, Jr. (Inventor)

2007-01-01

A method for fabricating a piezoelectric macro-fiber composite actuator comprises making a piezoelectric fiber sheet by providing a plurality of wafers of piezoelectric material, bonding the wafers together with an adhesive material to from a stack of alternating layers of piezoelectric material and adhesive material, and cutting through the stack in a direction substantially parallel to the thickness of the stack and across the alternating layers of piezoelectric material and adhesive material to provide at least one piezoelectric fiber sheet having two sides comprising a plurality of piezoelectric fibers in juxtaposition to the adhesive material. The method further comprises bonding two electrically conductive films to the two sides of the piezoelectric fiber sheet. At least one conductive film has first and second conductive patterns formed thereon which are electrically isolated from one another and in electrical contact with the piezoelectric fiber sheet.

Reduction of the potential energy barrier and resistance at wafer-bonded n-GaAs/n-GaAs interfaces by sulfur passivation

NASA Astrophysics Data System (ADS)

Jackson, Michael J.; Jackson, Biyun L.; Goorsky, Mark S.

2011-11-01

Sulfur passivation and subsequent wafer-bonding treatments are demonstrated for III-V semiconductor applications using GaAs-GaAs direct wafer-bonded structures. Two different sulfur passivation processes are addressed. A dry sulfur passivation method that utilizes elemental sulfur vapor activated by ultraviolet light in vacuum is compared with aqueous sulfide and native-oxide-etch treatments. The electrical conductivity across a sulfur-treated 400 - °C-bonded n-GaAs/n-GaAs interface significantly increased with a short anneal (1-2 min) at elevated temperatures (500-600 °C). Interfaces treated with the NH4OH oxide etch, on the other hand, exhibited only mild improvement in accordance with previously published studies in this area. TEM and STEM images revealed similar interfacial microstructure changes with annealing for both sulfur-treated and NH4OH interfaces, whereby some areas have direct semiconductor-semiconductor contact without any interfacial layer. Fitting the observed temperature dependence of zero-bias conductance using a model for tunneling through a grain boundary reveals that the addition of sulfur at the interface lowered the interfacial energy barrier by 0.2 eV. The interface resistance for these sulfur-treated structures is 0.03 Ω.cm at room temperature. These results emphasize that sulfur-passivation techniques reduce interface states that otherwise limit the implementation of wafer bonding for high-efficiency solar cells and other devices.

Low-cost fabrication and direct bond installation of flat, single-curvature and compound-curvature ablative heat shield panels

NASA Technical Reports Server (NTRS)

Norwood, L. B.

1972-01-01

Procedures for low cost fabrication and direct bond installation of flat, single curved, and compound curvature ablative heat shields on a DC-3 aircraft are discussed. The panel sizes and attachment locations are identified. In addition to the bonding of the four contoured panels, two flat panels were bonded to the nearly flat, lower surface of the center wing section. The detailed requirements and objectives of the investigation are described.

First principles study of the electronic properties and band gap modulation of two-dimensional phosphorene monolayer: Effect of strain engineering

NASA Astrophysics Data System (ADS)

Phuc, Huynh V.; Hieu, Nguyen N.; Ilyasov, Victor V.; Phuong, Le T. T.; Nguyen, Chuong V.

2018-06-01

The effect of strain on the structural and electronic properties of monolayer phosphorene is studied by using first-principle calculations based on the density functional theory. The intra- and inter-bond length and bond angle for monolayer phosphorene is also evaluated. The intra- and inter-bond length and the bond angle for phosphorene show an opposite tendency under different directions of the applied strain. At the equilibrium state, monolayer phosphorene is a semiconductor with a direct band gap at the Γ-point of 0.91 eV. A direct-indirect band gap transition is found in monolayer phosphorene when both the compression and tensile strain are simultaneously applied along both zigzag and armchair directions. Under the applied compression strain, a semiconductor-metal transition for monolayer phosphorene is observed at -13% and -10% along armchair and zigzag direction, respectively. The direct-indirect and phase transition will largely constrain application of monolayer phosphorene to electronic and optical devices.

Interrogating heterobimetallic co-catalytic responses for the electrocatalytic reduction of CO2 using supramolecular assembly.

PubMed

Machan, Charles W; Kubiak, Clifford P

2016-10-12

The use of hydrogen-bonding interactions to direct the non-covalent assembly of a heterobimetallic supramolecular system with Re and Mn bipyridine-based electrocatalysts is reported. Under catalytic conditions, the formation of hydrogen bonds generates a catalyst system which passes ∼10% more current than the individual current responses of the respective Re and Mn complexes for the reduction of CO 2 to CO and H 2 O. Infrared spectroelectrochemical studies indicate that the Re and Mn metal centers interact during the reduction mechanism, even forming heterobimetallic bonds under reducing conditions in the absence of substrate. These findings demonstrate that non-covalent assembly is a powerful method for generating new co-catalyst systems with greater reactivity and efficiency for transformations of interest.

Fabrication of power SDB SITH

NASA Astrophysics Data System (ADS)

Jiang, Yanfeng; Zhang, Changnian; Zhang, Xiaobo

2005-02-01

In this paper, a novel method for fabricating a static induction thyristor has been put forward, using silicon direct bonding instead of traditional epitaxy during the construction of a cathode. Thus, an obvious improvement of the breakdown value of gate-cathode junction has been observed and consequently the gate controllability on anode voltage has been enhanced. The bonded interface has been studied. Some adjustments in technology have been adopted to enhance the bonding quality. A way to guarantee the consistency of the breakdown voltage of gate junction with respect to the cathode has been advanced. Some measurements of I-V characteristic of SDB-SITH have been carried out and the practical result is also listed. A comparison between the SDB-SITH and epitaxial SITH has been made, mainly on I-V and the switching time.

Rhodium(III)-catalyzed vinylic sp2 C-H bond functionalization: efficient synthesis of pyrido[1,2-α]benzimidazoles and imidazo[1,2-α]pyridines.

PubMed

Dong, Lin; Huang, Ji-Rong; Qu, Chuan-Hua; Zhang, Qian-Ru; Zhang, Wei; Han, Bo; Peng, Cheng

2013-09-28

A simple approach for synthesis of novel aza-fused scaffolds such as pyrido[1,2-α]benzimidazoles and imidazo[1,2-α]pyridines was developed by Rh(III)-catalyzed direct oxidative coupling between alkenes and unactivated alkynes without an extra directing group. The method would allow a broad substrate scope, providing fused heterocycles with potential biological properties.

26 CFR 1.148-0 - Scope and table of contents.

Code of Federal Regulations, 2010 CFR

2010-04-01

... method. (b) Allocation of gross proceeds to an issue. (1) One-issue rule and general ordering rules. (2... for which the bonds were issued. To accomplish these purposes, section 148 restricts the direct and... substance. (4) Reasonable charge. (5) Guarantee of purpose investments. (6) Allocation of qualified...

Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

PubMed

Bovino, Michael T; Liwosz, Timothy W; Kendel, Nicole E; Miller, Yan; Tyminska, Nina; Zurek, Eva; Chemler, Sherry R

2014-06-16

Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancement of visible photoluminescence in the SiNx films by SiO2 buffer and annealing

NASA Astrophysics Data System (ADS)

Xu, M.; Xu, S.; Chai, J. W.; Long, J. D.; Ee, Y. C.

2006-12-01

The authors report a simple method to significantly enhance the photoluminescence (PL) of SiNx films by incorporating a SiO2 buffer and annealing treatment under N2 protection. Strong visible PL is achieved with annealing temperature above 650°C. Optimal PL is obtained at 800°C. The composition and structure analysis reveal that strong PL is directly related to the content of the Si-O and Si-N bonds in the SiNx films. These bonds provide effective luminescent centers and passivate the interface between Si core and the surrounding oxide.

Solid-Liquid Interdiffusion Bonding of Silicon Carbide to Steel for High Temperature MEMS Sensor Packaging and Bonding

NASA Astrophysics Data System (ADS)

Chan, Matthew Wei-Jen

Complex engineering systems ranging from automobile engines to geothermal wells require specialized sensors to monitor conditions such as pressure, acceleration and temperature in order to improve efficiency and monitor component lifetime in what may be high temperature, corrosive, harsh environments. Microelectromechanical systems (MEMS) have demonstrated their ability to precisely and accurately take measurements under such conditions. The systems being monitored are typically made from metals, such as steel, while the MEMS sensors used for monitoring are commonly fabricated from silicon, silicon carbide and aluminum nitride, and so there is a sizable thermal expansion mismatch between the two. For these engineering applications the direct bonding of MEMS sensors to the components being monitored is often required. This introduces several challenges, namely the development of a bond that is capable of surviving high temperature harsh environments while mitigating the thermally induced strains produced during bonding. This project investigates the development of a robust packaging and bonding process, using the gold-tin metal system and the solid-liquid interdiffusion (SLID) bonding process, to join silicon carbide substrates directly to type-316 stainless steel. The SLID process enables bonding at lower temperatures while producing a bond capable of surviving higher temperatures. Finite element analysis was performed to model the thermally induced strains generated in the bond and to understand the optimal way to design the bond. The cross-sectional composition of the bonds has been analyzed and the bond strength has been investigated using die shear testing. The effects of high temperature aging on the bond's strength and the metallurgy of the bond were studied. Additionally, loading of the bond was performed at temperatures over 415 °C, more than 100 °C, above the temperature used for bonding, with full survival of the bond, thus demonstrating the benefit of SLID bonding for high temperature applications. Lastly, this dissertation provides recommendations for improving the strength and durability of the bond at temperatures of 400 °C and provides the framework for future work in the area of high temperature harsh environment MEMS packaging that would take directly bonded MEMS to temperatures of 600 °C and beyond.

Flexure mechanism-based parallelism measurements for chip-on-glass bonding

NASA Astrophysics Data System (ADS)

Jung, Seung Won; Yun, Won Soo; Jin, Songwan; Kim, Bo Sun; Jeong, Young Hun

2011-08-01

Recently, liquid crystal displays (LCDs) have played vital roles in a variety of electronic devices such as televisions, cellular phones, and desktop/laptop monitors because of their enhanced volume, performance, and functionality. However, there is still a need for thinner LCD panels due to the trend of miniaturization in electronic applications. Thus, chip-on-glass (COG) bonding has become one of the most important aspects in the LCD panel manufacturing process. In this study, a novel sensor was developed to measure the parallelism between the tooltip planes of the bonding head and the backup of the COG main bonder, which has previously been estimated by prescale pressure films in industry. The sensor developed in this study is based on a flexure mechanism, and it can measure the total pressing force and the inclination angles in two directions that satisfy the quantitative definition of parallelism. To improve the measurement accuracy, the sensor was calibrated based on the estimation of the total pressing force and the inclination angles using the least-squares method. To verify the accuracy of the sensor, the estimation results for parallelism were compared with those from prescale pressure film measurements. In addition, the influence of parallelism on the bonding quality was experimentally demonstrated. The sensor was successfully applied to the measurement of parallelism in the COG-bonding process with an accuracy of more than three times that of the conventional method using prescale pressure films.

Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds

DOEpatents

Hartwig, John F.; Kawatsura, Motoi; Loeber, Oliver

2002-01-01

The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

Direct Detection of a Chemical Equilibrium between a Localized Singlet Diradical and Its σ-Bonded Species by Time-Resolved UV/Vis and IR Spectroscopy.

PubMed

Yoshidomi, Shohei; Mishima, Megumi; Seyama, Shin; Abe, Manabu; Fujiwara, Yoshihisa; Ishibashi, Taka-Aki

2017-03-06

Localized singlet diradicals are key intermediates in bond homolyses. The singlet diradicals are energetically much less stable than the σ-bonded species. In general, only one-way reactions from diradicals to σ-bonded species are observed. In this study, a thermal equilibrium between a singlet 1,2-diazacyclopentane-3,5-diyl diradical and the corresponding σ-bonded species was directly observed. The singlet diradical was more stable than the σ-bonded species. The solvent effect clarified key features, such as the zwitterionic character of the singlet diradical. The effect of the nitrogen atoms is discussed in detail. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

PubMed

Wang, He; Tang, Guodong; Li, Xingwei

2015-10-26

Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anisotropic effect of the magnetic sensor formed from metal/high-Tc superconductor contact

NASA Astrophysics Data System (ADS)

Miyake, S.; Aoyama, T.; Suzuki, Y.; Kusaka, T.; Yotsuya, T.

1991-03-01

The magnetic sensor formed via a metal/high-Tc superconductor small contact shows anisotropic properties below the lower critical field. An Ag wire was connected directly to the superconductor by an ultrasonic bonding method. It is shown that the resistance was changed by the field parallel to the superconductor surface, while it was not affected by the vertical field. The change is estimated to be 5 x 10 to the -5th ohm/G. No hysteresis is observed. Magnetic field direction can be detected by using these properties and a deferential measuring method of the resistance.

Applications of the silicon wafer direct-bonding technique to electron devices

NASA Astrophysics Data System (ADS)

Furukawa, K.; Nakagawa, A.

1990-01-01

A silicon wafer direct-bonding (SDB) technique has been developed. A pair of bare silicon wafers, as well as an oxidized wafer pair, are bonded throughout the wafer surfaces without any bonding material. Conventional semiconductor device processes can be used for the bonded wafers, since the bonded interface is stable thermally, chemically, mechanically and electrically. Therefore, the SDB technique is very attractive, and has been applied to several kinds of electron devices. Bare silicon to bare silicon bonding is an alternative for epitaxial growth. A thick, high quality and high resistivity layer on a low resistivity substrate was obtained without autodoping. 1800 V insulated gate bipolar transistors were developed using these SDB wafers. No electrical resistance was observed at the bonded bare silicon interfaces. If oxidized wafers are bonded, the two wafers are electrically isolated, providing silicon on insulator (SOI) wafers. Dielectrically isolated photodiode arrays were fabricated on the SOI wafers and 500 V power IC's are now being developed.

Robust, directed assembly of fluorescent nanodiamonds.

PubMed

Kianinia, Mehran; Shimoni, Olga; Bendavid, Avi; Schell, Andreas W; Randolph, Steven J; Toth, Milos; Aharonovich, Igor; Lobo, Charlene J

2016-10-27

Arrays of fluorescent nanoparticles are highly sought after for applications in sensing, nanophotonics and quantum communications. Here we present a simple and robust method of assembling fluorescent nanodiamonds into macroscopic arrays. Remarkably, the yield of this directed assembly process is greater than 90% and the assembled patterns withstand ultra-sonication for more than three hours. The assembly process is based on covalent bonding of carboxyl to amine functional carbon seeds and is applicable to any material, and to non-planar surfaces. Our results pave the way to directed assembly of sensors and nanophotonics devices.

Application of chiral critical clusters to assymetric synthesis

DOEpatents

Ferrieri, Richard A.

2002-01-01

Disclosed is a composition, a method of making and a method of using critical clusters for asymmetric synthesis using substantially optically-pure chiral solvent molecules in a supercritical fluid. The solvent molecules are capable of forming a multipoint hydrogen bonded solvate as they encage at least one solute molecule. The encaged solute molecule is capable of reacting to form an optically active chiral center. In another aspect, there is disclosed a method of directing the position of bonding between a solute molecule and a ligand involving encaging the solute molecule and the ligand with polar solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to change electric charge distribution in the solute molecule. In yet another aspect, disclosed is a method of making pharmaceutical compounds involving encaging a solute molecule, which is capable of forming a chiral center, and a ligand with polar solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to change electric charge distribution of the solute molecule. The solute molecule and ligand are then reacted whereby the ligand bonds to the solute molecule forming a chiral center. Also disclosed is a method for racemic resolution using critical clusters involving encaging racemic mixtures of solute molecules with substantially optically-pure chiral solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to form critical clusters. The solvent molecules are capable of multipoint hydrogen bonding with the solute molecules. The encaged solute molecules are then nonenzymatically reacted to enhance the optical purity of the solute molecules.

A comparison of retentive strength of implant cement depending on various methods of removing provisional cement from implant abutment

PubMed Central

Keum, Eun-Cheol

2013-01-01

PURPOSE This study evaluated the effectiveness of various methods for removing provisional cement from implant abutments, and what effect these methods have on the retention of prosthesis during the definitive cementation. MATERIALS AND METHODS Forty implant fixture analogues and abutments were embedded in resin blocks. Forty cast crowns were fabricated and divided into 4 groups each containing 10 implants. Group A was cemented directly with the definitive cement (Cem-Implant). The remainder were cemented with provisional cement (Temp-Bond NE), and classified according to the method for cleaning the abutments. Group B used a plastic curette and wet gauze, Group C used a rubber cup and pumice, and Group D used an airborne particle abrasion technique. The abutments were observed using a stereomicroscope after removing the provisional cement. The tensile bond strength was measured after the definitive cementation. Statistical analysis was performed using one-way analysis of variance test (α=.05). RESULTS Group B clearly showed provisional cement remaining, whereas the other groups showed almost no cement. Groups A and B showed a relatively smooth surface. More roughness was observed in Group C, and apparent roughness was noted in Group D. The tensile bond strength tests revealed Group D to have significantly the highest tensile bond strength followed in order by Groups C, A and B. CONCLUSION A plastic curette and wet gauze alone cannot effectively remove the residual provisional cement on the abutment. The definitive retention increased when the abutments were treated with rubber cup/pumice or airborne particle abraded to remove the provisional cement. PMID:24049563

σ-Hole Bond vs π-Hole Bond: A Comparison Based on Halogen Bond.

PubMed

Wang, Hui; Wang, Weizhou; Jin, Wei Jun

2016-05-11

The σ-hole and π-hole are the regions with positive surface electrostatic potential on the molecule entity; the former specifically refers to the positive region of a molecular entity along extension of the Y-Ge/P/Se/X covalent σ-bond (Y = electron-rich group; Ge/P/Se/X = Groups IV-VII), while the latter refers to the positive region in the direction perpendicular to the σ-framework of the molecular entity. The directional noncovalent interactions between the σ-hole or π-hole and the negative or electron-rich sites are named σ-hole bond or π-hole bond, respectively. The contributions from electrostatic, charge transfer, and other terms or Coulombic interaction to the σ-hole bond and π-hole bond were reviewed first followed by a brief discussion on the interplay between the σ-hole bond and the π-hole bond as well as application of the two types of noncovalent interactions in the field of anion recognition. It is expected that this review could stimulate further development of the σ-hole bond and π-hole bond in theoretical exploration and practical application in the future.

Theoretical study on the polar hydrogen-π (Hp-π) interactions between protein side chains

PubMed Central

2013-01-01

Background In the study of biomolecular structures and interactions the polar hydrogen-π bonds (Hp-π) are an extensive molecular interaction type. In proteins 11 of 20 natural amino acids and in DNA (or RNA) all four nucleic acids are involved in this type interaction. Results The Hp-π in proteins are studied using high level QM method CCSD/6-311 + G(d,p) + H-Bq (ghost hydrogen basis functions) in vacuum and in solutions (water, acetonitrile, and cyclohexane). Three quantum chemical methods (B3LYP, CCSD, and CCSD(T)) and three basis sets (6-311 + G(d,p), TZVP, and cc-pVTZ) are compared. The Hp-π donors include R2NH, RNH2, ROH, and C6H5OH; and the acceptors are aromatic amino acids, peptide bond unit, and small conjugate π-groups. The Hp-π interaction energies of four amino acid pairs (Ser-Phe, Lys-Phe, His-Phe, and Tyr-Phe) are quantitatively calculated. Conclusions Five conclusion points are abstracted from the calculation results. (1) The common DFT method B3LYP fails in describing the Hp-π interactions. On the other hand, CCSD/6-311 + G(d,p) plus ghost atom H-Bq can yield better results, very close to the state-of-the-art method CCSD(T)/cc-pVTZ. (2) The Hp-π interactions are point to π-plane interactions, possessing much more interaction conformations and broader energy range than other interaction types, such as common hydrogen bond and electrostatic interactions. (3) In proteins the Hp-π interaction energies are in the range 10 to 30 kJ/mol, comparable or even larger than common hydrogen bond interactions. (4) The bond length of Hp-π interactions are in the region from 2.30 to 3.00 Å at the perpendicular direction to the π-plane, much longer than the common hydrogen bonds (~1.9 Å). (5) Like common hydrogen bond interactions, the Hp-π interactions are less affected by solvation effects. PMID:23705926

Free energy simulations and MM-PBSA analyses on the affinity and specificity of steroid binding to antiestradiol antibody.

PubMed

Laitinen, Tuomo; Kankare, Jussi A; Peräkylä, Mikael

2004-04-01

Antiestradiol antibody 57-2 binds 17beta-estradiol (E2) with moderately high affinity (K(a) = 5 x 10(8) M(-1)). The structurally related natural estrogens estrone and estriol as well synthetic 17-deoxy-estradiol and 17alpha-estradiol are bound to the antibody with 3.7-4.9 kcal mol(-1) lower binding free energies than E2. Free energy perturbation (FEP) simulations and the molecular mechanics-Poisson-Boltzmann surface area (MM-PBSA) method were applied to investigate the factors responsible for the relatively low cross-reactivity of the antibody with these four steroids, differing from E2 by the substituents of the steroid D-ring. In addition, computational alanine scanning of the binding site residues was carried out with the MM-PBSA method. Both the FEP and MM-PBSA methods reproduced the experimental relative affinities of the five steroids in good agreement with experiment. On the basis of FEP simulations, the number of hydrogen bonds formed between the antibody and steroids, which varied from 0 to 3 in the steroids studied, determined directly the magnitude of the steroid-antibody interaction free energies. One hydrogen bond was calculated to contribute about 3 kcal mol(-1) to the interaction energy. Because the relative binding free energies of estrone (two antibody-steroid hydrogen bonds), estriol (three hydrogen bonds), 17-deoxy-estradiol (no hydrogen bonds), and 17alpha-estradiol (two hydrogen bonds) are close to each other and clearly lower than that of E2 (three hydrogen bonds), the water-steroid interactions lost upon binding to the antibody make an important contribution to the binding free energies. The MM-PBSA calculations showed that the binding of steroids to the antiestradiol antibody is driven by van der Waals interactions, whereas specificity is solely due to electrostatic interactions. In addition, binding of steroids to the antiestradiol antibody 57-2 was compared to the binding to the antiprogesterone antibody DB3 and antitestosterone antibody 3-C4F5, studied earlier with the MM-PBSA method. Copyright 2004 Wiley-Liss, Inc.

Optimizing dentin bond durability: strategies to prevent hydrolytic degradation of the hybrid layer

PubMed Central

Tjäderhane, Leo; Nascimento, Fabio D.; Breschi, Lorenzo; Mazzoni, Annalisa; Tersariol, Ivarne L.S.; Geraldeli, Saulo; Tezvergil-Mutluay, Arzu; Carrilho, Marcela; Carvalho, Ricardo M.; Tay, Franklin R.; Pashley, David H.

2014-01-01

Objectives Endogenous dentin collagenolytic enzymes, matrix metalloproteinases (MMPs) and cysteine cathepsins, are responsible for the time-related hydrolysis of collagen matrix of the hybrid layers. As the integrity of the collagen matrix is essential for the preservation of long-term dentin bond strength, inhibition or inactivation of endogenous dentin proteases is necessary for durable resin-bonded composite resin restorations. Methods Dentin contains collagenolytic enzymes, matrix metalloproteinases (MMPs) and cysteine cathepsins, which are responsible for the hydrolytic degradation of collagen matrix in the bonded interface. Several tentative approaches to prevent enzyme function either directly or indirectly have been proposed in the literature. Results Chlorhexidine, a general inhibitor of both MMPs and cysteine cathepsins, applied before primer/adhesive application is the most tested method. In general, these experiments have shown that enzyme inhibition is a promising scheme to improve hybrid layer preservation and bond strength durability. Other enzyme inhibitors, e.g. enzyme-inhibiting monomers and antimicrobial compounds, may be considered promising alternatives that would allow more simple clinical application than chlorhexidine. Cross-linking collagen and/or dentin organic matrix-bound enzymes could render hybrid layer organic matrix resistant to degradation, and complete removal of water from the hybrid layer with ethanol wet bonding or biomimetic remineralization should eliminate hydrolysis of both collagen and resin components. Significance Identification of the enzymes responsible for the hydrolysis of hybrid layer collagen and understanding their function has prompted several innovative approaches to retain the hybrid layer integrity and strong dentin bonding. The ultimate goal, prevention of collagen matrix degradation with techniques and commercially available materials that are simple and effective in clinical settings may be achievable in several ways, and will likely become reality in the near future. PMID:23953737

Evaluation of bonding agent application on concrete patch performance.

DOT National Transportation Integrated Search

2014-08-01

The durability of partial depth repair is directly related to the bond strength between the repair material and existing : concrete. Bond strength development sensitivity to wait time with the use of bonding agents in partial depth repair was : inves...

Low-temperature direct copper-to-copper bonding enabled by creep on (111) surfaces of nanotwinned Cu

PubMed Central

Liu, Chien-Min; Lin, Han-Wen; Huang, Yi-Sa; Chu, Yi-Cheng; Chen, Chih; Lyu, Dian-Rong; Chen, Kuan-Neng; Tu, King-Ning

2015-01-01

Direct Cu-to-Cu bonding was achieved at temperatures of 150–250 °C using a compressive stress of 100 psi (0.69 MPa) held for 10–60 min at 10−3 torr. The key controlling parameter for direct bonding is rapid surface diffusion on (111) surface of Cu. Instead of using (111) oriented single crystal of Cu, oriented (111) texture of extremely high degree, exceeding 90%, was fabricated using the oriented nano-twin Cu. The bonded interface between two (111) surfaces forms a twist-type grain boundary. If the grain boundary has a low angle, it has a hexagonal network of screw dislocations. Such network image was obtained by plan-view transmission electron microscopy. A simple kinetic model of surface creep is presented; and the calculated and measured time of bonding is in reasonable agreement. PMID:25962757

7 CFR 3560.62 - Technical, legal, insurance, and other services.

Code of Federal Regulations, 2010 CFR

2010-01-01

... SERVICE, DEPARTMENT OF AGRICULTURE DIRECT MULTI-FAMILY HOUSING LOANS AND GRANTS Direct Loan and Grant... requirements in § 3560.105. (e) Surety bonding. Applicants must comply with the surety bonding provisions of 7...

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.

Hydrogen bonding directed self-assembly of small-molecule amphiphiles in water.

PubMed

Xu, Jiang-Fei; Niu, Li-Ya; Chen, Yu-Zhe; Wu, Li-Zhu; Tung, Chen-Ho; Yang, Qing-Zheng

2014-08-01

Compounds comprising one or two quadruply hydrogen bonding units, 2-ureido-4[1H]-pyrimidinone (UPy) and tris(tetraethylene glycol monomethyl ether) moieties, were reported to form highly stable hydrogen-bonded assemblies in water. Compound 1, containing one UPy, assembles into vesicles, and compound 2, containing two UPy units, forms micelles. The aggregates disassemble reversibly when the solution pH is raised to 9.0 or above. The results demonstrate the utility of hydrogen bonding to direct the self-assembly of small-molecule building blocks in aqueous media.

Bi-directional ultrasonic wave coupling to FBGs in continuously bonded optical fiber sensing.

PubMed

Wee, Junghyun; Hackney, Drew; Bradford, Philip; Peters, Kara

2017-09-01

Fiber Bragg grating (FBG) sensors are typically spot-bonded onto the surface of a structure to detect ultrasonic waves in laboratory demonstrations. However, to protect the rest of the optical fiber from any environmental damage during real applications, bonding the entire length of fiber, called continuous bonding, is commonly done. In this paper, we investigate the impact of continuously bonding FBGs on the measured Lamb wave signal. In theory, the ultrasonic wave signal can bi-directionally transfer between the optical fiber and the plate at any adhered location, which could potentially produce output signal distortion for the continuous bonding case. Therefore, an experiment is performed to investigate the plate-to-fiber and fiber-to-plate signal transfer, from which the signal coupling coefficient of each case is theoretically estimated based on the experimental data. We demonstrate that the two coupling coefficients are comparable, with the plate-to-fiber case approximately 19% larger than the fiber-to-plate case. Finally, the signal waveform and arrival time of the output FBG responses are compared between the continuous and spot bonding cases. The results indicate that the resulting Lamb wave signal output is only that directly detected at the FBG location; however, a slight difference in signal waveform is observed between the two bonding configurations. This paper demonstrates the practicality of using continuously bonded FBGs for ultrasonic wave detection in structural health monitoring (SHM) applications.

Molecular dynamics simulations of the amino acid-ZnO (10-10) interface: a comparison between density functional theory and density functional tight binding results.

PubMed

grosse Holthaus, Svea; Köppen, Susan; Frauenheim, Thomas; Ciacchi, Lucio Colombi

2014-06-21

We investigate the adsorption behavior of four different amino acids (glutamine, glutamate, serine, cysteine) on the zinc oxide (101̄0) surface, comparing the geometry and energy associated with a number of different adsorption configurations. In doing this, we highlight the benefits and limits of using density-functional tight-binding (DFTB) with respect to standard density functional theory (DFT). The DFTB method is found to reliably reproduce the DFT adsorption geometries. Analysis of the adsorption configurations emphasizes the fundamental role of the first hydration layer in mediating the interactions between the amino acids and the surface. Direct surface-molecule bonds are found to form predominantly via the carboxylate groups of the studied amino acids. No surface-mediated chemical reactions are observed, with the notable exception of a proton transfer from the thiol group of cysteine to a hydroxyl group of the surface hydration layer. The adsorption energies are found to be dominated both by the formation of direct or indirect surface-molecule hydrogen bonds, but also by the rearrangement of the hydrogen-bond network in surface proximity in a non-intuitive way. Energetic comparisons between DFTB and DFT are made difficult on one side by the long time necessary to achieve convergence of potential energy values in MD simulations and on the other side by the necessity of including higher-order corrections to DFTB to obtain a good description of the hydrogen bond energetics. Overall, our results suggest that DFTB is a good reference method to set the correct chemical states and the initial geometries of hybrid biomolecule/ZnO systems to be simulated with non-reactive force fields.

Molecular dynamics simulations of the amino acid-ZnO (10-10) interface: A comparison between density functional theory and density functional tight binding results

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

Holthaus, Svea große; Köppen, Susan, E-mail: koeppen@hmi.uni-bremen.de; Frauenheim, Thomas

2014-06-21

We investigate the adsorption behavior of four different amino acids (glutamine, glutamate, serine, cysteine) on the zinc oxide (101{sup ¯}0) surface, comparing the geometry and energy associated with a number of different adsorption configurations. In doing this, we highlight the benefits and limits of using density-functional tight-binding (DFTB) with respect to standard density functional theory (DFT). The DFTB method is found to reliably reproduce the DFT adsorption geometries. Analysis of the adsorption configurations emphasizes the fundamental role of the first hydration layer in mediating the interactions between the amino acids and the surface. Direct surface-molecule bonds are found to formmore » predominantly via the carboxylate groups of the studied amino acids. No surface-mediated chemical reactions are observed, with the notable exception of a proton transfer from the thiol group of cysteine to a hydroxyl group of the surface hydration layer. The adsorption energies are found to be dominated both by the formation of direct or indirect surface-molecule hydrogen bonds, but also by the rearrangement of the hydrogen-bond network in surface proximity in a non-intuitive way. Energetic comparisons between DFTB and DFT are made difficult on one side by the long time necessary to achieve convergence of potential energy values in MD simulations and on the other side by the necessity of including higher-order corrections to DFTB to obtain a good description of the hydrogen bond energetics. Overall, our results suggest that DFTB is a good reference method to set the correct chemical states and the initial geometries of hybrid biomolecule/ZnO systems to be simulated with non-reactive force fields.« less

Method of fabricating a PbS-PbSe IR detector array

NASA Technical Reports Server (NTRS)

Barrett, John R. (Inventor)

1987-01-01

A silicon wafer is provided which does not employ individually bonded leads between the IR sensitive elements and the input stages of multiplexers. The wafer is first coated with lead selenide in a first detector array area and is thereafter coated with lead sulfide within a second detector array area. The described steps result in the direct chemical deposition of lead selenide and lead sulfide upon the silicon wafer to eliminate individual wire bonding, bumping, flip chiping, planar interconnecting methods of connecting detector array elements to silicon chip circuitry, e.g., multiplexers, to enable easy fabrication of very long arrays. The electrode structure employed, produces an increase in the electrical field gradient between the electrodes for a given volume of detector material, relative to conventional electrode configurations.

‘Umpolung’ Reactivity in Semiaqueous Amide and Peptide Synthesis

PubMed Central

Shen, Bo; Makley, Dawn M.; Johnston, Jeffrey N.

2010-01-01

The amide functional group is one of Nature’s key functional and structural elements, most notably within peptides. Amides are also key intermediates in the preparation of a diverse range of therapeutic small molecules. Its construction using available methods focuses principally upon dehydrative approaches, although oxidative and radical-based methods are representative alternatives. During the carbon-nitrogen bond forming step in most every example, the carbon and nitrogen bear electrophilic and nucleophilic character, respectively. Here we show that activation of amines and nitroalkanes with an electrophilic iodine source in wet THF can lead directly to amide products. Preliminary observations support a mechanistic construct in which reactant polarity is reversed (umpolung) during C-N bond formation relative to traditional approaches. The use of nitroalkanes as acyl anion equivalents provides a conceptually innovative approach to amide and peptide synthesis, and one that might ultimately provide for efficient peptide synthesis that is fully reliant on enantioselective methods. PMID:20577205

Reduction of the coupling vibration between the bending vibrators of the frequency-change-type two-axis acceleration sensor

NASA Astrophysics Data System (ADS)

Sugawara, Sumio; Sasaki, Yoshifumi; Kudo, Subaru

2018-07-01

The frequency-change-type two-axis acceleration sensor uses a cross-type vibrator consisting of four bending vibrators. When coupling vibration exists between these four bending vibrators, the resonance frequency of each vibrator cannot be adjusted independently. In this study, methods of reducing the coupling vibration were investigated by finite-element analysis. A method of adjusting the length of the short arm of each vibrator was proposed for reducing the vibration. When piezoelectric ceramics were bonded to the single-sided surface of the vibrator, the method was not sufficient. Thus, the ceramics with the same dimensions were bonded to double-sided surfaces. As a result, a marked reduction was obtained in this case. Also, the linearity of the sensor characteristics was significantly improved in a small acceleration range. Accordingly, it was clarified that considering the symmetry along the thickness direction of the vibrator is very important.

Block correlated second order perturbation theory with a generalized valence bond reference function.

PubMed

Xu, Enhua; Li, Shuhua

2013-11-07

The block correlated second-order perturbation theory with a generalized valence bond (GVB) reference (GVB-BCPT2) is proposed. In this approach, each geminal in the GVB reference is considered as a "multi-orbital" block (a subset of spin orbitals), and each occupied or virtual spin orbital is also taken as a single block. The zeroth-order Hamiltonian is set to be the summation of the individual Hamiltonians of all blocks (with explicit two-electron operators within each geminal) so that the GVB reference function and all excited configuration functions are its eigenfunctions. The GVB-BCPT2 energy can be directly obtained without iteration, just like the second order Mo̸ller-Plesset perturbation method (MP2), both of which are size consistent. We have applied this GVB-BCPT2 method to investigate the equilibrium distances and spectroscopic constants of 7 diatomic molecules, conformational energy differences of 8 small molecules, and bond-breaking potential energy profiles in 3 systems. GVB-BCPT2 is demonstrated to have noticeably better performance than MP2 for systems with significant multi-reference character, and provide reasonably accurate results for some systems with large active spaces, which are beyond the capability of all CASSCF-based methods.

Distinguishing between Positive and Negative Social Bonding in Problem Drinking among College Students

ERIC Educational Resources Information Center

Zullig, Keith J.; Young, Michael; Hussain, Mohammad

2010-01-01

Background: To reduce problem drinking, interventions must be directed toward those factors associated with problem drinking. Purpose: This study examined how perceptions of the role of alcohol related to problem drinking among a convenience sample of 301 college students. Methods: Fifteen items concerned with drinking behavior or perceptions…

75 FR 12150 - Airworthiness Directives; PILATUS Aircraft Ltd. Model PC-7 Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-15

... the left and right lower longerons between fuselage frames 1 and 1A. The possibility of corrosion is... methods: Federal eRulemaking Portal: Go to http://www.regulations.gov . Follow the instructions for... at the bonding strap connections on the left and right lower longerons between fuselage frames 1 and...

The Utility of Implicit Learning in the Teaching of Rules

ERIC Educational Resources Information Center

Saetrevik, Bjorn; Reber, Rolf; Sannum, Petter

2006-01-01

The potential impact of implicit learning on education has been repeatedly stressed, though little research has examined this connection directly. The current paper describes two experiments that, inspired by artificial grammar learning experiments, examine the utility of implicit learning as a method for teaching atomic bonding rules to 11-12…

Dislocations and charge density distributions of {gamma} phase in Ti47.5Al2.5V deformed at room temperature and 400 {degree}C

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

Zhu, J.; Gao, Y.; Miao, Y.

The observations on quantity and configuration of dislocations by TEM conventional diffraction contrast method as well as the determinations of the electron charge density distributions by the quantitative electron crystallography method in Ti47.5Al2.5V deformed at 400 C and room temperature (R.T.) have been carried out. The metallic bonding between Al-Al or Ti-Ti atom pair along {l_angle}110] and Ti-Ti along {l_angle}112] direction is strengthened; while the metallic bonding between Ti-Al atom pair both along {l_angle}101] and {l_angle}121] direction is weakened at 400 C. The quantities of a/2{l_angle}110], a/2{l_angle}112] and dissociated a{l_angle}101] (a[101]{yields}a/2[1{bar 1}0] + a/3[112] + SISF + a/6[112]) dislocations aremore » increased at 400 C, compared with that at R. T.. The a/2 {l_angle}121] super dislocations have not been seen both at 400 C and R.T.« less

Direct heteroarylation polymerization: guidelines for defect-free conjugated polymers.

PubMed

Bura, Thomas; Beaupré, Serge; Légaré, Marc-André; Quinn, Jesse; Rochette, Etienne; Blaskovits, J Terence; Fontaine, Frédéric-Georges; Pron, Agnieszka; Li, Yuning; Leclerc, Mario

2017-05-01

Direct (hetero)arylation polymerization (DHAP) has emerged as a valuable and atom-economical alternative to traditional cross-coupling methods for the synthesis of low-cost and efficient conjugated polymers for organic electronics. However, when applied to the synthesis of certain (hetero)arene-based materials, a lack of C-H bond selectivity has been observed. To prevent such undesirable side-reactions, we report the design and synthesis of new, bulky, phosphine-based ligands that significantly enhance selectivity of the DHAP process for both halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. To better understand the selectivity issues, density functional theory (DFT) calculations have been performed on various halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. Calculations showed that the presence of bromine atoms decreases the energy of activation ( E a ) of the adjacent C-H bonds, allowing undesirable β-defects for some brominated aromatic units. Both calculations and the new ligands should lead to the rational design of monomers and methods for the preparation of defect-free conjugated polymers from DHAP.

Reflow-oven-processing of pressureless sintered-silver interconnects

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

Wereszczak, Andrew A.; Chen, Branndon R.; Oistad, Brian A.

Here, a method was developed to pressurelessly fabricate strong and consistent sinterable-silver joints or interconnects using reflow oven heating. Circular sinterable-silver interconnects, having nominal diameter of 5 mm and 0.1 mm thickness were stencil printed, contact-dried, and then pressurelessly sinter-bonded to Au-plated direct copper bonded ceramic substrates at 250 °C in ambient air. That sintering was done in either a reflow oven or a convective oven (latter being a conventional heating source for processing sinterable-silver). Consistently strong (>40 MPa) interconnects were produced with reflow oven heating and were as strong as those produced with convective oven heating. This is significantmore » because reflow oven technology affords better potential for continuous mass production and it was shown that strong sintered-silver bonds can indeed be achieved with its use.« less

Reflow-oven-processing of pressureless sintered-silver interconnects

DOE PAGES

Wereszczak, Andrew A.; Chen, Branndon R.; Oistad, Brian A.

2018-01-04

Here, a method was developed to pressurelessly fabricate strong and consistent sinterable-silver joints or interconnects using reflow oven heating. Circular sinterable-silver interconnects, having nominal diameter of 5 mm and 0.1 mm thickness were stencil printed, contact-dried, and then pressurelessly sinter-bonded to Au-plated direct copper bonded ceramic substrates at 250 °C in ambient air. That sintering was done in either a reflow oven or a convective oven (latter being a conventional heating source for processing sinterable-silver). Consistently strong (>40 MPa) interconnects were produced with reflow oven heating and were as strong as those produced with convective oven heating. This is significantmore » because reflow oven technology affords better potential for continuous mass production and it was shown that strong sintered-silver bonds can indeed be achieved with its use.« less

Anisotropic toughness and strength in graphene and its atomistic origin

NASA Astrophysics Data System (ADS)

Hossain, M. Zubaer; Ahmed, Tousif; Silverman, Benjamin; Khawaja, M. Shehroz; Calderon, Justice; Rutten, Andrew; Tse, Stanley

2018-01-01

This paper presents the implication of crystallographic orientation on toughness and ideal strength in graphene under lattice symmetry-preserving and symmetry-breaking deformations. In symmetry-preserving deformation, both toughness and strength are isotropic, regardless of the chirality of the lattice; whereas, in symmetry-breaking deformation they are strongly anisotropic, even in the presence of vacancy defects. The maximum and minimum of toughness or strength occur for loading along the zigzag direction and the armchair direction, respectively. The anisotropic behavior is governed by a complex interplay among bond-stretching deformation, bond-bending deformation, and the chirality of the lattice. Nevertheless, the condition for crack-nucleation is dictated by the maximum bond-force required for bond rupture, and it is independent of the chiral angle of the lattice or loading direction. At the onset of crack-nucleation a localized nucleation zone is formed, wherein the bonds rupture locally satisfying the maximum bond-force criterion. The nucleation zone acts as the physical origin in triggering the fracture nucleation process, but its presence is undetectable from the macroscopic stress-strain data.

Dispensing Processes Impact Apparent Biological Activity as Determined by Computational and Statistical Analyses

PubMed Central

Ekins, Sean; Olechno, Joe; Williams, Antony J.

2013-01-01

Dispensing and dilution processes may profoundly influence estimates of biological activity of compounds. Published data show Ephrin type-B receptor 4 IC50 values obtained via tip-based serial dilution and dispensing versus acoustic dispensing with direct dilution differ by orders of magnitude with no correlation or ranking of datasets. We generated computational 3D pharmacophores based on data derived by both acoustic and tip-based transfer. The computed pharmacophores differ significantly depending upon dispensing and dilution methods. The acoustic dispensing-derived pharmacophore correctly identified active compounds in a subsequent test set where the tip-based method failed. Data from acoustic dispensing generates a pharmacophore containing two hydrophobic features, one hydrogen bond donor and one hydrogen bond acceptor. This is consistent with X-ray crystallography studies of ligand-protein interactions and automatically generated pharmacophores derived from this structural data. In contrast, the tip-based data suggest a pharmacophore with two hydrogen bond acceptors, one hydrogen bond donor and no hydrophobic features. This pharmacophore is inconsistent with the X-ray crystallographic studies and automatically generated pharmacophores. In short, traditional dispensing processes are another important source of error in high-throughput screening that impacts computational and statistical analyses. These findings have far-reaching implications in biological research. PMID:23658723

Hydrogen bonding interactions and supramolecular assemblies in 2-amino guanidinium 4-methyl benzene sulphonate crystal structure: Hirshfeld surfaces and computational calculations

NASA Astrophysics Data System (ADS)

Muthuraja, P.; Joselin Beaula, T.; Balachandar, S.; Bena Jothy, V.; Dhandapani, M.

2017-10-01

2-aminoguanidinium 4-methyl benzene sulphonate (AGMS), an organic compound with big assembly of hydrogen bonding interactions was crystallized at room temperature. The structure of the compound was confirmed by FT-IR, NMR and single crystal X-ray diffraction analysis. Numerous hydrogen bonded interactions were found to form supramolecular assemblies in the molecular structure. Fingerprint plots of Hirshfeld surface analysis spells out the interactions in various directions. The molecular structure of AGMS was optimised by HF, MP2 and DFT (B3LYP and CAM-B3LYP) methods at 6-311G (d,p) basis set and the geometrical parameters were compared. Electrostatic potential calculations of the reactants and product confirm the transfer of proton. Optical properties of AGMS were ascertained by UV-Vis absorbance and reflectance spectra. The band gap of AGMS is found to be 2.689 eV. Due to numerous hydrogen bonds, the crystal is thermally stable up to 200 °C. Hyperconjugative interactions which are responsible for the second hyperpolarizabilities were accounted by NBO analysis. Static and frequency dependent optical properties were calculated at HF and DFT methods. The hyperpolarizabilities of AGMS increase rapidly at frequencies 0.0428 and 0.08 a.u. compared to static one. The compound exhibits violet and blue emission.

Cobalt-catalysed site-selective intra- and intermolecular dehydrogenative amination of unactivated sp3 carbons

PubMed Central

Wu, Xuesong; Yang, Ke; Zhao, Yan; Sun, Hao; Li, Guigen; Ge, Haibo

2015-01-01

Cobalt-catalysed sp2 C–H bond functionalization has attracted considerable attention in recent years because of the low cost of cobalt complexes and interesting modes of action in the process. In comparison, much less efforts have been devoted to the sp3 carbons. Here we report the cobalt-catalysed site-selective dehydrogenative cyclization of aliphatic amides via a C–H bond functionalization process on unactivated sp3 carbons with the assistance of a bidentate directing group. This method provides a straightforward synthesis of monocyclic and spiro β- or γ-lactams with good to excellent stereoselectivity and functional group tolerance. In addition, a new procedure has been developed to selectively remove the directing group, which enables the synthesis of free β- or γ-lactam compounds. Furthermore, the first cobalt-catalysed intermolecular dehydrogenative amination of unactivated sp3 carbons is also realized. PMID:25753366

How many hydrogen-bonded α-turns are possible?

PubMed

Schreiber, Anette; Schramm, Peter; Hofmann, Hans-Jörg

2011-06-01

The formation of α-turns is a possibility to reverse the direction of peptide sequences via five amino acids. In this paper, a systematic conformational analysis was performed to find the possible isolated α-turns with a hydrogen bond between the first and fifth amino acid employing the methods of ab initio MO theory in vacuum (HF/6-31G*, B3LYP/6-311 + G*) and in solution (CPCM/HF/6-31G*). Only few α-turn structures with glycine and alanine backbones fulfill the geometry criteria for the i←(i + 4) hydrogen bond satisfactorily. The most stable representatives agree with structures found in the Protein Data Bank. There is a general tendency to form additional hydrogen bonds for smaller pseudocycles corresponding to β- and γ-turns with better hydrogen bond geometries. Sometimes, this competition weakens or even destroys the i←(i + 4) hydrogen bond leading to very stable double β-turn structures. This is also the reason why an "ideal" α-turn with three central amino acids having the perfect backbone angle values of an α-helix could not be localized. There are numerous hints for stable α-turns with a distance between the C(α)-atoms of the first and fifth amino acid smaller than 6-7 Å, but without an i←(i + 4) hydrogen bond.

Direct folding simulation of a long helix in explicit water

NASA Astrophysics Data System (ADS)

Gao, Ya; Lu, Xiaoliang; Duan, Lili; Zhang, Dawei; Mei, Ye; Zhang, John Z. H.

2013-05-01

A recently proposed Polarizable Hydrogen Bond (PHB) method has been employed to simulate the folding of a 53 amino acid helix (PDB ID 2KHK) in explicit water. Under PHB simulation, starting from a fully extended structure, the peptide folds into the native state as confirmed by measured time evolutions of radius of gyration, root mean square deviation (RMSD), and native hydrogen bond. Free energy and cluster analysis show that the folded helix is thermally stable under the PHB model. Comparison of simulation results under, respectively, PHB and standard nonpolarizable force field demonstrates that polarization is critical for stable folding of this long α-helix.

Investigation of Test Methods, Material Properties, and Processes for Solar Cell Encapsulants

NASA Technical Reports Server (NTRS)

1979-01-01

During this quarter the technical activities were directed toward the reformulation of ethylene/vinyl acetate copolymer for use as a compound in solar cell module fabrication. Successful formulations were devised that lowered the temperature required for cure and raised the gel content. A major volatile component was also eliminated (acrylate crosslinking agent) which should aid in the production of bubble free laminates. Adhesive strengths and primers for the bonding of ethylene/vinyl acetate to supersyrate and substrate materials was assessed with encouraging results. The incorporation of silane compounds gave high bond strengths. A survey of scrim materials was also conducted.

A static induction device manufactured by silicon direct bonding

NASA Astrophysics Data System (ADS)

Chen, Xin'an; Liu, Su; Huang, Qing'an

2004-07-01

It is always a key problem how to improve the gate-source breakdown voltage (VGK) of static induction devices during manufacturing. By using a silicon direct bonding process to replace the high resistivity epitaxy process, a bonding buried gate structure is formed, which is different from an epitaxy buried gate structure. The new structure can improve the gate-source breakdown voltage from the process and the structure. It is shown that the bonding buried gate structure is a promising structure, that can improve the VGK and other performances of devices, by manufacture of a static induction thyristor.

Catalytic Arylation and Vinylation Reactions Directed by Anionic Oxygen Functions via Cleavage of C - H and C - C Bonds

NASA Astrophysics Data System (ADS)

Satoh, Tetsuya; Miura, Masahiro

Aromatic compounds having oxygen-containing substituents such as phenols, phenyl ketones, benzyl alcohols, and benzoic acids undergo regioselective arylation and vinylation via C-H bond cleavage in the presence of transition-metal catalysts. The latter two substrates are also arylated and vinylated via C-C bond cleavage accompanied by liberation of ketones and CO2, respectively. Coordination of their anionic oxygen to the metal center is the key to activate the inert bonds effectively and regioselectively. The recent progress of these oxygen-directed reactions is summarized herein.

Prototype to measure bracket debonding force in vivo

PubMed Central

Tonus, Jéssika Lagni; Manfroi, Fernanda Borguetti; Borges, Gilberto Antonio; Grigolo, Eduardo Correa; Helegda, Sérgio; Spohr, Ana Maria

2017-01-01

ABSTRACT Introduction: Material biodegradation that occurs in the mouth may interfere in the bonding strength between the bracket and the enamel, causing lower bond strength values in vivo, in comparison with in vitro studies. Objective: To develop a prototype to measure bracket debonding force in vivo and to evaluate, in vitro, the bond strength obtained with the prototype. Methods: A original plier (3M Unitek) was modified by adding one strain gauge directly connected to its claw. An electronic circuit performed the reading of the strain gauge, and the software installed in a computer recorded the values of the bracket debonding force, in kgf. Orthodontic brackets were bonded to the facial surface of 30 bovine incisors with adhesive materials. In Group 1 (n = 15), debonding was carried out with the prototype, while tensile bond strength testing was performed in Group 2 (n = 15). A universal testing machine was used for the second group. The adhesive remnant index (ARI) was recorded. Results: According to Student’s t test (α = 0.05), Group 1 (2.96 MPa) and Group 2 (3.08 MPa) were not significantly different. ARI score of 3 was predominant in the two groups. Conclusion: The prototype proved to be reliable for obtaining in vivo bond strength values for orthodontic brackets. PMID:28444011

Measurement and control of in-plane surface chemistry during the oxidation of H-terminated (111) Si

PubMed Central

Gokce, Bilal; Adles, Eric J.; Aspnes, David E.; Gundogdu, Kenan

2010-01-01

In-plane directional control of surface chemistry during interface formation can lead to new opportunities regarding device structures and applications. Control of this type requires techniques that can probe and hence provide feedback on the chemical reactivity of bonds not only in specific directions but also in real time. Here, we demonstrate both control and measurement of the oxidation of H-terminated (111) Si. Control is achieved by externally applying uniaxial strain, and measurement by second-harmonic generation (SHG) together with the anisotropic-bond model of nonlinear optics. In this system anisotropy results because bonds in the strain direction oxidize faster than those perpendicular to it, leading in addition to transient structural changes that can also be detected at the bond level by SHG. PMID:20876145

Investigation of two- and three-bond carbon-hydrogen coupling constants in cinnamic acid based compounds.

PubMed

Pierens, Gregory K; Venkatachalam, Taracad K; Reutens, David C

2016-12-01

Two- and three-bond coupling constants ( 2 J HC and 3 J HC ) were determined for a series of 12 substituted cinnamic acids using a selective 2D inphase/antiphase (IPAP)-single quantum multiple bond correlation (HSQMBC) and 1D proton coupled 13 C NMR experiments. The coupling constants from two methods were compared and found to give very similar values. The results showed coupling constant values ranging from 1.7 to 9.7 Hz and 1.0 to 9.6 Hz for the IPAP-HSQMBC and the direct 13 C NMR experiments, respectively. The experimental values of the coupling constants were compared with discrete density functional theory (DFT) calculated values and were found to be in good agreement for the 3 J HC . However, the DFT method under estimated the 2 J HC coupling constants. Knowing the limitations of the measurement and calculation of these multibond coupling constants will add confidence to the assignment of conformation or stereochemical aspects of complex molecules like natural products. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Individual breathing reactions measured in hemoglobin by hydrogen exchange methods.

PubMed Central

Englander, S W; Calhoun, D B; Englander, J J; Kallenbach, N R; Liem, R K; Malin, E L; Mandal, C; Rogero, J R

1980-01-01

Protein hydrogen exchange is generally believed to register some aspects of internal protein dynamics, but the kind of motion at work is not clear. Experiments are being done to identify the determinants of protein hydrogen exchange and to distinguish between local unfolding and accessibility-penetration mechanisms. Results with small molecules, polynucleotides, and proteins demonstrate that solvent accessibility is by no means sufficient for fast exchange. H-exchange slowing is quite generally connected with intramolecular H-bonding, and the exchange process depends pivotally on transient H-bond cleavage. At least in alpha-helical structures, the cooperative aspect of H-bond cleavage must be expressed in local unfolding reactions. Results obtained by use of a difference hydrogen exchange method appear to provide a direct measurement of transient, cooperative, local unfolding reactions in hemoglobin. The reality of these supposed coherent breathing units is being tested by using the difference H-exchange approach to tritium label the units one at a time and then attempting to locate the tritium by fragmenting the protein, separating the fragments, and testing them for label. Early results demonstrate the feasibility of this approach. PMID:7248462

Accurate characterization of wafer bond toughness with the double cantilever specimen

NASA Astrophysics Data System (ADS)

Turner, Kevin T.; Spearing, S. Mark

2008-01-01

The displacement loaded double cantilever test, also referred to as the "Maszara test" and the "crack opening method" by the wafer bonding community, is a common technique used to evaluate the interface toughness or surface energy of direct wafer bonds. While the specimen is widely used, there has been a persistent question as to the accuracy of the method since the actual specimen geometry differs from the ideal beam geometry assumed in the expression used for data reduction. The effect of conducting the test on whole wafer pairs, in which the arms of cantilevers are wide plates rather than slender beams, is examined in this work using finite element analysis. A model is developed to predict the equilibrium shape of the crack front and to develop a corrected expression for calculating interface toughness from crack length measurements obtained in tests conducted on whole wafer pairs. The finite element model, which is validated through comparison to experiments, demonstrates that using the traditional beam theory-based expressions for data reduction can lead to errors of up to 25%.

Asymmetric oxidation of vinyl- and ethynyl terthiophene ligands in triruthenium complexes.

PubMed

Zhang, Jing; Sun, Chao-Fang; Zhang, Ming-Xing; Hartl, František; Yin, Jun; Yu, Guang-Ao; Rao, Li; Liu, Sheng Hua

2016-01-14

A series of ruthenium(ii) complexes [{RuCl(CO)(PMe3)3(-CH[double bond, length as m-dash]CH-)}nX], (: n = 3, X = 3,3''-dimethyl-2,2':3',2''-terthiophene; : n = 2, X = 2,2'-bithiophene; : n = 2, X = 2,3-bis(3-methylthiophen-2-yl)benzothiophene) and [{Cp*(dppe)2Ru(-C[triple bond, length as m-dash]C-)}3X], (X = 3,3''-dimethyl-2,2':3',2''-terthiophene), were prepared and characterized by (1)H, (13)C and (31)P NMR. Their redox, spectroscopic and bonding properties were studied with a range of spectro-electrochemical methods in combination with density functional theory calculations. The first two anodic steps observed for and are largely localized on the lateral frameworks of the molecular triangle, the direct conjugation between them being precluded due to the photostable open form of the dithienyl ethene moiety. The third anodic step is then mainly localized on the centerpiece of the triangular structure, affecting both bithiophene laterals. The experimental IR and UV-vis-NIR spectroelectrochemical data and, largely, also DFT calculations account for this explanation, being further supported by direct comparison with the anodic behavior of reference diruthenium complexes and .

Welding methods for joining thermoplastic polymers for the hermetic enclosure of medical devices.

PubMed

Amanat, Negin; James, Natalie L; McKenzie, David R

2010-09-01

New high performance polymers have been developed that challenge traditional encapsulation materials for permanent active medical implants. The gold standard for hermetic encapsulation for implants is a titanium enclosure which is sealed using laser welding. Polymers may be an alternative encapsulation material. Although many polymers are biocompatible, and permeability of polymers may be reduced to acceptable levels, the ability to create a hermetic join with an extended life remains the barrier to widespread acceptance of polymers for this application. This article provides an overview of the current techniques used for direct bonding of polymers, with a focus on thermoplastics. Thermal bonding methods are feasible, but some take too long and/or require two stage processing. Some methods are not suitable because of excessive heat load which may be delivered to sensitive components within the capsule. Laser welding is presented as the method of choice; however the establishment of suitable laser process parameters will require significant research. 2010. Published by Elsevier Ltd.

The structure of poly(carbonsuboxide) on the atomic scale: a solid-state NMR study.

PubMed

Schmedt auf der Günne, Jörn; Beck, Johannes; Hoffbauer, Wilfried; Krieger-Beck, Petra

2005-07-18

In this contribution we present a study of the structure of amorphous poly(carbonsuboxide) (C3O2)x by 13C solid-state NMR spectroscopy supported by infrared spectroscopy and chemical analysis. Poly(carbonsuboxide) was obtained by polymerization of carbonsuboxide C3O2, which in turn was synthesized from malonic acid bis(trimethylsilylester). Two different 13C labeling schemes were applied to probe inter- and intramonomeric bonds in the polymer by dipolar solid-state NMR methods and also to allow quantitative 13C MAS NMR spectra. Four types of carbon environments can be distinguished in the NMR spectra. Double-quantum and triple-quantum 2D correlation experiments were used to assign the observed peaks using the through-space and through-bond dipolar coupling. In order to obtain distance constraints for the intermonomeric bonds, double-quantum constant-time experiments were performed. In these experiments an additional filter step was applied to suppress contributions from not directly bonded 13C,13C spin pairs. The 13C NMR intensities, chemical shifts, connectivities and distances gave constraints for both the polymerization mechanism and the short-range order of the polymer. The experimental results were complemented by bond lengths predicted by density functional theory methods for several previously suggested models. Based on the presented evidence we can unambiguously exclude models based on gamma-pyronic units and support models based on alpha-pyronic units. The possibility of planar ladder- and bracelet-like alpha-pyronic structures is discussed.

Effective scheme for partitioning covalent bonds in density-functional embedding theory: From molecules to extended covalent systems.

PubMed

Huang, Chen; Muñoz-García, Ana Belén; Pavone, Michele

2016-12-28

Density-functional embedding theory provides a general way to perform multi-physics quantum mechanics simulations of large-scale materials by dividing the total system's electron density into a cluster's density and its environment's density. It is then possible to compute the accurate local electronic structures and energetics of the embedded cluster with high-level methods, meanwhile retaining a low-level description of the environment. The prerequisite step in the density-functional embedding theory is the cluster definition. In covalent systems, cutting across the covalent bonds that connect the cluster and its environment leads to dangling bonds (unpaired electrons). These represent a major obstacle for the application of density-functional embedding theory to study extended covalent systems. In this work, we developed a simple scheme to define the cluster in covalent systems. Instead of cutting covalent bonds, we directly split the boundary atoms for maintaining the valency of the cluster. With this new covalent embedding scheme, we compute the dehydrogenation energies of several different molecules, as well as the binding energy of a cobalt atom on graphene. Well localized cluster densities are observed, which can facilitate the use of localized basis sets in high-level calculations. The results are found to converge faster with the embedding method than the other multi-physics approach ONIOM. This work paves the way to perform the density-functional embedding simulations of heterogeneous systems in which different types of chemical bonds are present.

Bond financing in volatile times.

PubMed

Gould, Kenneth A; Blanda, Christopher M

2014-03-01

A competitive landscape for providers and changing market conditions require an understanding of key capital sources: tax-exempt bonds remain an attractive capital source. Credit enhancement for bonds is more expensive and more difficult to find than it was in years past. Direct bond purchases by commercial banks mitigate the traditional risks.

Radical O-O coupling reaction in diferrate-mediated water oxidation studied using multireference wave function theory.

PubMed

Kurashige, Yuki; Saitow, Masaaki; Chalupský, Jakub; Yanai, Takeshi

2014-06-28

The O-O (oxygen-oxygen) bond formation is widely recognized as a key step of the catalytic reaction of dioxygen evolution from water. Recently, the water oxidation catalyzed by potassium ferrate (K2FeO4) was investigated on the basis of experimental kinetic isotope effect analysis assisted by density functional calculations, revealing the intramolecular oxo-coupling mechanism within a di-iron(vi) intermediate, or diferrate [Sarma et al., J. Am. Chem. Soc., 2012, 134, 15371]. Here, we report a detailed examination of this diferrate-mediated O-O bond formation using scalable multireference electronic structure theory. High-dimensional correlated many-electron wave functions beyond the one-electron picture were computed using the ab initio density matrix renormalization group (DMRG) method along the O-O bond formation pathway. The necessity of using large active space arises from the description of complex electronic interactions and varying redox states both associated with two-center antiferromagnetic multivalent iron-oxo coupling. Dynamic correlation effects on top of the active space DMRG wave functions were additively accounted for by complete active space second-order perturbation (CASPT2) and multireference configuration interaction (MRCI) based methods, which were recently introduced by our group. These multireference methods were capable of handling the double shell effects in the extended active space treatment. The calculations with an active space of 36 electrons in 32 orbitals, which is far over conventional limitation, provide a quantitatively reliable prediction of potential energy profiles and confirmed the viability of the direct oxo coupling. The bonding nature of Fe-O and dual bonding character of O-O are discussed using natural orbitals.

Carbon films produced from ionic liquid carbon precursors

DOEpatents

Dai, Sheng; Luo, Huimin; Lee, Je Seung

2013-11-05

The invention is directed to a method for producing a film of porous carbon, the method comprising carbonizing a film of an ionic liquid, wherein the ionic liquid has the general formula (X.sup.+a).sub.x(Y.sup.-b).sub.y, wherein the variables a and b are, independently, non-zero integers, and the subscript variables x and y are, independently, non-zero integers, such that ax=by, and at least one of X.sup.+ and Y.sup.- possesses at least one carbon-nitrogen unsaturated bond. The invention is also directed to a composition comprising a porous carbon film possessing a nitrogen content of at least 10 atom %.

Effectiveness and efficiency of a CAD/CAM orthodontic bracket system.

PubMed

Brown, Matthew W; Koroluk, Lorne; Ko, Ching-Chang; Zhang, Kai; Chen, Mengqi; Nguyen, Tung

2015-12-01

The first straight-wire appliance was introduced over 40 years ago to increase the consistency and efficiency of orthodontic treatment. More recently, computer-aided design and computer-aided manufacturing (CAD/CAM) technology has been used to create individualized orthodontic appliances. The purpose of this study was to investigate the clinical effectiveness and efficiency of CAD/CAM customized orthodontic appliances compared with direct and indirect bonded stock orthodontic brackets. This retrospective study included 3 treatment groups: group 1 patients were direct bonded with self-ligating appliances, group 2 patients were indirect bonded with self-ligating appliances, and group 3 patients were indirect bonded with CAD/CAM self-ligating appliances. Complete pretreatment and posttreatment records were obtained for all patients. The American Board of Orthodontics (ABO) Discrepancy Index was used to evaluate the pretreatment records, and the posttreatment outcomes were analyzed using the ABO Cast-Radiograph Evaluation. All data collection and analysis were completed by 1 evaluator. There were no statistically significant differences in the ABO Discrepancy Index or the ABO Cast-Radiograph Evaluation among the groups. Treatment times for the 3 groups were significantly different; the CAD/CAM group was the shortest at 13.8 ± 3.4 months, compared with 21.9 ± 5.0 and 16.9 ± 4.1 months for the direct bonded and indirect bonded groups, respectively. The number of treatment appointments for the CAD/CAM group was significantly fewer than for the direct bonded group. The CAD/CAM orthodontic bracket system evaluated in this study was as effective in treatment outcome measures as were standard brackets bonded both directly and indirectly. The CAD/CAM appliance was more efficient in regard to treatment duration, although the decrease in total archwire appointments was minimal. Further investigation is needed to better quantify the clinical benefits of CAD/CAM orthodontic appliances. Copyright © 2015 American Association of Orthodontists. Published by Elsevier Inc. All rights reserved.

Measurement and Control of In-plane Surface Chemistry at the Silicon/Silicon Dioxide Interface

NASA Astrophysics Data System (ADS)

Gokce, Bilal

In-plane directional control of surface chemistry during interface formation can lead to new opportunities regarding device structures and applications. Control of this type requires techniques that can probe and hence provide feedback on the chemical reactivity of bonds not only in specific directions but also in real time. In this thesis work, I demonstrate both control and measurement of the oxidation of H-terminated Si(111). The nonlinear optical tool of Second-Harmonic-Generation (SHG) is used to show that Si oxidation in air is a two-stage process where the H of the "up" bonds of the outermost Si layer is replaced by OH, followed by O insertion into the "back" bonds. Detailed information about both stages is revealed by investigating the effect of uniaxial strain and carrier concentration on this chemical reaction. It is shown that even small amounts of strain manipulate the reaction kinetics of surface bonds significantly, with tensile strain enhancing oxidation and compressive strain retarding it. This dramatic change suggests a strain-driven charge transfer mechanism between Si--H up bonds and Si--Si back bonds in the outer layer of Si atoms. Data on differently doped samples reveal that high concentrations of electrons increase the chemical reactivity of the outer-layer Si--Si back bonds relative to the Si--H up bonds while high concentrations of holes cause a greater increase in the reactivity of the Si--H up bonds than that of the Si--Si back bonds. However, the thicknesses of the natural oxides of all samples follow the same path and stabilize near 1 nm at room temperature, regardless of the chemical kinetics of the different bonds, as determined by spectroscopic ellipsometry. Real-time measurement during SHG experiments is achieved by analyzing SHG anisotropy data with the anisotropic bond-charge model of nonlinear optics where peaks in the SHG spectrum are correlated with the near alignment of bonds to the direction of the excitation field.

Effect of Cementation Technique of Individually Formed Fiber-Reinforced Composite Post on Bond Strength and Microleakage

PubMed Central

Makarewicz, Dominika; Le Bell-Rönnlöf, Anna-Maria B; Lassila, Lippo V.J.; Vallittu, Pekka K.

2013-01-01

Objectives: The aim of this study was to evaluate the effect of two different cementation techniques of individually formed E-glass fiber-reinforced composite (FRC) post on bond strength and microleakage. Methods: The crowns of extracted third molars were removed and post preparation was carried out with parapost drills (diameter 1.5 mm). After application of bonding agents individually formed FRC posts (everStick POST, diameter 1.5 mm) were cemented into the post spaces with either ParaCem®Universal or self-adhesive RelyX™Unicem, using two different cementation techniques: 1) an “indirect (traditional) technique” where the post was prepolymerized prior application of luting cement and insertion into the post space or 2) a “direct technique” where the uncured post was inserted to the post space with luting cement and light-polymerized in situ at the same time. After water storage of 48 hours, the roots (n = 10/group) were cut into discs of thickness of 2 mm. A push-out force was applied until specimen fracture or loosening of the post. A microleakage test was carried out on roots which were not subjected to the loading test (n= 32) to evaluate the sealing capacity of the post-canal interface. The microleakage was measured using dye penetration depth under a stereomicroscope. Results: Higher bond strength values (p<0.05) and less microleakage (p<0.05) were obtained with the “direct technique” compared to the “indirect technique”. None of the FRC posts revealed any dye penetration between the post and the cement. Conclusions: The “direct technique” seems to be beneficial when cementing individually formed FRC posts. PMID:23986792

Shear test of composite bonded to dentin: Er:YAG laser versus dental handpiece preparations

NASA Astrophysics Data System (ADS)

Visuri, Steven R.; Gilbert, Jeremy L.; Walsh, Joseph T., Jr.; Wigdor, Harvey A.

1995-05-01

The erbium:YAG laser coupled with a cooling stream of water appears to be an effective means of removing dental hard tissues. However, before the procedure is deemed clinically viable, there are several important issues of safety and efficacy that need to be explored. In this study we investigated the surface that remains following laser ablation of dentin and compared the results to the use of a dental handpiece. Specifically, we studied the effect the laser radiation had on the bonding of composite to dentin. The crowns of extracted human molars were removed revealing the underlying dentin. An additional thickness of material was removed with either a dental handpiece or an Er:YAG laser by raster scanning the samples under a fixed handpiece or laser. Comparable surface roughnesses were achieved. A cylinder of composite was bonded onto the prepared surfaces following the manufacturer's directions. The dentin-composite bond was then shear stressed to failure on a universal testing apparatus and the maximum load recorded. Preliminary results indicated that laser irradiated samples had improved bond strengths. SEM photographs of the surfaces were also taken to compare the two methods of tooth preparation.

The role of H-bond in the high-pressure chemistry of model molecules

NASA Astrophysics Data System (ADS)

Fanetti, Samuele; Citroni, Margherita; Dziubek, Kamil; Medre Nobrega, Marcelo; Bini, Roberto

2018-03-01

Pressure is an extraordinary tool to modify direction and strength of intermolecular interactions with important consequences on the chemical stability of molecular materials. The decrease of the distance among nearest neighbour molecules can give rise to reactive configurations reflecting the crystal arrangement and leading to association processes. In this context, the role of the H-bonds is very peculiar because their usual strengthening with rising pressure does not necessarily configure a decrease of the reaction activation energy but, on the contrary, can give rise to an anomalous stability of the system. In spite of this central role, the mechanisms by which a chemical reaction is favoured or prevented by H-bonding under high pressure conditions is a poorly explored field. Here we review a few studies where the chemical behaviour of simple molecular systems under static compression was related to the H-bonding evolution with pressure. These results are able to clarify a wealth of changes of the chemical and physical properties caused by the strengthening with pressure of the H-bonding network and provide additional tools to understand the mechanisms of high-pressure reactivity, a mandatory step to make these synthetic methods of potential interest for applicative purposes.

Bond-rearrangement and ionization mechanisms in the photo-double-ionization of simple hydrocarbons (C 2H 4, C 2H 3F, and 1,1-C 2H 2F 2) near and above threshold

DOE PAGES

Gaire, B.; Gatton, A. S.; Wiegandt, F.; ...

2016-09-14

We have investigated bond-rearrangement driven by photo-double-ionization (PDI) near and above the double ionization threshold in a sequence of carbon-carbon double bonded hydrocarbon molecules: ethylene, fluoroethylene, and 1,1-difluoroethylene. We employ the kinematically complete cold target recoil ion momentum spectroscopy (COLTRIMS) method to resolve all photo-double-ionization events leading to two-ionic fragments. We observe changes in the branching ratios of different dissociative ionization channels depending on the presence of none, one, or two fluorine atoms. The role of the fluorine atom in the bond-rearrangement channels is intriguing as evident by the re-ordering of the threshold energies of the PDI in the fluorinatedmore » molecules. These effects offer a compelling argument that the electronegativity of the fluorine (or the polarity of the molecule) strongly influences the potential energy surfaces of the molcules and drives bond-rearrangement during the dissociation process. The energy sharing and the relative angle between the 3D-momentum vectors of the two electrons provide clear evidence of direct and indirect PDI processes.« less

Method to improve commercial bonded SOI material

DOEpatents

Maris, Humphrey John; Sadana, Devendra Kumar

2000-07-11

A method of improving the bonding characteristics of a previously bonded silicon on insulator (SOI) structure is provided. The improvement in the bonding characteristics is achieved in the present invention by, optionally, forming an oxide cap layer on the silicon surface of the bonded SOI structure and then annealing either the uncapped or oxide capped structure in a slightly oxidizing ambient at temperatures greater than 1200.degree. C. Also provided herein is a method for detecting the bonding characteristics of previously bonded SOI structures. According to this aspect of the present invention, a pico-second laser pulse technique is employed to determine the bonding imperfections of previously bonded SOI structures.

The use of natural abundance stable isotopic ratios to indicate the presence of oxygen-containing chemical linkages between cellulose and lignin in plant cell walls.

PubMed

Zhou, Youping; Stuart-Williams, Hilary; Farquhar, Graham D; Hocart, Charles H

2010-06-01

Qualitative and quantitative understanding of the chemical linkages between the three major biochemical components (cellulose, hemicellulose and lignin) of plant cell walls is crucial to the understanding of cell wall structure. Although there is convincing evidence for chemical bonds between hemicellulose and lignin and the absence of chemical bonds between hemicellulose and cellulose, there is no conclusive evidence for the presence of covalent bonds between cellulose and lignin. This is caused by the lack of selectivity of current GC/MS-, NMR- and IR-based methods for lignin characterisation as none of these techniques directly targets the possible ester and ether linkages between lignin and cellulose. We modified the widely-accepted "standard" three-step extraction method for isolating cellulose from plants by changing the order of the steps for hemicellulose and lignin removal (solubilisation with concentrated NaOH and oxidation with acetic acid-containing NaClO(2), respectively) so that cellulose and lignin could be isolated with the possible chemical bonds between them intact. These linkages were then cleaved with NaClO(2) reagent in aqueous media of contrasting (18)O/(16)O ratios. We produced cellulose with higher purity (a lower level of residual hemicellulose and no detectable lignin) than that produced by the "standard" method. Oxidative artefacts may potentially be introduced at the lignin removal stage; but testing showed this to be minimal. Cellulose samples isolated from processing plant-derived cellulose-lignin mixtures in media of contrasting (18)O/(16)O ratios were compared to provide the first quantitative evidence for the presence of oxygen-containing ester and ether bonds between cellulose and lignin in Zea mays leaves. However, no conclusive evidence for the presence or lack of similar bonds in Araucaria cunninghamii wood was obtained. Copyright 2010 Elsevier Ltd. All rights reserved.

Engineering Graphene Mechanical Systems

DTIC Science & Technology

2012-07-05

strength material. On the basis of chemical /defect manipulation and recrystallization this technique allows wide-range engineering of mechanical... Engineering Graphene Mechanical Systems Maxim K. Zalalutdinov,† Jeremy T. Robinson,*,† Chad E. Junkermeier,‡ James C. Culbertson, Thomas L. Reinecke...Information ABSTRACT: We report a method to introduce direct bonding between graphene platelets that enables the transformation of a multilayer chemically

Silicon cantilever functionalization for cellulose-specific chemical force imaging of switchgrass

DOE PAGES

Lee, Ida; Evans, Barbara R.; Foston, Marcus B.; ...

2015-05-08

A method for direct functionalization of silicon and silicon nitride cantilevers with bifunctional silanes was tested with model surfaces to determine adhesive forces for different hydrogen-bonding chemistries. Application for biomass surface characterization was tested by mapping switchgrass and isolated switchgrass cellulose in topographic and force-volume mode using a cellulose-specific cantilever.

Direct reciprocity in animals: The roles of bonding and affective processes.

PubMed

Freidin, Esteban; Carballo, Fabricio; Bentosela, Mariana

2017-04-01

The presence of direct reciprocity in animals is a debated topic, because, despite its evolutionary plausibility, it is believed to be uncommon. Some authors claim that stable reciprocal exchanges require sophisticated cognition which has acted as a constraint on its evolution across species. In contrast, a more recent trend of research has focused on the possibility that direct reciprocity occurs within long-term bonds and relies on simple as well as more complex affective mechanisms such as emotional book-keeping, rudimentary and higher forms of empathy, and inequity aversion, among others. First, we present evidence supporting the occurrence of long-term reciprocity in the context of existing bonds in social birds and mammals. Second, we discuss the evidence for affective responses which, modulated by bonding, may underlie altruistic behaviours in different species. We conclude that the mechanisms that may underlie reciprocal exchanges are diverse, and that some act in interaction with bonding processes. From simple associative learning in social contexts, through emotional contagion and behavioural mimicry, to empathy and a sense of fairness, widespread and diverse social affective mechanisms may explain why direct reciprocity may not be a rare phenomenon among social vertebrates. © 2015 International Union of Psychological Science.

Room temperature bonding and debonding of polyimide film and glass substrate based on surface activate bonding method

NASA Astrophysics Data System (ADS)

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

2018-02-01

The temporary bonding of polyimide (PI) films and glass substrates is a key technology for realizing flexible devices with thin-film transistors (TFTs). In this paper, we report the surface activated bonding (SAB) method using Si intermediate layers and its bonding and debonding mechanisms after heating. The bonding interface composed of Si and Fe shows a higher bond strength than the interface of only Si, while the bond strengths of both interfaces decrease with post bonding heating. It is also clarified by composition analysis on the debonded surfaces and cross-sectional observation of the bonding interface that the bond strength depends on the toughness of the intermediated layers and PI. The SAB method using Si intermediate layers is found to be applicable to the bonding and debonding of PI and glass.

Destructive and non-destructive evaluation of cu/cu diffusion bonding with interlayer aluminum

NASA Astrophysics Data System (ADS)

Santosh Kumar, A.; Mohan, T.; Kumar, S. Suresh; Ravisankar, B.

2018-03-01

The current study is established an inspection procedure for assessing quality of diffusion bonded joints using destructive and non-destructive method. Diffusion bonding of commercially pure copper with aluminium interlayer was carried out uniaxial load at 15MPa for different temperatures under holding time 60 min in vacuum atmosphere. The bond qualities were determined by destructive and non-destructive testing method (ultrasonic C- scan). The bond interface and bonded samples were analysed using optical and scanning electron microscopy (SEM). The element composition of the fractured and bonded area is determined using the Energy Dispersive Spectrometry (EDS). The bond quality obtained by both testing methods and its parameters are correlated. The optimized bonding parameter for best bonding characteristics for copper diffusion bonding with aluminum interlayer is reported.

Fabrication of SOI structures with buried cavities using Si wafer direct bonding and electrochemical etch-stop

NASA Astrophysics Data System (ADS)

Chung, Gwiy-Sang

2003-10-01

This paper describes the fabrication of SOI structures with buried cavities using SDB and electrochemical etch-stop. These methods are suitable for thick membrane fabrication with accurate thickness, uniformity, and flatness. After a feed-through hole for supplied voltage and buried cavities was formed on a handle Si wafer with p-type, the handle wafer was bonded to an active Si wafer consisting of a p-type substrate with an n-type epitaxial layer corresponding to membrane thickness. The bonded pair was then thinned until electrochemical etch-stop occurred at the pn junction during electrochemical etchback. By using the SDB SOI structure with buried cavities, active membranes, which have a free standing structure with a dimension of 900×900 μm2, were fabricated. It is confirmed that the fabrication process of the SDB SOI structure with buried cavities is a powerful and versatile technology for new MEMS applications.

Carbon–hydrogen (C–H) bond activation at PdIV: a Frontier in C–H functionalization catalysis

PubMed Central

Topczewski, Joseph J.

2015-01-01

The direct functionalization of carbon–hydrogen (C–H) bonds has emerged as a versatile strategy for the synthesis and derivatization of organic molecules. Among the methods for C–H bond activation, catalytic processes that utilize a PdII/PdIV redox cycle are increasingly common. The C–H activation step in most of these catalytic cycles is thought to occur at a PdII centre. However, a number of recent reports have suggested the feasibility of C–H cleavage occurring at PdIV complexes. Importantly, these latter processes often result in complementary reactivity and selectivity relative to analogous transformations at PdII. This mini review highlights proposed examples of C–H activation at PdIV centres. Applications of this transformation in catalysis as well as mechanistic details obtained from stoichiometric model studies are discussed. Furthermore, challenges and future perspectives for the field are reviewed. PMID:25544882

Carbon-Hydrogen (C-H) Bond Activation at PdIV: A Frontier in C-H Functionalization Catalysis.

PubMed

Topczewski, Joseph J; Sanford, Melanie S

2015-01-01

The direct functionalization of carbon-hydrogen (C-H) bonds has emerged as a versatile strategy for the synthesis and derivatization of organic molecules. Among the methods for C-H bond activation, catalytic processes that utilize a Pd II /Pd IV redox cycle are increasingly common. The C-H activation step in most of these catalytic cycles is thought to occur at a Pd II centre. However, a number of recent reports have suggested the feasibility of C-H cleavage occurring at Pd IV complexes. Importantly, these latter processes often result in complementary reactivity and selectivity relative to analogous transformations at Pd II . This Mini Review highlights proposed examples of C-H activation at Pd IV centres. Applications of this transformation in catalysis as well as mechanistic details obtained from stoichiometric model studies are discussed. Furthermore, challenges and future perspectives for the field are reviewed.

Three-Point Flexural Properties of Bonded Reinforcement Elements for Pleasure Craft Decks

NASA Astrophysics Data System (ADS)

Di Bella, G.; Galtieri, G.; Borsellino, C.

2018-02-01

The aim of this work was both to study the performances of pleasure craft reinforced components, bonded using a structural adhesive, and to compare them with those obtained using over-lamination as joining system, typically employed in the shipbuilding. With such aim, two different lots of components were prepared: in the first lot, the reinforcement structures were laminated directly on the investigated composite components and, in the second one; they were made separately in a mould and, then, bonded to the composite components. This last method allowed to evaluate the introduction of a product/process innovation in a field typically unwilling to innovation, still tied to craft, and non-standardized procedures. The results of bending tests, performed in order to evaluate the mechanical behaviour of the reinforced components, evidenced the goodness of this innovative design choice. Finally, a finite element analysis was performed. [Figure not available: see fulltext.

Direct α-C-H bond functionalization of unprotected cyclic amines

NASA Astrophysics Data System (ADS)

Chen, Weijie; Ma, Longle; Paul, Anirudra; Seidel, Daniel

2018-02-01

Cyclic amines are ubiquitous core structures of bioactive natural products and pharmaceutical drugs. Although the site-selective abstraction of C-H bonds is an attractive strategy for preparing valuable functionalized amines from their readily available parent heterocycles, this approach has largely been limited to substrates that require protection of the amine nitrogen atom. In addition, most methods rely on transition metals and are incompatible with the presence of amine N-H bonds. Here we introduce a protecting-group-free approach for the α-functionalization of cyclic secondary amines. An operationally simple one-pot procedure generates products via a process that involves intermolecular hydride transfer to generate an imine intermediate that is subsequently captured by a nucleophile, such as an alkyl or aryl lithium compound. Reactions are regioselective and stereospecific and enable the rapid preparation of bioactive amines, as exemplified by the facile synthesis of anabasine and (-)-solenopsin A.

Biocarrier composition for and method of degrading pollutants

DOEpatents

Fliermans, C.B.

1994-01-01

The present invention relates to biocarrier compositions that attract and bond pollutant-degrading antigens that will degrade the pollutants. Biocarriers are known generally as a variety of inert or semi-inert compounds or structures having the ability to sequester (attract), hold and biomagnify (enhance) specific microorganisms within their structure. Glass or polystyrene beads are the most well known biocarriers. The biocarrier, which is preferably in the form of glass microspheres, is coated with an antibody or group of antibodies that attract and react specifically with certain pollutant-degrading antigens. The antibody, once bonded to the biocarrier, is used by the composition to attract and bond those pollutant-degrading antigens. Each antibody is specific for an antigen that is specific for a given pollutant. The resulting composition is subsequently exposed to an environment contaminated with pollutants for degradation. In the preferred use, the degrading composition is formed and then injected directly into or near a plume or source of contamination.

Nanostructure of cellulose microfibrils in spruce wood.

PubMed

Fernandes, Anwesha N; Thomas, Lynne H; Altaner, Clemens M; Callow, Philip; Forsyth, V Trevor; Apperley, David C; Kennedy, Craig J; Jarvis, Michael C

2011-11-22

The structure of cellulose microfibrils in wood is not known in detail, despite the abundance of cellulose in woody biomass and its importance for biology, energy, and engineering. The structure of the microfibrils of spruce wood cellulose was investigated using a range of spectroscopic methods coupled to small-angle neutron and wide-angle X-ray scattering. The scattering data were consistent with 24-chain microfibrils and favored a "rectangular" model with both hydrophobic and hydrophilic surfaces exposed. Disorder in chain packing and hydrogen bonding was shown to increase outwards from the microfibril center. The extent of disorder blurred the distinction between the I alpha and I beta allomorphs. Chains at the surface were distinct in conformation, with high levels of conformational disorder at C-6, less intramolecular hydrogen bonding and more outward-directed hydrogen bonding. Axial disorder could be explained in terms of twisting of the microfibrils, with implications for their biosynthesis.

Single-crystal X-ray diffraction study of SrGeO3 high-pressure perovskite phase at 100 K

NASA Astrophysics Data System (ADS)

Nakatsuka, Akihiko; Arima, Hiroshi; Ohtaka, Osamu; Fujiwara, Keiko; Yoshiasa, Akira

2017-10-01

Single-crystal X-ray diffraction study of SrGeO3 perovskite (cubic; space group Pmɜ¯m) synthesized at 6 GPa and 1223 K was conducted at a low temperature of 100 K. The residual electron density revealed the presence of the bonding electron at the center of the Ge-O bond, in accordance with our previous conclusion that the Ge-O bond is strongly covalent. From comparison with our previous structure-refinement result at 296 K, the mean square displacement (MSD) of the O atom in the direction of the Ge-O bond is suggested to exhibit no significant temperature dependence, in contrast to that in the direction perpendicular to the bond. Thus, the strong covalency of the Ge-O bond can have a large influence on the temperature dependence of thermal vibration of the O atom.

31 CFR 363.171 - How do I redeem a converted savings bond?

Code of Federal Regulations, 2014 CFR

2014-07-01

... converted savings bond? (a) Before final maturity—(1) Savings bond of any series registered in the single... bond of any series registered either in the single owner, owner with beneficiary, or entity form of registration any time prior to final maturity after the minimum holding period through your TreasuryDirect...

31 CFR 363.171 - How do I redeem a converted savings bond?

Code of Federal Regulations, 2011 CFR

2011-07-01

... converted savings bond? (a) Before final maturity—(1) Savings bond of any series registered in the single... bond of any series registered either in the single owner, owner with beneficiary, or entity form of registration any time prior to final maturity after the minimum holding period through your TreasuryDirect...

31 CFR 363.171 - How do I redeem a converted savings bond?

Code of Federal Regulations, 2010 CFR

2010-07-01

... converted savings bond? (a) Before final maturity—(1) Savings bond of any series registered in the single... bond of any series registered either in the single owner, owner with beneficiary, or entity form of registration any time prior to final maturity after the minimum holding period through your TreasuryDirect...

31 CFR 363.171 - How do I redeem a converted savings bond?

Code of Federal Regulations, 2013 CFR

2013-07-01

... converted savings bond? (a) Before final maturity—(1) Savings bond of any series registered in the single... bond of any series registered either in the single owner, owner with beneficiary, or entity form of registration any time prior to final maturity after the minimum holding period through your TreasuryDirect...

31 CFR 363.171 - How do I redeem a converted savings bond?

Code of Federal Regulations, 2012 CFR

2012-07-01

... converted savings bond? (a) Before final maturity—(1) Savings bond of any series registered in the single... bond of any series registered either in the single owner, owner with beneficiary, or entity form of registration any time prior to final maturity after the minimum holding period through your TreasuryDirect...

Entropic-elasticity-controlled dissociation and energetic-elasticity-controlled rupture induce catch-to-slip bonds in cell-adhesion molecules.

PubMed

Wei, YuJie

2008-03-01

We develop a physical model to describe the kinetic behavior in cell-adhesion molecules. Unbinding of noncovalent biological bonds is assumed to occur by both bond dissociation and bond rupture. Such a decomposition of debonding processes is a space decomposition of the debonding events. Dissociation under thermal fluctuation is nondirectional in a three-dimensional space, and its energy barrier to escape is not influenced by a tensile force, but the microstates that could lead to dissociation are changed by the tensile force; rupture happens along the tensile force direction. An applied force effectively lowers the energy barrier to escape along the loading direction. The lifetime of the biological bond, due to the two concurrent off rates, may grow with increasing tensile force to a moderate amount and then decrease with further increasing load. We hypothesize that a catch-to-slip bond transition is a generic feature in biological bonds. The model also predicts that catch bonds in a more flexible molecular structure have longer lifetimes and need less force to be fully activated.

Structure-based approach to the prediction of disulfide bonds in proteins.

PubMed

Salam, Noeris K; Adzhigirey, Matvey; Sherman, Woody; Pearlman, David A

2014-10-01

Protein engineering remains an area of growing importance in pharmaceutical and biotechnology research. Stabilization of a folded protein conformation is a frequent goal in projects that deal with affinity optimization, enzyme design, protein construct design, and reducing the size of functional proteins. Indeed, it can be desirable to assess and improve protein stability in order to avoid liabilities such as aggregation, degradation, and immunogenic response that may arise during development. One way to stabilize a protein is through the introduction of disulfide bonds. Here, we describe a method to predict pairs of protein residues that can be mutated to form a disulfide bond. We combine a physics-based approach that incorporates implicit solvent molecular mechanics with a knowledge-based approach. We first assign relative weights to the terms that comprise our scoring function using a genetic algorithm applied to a set of 75 wild-type structures that each contains a disulfide bond. The method is then tested on a separate set of 13 engineered proteins comprising 15 artificial stabilizing disulfides introduced via site-directed mutagenesis. We find that the native disulfide in the wild-type proteins is scored well, on average (within the top 6% of the reasonable pairs of residues that could form a disulfide bond) while 6 out of the 15 artificial stabilizing disulfides scored within the top 13% of ranked predictions. Overall, this suggests that the physics-based approach presented here can be useful for triaging possible pairs of mutations for disulfide bond formation to improve protein stability. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Recent mass spectrometry-based techniques and considerations for disulfide bond characterization in proteins.

PubMed

Lakbub, Jude C; Shipman, Joshua T; Desaire, Heather

2018-04-01

Disulfide bonds are important structural moieties of proteins: they ensure proper folding, provide stability, and ensure proper function. With the increasing use of proteins for biotherapeutics, particularly monoclonal antibodies, which are highly disulfide bonded, it is now important to confirm the correct disulfide bond connectivity and to verify the presence, or absence, of disulfide bond variants in the protein therapeutics. These studies help to ensure safety and efficacy. Hence, disulfide bonds are among the critical quality attributes of proteins that have to be monitored closely during the development of biotherapeutics. However, disulfide bond analysis is challenging because of the complexity of the biomolecules. Mass spectrometry (MS) has been the go-to analytical tool for the characterization of such complex biomolecules, and several methods have been reported to meet the challenging task of mapping disulfide bonds in proteins. In this review, we describe the relevant, recent MS-based techniques and provide important considerations needed for efficient disulfide bond analysis in proteins. The review focuses on methods for proper sample preparation, fragmentation techniques for disulfide bond analysis, recent disulfide bond mapping methods based on the fragmentation techniques, and automated algorithms designed for rapid analysis of disulfide bonds from liquid chromatography-MS/MS data. Researchers involved in method development for protein characterization can use the information herein to facilitate development of new MS-based methods for protein disulfide bond analysis. In addition, individuals characterizing biotherapeutics, especially by disulfide bond mapping in antibodies, can use this review to choose the best strategies for disulfide bond assignment of their biologic products. Graphical Abstract This review, describing characterization methods for disulfide bonds in proteins, focuses on three critical components: sample preparation, mass spectrometry data, and software tools.

Activation of remote meta-C-H bonds assisted by an end-on template.

PubMed

Leow, Dasheng; Li, Gang; Mei, Tian-Sheng; Yu, Jin-Quan

2012-06-27

Functionalization of unactivated carbon-hydrogen (C-H) single bonds is an efficient strategy for rapid generation of complex molecules from simpler ones. However, it is difficult to achieve selectivity when multiple inequivalent C-H bonds are present in the target molecule. The usual approach is to use σ-chelating directing groups, which lead to ortho-selectivity through the formation of a conformationally rigid six- or seven-membered cyclic pre-transition state. Despite the broad utility of this approach, proximity-driven reactivity prevents the activation of remote C-H bonds. Here we report a class of easily removable nitrile-containing templates that direct the activation of distal meta-C-H bonds (more than ten bonds away) of a tethered arene. We attribute this new mode of C-H activation to a weak 'end-on' interaction between the linear nitrile group and the metal centre. The 'end-on' coordination geometry relieves the strain of the cyclophane-like pre-transition state of the meta-C-H activation event. In addition, this template overrides the intrinsic electronic and steric biases as well as ortho-directing effects with two broadly useful classes of arene substrates (toluene derivatives and hydrocinnamic acids).

Indirect vs direct bonding of mandibular fixed retainers in orthodontic patients: a single-center randomized controlled trial comparing placement time and failure over a 6-month period.

PubMed

Bovali, Efstathia; Kiliaridis, Stavros; Cornelis, Marie A

2014-12-01

The objective of this 2-arm parallel single-center trial was to compare placement time and numbers of failures of mandibular lingual retainers bonded with an indirect procedure vs a direct bonding procedure. Sixty-four consecutive patients at the postgraduate orthodontic clinic of the University of Geneva in Switzerland scheduled for debonding and mandibular fixed retainer placement were randomly allocated to either an indirect bonding procedure or a traditional direct bonding procedure. Eligibility criteria were the presence of the 4 mandibular incisors and the 2 mandibular canines, and no active caries, restorations, fractures, or periodontal disease of these teeth. The patients were randomized in blocks of 4; the randomization sequence was generated using an online randomization service (www.randomization.com). Allocation concealment was secured by contacting the sequence generator for treatment assignment; blinding was possible for outcome assessment only. Bonding time was measured for each procedure. Unpaired t tests were used to assess differences in time. Patients were recalled at 1, 2, 4, and 6 months after bonding. Mandibular fixed retainers having at least 1 composite pad debonded were considered as failures. The log-rank test was used to compare the Kaplan-Meier survival curves of both procedures. A test of proportion was applied to compare the failures at 6 months between the treatment groups. Sixty-four patients were randomized in a 1:1 ratio. One patient dropped out at baseline after the bonding procedure, and 3 patients did not attend the recalls at 4 and 6 months. Bonding time was significantly shorter for the indirect procedure (321 ± 31 seconds, mean ± SD) than for the direct procedure (401 ± 40 seconds) (per protocol analysis of 63 patients: mean difference = 80 seconds; 95% CI = 62.4-98.1; P <0.001). The 6-month numbers of failures were 10 of 31 (32%) with the indirect technique and 7 of 29 (24%) with the direct technique (log rank: P = 0.35; test of proportions: risk difference = 0.08; 95% CI = -0.15 to 0.31; P = 0.49). No serious harm was observed except for plaque accumulation. Indirect bonding was statistically significantly faster than direct bonding, with both techniques showing similar risks of failure. This trial was not registered. The protocol was not published before trial commencement. No funding or conflict of interest to be declared. Copyright © 2014 American Association of Orthodontists. Published by Elsevier Inc. All rights reserved.

Cysteine-containing peptide tag for site-specific conjugation of proteins

DOEpatents

Backer, Marina V.; Backer, Joseph M.

2008-04-08

The present invention is directed to a biological conjugate, comprising: (a) a targeting moiety comprising a polypeptide having an amino acid sequence comprising the polypeptide sequence of SEQ ID NO:2 and the polypeptide sequence of a selected targeting protein; and (b) a binding moiety bound to the targeting moiety; the biological conjugate having a covalent bond between the thiol group of SEQ ID NO:2 and a functional group in the binding moiety. The present invention is directed to a biological conjugate, comprising: (a) a targeting moiety comprising a polypeptide having an amino acid sequence comprising the polypeptide sequence of SEQ ID NO:2 and the polypeptide sequence of a selected targeting protein; and (b) a binding moiety that comprises an adapter protein, the adapter protein having a thiol group; the biological conjugate having a disulfide bond between the thiol group of SEQ ID NO:2 and the thiol group of the adapter protein. The present invention is also directed to biological sequences employed in the above biological conjugates, as well as pharmaceutical preparations and methods using the above biological conjugates.

Cysteine-containing peptide tag for site-specific conjugation of proteins

DOEpatents

Backer, Marina V.; Backer, Joseph M.

2010-10-05

The present invention is directed to a biological conjugate, comprising: (a) a targeting moiety comprising a polypeptide having an amino acid sequence comprising the polypeptide sequence of SEQ ID NO:2 and the polypeptide sequence of a selected targeting protein; and (b) a binding moiety bound to the targeting moiety; the biological conjugate having a covalent bond between the thiol group of SEQ ID NO:2 and a functional group in the binding moiety. The present invention is directed to a biological conjugate, comprising: (a) a targeting moiety comprising a polypeptide having an amino acid sequence comprising the polypeptide sequence of SEQ ID NO:2 and the polypeptide sequence of a selected targeting protein; and (b) a binding moiety that comprises an adapter protein, the adapter protein having a thiol group; the biological conjugate having a disulfide bond between the thiol group of SEQ ID NO:2 and the thiol group of the adapter protein. The present invention is also directed to biological sequences employed in the above biological conjugates, as well as pharmaceutical preparations and methods using the above biological conjugates.

Hydroxylation of organic polymer surface: method and application.

PubMed

Yang, Peng; Yang, Wantai

2014-03-26

It may be hardly believable that inert C-H bonds on a polymeric material surface could be quickly and efficiently transformed into C-OH by a simple and mild way. Thanks to the approaches developed recently, it is now possible to transform surface H atoms of a polymeric substrate into monolayer OH groups by a simple/mild photochemical reaction. Herein the method and application of this small-molecular interfacial chemistry is highlighted. The existence of hydroxyl groups on material surfaces not only determines the physical and chemical properties of materials but also provides effective reaction sites for postsynthetic sequential modification to fulfill the requirements of various applications. However, organic synthetic materials based on petroleum, especially polyolefins comprise mainly C and H atoms and thus present serious surface problems due to low surface energy and inertness in reactivity. These limitations make it challenging to perform postsynthetic surface sequential chemical derivatization toward enhanced functionalities and properties and also cause serious interfacial problems when bonding or integrating polymer substrates with natural or inorganic materials. Polymer surface hydroxylation based on direct conversion of C-H bonds on polymer surfaces is thus of significant importance for academic and practical industrial applications. Although highly active research results have reported on small-molecular C-H bond activation in solution (thus homogeneous), most of them, featuring the use of a variety of transition metals as catalysts, present a slow reaction rate, a low atom economy and an obvious environmental pollution. In sharp contrast to these conventional C-H activation strategies, the present Spotlight describes a universal confined photocatalytic oxidation (CPO) system that is able to directly convert polymer surface C-H bonds to C-OSO3(-) and, subsequently, to C-OH through a simple hydrolysis. Generally speaking, these newly implanted hydroxyl groups preserve their own reactivity toward other complementary compounds, thus creating a novel base with distinct surface properties. Thanks to this functionalized platform, a wide range of organic, inorganic and metal materials have been attached to conventional organic polymer substrates through the rational engineering of surface molecular templates from small functional groups to macromolecules. It is expected that the proposed novel CPO method and its versatile usages in advanced material applications will offer new opportunities for a variety of scientific communities, especially for those working on surface/interface modulation.

Expedient Spall Repair Methods and Equipment for Airfield Pavements Preprint

DTIC Science & Technology

2009-08-01

placement (3). RESEACH OBJECTIVES AND SCOPE The objective of this research was to develop one or more methods that will allow field personnel to...cores were used to perform in-situ tensile pull-off tests to evaluate the bond between the repair material and the substrate. Also, a series of 4...inch diameters cores were cut, and direct shear tests were performed on the repair material/substrate interface. Finally, all spalls were trafficked for

Cohesive zone model for direct silicon wafer bonding

NASA Astrophysics Data System (ADS)

Kubair, D. V.; Spearing, S. M.

2007-05-01

Direct silicon wafer bonding and decohesion are simulated using a spectral scheme in conjunction with a rate-dependent cohesive model. The cohesive model is derived assuming the presence of a thin continuum liquid layer at the interface. Cohesive tractions due to the presence of a liquid meniscus always tend to reduce the separation distance between the wafers, thereby opposing debonding, while assisting the bonding process. In the absence of the rate-dependence effects the energy needed to bond a pair of wafers is equal to that needed to separate them. When rate-dependence is considered in the cohesive law, the experimentally observed asymmetry in the energetics can be explained. The derived cohesive model has the potential to form a bridge between experiments and a multiscale-modelling approach to understand the mechanics of wafer bonding.

Structure, bonding nature, and binding energy of alkanethiolate on As-rich GaAs (001) surface: a density functional theory study.

PubMed

Voznyy, Oleksandr; Dubowski, Jan J

2006-11-30

Chemisorption of alkanethiols on As-rich GaAs (001) surface under a low coverage condition was studied using first principles density functional calculations in a periodic supercell approach. The thiolate adsorption site, tilt angle and its direction are dictated by the high directionality of As dangling bond and sulfur 3p orbital participating in bonding and steric repulsion of the first three CH2 units from the surface. Small charge transfer between thiolate and surface, strong dependence of total energy on tilt angle, and a relatively short length of 2.28 A of the S-As bond indicate the highly covalent nature of the bonding. Calculated binding energy of 2.1 eV is consistent with the available experimental data.

31 CFR 351.60 - How are book-entry Series EE savings bonds purchased and held?

Code of Federal Regulations, 2014 CFR

2014-07-01

...-entry Series EE savings bonds purchased and held? Book-entry bonds must be purchased and held online through your New Treasury Direct account. We provide instructions for opening an account online at . ...

31 CFR 351.60 - How are book-entry Series EE savings bonds purchased and held?

Code of Federal Regulations, 2012 CFR

2012-07-01

...-entry Series EE savings bonds purchased and held? Book-entry bonds must be purchased and held online through your New Treasury Direct account. We provide instructions for opening an account online at . ...

29 CFR 453.17 - Term of the bond.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., however, that a new bond must be obtained each year. There is nothing in the Act which prohibits a bond... either event, the terms upon which this could best be done would be left to the parties directly...

29 CFR 453.17 - Term of the bond.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., however, that a new bond must be obtained each year. There is nothing in the Act which prohibits a bond... either event, the terms upon which this could best be done would be left to the parties directly...

Rapid adhesive bonding of advanced composites and titanium

NASA Technical Reports Server (NTRS)

Stein, B. A.; Tyeryart, J. R.; Hodgest, W. T.

1985-01-01

Rapid adhesive bonding (RAB) concepts utilize a toroid induction technique to heat the adhesive bond line directly. This technique was used to bond titanium overlap shear specimens with 3 advanced thermoplastic adhesives and APC-2 (graphite/PEEK) composites with PEEK film. Bond strengths equivalent to standard heated-platen press bonds were produced with large reductions in process time. RAB produced very strong bonds in APC-2 adherend specimens; the APC-2 adherends were highly resistant to delamination. Thermal cycling did not significantly affect the shear strengths of RAB titanium bonds with polyimide adhesives. A simple ultrasonic non-destructive evaluation process was found promising for evaluating bond quality.

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

IMPROVED BONDING METHOD

DOEpatents

Padgett, E.V. Jr.; Warf, D.H.

1964-04-28

An improved process of bonding aluminum to aluminum without fusion by ultrasonic vibrations plus pressure is described. The surfaces to be bonded are coated with an aqueous solution of alkali metal stearate prior to assembling for bonding. (AEC) O H19504 Present information is reviewed on steady state proliferation, differentiation, and maturation of blood cells in mammals. Data are cited from metabolic tracer studies, autoradiographic studies, cytologic studies, studies of hematopoietic response to radiation injuries, and computer analyses of blood cell production. A 3-step model for erythropoiesis and a model for granulocyte kinetics are presented. New approaches to the study of lymphocytopoiesis described include extracorporeal blood irradiation to deplete lymphocytic tissue without direct injury to the formative tissues as a means to study the stressed system, function control, and rates of proliferation. It is pointed out that present knowledge indicates that lymphocytes comprise a mixed family, with diverse life spans, functions, and migration patterns with apparent aimless recycling from modes to lymph to blood to nodes that has not yet been quantitated. Areas of future research are postulated. (70 references.) (C.H.)

Generating carbyne equivalents with photoredox catalysis

NASA Astrophysics Data System (ADS)

Wang, Zhaofeng; Herraiz, Ana G.; Del Hoyo, Ana M.; Suero, Marcos G.

2018-02-01

Carbon has the unique ability to bind four atoms and form stable tetravalent structures that are prevalent in nature. The lack of one or two valences leads to a set of species—carbocations, carbanions, radicals and carbenes—that is fundamental to our understanding of chemical reactivity. In contrast, the carbyne—a monovalent carbon with three non-bonded electrons—is a relatively unexplored reactive intermediate; the design of reactions involving a carbyne is limited by challenges associated with controlling its extreme reactivity and the lack of efficient sources. Given the innate ability of carbynes to form three new covalent bonds sequentially, we anticipated that a catalytic method of generating carbynes or related stabilized species would allow what we term an ‘assembly point’ disconnection approach for the construction of chiral centres. Here we describe a catalytic strategy that generates diazomethyl radicals as direct equivalents of carbyne species using visible-light photoredox catalysis. The ability of these carbyne equivalents to induce site-selective carbon-hydrogen bond cleavage in aromatic rings enables a useful diazomethylation reaction, which underpins sequencing control for the late-stage assembly-point functionalization of medically relevant agents. Our strategy provides an efficient route to libraries of potentially bioactive molecules through the installation of tailored chiral centres at carbon-hydrogen bonds, while complementing current translational late-stage functionalization processes. Furthermore, we exploit the dual radical and carbene character of the generated carbyne equivalent in the direct transformation of abundant chemical feedstocks into valuable chiral molecules.

Significance of DNA bond strength in programmable nanoparticle thermodynamics and dynamics.

PubMed

Yu, Qiuyan; Hu, Jinglei; Hu, Yi; Wang, Rong

2018-04-04

Assembly of nanoparticles (NPs) coated with complementary DNA strands leads to novel crystals with nanosized basic units rather than classic atoms, ions or molecules. The assembly process is mediated by hybridization of DNA via specific base pairing interaction, and is kinetically linked to the disassociation of DNA duplexes. DNA-level physiochemical quantities, both thermodynamic and kinetic, are key to understanding this process and essential for the design of DNA-NP crystals. The melting transition properties are helpful to judge the thermostability and sensitivity of relative DNA probes or other applications. Three different cases are investigated by changing the linker length and the spacer length on which the melting properties depend using the molecular dynamics method. Melting temperature is determined by sigmoidal melting curves based on hybridization percentage versus temperature and the Lindemann melting rule simultaneously. We provide a computational strategy based on a coarse-grained model to estimate the hybridization enthalpy, entropy and free energy from percentages of hybridizations which are readily accessible in experiments. Importantly, the lifetime of DNA bond dehybridization based on temperature and the activation energy depending on DNA bond strength are also calculated. The simulation results are in good agreement with the theoretical analysis and the present experimental data. Our study provides a good strategy to predict the melting temperature which is important for the DNA-directed nanoparticle system, and bridges the dynamics and thermodynamics of DNA-directed nanoparticle systems by estimating the equilibrium constant from the hybridization of DNA bonds quantitatively.

Determining the Energetics of the Hydrogen Bond through FTIR: A Hands-On Physical Chemistry Lab Experiment

ERIC Educational Resources Information Center

Guerin, Abby C.; Riley, Kristi; Rupnik, Kresimir; Kuroda, Daniel G.

2016-01-01

Hydrogen bonds are very important chemical structures that are responsible for many unique and important properties of solvents, such as the solvation power of water. These distinctive features are directly related to the stabilization energy conferred by hydrogen bonds to the solvent. Thus, the characterization of hydrogen bond energetics has…

The origins of femtomolar protein-ligand binding: hydrogen-bond cooperativity and desolvation energetics in the biotin-(strept)avidin binding site.

PubMed

DeChancie, Jason; Houk, K N

2007-05-02

The unusually strong reversible binding of biotin by avidin and streptavidin has been investigated by density functional and MP2 ab initio quantum mechanical methods. The solvation of biotin by water has also been studied through QM/MM/MC calculations. The ureido moiety of biotin in the bound state hydrogen bonds to five residues, three to the carbonyl oxygen and one for each--NH group. These five hydrogen bonds act cooperatively, leading to stabilization that is larger than the sum of individual hydrogen-bonding energies. The charged aspartate is the key residue that provides the driving force for cooperativity in the hydrogen-bonding network for both avidin and streptavidin by greatly polarizing the urea of biotin. If the residue is removed, the network is disrupted, and the attenuation of the energetic contributions from the neighboring residues results in significant reduction of cooperative interactions. Aspartate is directly hydrogen-bonded with biotin in streptavidin and is one residue removed in avidin. The hydrogen-bonding groups in streptavidin are computed to give larger cooperative hydrogen-bonding effects than avidin. However, the net gain in electrostatic binding energy is predicted to favor the avidin-bicyclic urea complex due to the relatively large penalty for desolvation of the streptavidin binding site (specifically expulsion of bound water molecules). QM/MM/MC calculations involving biotin and the ureido moiety in aqueous solution, featuring PDDG/PM3, show that water interactions with the bicyclic urea are much weaker than (strept)avidin interactions due to relatively low polarization of the urea group in water.

78 FR 64292 - Community Development Financial Institutions Fund Proposed Collection; Comment Request

Federal Register 2010, 2011, 2012, 2013, 2014

2013-10-28

.... ADDRESSES: Direct all comments to Lisa Jones, CDFI Bond Guarantee Program Manager, at the Community... should be directed to Lisa Jones, CDFI Bond Guarantee Program Manager, at the Community Development... on respondents, including through the use of technology; and (e) estimates of capital or start-up...

19 CFR 146.40 - Operator responsibilities for direct delivery.

Code of Federal Regulations, 2013 CFR

2013-04-01

...; DEPARTMENT OF THE TREASURY (CONTINUED) FOREIGN TRADE ZONES Admission of Merchandise to a Zone § 146.40 Operator responsibilities for direct delivery. (a) Arrival of conveyance. Upon arrival at a subzone or zone... Zone Operator's Bond and to relieve the carrier of responsibility. (5) Forward the in-bond or cartage...

19 CFR 146.40 - Operator responsibilities for direct delivery.

Code of Federal Regulations, 2014 CFR

2014-04-01

...; DEPARTMENT OF THE TREASURY (CONTINUED) FOREIGN TRADE ZONES Admission of Merchandise to a Zone § 146.40 Operator responsibilities for direct delivery. (a) Arrival of conveyance. Upon arrival at a subzone or zone... Zone Operator's Bond and to relieve the carrier of responsibility. (5) Forward the in-bond or cartage...

19 CFR 146.40 - Operator responsibilities for direct delivery.

Code of Federal Regulations, 2011 CFR

2011-04-01

...; DEPARTMENT OF THE TREASURY (CONTINUED) FOREIGN TRADE ZONES Admission of Merchandise to a Zone § 146.40 Operator responsibilities for direct delivery. (a) Arrival of conveyance. Upon arrival at a subzone or zone... Zone Operator's Bond and to relieve the carrier of responsibility. (5) Forward the in-bond or cartage...

19 CFR 146.40 - Operator responsibilities for direct delivery.

Code of Federal Regulations, 2012 CFR

2012-04-01

...; DEPARTMENT OF THE TREASURY (CONTINUED) FOREIGN TRADE ZONES Admission of Merchandise to a Zone § 146.40 Operator responsibilities for direct delivery. (a) Arrival of conveyance. Upon arrival at a subzone or zone... Zone Operator's Bond and to relieve the carrier of responsibility. (5) Forward the in-bond or cartage...

19 CFR 146.40 - Operator responsibilities for direct delivery.

Code of Federal Regulations, 2010 CFR

2010-04-01

...; DEPARTMENT OF THE TREASURY (CONTINUED) FOREIGN TRADE ZONES Admission of Merchandise to a Zone § 146.40 Operator responsibilities for direct delivery. (a) Arrival of conveyance. Upon arrival at a subzone or zone... Zone Operator's Bond and to relieve the carrier of responsibility. (5) Forward the in-bond or cartage...

31 CFR 359.45 - How are book-entry Series I savings bonds purchased and held?

Code of Federal Regulations, 2010 CFR

2010-07-01

...-entry Series I savings bonds purchased and held? Book-entry bonds must be purchased and held online through your New Treasury Direct account. We provide instructions for opening an account online at http...

31 CFR 359.45 - How are book-entry Series I savings bonds purchased and held?

Code of Federal Regulations, 2014 CFR

2014-07-01

...-entry Series I savings bonds purchased and held? Book-entry bonds must be purchased and held online through your New Treasury Direct account. We provide instructions for opening an account online at http...

31 CFR 359.45 - How are book-entry Series I savings bonds purchased and held?

Code of Federal Regulations, 2012 CFR

2012-07-01

...-entry Series I savings bonds purchased and held? Book-entry bonds must be purchased and held online through your New Treasury Direct account. We provide instructions for opening an account online at http...

31 CFR 359.45 - How are book-entry Series I savings bonds purchased and held?

Code of Federal Regulations, 2013 CFR

2013-07-01

...-entry Series I savings bonds purchased and held? Book-entry bonds must be purchased and held online through your New Treasury Direct account. We provide instructions for opening an account online at http...

Chemoselective Amination of Propargylic C(sp3)–H Bonds via Co(II)-Based Metalloradical Catalysis**

PubMed Central

Li, Chaoqun; Jiang, Huiling; Lizardi, Christopher L.

2014-01-01

Highly chemoselective intramolecular amination of propargylic C(sp3)–H bonds has been demonstrated for N-bishomopropargylic sulfamoyl azides via Co(II)-based metalloradical catalysis. Supported by D2h-symmetric amidoporphyrin ligand 3,5-DitBu-IbuPhyrin, the Co(II)-catalyzed C–H amination process can proceed effectively under neutral and nonoxidative conditions without the need of any additives, generating N2 as the only byproduct. The metalloradical amination is suitable to both secondary and tertiary propargylic C–H substrates with an unusually high degree of functional group tolerance, providing a direct method for high-yielding synthesis of functionalized propargylamine derivatives. PMID:24840605

Simulating Energy Relaxation in Pump-Probe Vibrational Spectroscopy of Hydrogen-Bonded Liquids.

PubMed

Dettori, Riccardo; Ceriotti, Michele; Hunger, Johannes; Melis, Claudio; Colombo, Luciano; Donadio, Davide

2017-03-14

We introduce a nonequilibrium molecular dynamics simulation approach, based on the generalized Langevin equation, to study vibrational energy relaxation in pump-probe spectroscopy. A colored noise thermostat is used to selectively excite a set of vibrational modes, leaving the other modes nearly unperturbed, to mimic the effect of a monochromatic laser pump. Energy relaxation is probed by analyzing the evolution of the system after excitation in the microcanonical ensemble, thus providing direct information about the energy redistribution paths at the molecular level and their time scale. The method is applied to hydrogen-bonded molecular liquids, specifically deuterated methanol and water, providing a robust picture of energy relaxation at the molecular scale.

Metal-ligand bond directionality in the M2-NH3 complexes (M = Cu, Ag and Au)

NASA Astrophysics Data System (ADS)

Eskandari, K.; Ebadinejad, F.

2018-05-01

The metal-ligand bonds in the M2-NH3 complexes (M = Au, Ag and Cu) are directional and the M-M-N angles tend to be linear. Natural energy decomposition analysis (NEDA) and localised molecular orbital energy decomposition analysis (LMOEDA) approaches indicate that the metal-ligand bonds in these complexes are mainly electrostatic in nature, however, the electrostatic is not the cause of the linearity of M-M-N arrangements. Instead, NEDA shows that the charge transfer and core repulsion are mainly responsible for the directionality of these bonds. In the LMOEDA point of view, the repulsion term is the main reason for the linearity of these complexes. Interacting quantum atoms (IQA) analysis shows that inter-atomic and inter-fragment interactions favour the nonlinear arrangements; however, these terms are compensated by the atomic self-energies, which stabilise the linear structure.

Assessment of antibacterial properties of newer dentin bonding agents: An in vitro study.

PubMed

Sampath, Pavitra B; Hegde, Mithra N; Hegde, Priyadarshini

2011-07-01

To evaluate and compare the antibacterial activity of newer dentin bonding agents on Streptococcus mutans using the direct contact test. Streptococcus mutans was used as test organism and a direct contact test was performed. The dentin bonding agents to be tested were grouped as Group I, Clearfil Protect Bond, Group II, Adper Easy One, and Group III, Prime and Bond NT. For the direct contact test, three microtiter plates consisting of 96 wells each were taken (288 wells). These wells were divided into three groups of 96 wells; 16 wells of a microtiter plate were utilized, of which four were designated as 'A' wells (with the dentin bonding agent and bacterial suspension), another four as 'B' wells (without the dentin bonding agent, but with the bacterial suspension), another four as the 'C' wells (with the tested material, but without bacteria, which served as the negative control), and the remaining four as the 'D' wells (without the dentin bonding agent, which served as the positive control). Each group was treated with their respective bonding agents as per the manufactures instructions. Broth of 15 μL was then transferred from the A wells into an adjacent set of B wells containing fresh medium (215 μL). This resulted in two sets of four wells for each tested material containing an equal volume of liquid medium, so that bacterial growth was monitored both in the presence and in the absence of the tested material. The plate was placed for incubation at 37°C in the microplate reader and the optical density in each well was measured at 600 nm. The readings were taken at regular intervals. (Every 30 minutes for 16 hours). The Dentin bonding agents evaluated in this study showed different inhibitory effects. Clearfil Protect Bond and Prime and Bond NT were most effective, and Adper Easy One was least effective against Streptococcus mutans. The Dentin bonding agents evaluated in this study showed different inhibitory effects. Clearfil Protect Bond and Prime and Bond NT were most effective, and Adper Easy One was the least effective against Streptococcus mutans. Hence, the incorporation of antibacterial agents into the dentin bonding agents may become an essential factor in inhibiting residual bacteria in the cavity and secondary caries.

Multi-wafer bonding technology for the integration of a micromachined Mirau interferometer

NASA Astrophysics Data System (ADS)

Wang, Wei-Shan; Lullin, Justine; Froemel, Joerg; Wiemer, Maik; Bargiel, Sylwester; Passilly, Nicolas; Gorecki, Christophe; Gessner, Thomas

2015-02-01

The paper presents the multi-wafer bonding technology as well as the integration of electrical connection to the zscanner wafer of the micromachined array-type Mirau interferometer. A Mirau interferometer, which is a key-component of optical coherence tomography (OCT) microsystem, consists of a microlens doublet, a MOEMS Z-scanner, a focusadjustment spacer and a beam splitter plate. For the integration of this MOEMS device heterogeneous bonding of Si, glass and SOI wafers is necessary. Previously, most of the existing methods for multilayer wafer bonding require annealing at high temperature, i.e., 1100°C. To be compatible with MEMS devices, bonding of different material stacks at temperatures lower than 400°C has also been investigated. However, if more components are involved, it becomes less effective due to the alignment accuracy or degradation of surface quality of the not-bonded side after each bonding operation. The proposed technology focuses on 3D integration of heterogeneous building blocks, where the assembly process is compatible with the materials of each wafer stack and with position accuracy which fits optical requirement. A demonstrator with up to 5 wafers bonded lower than 400°C is presented and bond interfaces are evaluated. To avoid the complexity of through wafer vias, a design which creates electrical connections along vertical direction by mounting a wafer stack on a flip chip PCB is proposed. The approach, which adopts vertically-stacked wafers along with electrical connection functionality, provides not only a space-effective integration of MOEMS device but also a design where the Mirau stack can be further integrated with other components of the OCT microsystem easily.

A method of coupling the Paternò-Büchi reaction with direct infusion ESI-MS/MS for locating the C[double bond, length as m-dash]C bond in glycerophospholipids.

PubMed

Stinson, Craig A; Xia, Yu

2016-06-21

Tandem mass spectrometry (MS/MS) coupled with soft ionization is established as an essential platform for lipid analysis; however, determining high order structural information, such as the carbon-carbon double bond (C[double bond, length as m-dash]C) location, remains challenging. Recently, our group demonstrated a method for sensitive and confident lipid C[double bond, length as m-dash]C location determination by coupling online the Paternò-Büchi (PB) reaction with nanoelectrospray ionization (nanoESI) and MS/MS. Herein, we aimed to expand the scope of the PB reaction for lipid analysis by enabling the reaction with infusion ESI-MS/MS at much higher flow rates than demonstrated in the nanoESI setup (∼20 nL min(-1)). In the new design, the PB reaction was effected in a fused silica capillary solution transfer line, which also served as a microflow UV reactor, prior to ESI. This setup allowed PB reaction optimization and kinetics studies. Under optimized conditions, a maximum of 50% PB reaction yield could be achieved for a standard glycerophosphocholine (PC) within 6 s of UV exposure over a wide flow rate range (0.1-10 μL min(-1)). A solvent composition of 7 : 3 acetone : H2O (with 1% acid or base modifier) allowed the highest PB yields and good lipid ionization, while lower yields were obtained with an addition of a variety of organic solvents. Radical induced lipid peroxidation was identified to induce undesirable side reactions, which could be effectively suppressed by eliminating trace oxygen in the solution via N2 purge. Finally, the utility of coupling the PB reaction with infusion ESI-MS/MS was demonstrated by analyzing a yeast polar lipid extract where C[double bond, length as m-dash]C bond locations were revealed for 35 glycerophospholipids (GPs).

The Ties That Bind: Bonding Versus Bridging Social Capital and College Student Party Attendance

PubMed Central

Buettner, Cynthia K.; Debies-Carl, Jeffrey S.

2012-01-01

Objective: This study explored the relationship between bonding and bridging social capital and college student attendance at alcohol-present parties, a common method for building informal social networks. Method: A random sample of students (n = 6,291; 52% female) from a large public midwestern university completed a survey regarding their alcohol use and party-related behaviors on targeted weekends. The survey also included questions regarding students’ living arrangements, romantic relationships, and membership in student and community organizations. Results: Based on a dichotomous logistic regression analysis, we concluded that the act of attending parties largely serves as a complement to, rather than a substitute for, more conventional and formal social capital. Membership in bonding groups is associated with increased odds of party attendance, and bridging exerts no direct effect on party attendance. However, bridging capital does mitigate the effect of bonding capital, reducing its apparent tendency to promote or contribute to partying. Conclusions: Off-campus parties may offer an informal supplement to more conventional social capital as students establish themselves in their new context. These findings may have implications for structural decisions (e.g., number of roommates) as well as the design of context-based prevention programs that address students’ need to quickly build social capital without exposing both themselves and the students around them to the harms associated with high-risk drinking. PMID:22630799

Infrared signature of micro-hydration in the organophosphate sarin: An ab initio study

DOE PAGES

Alam, Todd M.; Pearce, Charles Joseph

2015-06-28

The infrared (IR) spectra of micro-hydrated Sarin•(H 2O) n clusters containing between one and four explicit waters have been studied using ab initio density functional theory (DFT) methods. The phosphate group P=O bond vibration region (~1270 to 1290 cm –1) revealed the largest frequency variation with hydration, with a frequency red shift reflecting the direct hydrogen bond formation between the P=O of Sarin and water. Small variations to the P-F stretch (~810 to 815 cm –1) and the C-O-P vibrational modes (~995 to 1004 cm –1) showed that the water interactions with these functional groups were minor, and that themore » structures of Sarin were not extensively perturbed in the hydrated complexes. Increasing the number of explicit hydration waters produced only small vibrational changes in the lowest free energy complexes. These minor changes were consistent with a single water-phosphate hydrogen bond being the dominant structure, though a second water-phosphate hydrogen bond was observed in some complexes and was identified by an additional red shift of the P=O bond vibration. As a result, the H 2O•H 2O vibrational modes (~3450 to 3660 cm –1) increased in complexity with higher hydration levels and reflect the extended hydrogen bonding networks formed between the explicit waters in the hydrated Sarin clusters.« less

Speciation of sulfur in humic and fulvic acids using X-ray absorption near-edge structure (XANES) spectroscopy

NASA Astrophysics Data System (ADS)

Morra, Matthew J.; Fendorf, Scott E.; Brown, Paul D.

1997-02-01

Sulfur species in soils and sediments have previously been determined indirectly using destructive techniques. A direct and more accurate method for S speciation would improve our understanding of S biogeochemistry. X-ray absorption near edge structure (XANES) spectroscopy was performed on purified humic and fulvic acids from terrestrial and aquatic environments. This methodology allows direct determination of S species using the relationship that exists with the energy required for core electron transitions and in some cases, correlation with additional spectral features. Soil, peat, and aquatic humic acids were dominated by sulfonates with an oxidation state of +5, but also contained ester-bonded sulfates with an oxidation state of +6. Leonardite humic acid contained ester-bonded sulfate and an unidentified S compound with an oxidation state of +4.0. In contrast, high-valent S in soil, peat, and aquatic fulvic acids was exclusively in the form of sulfonic acids. Reduced S species were also present in both humic and fulvic acids. XANES is a valuable method for the speciation of S in humic materials and of potential use in S speciation of unfractionated soils.

Direct Wafer Bonding and Its Application to Waveguide Optical Isolators

PubMed Central

Mizumoto, Tetsuya; Shoji, Yuya; Takei, Ryohei

2012-01-01

This paper reviews the direct bonding technique focusing on the waveguide optical isolator application. A surface activated direct bonding technique is a powerful tool to realize a tight contact between dissimilar materials. This technique has the potential advantage that dissimilar materials are bonded at low temperature, which enables one to avoid the issue associated with the difference in thermal expansion. Using this technique, a magneto-optic garnet is successfully bonded on silicon, III-V compound semiconductors and LiNbO3. As an application of this technique, waveguide optical isolators are investigated including an interferometric waveguide optical isolator and a semileaky waveguide optical isolator. The interferometric waveguide optical isolator that uses nonreciprocal phase shift is applicable to a variety of waveguide platforms. The low refractive index of buried oxide layer in a silicon-on-insulator (SOI) waveguide enhances the magneto-optic phase shift, which contributes to the size reduction of the isolator. A semileaky waveguide optical isolator has the advantage of large fabrication-tolerance as well as a wide operation wavelength range. PMID:28817020

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.

31 CFR 363.96 - What do I need to know if I initially purchase a bond as a gift?

Code of Federal Regulations, 2010 CFR

2010-07-01

... purchase a bond as a gift? 363.96 Section 363.96 Money and Finance: Treasury Regulations Relating to Money...Direct Gifts § 363.96 What do I need to know if I initially purchase a bond as a gift? (a) An entity may not purchase a gift savings bond. (b) The gift bond will be registered in the name of the recipient(s...

C–H bond halogenation catalyzed or mediated by copper: an overview

PubMed Central

Hao, Wenyan

2015-01-01

Summary Carbon–halogen (C–X) bonds are amongst the most fundamental groups in organic synthesis, they are frequently and widely employed in the synthesis of numerous organic products. The generation of a C–X bond, therefore, constitutes an issue of universal interest. Herein, the research advances on the copper-catalyzed and mediated C–X (X = F, Cl, Br, I) bond formation via direct C–H bond transformation is reviewed. PMID:26664634

Determination of high-strength materials diamond grinding rational modes

NASA Astrophysics Data System (ADS)

Arkhipov, P. V.; Lobanov, D. V.; Rychkov, D. A.; Yanyushkin, A. S.

2018-03-01

The analysis of methods of high-strength materials abrasive processing is carried out. This method made it possible to determine the necessary directions and prospects for the development of shaping combined methods. The need to use metal bonded diamond abrasive tools in combination with a different kind of energy is noted to improve the processing efficiency and reduce the complexity of operations. The complex of experimental research on revealing the importance of mechanical and electrical components of cutting regimes, on the cutting ability of diamond tools, as well as the need to reduce the specific consumption of an abrasive wheel as one of the important economic indicators of the processing process is performed. It is established that combined diamond grinding with simultaneous continuous correction of the abrasive wheel contributes to an increase in the cutting ability of metal bonded diamond abrasive tools when processing high-strength materials by an average of 30% compared to diamond grinding. Particular recommendations on the designation of technological factors are developed depending on specific production problems.

Methods of measurement for semiconductor materials, process control, and devices

NASA Technical Reports Server (NTRS)

Bullis, W. M. (Editor)

1973-01-01

This progress report describes NBS activities directed toward the development of methods of measurement for semiconductor materials, process control, and devices. Significant accomplishments during this reporting period include design of a plan to provide standard silicon wafers for four-probe resistivity measurements for the industry, publication of a summary report on the photoconductive decay method for measuring carrier lifetime, publication of a comprehensive review of the field of wire bond fabrication and testing, and successful completion of organizational activity leading to the establishment of a new group on quality and hardness assurance in ASTM Committee F-1 on Electronics. Work is continuing on measurement of resistivity of semiconductor crystals; characterization of generation-recombination-trapping centers in silicon; study of gold-doped silicon; development of the infrared response technique; evaluation of wire bonds and die attachment; and measurement of thermal properties of semiconductor devices, delay time and related carrier transport properties in junction devices, and noise properties of microwave diodes.

Indirect Versus Direct Heating of Sheet Materials: Superplastic Forming and Diffusion Bonding Using Lasers

NASA Astrophysics Data System (ADS)

Jocelyn, Alan; Kar, Aravinda; Fanourakis, Alexander; Flower, Terence; Ackerman, Mike; Keevil, Allen; Way, Jerome

2010-06-01

Many from within manufacturing industry consider superplastic forming (SPF) to be ‘high tech’, but it is often criticized as too complicated, expensive, slow and, in general, an unstable process when compared to other methods of manipulating sheet materials. Perhaps, the fundamental cause of this negative perception of SPF, and also of diffusion bonding (DB), is the fact that the current process of SPF/DB relies on indirect sources of heating to produce the conditions necessary for the material to be formed. Thus, heat is usually derived from the electrically heated platens of hydraulic presses, to a lesser extent from within furnaces and, sometimes, from heaters imbedded in ceramic moulds. Recent evaluations of these isothermal methods suggest they are slow, thermally inefficient and inappropriate for the process. In contrast, direct heating of only the material to be formed by modern, electrically efficient, lasers could transform SPF/DB into the first choice of designers in aerospace, automotive, marine, medical, architecture and leisure industries. Furthermore, ‘variable temperature’ direct heating which, in theory, is possible with a laser beam(s) may provide a means to control material thickness distribution, a goal of enormous importance as fuel efficient, lightweight structures for transportation systems are universally sought. This paper compares, and contrasts, the two systems and suggests how a change to laser heating might be achieved.

Chemical Bonding Technology: Direct Investigation of Interfacial Bonds

NASA Technical Reports Server (NTRS)

Koenig, J. L.; Boerio, F. J.; Plueddemann, E. P.; Miller, J.; Willis, P. B.; Cuddihy, E. F.

1986-01-01

This is the third Flat-Plate Solar Array (FSA) Project document reporting on chemical bonding technology for terrestrial photovoltaic (PV) modules. The impetus for this work originated in the late 1970s when PV modules employing silicone encapsulation materials were undergoing delamination during outdoor exposure. At that time, manufacturers were not employing adhesion promoters and, hence, module interfaces in common with the silicone materials were only in physical contact and therefore easily prone to separation if, for example, water were to penetrate to the interfaces. Delamination with silicone materials virtually vanished when adhesion promoters, recommended by silicone manufacturers, were used. The activities related to the direct investigation of chemically bonded interfaces are described.

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.

Probing Competitive and Co-operative Hydroxyl and Ammonium Hydrogen-Bonding Directed Epoxidations.

PubMed

Brambilla, Marta; Brennan, Méabh B; Csatayová, Kristína; Davies, Stephen G; Fletcher, Ai M; Kennett, Alice M R; Lee, James A; Roberts, Paul M; Russell, Angela J; Thomson, James E

2017-10-06

The diastereoselectivities and rates of epoxidation (upon treatment with Cl 3 CCO 2 H then m-CPBA) of a range of cis- and trans-4-aminocycloalk-2-en-1-ol derivatives (containing five-, six-, and seven-membered rings) have been investigated. In all cases where the two potential directing groups can promote epoxidation on opposite faces of the ring scaffold, evidence of competitive epoxidation pathways, promoted by hydrogen-bonding to either the in situ formed ammonium moiety or the hydroxyl group, was observed. In contrast to the relative directing group abilities already established for the six-membered ring system (NHBn ≫ OH > NBn 2 ), an N,N-dibenzylammonium moiety appeared more proficient than a hydroxyl group at directing the stereochemical course of the epoxidation reaction in a five- or seven-membered system. In the former case, this was rationalized by the drive to minimize torsional strain in the transition state being coupled with assistance from hydrogen-bonding to the ammonium moiety. In the latter case, this was ascribed to the steric bulk of the ammonium moiety disfavoring conformations in which hydrogen-bonding to the hydroxyl group results in direction of the epoxidation to the syn face. In cases where the two potential directing groups can promote epoxidation on the same face of the ring scaffold, an enhancement of epoxidation diastereoselectivity was not observed, while introduction of a second, allylic heteroatom to the substrate results in diminishment of the rate of epoxidation in all cases. Presumably, reduction of the nucleophilicity of the olefin by the second, inductively electron-withdrawing heteroatom is the dominant factor, and any assistance to the epoxidation reaction by the potential to form hydrogen-bonds to two directing groups rather than one is clearly unable to overwhelm it.

Low-Cost Radiator for Fission Power Thermal Control

NASA Technical Reports Server (NTRS)

Maxwell, Taylor; Tarau, Calin; Anderson, William; Hartenstine, John; Stern, Theodore; Walmsley, Nicholas; Briggs, Maxwell

2014-01-01

NASA Glenn Research Center (GRC) is developing fission power system technology for future Lunar surface power applications. The systems are envisioned in the 10 to 100kW(sub e) range and have an anticipated design life of 8 to 15 years with no maintenance. NASA GRC is currently setting up a 55 kW(sub e) non-nuclear system ground test in thermal-vacuum to validate technologies required to transfer reactor heat, convert the heat into electricity, reject waste heat, process the electrical output, and demonstrate overall system performance. Reducing the radiator mass, size, and cost is essential to the success of the program. To meet these goals, Advanced Cooling Technologies, Inc. (ACT) and Vanguard Space Technologies, Inc. (VST) are developing a single facesheet radiator with heat pipes directly bonded to the facesheet. The facesheet material is a graphite fiber reinforced composite (GFRC) and the heat pipes are titanium/water. By directly bonding a single facesheet to the heat pipes, several heavy and expensive components can be eliminated from the traditional radiator design such as, POC(TradeMark) foam saddles, aluminum honeycomb, and a second facesheet. A two-heat pipe radiator prototype, based on the single facesheet direct-bond concept, was fabricated and tested to verify the ability of the direct-bond joint to withstand coefficient of thermal expansion (CTE) induced stresses during thermal cycling. The thermal gradients along the bonds were measured before and after thermal cycle tests to determine if the performance degraded. Overall, the results indicated that the initial uniformity of the adhesive was poor along one of the heat pipes. However, both direct bond joints showed no measureable amount of degradation after being thermally cycled at both moderate and aggressive conditions.

Apparatus and method for performing microfluidic manipulations for chemical analysis

DOEpatents

Ramsey, J. Michael

1999-01-01

A microchip apparatus and method provide fluidic manipulations for a variety of applications, including sample injection for microchip liquid chromatography. The microchip is fabricated using standard photolithographic procedures and chemical wet etching, with the substrate and cover plate joined using direct bonding. Capillary electrophoresis is performed in channels formed in the substrate. Injections are made by electro-osmotically pumping sample through the injection channel that crosses the separation channel, followed by a switching of the potentials to force a plug into the separation channel.

Apparatus and method for performing microfluidic manipulations for chemical analysis

DOEpatents

Ramsey, J. Michael

2002-01-01

A microchip apparatus and method provide fluidic manipulations for a variety of applications, including sample injection for microchip liquid chromatography. The microchip is fabricated using standard photolitographic procedures and chemical wet etching, with the substrate and cover plate joined using direct bonding. Capillary electrophoresis is performed in channels formed in the substrate. Injections are made by electro-osmotically pumping sample through the injection channel that crosses the separation channel, followed by a switching of the potentials to force a plug into the separation channel.

Methods of measurement for semiconductor materials, process control, and devices

NASA Technical Reports Server (NTRS)

Bullis, W. M. (Editor)

1972-01-01

Activities directed toward the development of methods of measurement for semiconductor materials, process control, and devices are described. Topics investigated include: measurements of transistor delay time; application of the infrared response technique to the study of radiation-damaged, lithium-drifted silicon detectors; and identification of a condition that minimizes wire flexure and reduces the failure rate of wire bonds in transistors and integrated circuits under slow thermal cycling conditions. Supplementary data concerning staff, standards committee activities, technical services, and publications are included as appendixes.

Synthesis of new kojic acid based unnatural α-amino acid derivatives.

PubMed

Balakrishna, C; Payili, Nagaraju; Yennam, Satyanarayana; Uma Devi, P; Behera, Manoranjan

2015-11-01

An efficient method for the preparation of kojic acid based α-amino acid derivatives by alkylation of glycinate schiff base with bromokojic acids have been described. Using this method, mono as well as di alkylated kojic acid-amino acid conjugates have been prepared. This is the first synthesis of C-linked kojic acid-amino acid conjugate where kojic acid is directly linked to amino acid through a C-C bond. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influence of light intensity on surface free energy and dentin bond strength of core build-up resins.

PubMed

Shimizu, Y; Tsujimoto, A; Furuichi, T; Suzuki, T; Tsubota, K; Miyazaki, M; Platt, J A

2015-01-01

We examined the influence of light intensity on surface free energy characteristics and dentin bond strength of dual-cure direct core build-up resin systems. Two commercially available dual-cure direct core build-up resin systems, Clearfil DC Core Automix with Clearfil Bond SE One and UniFil Core EM with Self-Etching Bond, were studied. Bovine mandibular incisors were mounted in acrylic resin and the facial dentin surfaces were wet ground on 600-grit silicon carbide paper. Adhesives were applied to dentin surfaces and cured with light intensities of 0 (no irradiation), 200, 400, and 600 mW/cm(2). The surface free energy of the adhesives (five samples per group) was determined by measuring the contact angles of three test liquids placed on the cured adhesives. To determine the strength of the dentin bond, the core build-up resin pastes were condensed into the mold on the adhesive-treated dentin surfaces according to the methods described for the surface free energy measurement. The resin pastes were cured with the same light intensities as those used for the adhesives. Ten specimens per group were stored in water maintained at 37°C for 24 hours, after which they were shear tested at a crosshead speed of 1.0 mm/minute in a universal testing machine. Two-way analysis of variance (ANOVA) and a Tukey-Kramer test were performed, with the significance level set at 0.05. The surface free energies of the adhesive-treated dentin surfaces decreased with an increase in the light intensity of the curing unit. Two-way ANOVA revealed that the type of core build-up system and the light intensity significantly influence the bond strength, although there was no significant interaction between the two factors. The highest bond strengths were achieved when the resin pastes were cured with the strongest light intensity for all the core build-up systems. When polymerized with a light intensity of 200 mW/cm(2) or less, significantly lower bond strengths were observed. CONClUSIONS: The data suggest that the dentin bond strength of core build-up systems are still affected by the light intensity of the curing unit, which is based on the surface free energy of the adhesives. On the basis of the results and limitations of the test conditions used in this study, it appears that a light intensity of >400 mW/cm(2) may be required for achieving the optimal dentin bond strength.

Rhodium-catalysed syn-carboamination of alkenes via a transient directing group.

PubMed

Piou, Tiffany; Rovis, Tomislav

2015-11-05

Alkenes are the most ubiquitous prochiral functional groups--those that can be converted from achiral to chiral in a single step--that are accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes (whereby two functional groups are added to the same double bond) are particularly important, as they can be used to produce highly complex molecular architectures. Stereoselective oxidation reactions, including dihydroxylation, aminohydroxylation and halogenation, are well established methods for functionalizing alkenes. However, the intermolecular incorporation of both carbon- and nitrogen-based functionalities stereoselectively across an alkene has not been reported. Here we describe the rhodium-catalysed carboamination of alkenes at the same (syn) face of a double bond, initiated by a carbon-hydrogen activation event that uses enoxyphthalimides as the source of both the carbon and the nitrogen functionalities. The reaction methodology allows for the intermolecular, stereospecific formation of one carbon-carbon and one carbon-nitrogen bond across an alkene, which is, to our knowledge, unprecedented. The reaction design involves the in situ generation of a bidentate directing group and the use of a new cyclopentadienyl ligand to control the reactivity of rhodium. The results provide a new way of synthesizing functionalized alkenes, and should lead to the convergent and stereoselective assembly of amine-containing acyclic molecules.

Electrical assembly having heat sink protrusions

DOEpatents

Rinehart, Lawrence E.; Romero, Guillermo L.

2009-04-21

An electrical assembly, comprising a heat producing semiconductor device supported on a first major surface of a direct bond metal substrate that has a set of heat sink protrusions supported by its second major surface. In one preferred embodiment the heat sink protrusions are made of the same metal as is used in the direct bond copper.

31 CFR 353.0 - Applicability.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., DEPARTMENT OF THE TREASURY BUREAU OF THE PUBLIC DEBT REGULATIONS GOVERNING DEFINITIVE UNITED STATES SAVINGS BONDS, SERIES EE AND HH General Information § 353.0 Applicability. (a) The regulations in this part... through New Treasury Direct and definitive Series HH savings bonds. These bonds bear issue dates of...

On the origin of red and blue shifts of X-H and C-H stretching vibrations in formic acid (formate ion) and proton donor complexes.

PubMed

Tâme Parreira, Renato Luis; Galembeck, Sérgio Emanuel; Hobza, Pavel

2007-01-08

Complexes between formic acid or formate anion and various proton donors (HF, H(2)O, NH(3), and CH(4)) are studied by the MP2 and B3LYP methods with the 6-311++G(3df,3pd) basis set. Formation of a complex is characterized by electron-density transfer from electron donor to ligands. This transfer is much larger with the formate anion, for which it exceeds 0.1 e. Electron-density transfer from electron lone pairs of the electron donor is directed into sigma* antibonding orbitals of X--H bonds of the electron acceptor and leads to elongation of the bond and a red shift of the X--H stretching frequency (standard H-bonding). However, pronounced electron-density transfer from electron lone pairs of the electron donor also leads to reorganization of the electron density in the electron donor, which results in changes in geometry and vibrational frequency. These changes are largest for the C--H bonds of formic acid and formate anion, which do not participate in H-bonding. The resulting blue shift of this stretching frequency is substantial and amounts to almost 35 and 170 cm(-1), respectively.

Use of π-π forces to steer the assembly of a NTA complex of Cu(II) into hydrogen bonded supramolecular layers (H 3NTA = nitrilotriacetic acid)

NASA Astrophysics Data System (ADS)

Dey, Biswajit; Choudhury, Somnath Ray; Suresh, Eringathodi; Jana, Atish Dipankar; Mukhopadhyay, Subrata

2009-03-01

We propose a crystal engineering principle where we show that it might be possible to direct the organization of molecular complexes into hydrogen bonded supramolecular layers through the use of suitable co-ligands possessing both the hydrogen-bonding as well as π-π stacking capability. This principle has been tested for the organization of [Cu(NTA) 2] units (H 3NTA = nitrilotriacetic acid, N(CH 2CO 2H) 3) in the molecular complex with formula (2-A-PH) 4[Cu(NTA) 2]·6H 2O ( 1), where 2-A-PH is protonated 2-amino-4-picoline. In 1, the 2-amino-4-picoline co-ligands have been utilized to direct the organization of [Cu(NTA) 2] units into hydrogen bonded layers. The linear stacking of π-π bonded protonated 2-amino-4-picoline molecules can be thought as the influencing agent for the organization of [Cu(NTA) 2] units into hydrogen bonded layers.

Behavior of oxide film at the interface between particles in sintered Al powders by pulse electric-current sintering

NASA Astrophysics Data System (ADS)

Xie, Guoqiang; Ohashi, Osamu; Song, Minghui; Furuya, Kazuo; Noda, Tetsuji

2003-03-01

The microstructure of the bonding interfaces between particles in aluminum (Al) powder sintered specimens by the pulse electric-current sintering (PECS) process was observed, using conventional transmission electron microscopy (CTEM) and high-resolution transmission electron microscopy (HRTEM). The behavior of oxide film at the interface between Al particles and its effect on properties of the sintered specimens were investigated. The results showed there were two kinds of bonding interfaces in the sintered specimens, namely, the direct metal/metal bonding and the metal/oxide film layer/metal bonding interface. By increasing the fraction of the direct metal/metal bonding interfaces, the tensile strength of the sintered specimens increased, and the electrical resistivity decreased. By increasing the loading pressure at higher sintering temperatures or increasing the sintering temperature under loading pressure, the breakdown of oxide film was promoted. The broken oxide film debris was dispersed in aluminum metal near the bonding interfaces between particles.

Reliability of the pair-defect-sum approximation for the strength of valence-bond orbitals

PubMed Central

Pauling, Linus; Herman, Zelek S.; Kamb, Barclay J.

1982-01-01

The pair-defect-sum approximation to the bond strength of a hybrid orbital (angular wave functions only) is compared to the rigorous value as a function of bond angle for seven types of bonding situations, with between three and eight bond directions equivalent by geometrical symmetry operations and with only one independent bond angle. The approximation is seen to be an excellent one in all cases, and the results provide a rationale for the application of this approximation to a variety of problems. PMID:16593167

Activation of Remote meta-C–H Bonds Assisted by an “End-on” Template

PubMed Central

Leow, Dasheng; Li, Gang; Mei, Tiansheng; Yu, Jin-Quan

2012-01-01

Controlling positional selectivity of C–H activation in molecules possessing multiple inequivalent C–H bonds is one of the most important challenges in developing synthetically useful C–H activation reactions. One widely used approach utilizes σ-chelating directing groups to achieve ortho-selectivity through conformational rigid five- or six-membered cyclic pre-transition states (TS).1–14 We envisioned that an “end-on” chelating template capable of delivering catalysts to previously inaccessible remote meta-C–H bonds via a macrocyclic cyclophane-like pre-TS could overcome the limitations imposed by traditional ortho-directing groups. Herein, we report a class of readily removable nitrile-containing templates that direct the activation of distal meta-C–H bonds (≥ 10 bonds away) of a tethered arene. We attribute this new mode of C–H activation to the weak “end-on” coordination of the linear nitrile group to metal center, as previously observed by Schwarz in the study of remote C–H activation of alkyl nitriles in gas phase.15, 16 The coordination geometry relieves the strain of the cyclophane-like pre-transition state of the meta-C–H activation event. Remarkably, this template overrides electronic and steric biases and ortho-directing effects with two broadly useful classes of arene substrates (toluene derivatives and hydrocinnamic acids), thus constituting a fundamentally new mode of directed C–H activation that is anticipated to be widely adopted. PMID:22739317

Method of assembly of molecular-sized nets and scaffolding

DOEpatents

Michl, Josef; Magnera, Thomas F.; David, Donald E.; Harrison, Robin M.

1999-01-01

The present invention relates to methods and starting materials for forming molecular-sized grids or nets, or other structures based on such grids and nets, by creating molecular links between elementary molecular modules constrained to move in only two directions on an interface or surface by adhesion or bonding to that interface or surface. In the methods of this invention, monomers are employed as the building blocks of grids and more complex structures. Monomers are introduced onto and allowed to adhere or bond to an interface. The connector groups of adjacent adhered monomers are then polymerized with each other to form a regular grid in two dimensions above the interface. Modules that are not bound or adhered to the interface are removed prior to reaction of the connector groups to avoid undesired three-dimensional cross-linking and the formation of non-grid structures. Grids formed by the methods of this invention are useful in a variety of applications, including among others, for separations technology, as masks for forming regular surface structures (i.e., metal deposition) and as templates for three-dimensional molecular-sized structures.

Method of assembly of molecular-sized nets and scaffolding

DOEpatents

Michl, J.; Magnera, T.F.; David, D.E.; Harrison, R.M.

1999-03-02

The present invention relates to methods and starting materials for forming molecular-sized grids or nets, or other structures based on such grids and nets, by creating molecular links between elementary molecular modules constrained to move in only two directions on an interface or surface by adhesion or bonding to that interface or surface. In the methods of this invention, monomers are employed as the building blocks of grids and more complex structures. Monomers are introduced onto and allowed to adhere or bond to an interface. The connector groups of adjacent adhered monomers are then polymerized with each other to form a regular grid in two dimensions above the interface. Modules that are not bound or adhered to the interface are removed prior to reaction of the connector groups to avoid undesired three-dimensional cross-linking and the formation of non-grid structures. Grids formed by the methods of this invention are useful in a variety of applications, including among others, for separations technology, as masks for forming regular surface structures (i.e., metal deposition) and as templates for three-dimensional molecular-sized structures. 9 figs.

Regenerating Articular Tissue by Converging Technologies

PubMed Central

Paoluzzi, Luca; Pieper, Jeroen; de Wijn, Joost R.; van Blitterswijk, Clemens A.

2008-01-01

Scaffolds for osteochondral tissue engineering should provide mechanical stability, while offering specific signals for chondral and bone regeneration with a completely interconnected porous network for cell migration, attachment, and proliferation. Composites of polymers and ceramics are often considered to satisfy these requirements. As such methods largely rely on interfacial bonding between the ceramic and polymer phase, they may often compromise the use of the interface as an instrument to direct cell fate. Alternatively, here, we have designed hybrid 3D scaffolds using a novel concept based on biomaterial assembly, thereby omitting the drawbacks of interfacial bonding. Rapid prototyped ceramic particles were integrated into the pores of polymeric 3D fiber-deposited (3DF) matrices and infused with demineralized bone matrix (DBM) to obtain constructs that display the mechanical robustness of ceramics and the flexibility of polymers, mimicking bone tissue properties. Ostechondral scaffolds were then fabricated by directly depositing a 3DF structure optimized for cartilage regeneration adjacent to the bone scaffold. Stem cell seeded scaffolds regenerated both cartilage and bone in vivo. PMID:18716660

The competition of charge remote and charge directed fragmentation mechanisms in quaternary ammonium salt derivatized peptides--an isotopic exchange study.

PubMed

Cydzik, Marzena; Rudowska, Magdalena; Stefanowicz, Piotr; Szewczuk, Zbigniew

2011-12-01

Derivatization of peptides as quaternary ammonium salts (QAS) is a promising method for sensitive detection by electrospray ionization tandem mass spectrometry (Cydzik et al. J. Pept. Sci. 2011, 17, 445-453). The peptides derivatized by QAS at their N-termini undergo fragmentation according to the two competing mechanisms - charge remote (ChR) and charge directed (ChD). The absence of mobile proton in the quaternary salt ion results in ChR dissociation of a peptide bond. However, Hofmann elimination of quaternary salt creates an ion with one mobile proton leading to the ChD fragmentation. The experiments on the quaternary ammonium salts with deuterated N-alkyl groups or amide NH bonds revealed that QAS derivatized peptides dissociate according to the mixed ChR-ChD mechanism. The isotopic labeling allows differentiation of fragments formed according to ChR and ChD mechanisms. © The Author(s) 2011. This article is published with open access at Springerlink.com

Direct fluorescence in situ hybridization on human metaphase chromosomes using quantum dot-platinum labeled DNA probes

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

Hwang, Gyoyeon; Biological Chemistry, Korea University of Science and Technology, 217, Gajeong-ro, Yuseong-gu, Deajeon; Lee, Hansol

The telomere shortening in chromosomes implies the senescence, apoptosis, or oncogenic transformation of cells. Since detecting telomeres in aging and diseases like cancer, is important, the direct detection of telomeres has been a very useful biomarker. We propose a telomere detection method using a newly synthesized quantum dot (QD) based probe with oligonucleotide conjugation and direct fluorescence in situ hybridization (FISH). QD-oligonucleotides were prepared with metal coordination bonding based on platinum-guanine binding reported in our previous work. The QD-oligonucleotide conjugation method has an advantage where any sequence containing guanine at the end can be easily bound to the starting QD-Ptmore » conjugate. A synthesized telomeric oligonucleotide was bound to the QD-Pt conjugate successfully and this probe hybridized specifically on the telomere of fabricated MV-4-11 and MOLT-4 chromosomes. Additionally, the QD-telomeric oligonucleotide probe successfully detected the telomeres on the CGH metaphase slide. Due to the excellent photostability and high quantum yield of QDs, the QD-oligonucleotide probe has high fluorescence intensity when compared to the organic dye-oligonucleotide probe. Our QD-oligonucleotide probe, conjugation method of this QD probe, and hybridization protocol with the chromosomes can be a useful tool for chromosome painting and FISH. - Highlights: • We prepared a probe linked between QD and telomeric oligonucleotide with platinum-guanine bonding. • Telomeres were detected by our new telomere probes successfully in three different human metaphase chromosomes. • QDPt-DNA probe has high fluorescence intensity in comparison with organic dye-DNA probe.« less

Thermodynamics and dynamics of supercooled water

NASA Astrophysics Data System (ADS)

Stokely, Kevin C.

This thesis utilizes the methods of statistical physics and computer simulation to study the thermodynamic and dynamic behavior of liquid water at supercooled temperatures. The behavior of water deviates from that of a simple liquid in a number of remarkable ways, many of which become more apparent as the liquid is supercooled below its equilibrium freezing temperature. Yet, due to nucleation to the crystalline state, a large region of the phase diagram of the supercooled liquid remains unexplored. We make use of a simple model for liquid water to shed light on the behavior of real water in the experimentally inaccessible region. The model predicts a line of phase transitions in the pressure—temperature plane, between high- and low-density forms of liquid water, ending in a liquid-liquid critical point (LLCP). Such a LLCP provides a thermodynamic origin for one of liquid water's anomalies—the rapid rise, and extrapolated divergence, of thermodynamic response functions upon cooling. We find one such response function, the isobaric specific heat, CP, displays two distinct maxima as a function of temperature T in the supercooled region. One maximum is a consequence of the directional nature of hydrogen (H) bonding among molecules; the other is a consequence of the cooperative nature of H bonding. With pressurization, these two maxima move closer in T, finally coinciding at the LLCP. This suggests that measurement of CP far from any LLCP could provide evidence for the existence of water's LLCP. Recent experiments find that the T-dependence of the characteristic time for H bond rearrangement displays three distinct regimes. Our observed behavior of CP, combined with Adam-Gibbs theory, allows for a thermodynamic interpretation of this feature of water's dynamics. The dynamics of the model are also measured directly by a Monte Carlo procedure, and are found in agreement with experiment. Further, the model allows the directional and cooperative components of the H bond interaction to be varied independently. By varying only these two energy scales, the low-T phase diagram changes dramatically, exhibiting one of several previously proposed thermodynamic scenarios. Our results link each of these scenarios, by recognizing the energetics of the H bond as the underlying physical mechanism responsible for each.

31 CFR 363.100 - What are the rules for purchasing and delivering gift savings bonds to minors?

Code of Federal Regulations, 2011 CFR

2011-07-01

... delivering gift savings bonds to minors? 363.100 Section 363.100 Money and Finance: Treasury Regulations... minors? (a) A TreasuryDirect ® account owner can purchase a savings bond as a gift with a minor as the recipient. (b) An account owner can deliver a bond purchased as a gift to a minor. The account owner must...

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.

A density functional theory study on peptide bond cleavage at aspartic residues: direct vs cyclic intermediate hydrolysis.

PubMed

Sang-aroon, Wichien; Amornkitbamrung, Vittaya; Ruangpornvisuti, Vithaya

2013-12-01

In this work, peptide bond cleavages at carboxy- and amino-sides of the aspartic residue in a peptide model via direct (concerted and step-wise) and cyclic intermediate hydrolysis reaction pathways were explored computationally. The energetics, thermodynamic properties, rate constants, and equilibrium constants of all hydrolysis reactions, as well as their energy profiles were computed at the B3LYP/6-311++G(d,p) level of theory. The result indicated that peptide bond cleavage of the Asp residue occurred most preferentially via the cyclic intermediate hydrolysis pathway. In all reaction pathways, cleavage of the peptide bond at the amino-side occurred less preferentially than at the carboxy-side. The overall reaction rate constants of peptide bond cleavage of the Asp residue at the carboxy-side for the assisted system were, in increasing order: concerted < step-wise < cyclic intermediate.

Diffusion Bonding of Silicon Carbide for a Micro-Electro-Mechanical Systems Lean Direct Injector

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Singh, Mrityunjay; Shpargel, Tarah P.; Kiser, James D.

2006-01-01

Robust approaches for joining silicon carbide (SiC) to silicon carbide sub-elements have been developed for a micro-electro-mechanical systems lean direct injector (MEMS LDI) application. The objective is to join SiC sub-elements to form a leak-free injector that has complex internal passages for the flow and mixing of fuel and air. Previous bonding technology relied upon silicate glass interlayers that were not uniform or leak free. In a newly developed joining approach, titanium foils and physically vapor deposited titanium coatings were used to form diffusion bonds between SiC materials during hot pressing. Microscopy results show the formation of well adhered diffusion bonds. Initial tests show that the bond strength is much higher than required for the component system. Benefits of the joining technology are fabrication of leak free joints with high temperature and mechanical capability.

Direction-dependent secondary bonds and their stepwise melting in a uracil-based molecular crystal studied by infrared spectroscopy and theoretical modeling

NASA Astrophysics Data System (ADS)

Szekrényes, Zsolt; Nagy, Péter R.; Tarczay, György; Maggini, Laura; Bonifazi, Davide; Kamarás, Katalin

2018-01-01

Three types of supramolecular interactions are identified in the three crystallographic directions in crystals of 1,4-bis[(1-hexylurac-6-yl) ethynyl]benzene, a uracil-based molecule with a linear backbone. These three interactions, characterized by their strongest component, are: intermolecular double H-bonds along the molecular axis, London dispersion interaction of hexyl chains connecting these linear assemblies, and π - π stacking of the aromatic rings perpendicular to the molecular planes. On heating, two transitions happen, disordering of hexyl chains at 473 K, followed by H-bond melting at 534 K. The nature of the bonds and transitions was established by matrix-isolation and temperature-dependent infrared spectroscopy and supported by theoretical computations.

Controlling formation of single-molecule junctions by electrochemical reduction of diazonium terminal groups.

PubMed

Hines, Thomas; Díez-Pérez, Ismael; Nakamura, Hisao; Shimazaki, Tomomi; Asai, Yoshihiro; Tao, Nongjian

2013-03-06

We report controlling the formation of single-molecule junctions by means of electrochemically reducing two axialdiazonium terminal groups on a molecule, thereby producing direct Au-C covalent bonds in situ between the molecule and gold electrodes. We report a yield enhancement in molecular junction formation as the electrochemical potential of both junction electrodes approach the reduction potential of the diazonium terminal groups. Step length analysis shows that the molecular junction is significantly more stable, and can be pulled over a longer distance than a comparable junction created with amine anchoring bonds. The stability of the junction is explained by the calculated lower binding energy associated with the direct Au-C bond compared with the Au-N bond.

A modified low-temperature wafer bonding method using spot pressing bonding technique and water glass adhesive layer

NASA Astrophysics Data System (ADS)

Xu, Yang; Wang, Shengkai; Wang, Yinghui; Chen, Dapeng

2018-02-01

A modified low-temperature wafer bonding method using a spot pressing bonding technique and a water glass adhesive layer is proposed. The electrical properties of the water glass layer has been studied by capacitance-voltage (C-V) and electric current-voltage (I-V) measurements. It is found that the adhesive layer can be regarded as a good insulator in terms of leakage current density. The bonding mechanism and the motion of bubbles during the thermal treatment are investigated. The dominant factor for the bubble motion in the modified bonding process is the gradient of pressure introduced by the spot pressing force. It is proved that the modified method achieves low-temperature adhesive bonding, minimizes the effect of water desorption, and provides good bonding performance.

A Reference-Free and Non-Contact Method for Detecting and Imaging Damage in Adhesive-Bonded Structures Using Air-Coupled Ultrasonic Transducers.

PubMed

Yonathan Sunarsa, Timotius; Aryan, Pouria; Jeon, Ikgeun; Park, Byeongjin; Liu, Peipei; Sohn, Hoon

2017-12-08

Adhesive bonded structures have been widely used in aerospace, automobile, and marine industries. Due to the complex nature of the failure mechanisms of bonded structures, cost-effective and reliable damage detection is crucial for these industries. Most of the common damage detection methods are not adequately sensitive to the presence of weakened bonding. This paper presents an experimental and analytical method for the in-situ detection of damage in adhesive-bonded structures. The method is fully non-contact, using air-coupled ultrasonic transducers (ACT) for ultrasonic wave generation and sensing. The uniqueness of the proposed method relies on accurate detection and localization of weakened bonding in complex adhesive bonded structures. The specimens tested in this study are parts of real-world structures with critical and complex damage types, provided by Hyundai Heavy Industries ® and IKTS Fraunhofer ® . Various transmitter and receiver configurations, including through transmission, pitch-catch scanning, and probe holder angles, were attempted, and the obtained results were analyzed. The method examines the time-of-flight of the ultrasonic waves over a target inspection area, and the spatial variation of the time-of-flight information was examined to visualize and locate damage. The proposed method works without relying on reference data obtained from the pristine condition of the target specimen. Aluminum bonded plates and triplex adhesive layers with debonding and weakened bonding were used to examine the effectiveness of the method.

A Reference-Free and Non-Contact Method for Detecting and Imaging Damage in Adhesive-Bonded Structures Using Air-Coupled Ultrasonic Transducers

PubMed Central

Yonathan Sunarsa, Timotius; Aryan, Pouria; Jeon, Ikgeun; Park, Byeongjin; Liu, Peipei

2017-01-01

Adhesive bonded structures have been widely used in aerospace, automobile, and marine industries. Due to the complex nature of the failure mechanisms of bonded structures, cost-effective and reliable damage detection is crucial for these industries. Most of the common damage detection methods are not adequately sensitive to the presence of weakened bonding. This paper presents an experimental and analytical method for the in-situ detection of damage in adhesive-bonded structures. The method is fully non-contact, using air-coupled ultrasonic transducers (ACT) for ultrasonic wave generation and sensing. The uniqueness of the proposed method relies on accurate detection and localization of weakened bonding in complex adhesive bonded structures. The specimens tested in this study are parts of real-world structures with critical and complex damage types, provided by Hyundai Heavy Industries® and IKTS Fraunhofer®. Various transmitter and receiver configurations, including through transmission, pitch-catch scanning, and probe holder angles, were attempted, and the obtained results were analyzed. The method examines the time-of-flight of the ultrasonic waves over a target inspection area, and the spatial variation of the time-of-flight information was examined to visualize and locate damage. The proposed method works without relying on reference data obtained from the pristine condition of the target specimen. Aluminum bonded plates and triplex adhesive layers with debonding and weakened bonding were used to examine the effectiveness of the method. PMID:29292752

Clinical Evaluation of Bond Failures and Survival of Mandibular Canine-to-canine Bonded Retainers during a 12-year Time Span

PubMed Central

Rota, Elisa; Mirabelli, Luca; M Venino, Pier; Porcaro, Gianluca

2017-01-01

Aim The aim of this study was to assess the effectiveness of the 3-3 mandibular lingual stainless steel retainer to prevent a relapse of orthodontic treatment during the 12-year time span of the survey. Materials and methods Fifty patients with canine-to-canine bonded retainers (placed at least 10 years earlier) were recalled. All patients had been followed up annually during this period. Patients were screened for stability of the retainer and for the condition of hard and soft oral tissues. Results None of the patients reported a complete loss of the retainer; 14 patients reported single element partial losses and 13 reported multiple losses. Most partial failures were not perceived by patients, but noted by the orthodontist during the control visit. There was no notable variation of the gingival index occurring in these patients. In two cases patients had caries in the six teeth bonded with the retainer, but never on the lingual side; only in three teeth areas of decalcification in the proximity of bonded sites were reported. All patients showed good compliance with this kind of retention. Conclusion The composite adhesive technique allowed a reliable positioning system for directly bonded retainers and did not influence the occurrence of carious lesions or demin-eralized spots on fixed teeth. Full teeth fixation offered the possibility of stabilizing the irregularity index highlighted in various studies without increasing any side effects on gums and hard tissues. How to cite this article: Maddalone M, Rota E, Mirabelli L, Venino PM, Porcaro G. Clinical Evaluation of Bond Failures and Survival of Mandibular Canine-to-canine Bonded Retainers during a 12-year Time Span. Int J Clin Pediatr Dent 2017;10(4):330-334. PMID:29403224

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.

Low-temperature wafer direct bonding of silicon and quartz glass by a two-step wet chemical surface cleaning

NASA Astrophysics Data System (ADS)

Wang, Chenxi; Xu, Jikai; Zeng, Xiaorun; Tian, Yanhong; Wang, Chunqing; Suga, Tadatomo

2018-02-01

We demonstrate a facile bonding process for combining silicon and quartz glass wafers by a two-step wet chemical surface cleaning. After a post-annealing at 200 °C, strong bonding interfaces with no defects or microcracks were obtained. On the basis of the detailed surface and bonding interface characterizations, the bonding mechanism was explored and discussed. The amino groups terminated on the cleaned surfaces might contribute to the bonding strength enhancement during the annealing. This cost-effective bonding process has great potentials for silicon- and glass-based heterogeneous integrations without requiring a vacuum system.

Ultra precision and reliable bonding method

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung (Inventor)

2001-01-01

The bonding of two materials through hydroxide-catalyzed hydration/dehydration is achieved at room temperature by applying hydroxide ions to at least one of the two bonding surfaces and by placing the surfaces sufficiently close to each other to form a chemical bond between them. The surfaces may be placed sufficiently close to each other by simply placing one surface on top of the other. A silicate material may also be used as a filling material to help fill gaps between the surfaces caused by surface figure mismatches. A powder of a silica-based or silica-containing material may also be used as an additional filling material. The hydroxide-catalyzed bonding method forms bonds which are not only as precise and transparent as optical contact bonds, but also as strong and reliable as high-temperature frit bonds. The hydroxide-catalyzed bonding method is also simple and inexpensive.

Bond slip detection of concrete-encased composite structure using shear wave based active sensing approach

NASA Astrophysics Data System (ADS)

Zeng, Lei; Parvasi, Seyed Mohammad; Kong, Qingzhao; Huo, Linsheng; Lim, Ing; Li, Mo; Song, Gangbing

2015-12-01

Concrete-encased composite structure exhibits improved strength, ductility and fire resistance compared to traditional reinforced concrete, by incorporating the advantages of both steel and concrete materials. A major drawback of this type of structure is the bond slip introduced between steel and concrete, which directly reduces the load capacity of the structure. In this paper, an active sensing approach using shear waves to provide monitoring and early warning of the development of bond slip in the concrete-encased composite structure is proposed. A specimen of concrete-encased composite structure was investigated. In this active sensing approach, shear mode smart aggregates (SAs) embedded in the concrete act as actuators and generate desired shear stress waves. Distributed piezoceramic transducers installed in the cavities of steel plates act as sensors and detect the wave response from shear mode SAs. Bond slip acts as a form of stress relief and attenuates the wave propagation energy. Experimental results from the time domain analysis clearly indicate that the amplitudes of received signal by lead zirconate titanate sensors decreased when bond slip occurred. In addition, a wavelet packet-based analysis was developed to compute the received signal energy values, which can be used to determine the initiation and development of bond slip in concrete-encased composite structure. In order to establish the validity of the proposed method, a 3D finite element analysis of the concrete-steel bond model is further performed with the aid of the commercial finite element package, Abaqus, and the numerical results are compared with the results obtained in experimental study.

Development and Validation of HPLC Method for Determination of Crocetin, a constituent of Saffron, in Human Serum Samples

PubMed Central

Mohammadpour, Amir Hooshang; Ramezani, Mohammad; Tavakoli Anaraki, Nasim; Malaekeh-Nikouei, Bizhan; Amel Farzad, Sara; Hosseinzadeh, Hossein

2013-01-01

Objective(s): The present study reports the development and validation of a sensitive and rapid extraction method beside high performance liquid chromatographic method for the determination of crocetin in human serum. Materials and Methods: The HPLC method was carried out by using a C18 reversed-phase column and a mobile phase composed of methanol/water/acetic acid (85:14.5:0.5 v/v/v) at the flow rate of 0.8 ml/min. The UV detector was set at 423 nm and 13-cis retinoic acid was used as the internal standard. Serum samples were pretreated with solid-phase extraction using Bond Elut C18 (200mg) cartridges or with direct precipitation using acetonitrile. Results: The calibration curves were linear over the range of 0.05-1.25 µg/ml for direct precipitation method and 0.5-5 µg/ml for solid-phase extraction. The mean recoveries of crocetin over a concentration range of 0.05-5 µg/ml serum for direct precipitation method and 0.5-5 µg/ml for solid-phase extraction were above 70 % and 60 %, respectively. The intraday coefficients of variation were 0.37- 2.6% for direct precipitation method and 0.64 - 5.43% for solid-phase extraction. The inter day coefficients of variation were 1.69 – 6.03% for direct precipitation method and 5.13-12.74% for solid-phase extraction, respectively. The lower limit of quantification for crocetin was 0.05 µg/ml for direct precipitation method and 0.5 µg/ml for solid-phase extraction. Conclusion: The validated direct precipitation method for HPLC satisfied all of the criteria that were necessary for a bioanalytical method and could reliably quantitate crocetin in human serum for future clinical pharmacokinetic study. PMID:23638292

Silylation of C-H bonds in aromatic heterocycles by an Earth-abundant metal catalyst

NASA Astrophysics Data System (ADS)

Toutov, Anton A.; Liu, Wen-Bo; Betz, Kerry N.; Fedorov, Alexey; Stoltz, Brian M.; Grubbs, Robert H.

2015-02-01

Heteroaromatic compounds containing carbon-silicon (C-Si) bonds are of great interest in the fields of organic electronics and photonics, drug discovery, nuclear medicine and complex molecule synthesis, because these compounds have very useful physicochemical properties. Many of the methods now used to construct heteroaromatic C-Si bonds involve stoichiometric reactions between heteroaryl organometallic species and silicon electrophiles or direct, transition-metal-catalysed intermolecular carbon-hydrogen (C-H) silylation using rhodium or iridium complexes in the presence of excess hydrogen acceptors. Both approaches are useful, but their limitations include functional group incompatibility, narrow scope of application, high cost and low availability of the catalysts, and unproven scalability. For this reason, a new and general catalytic approach to heteroaromatic C-Si bond construction that avoids such limitations is highly desirable. Here we report an example of cross-dehydrogenative heteroaromatic C-H functionalization catalysed by an Earth-abundant alkali metal species. We found that readily available and inexpensive potassium tert-butoxide catalyses the direct silylation of aromatic heterocycles with hydrosilanes, furnishing heteroarylsilanes in a single step. The silylation proceeds under mild conditions, in the absence of hydrogen acceptors, ligands or additives, and is scalable to greater than 100 grams under optionally solvent-free conditions. Substrate classes that are difficult to activate with precious metal catalysts are silylated in good yield and with excellent regioselectivity. The derived heteroarylsilane products readily engage in versatile transformations enabling new synthetic strategies for heteroaromatic elaboration, and are useful in their own right in pharmaceutical and materials science applications.

Dentine bond strength and antimicrobial activity evaluation of adhesive systems.

PubMed

André, Carolina Bosso; Gomes, Brenda Paula Figueiredo Almeida; Duque, Thais Mageste; Stipp, Rafael Nobrega; Chan, Daniel Chi Ngai; Ambrosano, Glaucia Maria Bovi; Giannini, Marcelo

2015-04-01

This study evaluated the dentine bond strength (BS) and the antibacterial activity (AA) of six adhesives against strict anaerobic and facultative bacteria. Three adhesives containing antibacterial components (Gluma 2Bond (glutaraldehyde)/G2B, Clearfil SE Protect (MDPB)/CSP and Peak Universal Bond (PUB)/chlorhexidine) and the same adhesive versions without antibacterial agents (Gluma Comfort Bond/GCB, Clearfil SE Bond/CSB and Peak LC Bond/PLB) were tested. The AA of adhesives and control groups was evaluated by direct contact method against four strict anaerobic and four facultative bacteria. After incubation, according to the appropriate periods of time for each microorganism, the time to kill microorganisms was measured. For BS, the adhesives were applied according to manufacturers' recommendations and teeth restored with composite. Teeth (n=10) were sectioned to obtain bonded beams specimens, which were tested after artificial saliva storage for one week and one year. BS data were analyzed using two-way ANOVA and Tukey test. Saliva storage for one year reduces the BS only for GCB. In general G2B and GCB required at least 24h for killing microorganisms. PUB and PLB killed only strict anaerobic microorganisms after 24h. For CSP the average time to eliminate the Streptococcus mutans and strict anaerobic oral pathogens was 30 min. CSB showed no AA against facultative bacteria, but had AA against some strict anaerobic microorganisms. Storage time had no effect on the BS for most of the adhesives. The time required to kill bacteria depended on the type of adhesive and never was less than 10 min. Most of the adhesives showed stable bond strength after one year and the Clearfil SE Protect may be a good alternative in restorative procedures performed on dentine, considering its adequate bond strength and better antibacterial activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

PbS-PbSe IR detector arrays

NASA Technical Reports Server (NTRS)

Barrett, John R. (Inventor)

1986-01-01

A silicon wafer is provided which does not employ individually bonded leads between the IR sensitive elements and the input stages of multiplexers. The wafer is first coated with lead selenide in a first detector array area and is thereafter coated with lead sulfide within a second detector array area. The described steps result in the direct chemical deposition of lead selenide and lead sulfide upon the silicon wafer to eliminate individual wire bonding, bumping, flip chipping, planar interconnecting methods of connecting detector array elements to silicon chip circuitry, e.g., multiplexers, to enable easy fabrication of very long arrays. The electrode structure employed, produces an increase in the electrical field gradient between the electrodes for a given volume of detector material, relative to conventional electrode configurations.

Low-temperature direct heterogeneous bonding of polyether ether ketone and platinum.

PubMed

Fu, Weixin; Shigetou, Akitsu; Shoji, Shuichi; Mizuno, Jun

2017-10-01

Direct heterogeneous bonding between polyether ether ketone (PEEK) and Pt was realized at the temperatures lower than 150°C. In order to create sufficient bondability to diverse materials, the surface was modified by vacuum ultraviolet (VUV) irradiation, which formed hydrate bridges. For comparison, direct bonding between surfaces atomically cleaned via Ar fast atom bombardment (FAB) was conducted in a vacuum. The VUV irradiation was found to be effective for creating an ultrathin hydrate bridge layer from the residual water molecules in the chamber. Tight bonds were formed through dehydration of the hydrate bridges by heating at 150°C, which also contributed to enhancing interdiffusion across the interface. The VUV-modified surfaces showed bondability as good as that of the FAB-treated surfaces, and the VUV-modified samples had shear strengths at the same level as those of FAB-treated surfaces. This technology will be of practical use in the packaging of lightweight, flexible biomedical devices. Copyright © 2017 Elsevier B.V. All rights reserved.

Complementary Strategies for Directed C(sp3 )-H Functionalization: A Comparison of Transition-Metal-Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer.

PubMed

Chu, John C K; Rovis, Tomislav

2018-01-02

The functionalization of C(sp 3 )-H bonds streamlines chemical synthesis by allowing the use of simple molecules and providing novel synthetic disconnections. Intensive recent efforts in the development of new reactions based on C-H functionalization have led to its wider adoption across a range of research areas. This Review discusses the strengths and weaknesses of three main approaches: transition-metal-catalyzed C-H activation, 1,n-hydrogen atom transfer, and transition-metal-catalyzed carbene/nitrene transfer, for the directed functionalization of unactivated C(sp 3 )-H bonds. For each strategy, the scope, the reactivity of different C-H bonds, the position of the reacting C-H bonds relative to the directing group, and stereochemical outcomes are illustrated with examples in the literature. The aim of this Review is to provide guidance for the use of C-H functionalization reactions and inspire future research in this area. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Surface passivation for tight-binding calculations of covalent solids.

PubMed

Bernstein, N

2007-07-04

Simulation of a cluster representing a finite portion of a larger covalently bonded system requires the passivation of the cluster surface. We compute the effects of an explicit hybrid orbital passivation (EHOP) on the atomic structure in a model bulk, three-dimensional, narrow gap semiconductor, which is very different from the wide gap, quasi-one-dimensional organic molecules where most passivation schemes have been studied in detail. The EHOP approach is directly applicable to minimal atomic orbital basis methods such as tight-binding. Each broken bond is passivated by a hybrid created from an explicitly expressed linear combination of basis orbitals, chosen to represent the contribution of the missing neighbour, e.g. a sp(3) hybrid for a single bond. The method is tested by computing the forces on atoms near a point defect as a function of cluster geometry. We show that, compared to alternatives such as pseudo-hydrogen passivation, the force on an atom converges to the correct bulk limit more quickly as a function of cluster radius, and that the force is more stable with respect to perturbations in the position of the cluster centre. The EHOP method also obviates the need for parameterizing the interactions between the system atoms and the passivating atoms. The method is useful for cluster calculations of non-periodic defects in large systems and for hybrid schemes that simulate large systems by treating finite regions with a quantum-mechanical model, coupled to an interatomic potential description of the rest of the system.

Surface passivation for tight-binding calculations of covalent solids

NASA Astrophysics Data System (ADS)

Bernstein, N.

2007-07-01

Simulation of a cluster representing a finite portion of a larger covalently bonded system requires the passivation of the cluster surface. We compute the effects of an explicit hybrid orbital passivation (EHOP) on the atomic structure in a model bulk, three-dimensional, narrow gap semiconductor, which is very different from the wide gap, quasi-one-dimensional organic molecules where most passivation schemes have been studied in detail. The EHOP approach is directly applicable to minimal atomic orbital basis methods such as tight-binding. Each broken bond is passivated by a hybrid created from an explicitly expressed linear combination of basis orbitals, chosen to represent the contribution of the missing neighbour, e.g. a sp3 hybrid for a single bond. The method is tested by computing the forces on atoms near a point defect as a function of cluster geometry. We show that, compared to alternatives such as pseudo-hydrogen passivation, the force on an atom converges to the correct bulk limit more quickly as a function of cluster radius, and that the force is more stable with respect to perturbations in the position of the cluster centre. The EHOP method also obviates the need for parameterizing the interactions between the system atoms and the passivating atoms. The method is useful for cluster calculations of non-periodic defects in large systems and for hybrid schemes that simulate large systems by treating finite regions with a quantum-mechanical model, coupled to an interatomic potential description of the rest of the system.

Phosphonic acid: preparation and applications

PubMed Central

Sevrain, Charlotte M; Berchel, Mathieu; Couthon, Hélène

2017-01-01

The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H3PO3) and that produce a phosphonic acid functional group simultaneously to the formation of the P–C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids. PMID:29114326

Phosphonic acid: preparation and applications.

PubMed

Sevrain, Charlotte M; Berchel, Mathieu; Couthon, Hélène; Jaffrès, Paul-Alain

2017-01-01

The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H 3 PO 3 ) and that produce a phosphonic acid functional group simultaneously to the formation of the P-C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids.

31 CFR 363.83 - May an account owner transfer a book-entry savings bond to a minor?

Code of Federal Regulations, 2011 CFR

2011-07-01

...-entry savings bond to a minor? 363.83 Section 363.83 Money and Finance: Treasury Regulations Relating to...Direct General § 363.83 May an account owner transfer a book-entry savings bond to a minor? An account owner may transfer a bond to a minor as a gift or pursuant to one of the specified exceptions in § 363...

31 CFR 363.166 - What happens when I convert a savings bond that is not registered in my name as owner, either...

Code of Federal Regulations, 2010 CFR

2010-07-01

... (including a bond registered in the name of a minor) was purchased by the account owner as a gift for the... name of someone other than the account owner will be converted to a book-entry bond, released as a gift...) Delivery of unmatured gift bond to registered owner. The TreasuryDirect account owner may deliver the...

Conjugated π electron engineering of generalized stacking fault in graphene and h-BN.

PubMed

Ouyang, Bin; Chen, Cheng; Song, J

2018-03-02

Generalized-stacking-fault energy (GSFE) serves as an important metric that prescribes dislocation behaviors in materials. In this paper, utilizing first-principle calculations and chemical bonding analysis, we studied the behaviors of generalized stacking fault in graphene and h-BN. It has been shown that the π bond formation plays a critical role in the existence of metastable stacking fault (MSF) in graphene and h-BN lattice along certain slip directions. Chemical functionalization was then proposed as an effective means to engineer the π bond, and subsequently MSF along dislocation slips within graphene and h-BN. Taking hydrogenation as a representative functionalization method, we demonstrated that, with the preferential adsorption of hydrogen along the slip line, π electrons along the slip would be saturated by adsorbed hydrogen atoms, leading to the moderation or elimination of MSF. Our study elucidates the atomic mechanism of MSF formation in graphene-like materials, and more generally, provides important insights towards predictive tuning of mechanic properties in two-dimensional nanomaterials.

Conjugated π electron engineering of generalized stacking fault in graphene and h-BN

NASA Astrophysics Data System (ADS)

Ouyang, Bin; Chen, Cheng; Song, J.

2018-03-01

Generalized-stacking-fault energy (GSFE) serves as an important metric that prescribes dislocation behaviors in materials. In this paper, utilizing first-principle calculations and chemical bonding analysis, we studied the behaviors of generalized stacking fault in graphene and h-BN. It has been shown that the π bond formation plays a critical role in the existence of metastable stacking fault (MSF) in graphene and h-BN lattice along certain slip directions. Chemical functionalization was then proposed as an effective means to engineer the π bond, and subsequently MSF along dislocation slips within graphene and h-BN. Taking hydrogenation as a representative functionalization method, we demonstrated that, with the preferential adsorption of hydrogen along the slip line, π electrons along the slip would be saturated by adsorbed hydrogen atoms, leading to the moderation or elimination of MSF. Our study elucidates the atomic mechanism of MSF formation in graphene-like materials, and more generally, provides important insights towards predictive tuning of mechanic properties in two-dimensional nanomaterials.

Fast and reliable method to estimate losses of single-mode waveguides with an arbitrary 2D trajectory.

PubMed

Negredo, F; Blaicher, M; Nesic, A; Kraft, P; Ott, J; Dörfler, W; Koos, C; Rockstuhl, C

2018-06-01

Photonic wire bonds, i.e., freeform waveguides written by 3D direct laser writing, emerge as a technology to connect different optical chips in fully integrated photonic devices. With the long-term vision of scaling up this technology to a large-scale fabrication process, the in situ optimization of the trajectory of photonic wire bonds is at stake. A prerequisite for the real-time optimization is the availability of a fast loss estimator for single-mode waveguides of arbitrary trajectory. Losses occur because of the bending of the waveguides and at transitions among sections of the waveguide with different curvatures. Here, we present an approach that resides on the fundamental mode approximation, i.e., the assumption that the photonic wire bonds predominantly carry their energy in a single mode. It allows us to predict in a quick and reliable way the pertinent losses from pre-computed modal properties of the waveguide, enabling fast design of optimum paths.

Unexpected mechanochemical complexity in the mechanistic scenarios of disulfide bond reduction in alkaline solution

NASA Astrophysics Data System (ADS)

Dopieralski, Przemyslaw; Ribas-Arino, Jordi; Anjukandi, Padmesh; Krupicka, Martin; Marx, Dominik

2017-02-01

The reduction of disulfides has a broad importance in chemistry, biochemistry and materials science, particularly those methods that use mechanochemical activation. Here we show, using isotensional simulations, that strikingly different mechanisms govern disulfide cleavage depending on the external force. Desolvation and resolvation processes are found to be crucial, as they have a direct impact on activation free energies. The preferred pathway at moderate forces, a bimolecular SN2 attack of OH- at sulfur, competes with unimolecular C-S bond rupture at about 2 nN, and the latter even becomes barrierless at greater applied forces. Moreover, our study unveils a surprisingly rich reactivity scenario that also includes the transformation of concerted SN2 reactions into pure bond-breaking processes at specific forces. Given that these forces are easily reached in experiments, these insights will fundamentally change our understanding of mechanochemical activation in general, which is now expected to be considerably more intricate than previously thought.

Conjugation in multi-tetrazole derivatives: a new design direction for energetic materials.

PubMed

Sun, Shuyang; Lu, Ming

2018-06-23

Multi-tetrazole derivatives with conjugated structures were designed and investigated in this study. Using quantum chemistry methods, the crystal structures, electrostatic potentials (ESPs), multicenter bond orders, HOMO-LUMO energy gaps, and detonation properties of the derivatives were calculated. As expected, these molecules with conjugated structures showed low energies of their crystal structures, molecular layering in their crystals, high average ESPs, high multicenter bond order values, and enhanced detonation properties. The derivative 1,2-di(1H-tetrazol-5-yl)diazene (N2) was predicted to have the best density (1.87 g/cm 3 ), detonation velocity (9006 m/s), and detonation pressure (36.8 GPa) of the designed molecules, while its total crystal energy was low, suggesting that it is relatively stable. Its sensitivity was also low, as the molecular stacking that occurs in its crystal allows external forces to be dissipated into movements of crystal layers. Finally, its multicenter bond order was high, indicating a highly conjugated structure.

The structure of the ends of α-helices in globular proteins: effect of additional hydrogen bonds and implications for helix formation.

PubMed

Leader, David P; Milner-White, E James

2011-03-01

We prepared a set of about 2000 α-helices from a relational database of high-resolution three-dimensional structures of globular proteins, and identified additional main chain i ← i+3 hydrogen bonds at the ends of the helices (i.e., where the hydrogen bonding potential is not fulfilled by canonical i ← i+4 hydrogen bonds). About one-third of α-helices have such additional hydrogen bonds at the N-terminus, and more than half do so at the C-terminus. Although many of these additional hydrogen bonds at the C-terminus are associated with Schellman loops, the majority are not. We compared the dihedral angles at the termini of α-helices having or lacking the additional hydrogen bonds. Significant differences were found, especially at the C-terminus, where the dihedral angles at positions C2 and C1 in the absence of additional hydrogen bonds deviate substantially from those occurring within the α-helix. Using a novel approach we show how the structure of the C-terminus of the α-helix can emerge from that of constituent overlapping α-turns and β-turns, which individually show a variation in dihedral angles at different positions. We have also considered the direction of propagation of the α-helix using this approach. If one assumes that helices start as a single α-turn and grow by successive addition of further α-turns, the paths for growth in the N → C and C → N directions differ in a way that suggests that extension in the C → N direction is favored. Copyright © 2010 Wiley-Liss, Inc.

Thioarsenides: A case for long-range Lewis acid-base-directed van der Waals interactions

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

Gibbs, Gerald V.; Wallace, Adam F.; Downs, R. T.

2011-04-01

Electron density distributions, bond paths, Laplacian and local energy density properties have been calculated for a number of As4Sn (n = 3,4,5) thioarsenide molecular crystals. On the basis of the distributions, the intramolecular As-S and As-As interactions classify as shared bonded interactions and the intermolecular As-S, As-As and S-S interactions classify as closed-shell van der Waals bonded interactions. The bulk of the intermolecular As-S bond paths link regions of locally concentrated electron density (Lewis base regions) with aligned regions of locally depleted electron density (Lewis acid regions) on adjacent molecules. The paths are comparable with intermolecular paths reported for severalmore » other molecular crystals that link aligned Lewis base and acid regions in a key-lock fashion, interactions that classified as long range Lewis acid-base directed van der Waals interactions. As the bulk of the intermolecular As-S bond paths (~70%) link Lewis acid-base regions on adjacent molecules, it appears that molecules adopt an arrangement that maximizes the number of As-S Lewis acid-base intermolecular bonded interactions. The maximization of the number of Lewis acid-base interactions appears to be connected with the close-packed array adopted by molecules: distorted cubic close-packed arrays are adopted for alacránite, pararealgar, uzonite, realgar and β-AsS and the distorted hexagonal close-packed arrays adopted by α- and β-dimorphite. A growth mechanism is proposed for thioarsenide molecular crystals from aqueous species that maximizes the number of long range Lewis acid-base vdW As-S bonded interactions with the resulting directed bond paths structuralizing the molecules as a molecular crystal.« less

Development and Validation of HPLC Method for Determination of Crocetin, a constituent of Saffron, in Human Serum Samples.

PubMed

Mohammadpour, Amir Hooshang; Ramezani, Mohammad; Tavakoli Anaraki, Nasim; Malaekeh-Nikouei, Bizhan; Amel Farzad, Sara; Hosseinzadeh, Hossein

2013-01-01

The present study reports the development and validation of a sensitive and rapid extraction method beside high performance liquid chromatographic method for the determination of crocetin in human serum. The HPLC method was carried out by using a C18 reversed-phase column and a mobile phase composed of methanol/water/acetic acid (85:14.5:0.5 v/v/v) at the flow rate of 0.8 ml/min. The UV detector was set at 423 nm and 13-cis retinoic acid was used as the internal standard. Serum samples were pretreated with solid-phase extraction using Bond Elut C18 (200mg) cartridges or with direct precipitation using acetonitrile. The calibration curves were linear over the range of 0.05-1.25 µg/ml for direct precipitation method and 0.5-5 µg/ml for solid-phase extraction. The mean recoveries of crocetin over a concentration range of 0.05-5 µg/ml serum for direct precipitation method and 0.5-5 µg/ml for solid-phase extraction were above 70 % and 60 %, respectively. The intraday coefficients of variation were 0.37- 2.6% for direct precipitation method and 0.64 - 5.43% for solid-phase extraction. The inter day coefficients of variation were 1.69 - 6.03% for direct precipitation method and 5.13-12.74% for solid-phase extraction, respectively. The lower limit of quantification for crocetin was 0.05 µg/ml for direct precipitation method and 0.5 µg/ml for solid-phase extraction. The validated direct precipitation method for HPLC satisfied all of the criteria that were necessary for a bioanalytical method and could reliably quantitate crocetin in human serum for future clinical pharmacokinetic study.

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.

Organic chemistry. Functionalization of C(sp3)-H bonds using a transient directing group.

PubMed

Zhang, Fang-Lin; Hong, Kai; Li, Tuan-Jie; Park, Hojoon; Yu, Jin-Quan

2016-01-15

Proximity-driven metalation has been extensively exploited to achieve reactivity and selectivity in carbon-hydrogen (C-H) bond activation. Despite the substantial improvement in developing more efficient and practical directing groups, their stoichiometric installation and removal limit efficiency and, often, applicability as well. Here we report the development of an amino acid reagent that reversibly reacts with aldehydes and ketones in situ via imine formation to serve as a transient directing group for activation of inert C-H bonds. Arylation of a wide range of aldehydes and ketones at the β or γ positions proceeds in the presence of a palladium catalyst and a catalytic amount of amino acid. The feasibility of achieving enantioselective C-H activation reactions using a chiral amino acid as the transient directing group is also demonstrated. Copyright © 2016, American Association for the Advancement of Science.

Retrospective study of combined splinting restorations in the aesthetic zone of periodontal patients

PubMed Central

Liu, X.; Zhang, Y.; Zhou, Z.; Ma, S.

2016-01-01

Aims This retrospective study evaluated the clinical performance of combining a fiber-reinforced, composite-resin (FRC) bonded splint; bridge; fiber post; and/or resin veneer for the restoration of periodontally-involved anterior teeth. Methods Sixty-three patients with periodontally-involved anterior teeth each received one of the following splinting restorations: FRC-bonded splint-bridges (SB), a combination of an FRC-bonded splint and resin veneer (SV), or FRC-bonded splints (S). Six patients with healthy periodontal teeth received orthodontic retainers with FRC-bonded splints (OS) as a control. Modified USPHS criteria were used to evaluate the effects of rehabilitation, and the periodontal pocket depth (PPD) and clinical attachment level (CAL) of the natural teeth were measured. Results All restorations resulted in good aesthetic outcomes. SV, S in combination with fiber posts and OS all resulted in 100% acceptable ratings for each category that was directly evaluated at each follow-up. The mean PPD was 3.5 ± 1.0 mm at baseline, decreased to 3.3 ± 1.0 mm after one year (p <0.05), and subsequently increased to 3.5±1.0 mm again after four years (p >0.05). These changes were similar to those in the mean CAL. Conclusion A combination of a FRC-bonded splint, bridge, fiber post and/or resin veneer for minimally invasive prosthodontic treatment in the aesthetic zone is a good choice for periodontal patients. PMID:26964599

Fabrication of Monolithic RERTR Fuels by Hot Isostatic Pressing

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

Jan-Fong Jue; Blair H. Park; Curtis R. Clark

2010-11-01

The RERTR (Reduced Enrichment for Research and Test Reactors) Program is developing advanced nuclear fuels for high-power test reactors. Monolithic fuel design provides higher uranium loading than that of the traditional dispersion fuel design. Hot isostatic pressing is a promising process for low-cost batch fabrication of monolithic RERTR fuel plates for these high-power reactors. Bonding U Mo fuel foil and 6061 Al cladding by hot isostatic press bonding was successfully developed at Idaho National Laboratory. Due to the relatively high processing temperature, the interaction between fuel meat and aluminum cladding is a concern. Two different methods were employed to mitigatemore » this effect: (1) a diffusion barrier and (2) a doping addition to the interface. Both types of fuel plates have been fabricated by hot isostatic press bonding. Preliminary results show that the direct fuel/cladding interaction during the bonding process was eliminated by introducing a thin zirconium diffusion barrier layer between the fuel and the cladding. Fuel plates were also produced and characterized with a silicon-rich interlayer between fuel and cladding. This paper reports the recent progress of this developmental effort and identifies the areas that need further attention.« less

Probing Fe-V Bonding in a C3-Symmetric Heterobimetallic Complex.

PubMed

Greer, Samuel M; McKay, Johannes; Gramigna, Kathryn M; Thomas, Christine M; Stoian, Sebastian A; Hill, Stephen

2018-04-30

Direct metal-metal bonding of two distinct first-row transition metals remains relatively unexplored compared to their second- and third-row heterobimetallic counterparts. Herein, a recently reported Fe-V triply bonded species, [V( i PrNPPh 2 ) 3 FeI] (1; Kuppuswamy, S.; Powers, T. M.; Krogman, J. P.; Bezpalko, M. W.; Foxman, B. M.; Thomas, C. M. Vanadium-iron complexes featuring metal-metal multiple bonds. Chem. Sci. 2013, 4, 3557-3565), is investigated using high-frequency electron paramagnetic resonance, field- and temperature-dependent 57 Fe nuclear gamma resonance (Mössbauer) spectroscopy, and high-field electron-electron double resonance detected nuclear magnetic resonance. From the use of this suite of physical methods, we have assessed the electronic structure of 1. These studies allow us to establish the effective g̃ tensors as well as the Fe/V electro-nuclear hyperfine interaction tensors of the spin S = 1 / 2 ground state. We have rationalized these tensors in the context of ligand field theory supported by quantum chemical calculations. This theoretical analysis suggests that the S = 1 / 2 ground state originates from a single unpaired electron predominately localized on the Fe site.

Origin of the Counterintuitive Dynamic Charge in the Transition-Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Pike, Nicholas; van Troeye, Benoit; Dewandre, Antoine; Gonze, Xavier; Verstraete, Matthieu

Our recent first-principles calculations of the electronic and vibrational properties of the hexagonal transition-metal dichalcogenides reveal that their Born effective charges display a counterintuitive sign when compared to most other materials or transition-metal dichalcogenides with trigonal symmetry. We determine the origin of this counterintuitive sign by calculating the electronic, vibrational, and optical properties of these systems. We show that the sign of the Born effective charge is directly related to the electric field response of the electronic density, and, in turn, to the bonding characteristics of the material.There is a filled anti-bonding molecular orbital at the Fermi level, which is localized on the transition-metal atom and corresponds to a form of solid state π back-bonding in these material. We propose a method of determining if other materials display a similar counterintuitive sign, based on their bonding characteristics, and propose experiments which could measure the sign of the Born effective charge using different spectroscopies. The authors acknowledge the Belgian Fonds National de la Recherche Scientifique FNRS under PDR T.1077.15-1/7, a FRIA Grant, ULg, and from the Communauté Française de Belgique (ARC AIMED 15/19-09).

Applying Molecular Bonding Concepts to the Solid State

NASA Astrophysics Data System (ADS)

Dunnington, Benjamin D.

In this thesis, we describe the extension and application of Natural Bond Orbital (NBO) analysis to periodic systems. This enables the translation of rigorous, quantum mechanical calculation results of solid systems into the localized lone pairs and two-center bonds of Lewis structures. Such localized bonding descriptions form the basic language of chemistry, and application of these ideas to solids allows for the understanding of complex phenomena in bulk systems using readily accessible concepts from molecular science. In addition to the algorithmic adjustments needed for to account for periodic boundary conditions in the NBO process, we also discuss methodology to interface the ubiquitous plane wave basis sets of the solid state with the atom-centered basis functions needed as input for NBO analysis. We will describe one method using projection of the plane wave eigenstates, and a second projection-free method that involves the direct calculation of matrix elements of the plane wave Hamiltonian in an atom-centered basis. The reliance of many localized, post-computational analysis techniques on an atom-centered description of the orbitals, means these interfaces will have applicability beyond our NBO development. An ideal area for application of such molecular descriptions of periodic systems is heterogeneous catalysis, where reactants from a gas/liquid phase react on a solid catalyst surface. Previous studies of these systems have originated from the delocalized perspective of the bulk catalyst. NBO provides an explicit description of the perturbative effect of the catalyst on the covalent bonds of the reactant, which is correlated with the catalytic activity of the material. Such a shift to an adsorbate focused description of surface reactivity will enable understanding of catalysis across a variety of materials.

Method for the growth of large low-defect single crystals

NASA Technical Reports Server (NTRS)

Powell, J. Anthony (Inventor); Neudeck, Philip G. (Inventor); Trunek, Andrew J. (Inventor); Spry, David J. (Inventor)

2008-01-01

A method and the benefits resulting from the product thereof are disclosed for the growth of large, low-defect single-crystals of tetrahedrally-bonded crystal materials. The process utilizes a uniquely designed crystal shape whereby the direction of rapid growth is parallel to a preferred crystal direction. By establishing several regions of growth, a large single crystal that is largely defect-free can be grown at high growth rates. This process is particularly suitable for producing products for wide-bandgap semiconductors, such as SiC, GaN, AlN, and diamond. Large low-defect single crystals of these semiconductors enable greatly enhanced performance and reliability for applications involving high power, high voltage, and/or high temperature operating conditions.

Iron-catalyzed stereospecific activation of olefinic C-H bonds with Grignard reagent for synthesis of substituted olefins.

PubMed

Ilies, Laurean; Asako, Sobi; Nakamura, Eiichi

2011-05-25

The reaction of an aryl Grignard reagent with a cyclic or acyclic olefin possessing a directing group such as pyridine or imine results in the stereospecific substitution of the olefinic C-H bond syn to the directing group. The reaction takes place smoothly and without isomerization of the product olefin in the presence of a mild oxidant (1,2-dichloro-2-methylpropane) and an aromatic cosolvent. Several lines of evidence suggest that the reaction proceeds via iron-catalyzed olefinic C-H bond activation rather than an oxidative Mizoroki-Heck-type reaction.

Sulfur passivation techniques for III-V wafer bonding

NASA Astrophysics Data System (ADS)

Jackson, Michael James

The use of direct wafer bonding in a multijunction III-V solar cell structure requires the formation of a low resistance bonded interface with minimal thermal treatment. A wafer bonded interface behaves as two independent surfaces in close proximity, hence a major source of resistance is Fermi level pinning common in III-V surfaces. This study demonstrates the use of sulfur passivation in III-V wafer bonding to reduce the energy barrier at the interface. Two different sulfur passivation processes are addressed. A dry sulfur passivation method that utilizes elemental sulfur vapor activated by ultraviolet light in vacuum is compared with aqueous sulfide and native oxide etch treatments. Through the addition of a sulfur desorption step in vacuum, the UV-S treatment achieves bondable surfaces free of particles contamination or surface roughening. X-ray photoelectron spectroscopy measurements of the sulfur treated GaAs surfaces find lower levels of oxide and the appearance of sulfide species. After 4 hrs of air exposure, the UV-S treated GaAs actually showed an increase in the amount of sulfide bonded to the semiconductor, resulting in less oxidation compared to the aqueous sulfide treatment. Large area bonding is achieved for sulfur treated GaAs / GaAs and InP / InP with bulk fracture strength achieved after annealing at 400 °C and 300 °C respectively, without large compressive forces. The electrical conductivity across a sulfur treated 400 °C bonded n-GaAs/n-GaAs interface significantly increased with a short anneal (1-2 minutes) at elevated temperatures (50--600 °C). Interfaces treated with the NH4OH oxide etch, on the other hand, exhibited only mild improvement in accordance with previously published studies in this area. TEM and STEM images revealed similar interfacial microstructure changes with annealing for both sulfur treated and NH4OH interfaces, whereby some areas have direct semiconductor-semiconductor contact without any interfacial layer. Fitting the observed temperature dependence of zero bias conductance using a model for tunneling through a grain boundary reveals that the addition of sulfur at the interface lowered the interfacial energy barrier by 0.2 eV. The interface resistance for these sulfur-treated structures is less than 0.03 O·cm 2 at room temperature. These results emphasize that sulfur passivation techniques reduce interface states that otherwise limit the implementation of wafer bonding for high efficiency solar cells and other devices.

Simplified computational methods for elastic and elastic-plastic fracture problems

NASA Technical Reports Server (NTRS)

Atluri, Satya N.

1992-01-01

An overview is given of some of the recent (1984-1991) developments in computational/analytical methods in the mechanics of fractures. Topics covered include analytical solutions for elliptical or circular cracks embedded in isotropic or transversely isotropic solids, with crack faces being subjected to arbitrary tractions; finite element or boundary element alternating methods for two or three dimensional crack problems; a 'direct stiffness' method for stiffened panels with flexible fasteners and with multiple cracks; multiple site damage near a row of fastener holes; an analysis of cracks with bonded repair patches; methods for the generation of weight functions for two and three dimensional crack problems; and domain-integral methods for elastic-plastic or inelastic crack mechanics.

K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

DOE PAGES

Baker, Michael L.; Mara, Michael W.; Yan, James J.; ...

2017-02-09

Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3dmore » orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.« less

K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

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

Baker, Michael L.; Mara, Michael W.; Yan, James J.

Continual advancements in the development of synchrotron radiation sources have resulted in X-ray based spectroscopic techniques capable of probing the electronic and structural properties of numerous systems. This review gives an overview of the application of metal K-edge and L-edge X-ray absorption spectroscopy (XAS), as well as Kα resonant inelastic X-ray scattering (RIXS), to the study of electronic structure in transition metal sites with emphasis on experimentally quantifying 3d orbital covalency. The specific sensitivities of K-edge XAS, L-edge XAS, and RIXS are discussed emphasizing the complementary nature of the methods. L-edge XAS and RIXS are sensitive to mixing between 3dmore » orbitals and ligand valence orbitals, and to the differential orbital covalency (DOC), that is, the difference in the covalencies for different symmetry sets of the d orbitals. Both L-edge XAS and RIXS are highly sensitive to and enable separation of σ and π donor bonding and π back bonding contributions to bonding. Applying ligand field multiplet simulations, including charge transfer via valence bond configuration interactions, DOC can be obtained for direct comparison with density functional theory calculations and to understand chemical trends. Here, the application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.« less

Polarizable atomic multipole X-ray refinement: application to peptide crystals

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

Schnieders, Michael J.; Fenn, Timothy D.; Howard Hughes Medical Institute

2009-09-01

A method to accelerate the computation of structure factors from an electron density described by anisotropic and aspherical atomic form factors via fast Fourier transformation is described for the first time. Recent advances in computational chemistry have produced force fields based on a polarizable atomic multipole description of biomolecular electrostatics. In this work, the Atomic Multipole Optimized Energetics for Biomolecular Applications (AMOEBA) force field is applied to restrained refinement of molecular models against X-ray diffraction data from peptide crystals. A new formalism is also developed to compute anisotropic and aspherical structure factors using fast Fourier transformation (FFT) of Cartesian Gaussianmore » multipoles. Relative to direct summation, the FFT approach can give a speedup of more than an order of magnitude for aspherical refinement of ultrahigh-resolution data sets. Use of a sublattice formalism makes the method highly parallelizable. Application of the Cartesian Gaussian multipole scattering model to a series of four peptide crystals using multipole coefficients from the AMOEBA force field demonstrates that AMOEBA systematically underestimates electron density at bond centers. For the trigonal and tetrahedral bonding geometries common in organic chemistry, an atomic multipole expansion through hexadecapole order is required to explain bond electron density. Alternatively, the addition of interatomic scattering (IAS) sites to the AMOEBA-based density captured bonding effects with fewer parameters. For a series of four peptide crystals, the AMOEBA–IAS model lowered R{sub free} by 20–40% relative to the original spherically symmetric scattering model.« less

Three-dimensional finite element analysis of the shear bond test.

PubMed

DeHoff, P H; Anusavice, K J; Wang, Z

1995-03-01

The purpose of this study was to use finite element analyses to model the planar shear bond test and to evaluate the effects of modulus values, bonding agent thickness, and loading conditions on the stress distribution in the dentin adjacent to the bonding agent-dentin interface. All calculations were performed with the ANSYS finite element program. The planar shear bond test was modeled as a cylinder of resin-based composite bonded to a cylindrical dentin substrate. The effects of material, geometry and loading variables were determined primarily by use of a three-dimensional structural element. Several runs were also made using an axisymmetric element with harmonic loading and a plane strain element to determine whether two-dimensional analyses yield valid results. Stress calculations using three-dimensional finite element analyses confirmed the presence of large stress concentration effects for all stress components at the bonding agent-dentin interface near the application of the load. The maximum vertical shear stress generally occurs approximately 0.3 mm below the loading site and then decreases sharply in all directions. The stresses reach relatively uniform conditions within about 0.5 mm of the loading site and then increase again as the lower region of the interface is approached. Calculations using various loading conditions indicated that a wire-loop method of loading leads to smaller stress concentration effects, but a shear bond strength determined by dividing a failure load by the cross-sectional area grossly underestimates the true interfacial bond strength. Most dental researchers are using tensile and shear bond tests to predict the effects of process and material variables on the clinical performance of bonding systems but no evidence has yet shown that bond strength is relevant to clinical performance. A critical factor in assessing the usefulness of bond tests is a thorough understanding of the stress states that cause failure in the bond test and then to assess whether these stress states also exist in the clinical situation. Finite element analyses can help to answer this question but much additional work is needed to identify the failure modes in service and to relate these failures to particular loading conditions. The present study represents only a first step in understanding the stress states in the planar shear bond test.

Pd-Catalyzed Acetoxylation of γ-C(sp3)-H Bonds of Amines Directed by a Removable Bts-Protecting Group.

PubMed

Zheng, Yong; Song, Weibin; Zhu, Yefu; Wei, Bole; Xuan, Lijiang

2018-02-16

Pd-catalyzed acetoxylation of γ-C(sp 3 )-H bonds directed by Bts-protected amines using inexpensive PhI(OAc) 2 as oxidant is reported. The Bts-protecting group is easily introduced and removed under mild conditions. This protocol provides an important strategy for the construction of γ-hydroxyl amine derivatives.

Impact of z-direction fiber orientation on performance of commercial and laboratory linerboards

Treesearch

David W. Vahey; John M. Considine; Roland Gleisner; Alan Rudie; Sabine Rolland du Roscoat; Jean-Francis Bloch

2009-01-01

Fibers tilted in z-direction by hydraulic forces associated with rushing or dragging the sheet can bond multiple strata together, resulting in improved out-of-plane shear strengths. Tilted fibers are difficult to identify microscopically; however, their presence can result in different measurements of Scott internal bond when tests are carried out in the two opposing...

Shift of semimetal-semiconductor bond direction on “0 1 1” to “1 1 1” Bismuth quazi-two-dimension system

NASA Astrophysics Data System (ADS)

Yazdani, Ahmad; Hamreh, Sajad

2018-03-01

The electronic structure of the nanocrystallines and quasi-two-dimensional systems strongly impressed by the thermodynamic- behavior mainly due to excess of hidden surface free energy. Therefore, the stability of crystalline structure’s change could be related to band-offset of bond rupturing of atomic displacements. whereas for the electronic-structure of "Bi" it seams the competition of L.S and bond exchange should be effectively dominated. Besides all of the characters behave spatial like strong sensitive oxidation here it is supposed that strong correlated electronic structure in the absence of oxygen is resulted on direction of redistribution of surface chemical bond formation before any reconstructive structure. Where • The metallic direction of electronic structure “0 1 1” is changed to “1 1 1” semiconductor direction. • the effect of L.S is more evident on the local density of state while it is not observable around the fermi level. • Strong effect of spin-orbit interaction on splitting of the valance to nearly conduction band around the fermi level is more evident.

76 FR 3856 - Airworthiness Directives; The Boeing Company Model 737-100, -200, -200C, -300, -400, and -500...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-01-21

... new relays having a GFI feature, performing certain bonding resistance measurements, and modifying... with new relays having a GFI feature, Doing certain bonding resistance measurements to verify certain... relay module assemblies and bond resistance measurements. In addition, we have reviewed Section 9 of...

31 CFR 315.2 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., DEPARTMENT OF THE TREASURY BUREAU OF THE PUBLIC DEBT REGULATIONS GOVERNING U.S. SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES General Information § 315.2 Definitions. As used in... the context indicates otherwise. General references to bonds and direct references to Series E bonds...

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.

Vertical and lateral heterogeneous integration

NASA Astrophysics Data System (ADS)

Geske, Jon; Okuno, Yae L.; Bowers, John E.; Jayaraman, Vijay

2001-09-01

A technique for achieving large-scale monolithic integration of lattice-mismatched materials in the vertical direction and the lateral integration of dissimilar lattice-matched structures has been developed. The technique uses a single nonplanar direct-wafer-bond step to transform vertically integrated epitaxial structures into lateral epitaxial variation across the surface of a wafer. Nonplanar wafer bonding is demonstrated by integrating four different unstrained multi-quantum-well active regions lattice matched to InP on a GaAs wafer surface. Microscopy is used to verify the quality of the bonded interface, and photoluminescence is used to verify that the bonding process does not degrade the optical quality of the laterally integrated wells. The authors propose this technique as a means to achieve greater levels of wafer-scale integration in optical, electrical, and micromechanical devices.

26 CFR 1.61-7 - Interest.

Code of Federal Regulations, 2010 CFR

2010-04-01

... coupon bonds; interest on an open account, a promissory note, a mortgage, or a corporate bond or... disbursements method of accounting who owns United States savings bonds issued at a discount has an election as... which received or accrued (depending on the method of accounting used by the taxpayer). (d) Bonds sold...

An In Situ Directing Group Strategy for Chiral Anion Phase-Transfer Fluorination of Allylic Alcohols

PubMed Central

2015-01-01

An enantioselective fluorination of allylic alcohols under chiral anion phase-transfer conditions is reported. The in situ generation of a directing group proved crucial for achieving effective enantiocontrol. In the presence of such a directing group, a range of acyclic substrates underwent fluorination to afford highly enantioenriched α-fluoro homoallylic alcohols. Mechanistic studies suggest that this transformation proceeds through a concerted enantiodetermining transition state involving both C–F bond formation and C–H bond cleavage. PMID:25203796

Applying a nonlinear, pitch-catch, ultrasonic technique for the detection of kissing bonds in friction stir welds.

PubMed

Delrue, Steven; Tabatabaeipour, Morteza; Hettler, Jan; Van Den Abeele, Koen

2016-05-01

Friction stir welding (FSW) is a promising technology for the joining of aluminum alloys and other metallic admixtures that are hard to weld by conventional fusion welding. Although FSW generally provides better fatigue properties than traditional fusion welding methods, fatigue properties are still significantly lower than for the base material. Apart from voids, kissing bonds for instance, in the form of closed cracks propagating along the interface of the stirred and heat affected zone, are inherent features of the weld and can be considered as one of the main causes of a reduced fatigue life of FSW in comparison to the base material. The main problem with kissing bond defects in FSW, is that they currently are very difficult to detect using existing NDT methods. Besides, in most cases, the defects are not directly accessible from the exposed surface. Therefore, new techniques capable of detecting small kissing bond flaws need to be introduced. In the present paper, a novel and practical approach is introduced based on a nonlinear, single-sided, ultrasonic technique. The proposed inspection technique uses two single element transducers, with the first transducer transmitting an ultrasonic signal that focuses the ultrasonic waves at the bottom side of the sample where cracks are most likely to occur. The large amount of energy at the focus activates the kissing bond, resulting in the generation of nonlinear features in the wave propagation. These nonlinear features are then captured by the second transducer operating in pitch-catch mode, and are analyzed, using pulse inversion, to reveal the presence of a defect. The performance of the proposed nonlinear, pitch-catch technique, is first illustrated using a numerical study of an aluminum sample containing simple, vertically oriented, incipient cracks. Later, the proposed technique is also applied experimentally on a real-life friction stir welded butt joint containing a kissing bond flaw. Copyright © 2016 Elsevier B.V. All rights reserved.

Direct Observation of Charge Transfer at a MgO(111) Surface

NASA Astrophysics Data System (ADS)

Subramanian, A.; Marks, L. D.; Warschkow, O.; Ellis, D. E.

2004-01-01

Transmission electron diffraction (TED) combined with direct methods have been used to study the √(3)×√(3)R30° reconstruction on the polar (111) surface of MgO and refine the valence charge distribution. The surface is nonstoichiometric and is terminated by a single magnesium atom. A charge-compensating electron hole is localized in the next oxygen layer and there is a nominal charge transfer from the oxygen atoms to the top magnesium atom. The partial charges that we obtain for the surface atoms are in reasonable agreement with empirical bond-valence estimations.

Rapid adhesive bonding concepts

NASA Technical Reports Server (NTRS)

Stein, B. A.; Tyeryar, J. R.; Hodges, W. T.

1984-01-01

Adhesive bonding in the aerospace industry typically utilizes autoclaves or presses which have considerable thermal mass. As a consequence, the rates of heatup and cooldown of the bonded parts are limited and the total time and cost of the bonding process is often relatively high. Many of the adhesives themselves do not inherently require long processing times. Bonding could be performed rapidly if the heat was concentrated in the bond lines or at least in the adherends. Rapid adhesive bonding concepts were developed to utilize induction heating techniques to provide heat directly to the bond line and/or adherends without heating the entire structure, supports, and fixtures of a bonding assembly. Bonding times for specimens are cut by a factor of 10 to 100 compared to standard press bonding. The development of rapid adhesive bonding for lap shear specimens (per ASTM D1003 and D3163), for aerospace panel bonding, and for field repair needs of metallic and advanced fiber reinforced polymeric matrix composite structures are reviewed.

31 CFR 363.99 - What is the minimum amount of a bond that I may transfer or deliver as a gift in any one...

Code of Federal Regulations, 2010 CFR

2010-07-01

... Savings Bonds Purchased Through TreasuryDirect Gifts § 363.99 What is the minimum amount of a bond that I may transfer or deliver as a gift in any one transaction? You may transfer or deliver gift bonds in... that I may transfer or deliver as a gift in any one transaction? 363.99 Section 363.99 Money and...

Grism manufacturing by low temperature mineral bonding

NASA Astrophysics Data System (ADS)

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

2017-09-01

By uniting a grating with a prism to a GRISM compound, the optical characteristics of diffractive and refractive elements can be favorably combined to achieve outstanding spectral resolution features. Ruling the grating structure into the prism surface is common for wavelengths around 1 μm and beyond, while adhesive bonding of two separate parts is generally used for shorter wavelengths and finer structures. We report on a manufacturing approach for joining the corresponding glass elements by the technology of hydrophilic direct bonding. This allows to manufacture the individual parts separately and subsequently combine them quasimonolithically by generating stiff and durable bonds of vanishing thickness, high strength and excellent transmission. With this approach for GRISM bonding, standard direct-write- or mask-lithography equipment may be used for the fabrication of the grating structure and the drawbacks of adhesive bonding (thermal mismatch, creep, aging) are avoided. The technology of hydrophilic bonding originates from "classical" optical contacting [1], but has been much improved and perfected during the last decades in the context of 3-dimensinal stacking Si-wafers for microelectronic applications [2]. It provides joins through covalent bonds of the Si-O-Si type at the nanometer scale, i.e. the elementary bond type in many minerals and glasses. The mineral nature of the bond is perfectly adapted to most optical materials and the extremely thin bonding layers generated with this technology are well suited for transmission optics. Creeping under mechanical load, as commonly observed with adhesive bonding, is not an issue. With respect to diffusion bonding, which operates at rather high temperatures close to the glass transition or crystal melting point, hydrophilic bonding is a low temperature process that needs only moderate heating. This facilitates provision of handling and alignment means for the individual parts during the set-up stages and greatly eases joining optical materials of different thermal expansion. The technology has been successfully used in the past for bonding various glasses as well as crystalline optical materials [3, 4]. Here we will focus on bonding prisms elements and binary gratings of fused silica with and without coatings at the bonding interface. Further, preliminary results on bonding prism-grating-prism (PGP) combinations will be presented.

Nondestructive tests of regenerative chambers. [evaluating nondestructive methods of determining metal bond integrity

NASA Technical Reports Server (NTRS)

Malone, G. A.; Vecchies, L.; Wood, R.

1974-01-01

The capabilities and limitations of nondestructive evaluation methods were studied to detect and locate bond deficiencies in regeneratively cooled thrust chambers for rocket engines. Flat test panels and a cylinder were produced to simulate regeneratively cooled thrust chamber walls. Planned defects with various bond integrities were produced in the panels to evaluate the sensitivity, accuracy, and limitations of nondestructive methods to define and locate bond anomalies. Holography, acoustic emission, and ultrasonic scan were found to yield sufficient data to discern bond quality when used in combination and in selected sequences. Bonding techniques included electroforming and brazing. Materials of construction included electroformed nickel bonded to Nickel 200 and OFHC copper, electroformed copper bonded to OFHC copper, and 300 series stainless steel brazed to OFHC copper. Variations in outer wall strength, wall thickness, and defect size were evaluated for nondestructive test response.

Method for bonding a transmission line to a downhole tool

DOEpatents

Hall, David R.; Fox, Joe

2007-11-06

An apparatus for bonding a transmission line to the central bore of a downhole tool includes a pre-formed interface for bonding a transmission line to the inside diameter of a downhole tool. The pre-formed interface includes a first surface that substantially conforms to the outside contour of a transmission line and a second surface that substantially conforms to the inside diameter of a downhole tool. In another aspect of the invention, a method for bonding a transmission line to the inside diameter of a downhole tool includes positioning a transmission line near the inside wall of a downhole tool and placing a mold near the transmission line and the inside wall. The method further includes injecting a bonding material into the mold and curing the bonding material such that the bonding material bonds the transmission line to the inside wall.

Direct heteroarylation polymerization: guidelines for defect-free conjugated polymers† †Electronic supplementary information (ESI) available. CCDC 1507660 and 1507661. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00589j Click here for additional data file.

PubMed Central

Bura, Thomas; Beaupré, Serge; Légaré, Marc-André; Quinn, Jesse; Rochette, Etienne; Blaskovits, J. Terence; Fontaine, Frédéric-Georges; Pron, Agnieszka; Li, Yuning

2017-01-01

Direct (hetero)arylation polymerization (DHAP) has emerged as a valuable and atom-economical alternative to traditional cross-coupling methods for the synthesis of low-cost and efficient conjugated polymers for organic electronics. However, when applied to the synthesis of certain (hetero)arene-based materials, a lack of C–H bond selectivity has been observed. To prevent such undesirable side-reactions, we report the design and synthesis of new, bulky, phosphine-based ligands that significantly enhance selectivity of the DHAP process for both halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. To better understand the selectivity issues, density functional theory (DFT) calculations have been performed on various halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. Calculations showed that the presence of bromine atoms decreases the energy of activation (E a) of the adjacent C–H bonds, allowing undesirable β-defects for some brominated aromatic units. Both calculations and the new ligands should lead to the rational design of monomers and methods for the preparation of defect-free conjugated polymers from DHAP. PMID:28966781

Apparatus and method for performing microfluidic manipulations for chemical analysis and synthesis

DOEpatents

Ramsey, J. Michael

2000-01-01

A microchip laboratory system and method provide fluid manipulations for a variety of applications, including sample injection for microchip chemical separations. The microchip is fabricated using standard photolithographic procedures and chemical wet etching, with the substrate and cover plate joined using direct bonding. Capillary electrophoresis and electrochromatography are performed in channels formed in the substrate. Analytes are loaded into a four-way intersection of channels by electrokinetically pumping the analyte through the intersection, followed by switching of the potentials to force an analyte plug into the separation channel.

Apparatus and method for performing microfluidic manipulations for chemical analysis and synthesis

DOEpatents

Ramsey, J. Michael

2000-01-01

A microchip laboratory system and method proved fluid manipulations for a variety of applications, including sample injection for microchip chemical separations. The microchip is fabricated using standard photolithographic procedures and chemical wet etching, with the substrate and cover plate joined using direct bonding. Capillary electrophoresis and electrochromatography are performed in channels formed in the substrate. Analytes are loaded into a four-way intersection of channels by electrokinetically pumping the analyte through the intersection, followed by switching of the potentials to force an analyte plug into the separation channel.

Apparatus and method for performing microfluidic manipulations for chemical analysis and synthesis

DOEpatents

Ramsey, J. Michael

2002-01-01

A microchip laboratory system and method provide fluid manipulations for a variety of applications, including sample injection for microchip chemical separations. The microchip is fabricated using standard photolithographic procedures and chemical wet etching, with the substrate and cover plate joined using direct bonding. Capillary electrophoresis and electrochromatography are performed in channels formed in the substrate. Analytes are loaded into a four-way intersection of channels by electrokinetically pumping the analyte through the intersection, followed by switching of the potentials to force an analyte plug into the separation channel.

Apparatus and method for performing microfluidic manipulations for chemical analysis and synthesis

DOEpatents

Ramsey, J. Michael

1999-01-01

A microchip laboratory system and method provide fluid manipulations for a variety of applications, including sample injection for microchip chemical separations. The microchip is fabricated using standard photolithographic procedures and chemical wet etching, with the substrate and cover plate joined using direct bonding. Capillary electrophoresis and electrochromatography are performed in channels formed in the substrate. Analytes are loaded into a four-way intersection of channels by electrokinetically pumping the analyte through the intersection, followed by switching of the potentials to force an analyte plug into the separation channel.

Apparatus and method for performing microfluidic manipulations for chemical analysis and synthesis

DOEpatents

Ramsey, J.M.

1999-01-12

A microchip laboratory system and method provide fluid manipulations for a variety of applications, including sample injection for microchip chemical separations. The microchip is fabricated using standard photolithographic procedures and chemical wet etching, with the substrate and cover plate joined using direct bonding. Capillary electrophoresis and electrochromatography are performed in channels formed in the substrate. Analytes are loaded into a four-way intersection of channels by electrokinetically pumping the analyte through the intersection, followed by switching of the potentials to force an analyte plug into the separation channel. 46 figs.

Evaluation of cytotoxic effects of six self-etching adhesives with direct and indirect contact tests.

PubMed

Kusdemir, Mahmut; Gunal, Solen; Ozer, Fusun; Imazato, Satoshi; Izutani, Naomi; Ebisu, Shigeyuki; Blatz, Markus B

2011-01-01

This study evaluated the cytotoxicity of self-etching primers/adhesives by direct contact and dentin barrier tests. The three two-step self-etching systems Clearfil SE Bond (CSE), Clearfil Protect Bond (CPB), Prime&Bond NT/NRC (PB) and one-step self-etching systems Reactmer Bond (RB), Clearfil Tri-S Bond (CTS), and Adper Prompt L-Pop (AP) were examined. In direct contact tests, L929 cells were cultured in the presence of diluted solutions (50, 20, 10, and 1%) of primer/conditioner of adhesive systems. For dentin barrier tests, each system was applied onto 0.5 or 1.5 mm thick human dentin assembled in a simple pulp chamber device and incubated for 24 h at 37°C to make the diffusive components contact the L929 cells placed at the bottom of the chamber. The cytotoxic effects were assessed by MTT assay. Cell culture without application of any primers/adhesives served as the control for both tests. One-way ANOVA and Tukey HSD tests were used for statistical analyses. The direct contact tests demonstrated that CSE and CPB were less toxic than the other materials at all dilutions. In the dentin barrier tests, toxic effects of materials were reduced with an increase in thickness of intervening dentin. CSE and CPB showed less cytotoxicity than the other adhesives (p<0.05) when applied to 0.5 mm-thick dentin, and CSE was the least toxic in the 1.5 mm-dentin group (p<0.05). Dentin thickness positively affected biocompatibility of the tested bonding systems. Two-step self-etching systems with HEMA-based primers were more biocompatible than other self-etching adhesives.

Method for maintaining precise suction strip porosities

NASA Technical Reports Server (NTRS)

Gallimore, Frank H. (Inventor)

1989-01-01

This invention relates to a masking method generally and, more particularly to a method of masking perforated titanium sheets having laminar control suction strips. As illustrated in the drawings, a nonaerodynamic surface of a perforated sheet has alternating suction strip areas and bonding land areas. Suction strip tapes overlie the bonding land areas during application of a masking material to an upper surface of the suction strip tapes. Prior to bonding the perforated sheet to a composite structure, the bonding land tapes are removed. The entire opposite aerodynamic surface is masked with tape before bonding. This invention provides a precise control of suction strip porosities by ensuring that no chemicals penetrate the suction strip areas during bonding.

Comparison of three different orthodontic wires for bonded lingual retainer fabrication

PubMed Central

Uysal, Tancan; Gul, Nisa; Alan, Melike Busra; Ramoglu, Sabri Ilhan

2012-01-01

Objective We evaluated the detachment force, amount of deformation, fracture mode, and pull-out force of 3 different wires used for bonded lingual retainer fabrication. Methods We tested 0.0215-inch five-stranded wire (PentaOne, Masel; group I), 0.016 × 0.022-inch dead-soft eight-braided wire (Bond-A-Braid, Reliance; group II), and 0.0195-inch dead-soft coaxial wire (Respond, Ormco; group III). To test detachment force, deformation, and fracture mode, we embedded 94 lower incisor teeth in acrylic blocks in pairs. Retainer wires were bonded to the teeth and vertically directed force was applied to the wire. To test pull-out force, wires were embedded in composite that was placed in a hole at the center of an acrylic block. Tensile force was applied along the long axis of the wire. Results Detachment force and mode of fracture were not different between groups. Deformation was significantly higher in groups II and III than in group I (p < 0.001). Mean pull-out force was significantly higher for group I compared to groups II and III (p < 0.001). Conclusions Detachment force and fracture mode were similar for all wires, but greater deformations were seen in dead-soft wires. Wire pull-out force was significantly higher for five-stranded coaxial wire than for the other wires tested. Five-stranded coaxial wires are suggested for use in bonded lingual retainers. PMID:23112930

Transition-metal-catalyzed direct arylation of (hetero)arenes by C-H bond cleavage.

PubMed

Ackermann, Lutz; Vicente, Rubén; Kapdi, Anant R

2009-01-01

The area of transition-metal-catalyzed direct arylation through cleavage of C-H bonds has undergone rapid development in recent years, and is becoming an increasingly viable alternative to traditional cross-coupling reactions with organometallic reagents. In particular, palladium and ruthenium catalysts have been described that enable the direct arylation of (hetero)arenes with challenging coupling partners--including electrophilic aryl chlorides and tosylates as well as simple arenes in cross-dehydrogenative arylations. Furthermore, less expensive copper, iron, and nickel complexes were recently shown to be effective for economically attractive direct arylations.

High activity of cubic PtRh alloys supported on graphene towards ethanol electrooxidation.

PubMed

Rao, Lu; Jiang, Yan-Xia; Zhang, Bin-Wei; Cai, Yuan-Rong; Sun, Shi-Gang

2014-07-21

Cubic PtRh alloys supported on graphene (PtxRhy/GN) with different atomic ratio of Pt and Rh were directly synthesized for the first time using the modified polyol method with Br(-) for the shape-directing agents. The process didn't use surface-capping agents such as PVP that easily occupy the active sites of electrocatalysts and are difficult to remove. Graphene is the key factor for cubic shape besides Br(-) and keeping catalysts high-dispersed. The X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to characterize the structure and morphology of these electrocatalysts. The results showed that they were composed of homogeneous cubic PtRh alloys. Traditional electrochemical methods, such as cyclic voltammetry and chronoamperometry, were used to investigate the electrocatalytic properties of PtxRhy/GN towards ethanol electrooxidation. It can be seen that PtxRhy/GN with all atomic ratios exhibited high catalytic activity, and the most active one has a composition with Pt : Rh = 9 : 1 atomic ratio. Electrochemical in situ FTIR spectroscopy was used to evaluate the cleavage of C-C bond in ethanol at room temperature in acidic solutions, the results illustrated that Rh in an alloy can promote the split of C-C bond in ethanol, and the alloy catalyst with atomic ratio Pt : Rh = 1 : 1 showed obviously better performance for the C-C bond breaking in ethanol and higher selectivity for the enhanced activity of ethanol complete oxidation to CO2 than alloys with other ratios of Pt and Rh. The investigation indicates that high activity of PtxRhy/GN electrocatalyst towards ethanol oxidation is due to the specific shape of alloys and the synergistic effect of two metal elements as well as graphene support.

Influence of different methods of cleaning custom bases on the shear bond strength of indirectly bonded brackets.

PubMed

Kanashiro, Lylian K; Robles-Ruíz, Julissa J; Ciamponi, Ana L; Medeiros, Igor S; Tortamano, André; Paiva, João B

2014-09-01

To determine the influence on shear bond strength and bond failure location of four cleaning methods for orthodontic bracket custom bases. In vitro laboratory study. Eighty bovine teeth were divided at random into four groups. The bracket custom bases were cleaned with different methods: group 1 with methyl methacrylate monomer, group 2 with acetone, group 3 with 50 μm aluminium oxide particles and group 4 with detergent. The brackets were indirectly bonded onto the teeth with the Sondhi Rapid-Set self-curing adhesive. The maximum required shear bond strength to debond the brackets was recorded. The bond failure location was evaluated using the Adhesive Remnant Index (ARI). One-way analysis of variance (ANOVA) analysis (P<0·05) was used to detect significant differences in the bond strength. Kaplan-Meier survival plots and log-rank test were done to compare the survival distribution between the groups. The Kruskal-Wallis test (P<0·05) was used to evaluate the differences in the ARI scores. The mean bond strengths in groups 1, 2, 3 and 4 were 23·7±5·0, 25·3±5·1, 25·6±3·7 and 25·7±4·2 MPa, respectively. There were no significant statistically differences in either the bond strength or the ARI score between the groups. The four custom base-cleaning methods presented the same efficiencies on indirect bond of the brackets; thus, practitioners can choose the method that works best for them. © 2014 British Orthodontic Society.

Bond Valuation for Colleges and Universities.

ERIC Educational Resources Information Center

National Association of College and University Business Officers, Washington, DC.

Bond valuation is examined to provide college administrators a more thorough understanding of the process to help them in developing their market values, or to help them in moving to a market valuation on bond holdings. Two methods presently used to value bonds, a matrix system and a trader quotation method, are described. An overview of bond…

Cantilever testing of sintered-silver interconnects

DOE PAGES

Wereszczak, Andrew A.; Chen, Branndon R.; Jadaan, Osama M.; ...

2017-10-19

Cantilever testing is an underutilized test method from which results and interpretations promote greater understanding of the tensile and shear failure responses of interconnects, metallizations, or bonded joints. The use and analysis of this method were pursued through the mechanical testing of sintered-silver interconnects that joined Ni/Au-plated copper pillars or Ti/Ni/Ag-plated silicon pillars to Ag-plated direct bonded copper substrates. Sintered-silver was chosen as the interconnect test medium because of its high electrical and thermal conductivities and high-temperature capability—attractive characteristics for a candidate interconnect in power electronic components and other devices. Deep beam theory was used to improve upon the estimationsmore » of the tensile and shear stresses calculated from classical beam theory. The failure stresses of the sintered-silver interconnects were observed to be dependent on test-condition and test-material-system. In conclusion, the experimental simplicity of cantilever testing, and the ability to analytically calculate tensile and shear stresses at failure, result in it being an attractive mechanical test method to evaluate the failure response of interconnects.« less

Cantilever testing of sintered-silver interconnects

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

Wereszczak, Andrew A.; Chen, Branndon R.; Jadaan, Osama M.

Cantilever testing is an underutilized test method from which results and interpretations promote greater understanding of the tensile and shear failure responses of interconnects, metallizations, or bonded joints. The use and analysis of this method were pursued through the mechanical testing of sintered-silver interconnects that joined Ni/Au-plated copper pillars or Ti/Ni/Ag-plated silicon pillars to Ag-plated direct bonded copper substrates. Sintered-silver was chosen as the interconnect test medium because of its high electrical and thermal conductivities and high-temperature capability—attractive characteristics for a candidate interconnect in power electronic components and other devices. Deep beam theory was used to improve upon the estimationsmore » of the tensile and shear stresses calculated from classical beam theory. The failure stresses of the sintered-silver interconnects were observed to be dependent on test-condition and test-material-system. In conclusion, the experimental simplicity of cantilever testing, and the ability to analytically calculate tensile and shear stresses at failure, result in it being an attractive mechanical test method to evaluate the failure response of interconnects.« less

Caul and method for bonding and curing intricate composite structures

NASA Technical Reports Server (NTRS)

Willden, Kurtis S. (Inventor); Goodno, Kenneth N. (Inventor)

1993-01-01

The invention disclosed here is a method for forming and curing an intricate structure of criss-crossing composite stringers and frames that are bonded to a skin panel. A structure constructed in accordance with the invention would be well-suited for use as a portion of an aircraft fuselage, a boat hull, or the like. The method is preferably practiced by applying uncured composite stringers to an uncured composite sheet panel. This is followed by placing cured frames crosswise over the stringers. The frames have openings at the locations where they intersect with the stringers which enables the frames to come into direct contact with the skin along most of their length. During the forming and curing process, the stringers are covered with a plurality of cauls, and the entire assembly of skin panel, stringers, frames and cauls is subjected to a vacuum bagging and curing process. The cauls serve to maintain both part shape and to control the flow of resin within the stringers as they are cured. Further, they probably eliminate the need for intermediate protective materials between the vacuum bag and the stringers.

A high voltage dielectrically isolated smart power technology based on silicon direct bonding

NASA Astrophysics Data System (ADS)

Macary, Veronique

1992-09-01

The feasibility of a dielectrically isolated technology based on the silicon direct bonding technique, for high voltage smart power applications in the 1000 to 1550 V/1 to 20 A range, where a vertical power switch is necessary, is investigated and demonstrated. Static and dynamic isolation of the low voltage circuitry integrated beside the vertical power transistor is the main concern of this family of circuits. The dielectric isolation offers better protection to the low voltage part than does the junction isolation, because of the elimination of the parasitic bipolar transistor inherent to the latter isolation technique. Silicon direct bonding provides a cost effective way to obtain a buried oxide isolation layer. In addition, the application requires a Si/Si bonded area in the active region of the vertical power switch. Strong influence of the prebonding cleaning in the electrical characteristics of the Si/Si interface is pointed out, and presence of crystalline defects is assumed to be at the origin of electrical failures. The main problems of silicon direct bonding process compatibility with standard processes were overcome, and a complete process flow, including the simultaneous integration of a vertical power bipolar transistor together with a bipolar control circuitry, was validated. Using a peripheral biased ring is shown to provide an easy way to optimize high voltage termination for the smart power circuit, while adding a non-additional technological step. This technique was studied by dimensional electrical simulations (BIDIM2 software), as well as analytically computed.

Vibrational Energy Transfer from Heme through Atomic Contacts in Proteins.

PubMed

Yamashita, Satoshi; Mizuno, Misao; Tran, Duy Phuoc; Dokainish, Hisham M; Kitao, Akio; Mizutani, Yasuhisa

2018-05-10

A pathway of vibrational energy flow in myoglobin was studied by time-resolved anti-Stokes ultraviolet resonance Raman spectroscopy combined with site-directed mutagenesis. Our previous study suggested that atomic contacts in proteins provide the dominant pathway for energy transfer while covalent bonds do not. In the present study, we directly examined the contributions of covalent bonds and atomic contacts to the pathway of vibrational energy flow by comparing the anti-Stokes resonance Raman spectra of two myoglobin mutants: one lacked a covalent bond between heme and the polypeptide chain and the other retained the intact bond. The two mutants showed no significant difference in temporal changes in the anti-Stokes Raman intensities of the tryptophan bands, implying that the dominant channel of vibrational energy transfer is not through the covalent bond but rather through van der Waals atomic contacts between heme and the protein moiety. The obtained insights contribute to our general understanding of energy transfer in the condensed phase.

Metal-free, visible-light-mediated direct C-H arylation of heteroarenes with aryl diazonium salts.

PubMed

Hari, Durga Prasad; Schroll, Peter; König, Burkhard

2012-02-15

Visible light along with 1 mol % eosin Y catalyzes the direct C-H bond arylation of heteroarenes with aryl diazonium salts by a photoredox process. We have investigated the scope of the reaction for several aryl diazonium salts and heteroarenes. The general and easy procedure provides a transition-metal-free alternative for the formation of aryl-heteroaryl bonds.

77 FR 5728 - Airworthiness Directives; Airbus Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-06

... between bonding lead and the harness, due to over length of the bonding lead. As the affected wire is not... chafing of the wires, and corrective actions, if necessary. We are proposing this AD to detect and correct contact or chafing of wires and bonding leads which, if not detected could be a source of sparks in the...

78 FR 57786 - Airworthiness Directives; AgustaWestland S.p.A. Helicopters

Federal Register 2010, 2011, 2012, 2013, 2014

2013-09-20

... to ensure that the windows are properly bonded within the doors. If the windows are not properly bonded, the AD requires applying bonding to the windows, the seals, and the window frames of the pilot and co-pilot doors. This AD was prompted by the loss of a pilot-door window during a test flight. The...

78 FR 24367 - Airworthiness Directives; AgustaWestland S.p.A. Helicopters

Federal Register 2010, 2011, 2012, 2013, 2014

2013-04-25

... to ensure that the windows are properly bonded within the doors. If the windows are not properly bonded, the proposed AD would require applying bonding to the windows, the seals, and the window frames of the pilot and co-pilot doors. This proposed AD is prompted by the loss of a pilot-door window...

76 FR 18062 - U.S. Securities; Sale and Issue of Marketable Book-Entry Treasury Bills, Notes, and Bonds; Book...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-04-01

...; Sale and Issue of Marketable Book-Entry Treasury Bills, Notes, and Bonds; Book-Entry Treasury Bonds... longer be opened and transfers of securities from other book-entry systems will no longer be [email protected] . SUPPLEMENTARY INFORMATION: Legacy Treasury Direct [supreg] is a book- entry, non...

Sequentially bridged graphene sheets with high strength, toughness, and electrical conductivity

PubMed Central

Wan, Sijie; Li, Yuchen; Mu, Jiuke; Aliev, Ali E.; Fang, Shaoli; Kotov, Nicholas A.; Jiang, Lei; Cheng, Qunfeng; Baughman, Ray H.

2018-01-01

We here show that infiltrated bridging agents can convert inexpensively fabricated graphene platelet sheets into high-performance materials, thereby avoiding the need for a polymer matrix. Two types of bridging agents were investigated for interconnecting graphene sheets, which attach to sheets by either π–π bonding or covalent bonding. When applied alone, the π–π bonding agent is most effective. However, successive application of the optimized ratio of π–π bonding and covalent bonding agents provides graphene sheets with the highest strength, toughness, fatigue resistance, electrical conductivity, electromagnetic interference shielding efficiency, and resistance to ultrasonic dissolution. Raman spectroscopy measurements of stress transfer to graphene platelets allow us to decipher the mechanisms of property improvement. In addition, the degree of orientation of graphene platelets increases with increasing effectiveness of the bonding agents, and the interlayer spacing increases. Compared with other materials that are strong in all directions within a sheet, the realized tensile strength (945 MPa) of the resin-free graphene platelet sheets was higher than for carbon nanotube or graphene platelet composites, and comparable to that of commercially available carbon fiber composites. The toughness of these composites, containing the combination of π–π bonding and covalent bonding, was much higher than for these other materials having high strengths for all in-plane directions, thereby opening the path to materials design of layered nanocomposites using multiple types of quantitatively engineered chemical bonds between nanoscale building blocks. PMID:29735659

A general strategy for the evolution of bond-forming enzymes using yeast display

PubMed Central

Chen, Irwin; Dorr, Brent M.; Liu, David R.

2011-01-01

The ability to routinely generate efficient protein catalysts of bond-forming reactions chosen by researchers, rather than nature, is a long-standing goal of the molecular life sciences. Here, we describe a directed evolution strategy for enzymes that catalyze, in principle, any bond-forming reaction. The system integrates yeast display, enzyme-mediated bioconjugation, and fluorescence-activated cell sorting to isolate cells expressing proteins that catalyze the coupling of two substrates chosen by the researcher. We validated the system using model screens for Staphylococcus aureus sortase A–catalyzed transpeptidation activity, resulting in enrichment factors of 6,000-fold after a single round of screening. We applied the system to evolve sortase A for improved catalytic activity. After eight rounds of screening, we isolated variants of sortase A with up to a 140-fold increase in LPETG-coupling activity compared with the starting wild-type enzyme. An evolved sortase variant enabled much more efficient labeling of LPETG-tagged human CD154 expressed on the surface of HeLa cells compared with wild-type sortase. Because the method developed here does not rely on any particular screenable or selectable property of the substrates or product, it represents a powerful alternative to existing enzyme evolution methods. PMID:21697512

Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond

NASA Astrophysics Data System (ADS)

Rožman, Marko

2016-01-01

Glycosphingolipid fragmentation behavior was investigated by combining results from analysis of a series of negative ion tandem mass spectra and molecular modeling. Fragmentation patterns extracted from 75 tandem mass spectra of mainly acidic glycosphingolipid species (gangliosides) suggest prominent cleavage of the glycosidic bonds with retention of the glycosidic oxygen atom by the species formed from the reducing end (B and Y ion formation). Dominant product ions arise from dissociation of sialic acids glycosidic bonds whereas product ions resulting from cleavage of other glycosidic bonds are less abundant. Potential energy surfaces and unimolecular reaction rates of several low-energy fragmentation pathways leading to cleavage of glycosidic bonds were estimated in order to explain observed dissociation patterns. Glycosidic bond cleavage in both neutral (unsubstituted glycosyl group) and acidic glycosphingolipids was the outcome of the charge-directed intramolecular nucleophilic substitution (SN2) mechanism. According to the suggested mechanism, the nucleophile in a form of carboxylate or oxyanion attacks the carbon at position one of the sugar ring, simultaneously breaking the glycosidic bond and yielding an epoxide. For gangliosides, unimolecular reaction rates suggest that dominant product ions related to the cleavage of sialic acid glycosidic bonds are formed via direct dissociation channels. On the other hand, low abundant product ions related to the dissociation of other glycosidic bonds are more likely to be the result of sequential dissociation. Although results from this study mainly contribute to the understanding of glycosphingolipid fragmentation chemistry, some mechanistic findings regarding cleavage of the glycosidic bond may be applicable to other glycoconjugates.

31 CFR 363.97 - What do I need to know if I transfer a book-entry savings bond to another person as a gift?

Code of Federal Regulations, 2010 CFR

2010-07-01

... Bonds Purchased Through TreasuryDirect Gifts § 363.97 What do I need to know if I transfer a book-entry savings bond to another person as a gift? (a) You must certify online that the transfer is a gift. (b) You... a book-entry savings bond to another person as a gift? 363.97 Section 363.97 Money and Finance...

Effects of Thermal Cycling on Thermal Expansion and Mechanical Properties of Sic Fiber-reinforced Reaction-bonded Si3n4 Composites

NASA Technical Reports Server (NTRS)

Bhatt, R. T.; Palczer, A. R.

1994-01-01

Thermal expansion curves for SiC fiber-reinforced reaction-bonded Si3N4 matrix composites (SiC/RBSN) and unreinforced RBSN were measured from 25 to 1400 C in nitrogen and in oxygen. The effects of fiber/matrix bonding and cycling on the thermal expansion curves and room-temperature tensile properties of unidirectional composites were determined. The measured thermal expansion curves were compared with those predicted from composite theory. Predicted thermal expansion curves parallel to the fiber direction for both bonding cases were similar to that of the weakly bonded composites, but those normal to the fiber direction for both bonding cases resulted in no net dimensional changes at room temperature, and no loss in tensile properties from the as-fabricated condition. In contrast, thermal cycling in oxygen for both composites caused volume expansion primarily due to internal oxidation of RBSN. Cyclic oxidation affected the mechanical properties of the weakly bonded SiC/RBSN composites the most, resulting in loss of strain capability beyond matrix fracture and catastrophic, brittle fracture. Increased bonding between the SiC fiber and RBSN matrix due to oxidation of the carbon-rich fiber surface coating and an altered residual stress pattern in the composite due to internal oxidation of the matrix are the main reasons for the poor mechanical performance of these composites.

Method for producing components with internal architectures, such as micro-channel reactors, via diffusion bonding sheets

DOEpatents

Alman, David E [Corvallis, OR; Wilson, Rick D [Corvallis, OR; Davis, Daniel L [Albany, OR

2011-03-08

This invention relates to a method for producing components with internal architectures, and more particularly, this invention relates to a method for producing structures with microchannels via the use of diffusion bonding of stacked laminates. Specifically, the method involves weakly bonding a stack of laminates forming internal voids and channels with a first generally low uniaxial pressure and first temperature such that bonding at least between the asperites of opposing laminates occurs and pores are isolated in interfacial contact areas, followed by a second generally higher isostatic pressure and second temperature for final bonding. The method thereby allows fabrication of micro-channel devices such as heat exchangers, recuperators, heat-pumps, chemical separators, chemical reactors, fuel processing units, and combustors without limitation on the fin aspect ratio.

Bonding thermoplastic polymers

DOEpatents

Wallow, Thomas I [Fremont, CA; Hunter, Marion C [Livermore, CA; Krafcik, Karen Lee [Livermore, CA; Morales, Alfredo M [Livermore, CA; Simmons, Blake A [San Francisco, CA; Domeier, Linda A [Danville, CA

2008-06-24

We demonstrate a new method for joining patterned thermoplastic parts into layered structures. The method takes advantage of case-II permeant diffusion to generate dimensionally controlled, activated bonding layers at the surfaces being joined. It is capable of producing bonds characterized by cohesive failure while preserving the fidelity of patterned features in the bonding surfaces. This approach is uniquely suited to production of microfluidic multilayer structures, as it allows the bond-forming interface between plastic parts to be precisely manipulated at micrometer length scales. The bond enhancing procedure is easily integrated in standard process flows and requires no specialized equipment.

Regioselective Acylation of Diols and Triols: The Cyanide Effect.

PubMed

Peng, Peng; Linseis, Michael; Winter, Rainer F; Schmidt, Richard R

2016-05-11

Central topics of carbohydrate chemistry embrace structural modifications of carbohydrates and oligosaccharide synthesis. Both require regioselectively protected building blocks that are mainly available via indirect multistep procedures. Hence, direct protection methods targeting a specific hydroxy group are demanded. Dual hydrogen bonding will eventually differentiate between differently positioned hydroxy groups. As cyanide is capable of various kinds of hydrogen bonding and as it is a quite strong sterically nondemanding base, regioselective O-acylations should be possible at low temperatures even at sterically congested positions, thus permitting formation and also isolation of the kinetic product. Indeed, 1,2-cis-diols, having an equatorial and an axial hydroxy group, benzoyl cyanide or acetyl cyanide as an acylating agent, and DMAP as a catalyst yield at -78 °C the thermodynamically unfavorable axial O-acylation product; acyl migration is not observed under these conditions. This phenomenon was substantiated with 3,4-O-unproteced galacto- and fucopyranosides and 2,3-O-unprotected mannopyranosides. Even for 3,4,6-O-unprotected galactopyranosides as triols, axial 4-O-acylation is appreciably faster than O-acylation of the primary 6-hydroxy group. The importance of hydrogen bonding for this unusual regioselectivity could be confirmed by NMR studies and DFT calculations, which indicate favorable hydrogen bonding of cyanide to the most acidic axial hydroxy group supported by hydrogen bonding of the equatorial hydroxy group to the axial oxygen. Thus, the "cyanide effect" is due to dual hydrogen bonding of the axial hydroxy group which enhances the nucleophilicity of the respective oxygen atom, permitting an even faster reaction for diols than for mono-ols. In contrast, fluoride as a counterion favors dual hydrogen bonding to both hydroxy groups leading to equatorial O-acylation.

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.

Fluxional σ-Bonds of the 2,5,8-Trimethylphenalenyl Dimer: Direct Observation of the Sixfold σ-Bond Shift via a π-Dimer.

PubMed

Uchida, Kazuyuki; Mou, Zhongyu; Kertesz, Miklos; Kubo, Takashi

2016-04-06

Direct evidence for σ-bond fluxionality in a phenalenyl σ-dimer was successfully obtained by a detailed investigation of the solution-state dynamics of 2,5,8-trimethylphenalenyl (TMPLY) using both experimental and theoretical approaches. TMPLY formed three diamagnetic dimers, namely, the σ-dimer (RR/SS), σ-dimer (RS), and π-dimer, which were fully characterized by (1)H NMR spectroscopy and electronic absorption measurements. The experimental findings gave the first quantitative insights into the essential preference of these competitive and unusual dimerization modes. The spectroscopic analyses suggested that the σ-dimer (RR/SS) is the most stable in terms of energy, whereas the others are metastable; the energy differences between these three isomers are less than 1 kcal mol(-1). Furthermore, the intriguing dynamics of the TMPLY dimers in the solution state were fully revealed by means of (1)H-(1)H exchange spectroscopy (EXSY) measurements and variable-temperature (1)H NMR studies. Surprisingly, the σ-dimer (RR/SS) demonstrated a sixfold σ-bond shift between the six sets of α-carbon pairs. This unusual σ-bond fluxionality is ascribed to the presence of a direct interconversion pathway between the σ-dimer (RR/SS) and the π-dimer, which was unambiguously corroborated by the EXSY measurements. The proposed mechanism of the sixfold σ-bond shift based on the experimental findings was well-supported by theoretical calculations.

Persistent homology analysis of ion aggregations and hydrogen-bonding networks.

PubMed

Xia, Kelin

2018-05-16

Despite the great advancement of experimental tools and theoretical models, a quantitative characterization of the microscopic structures of ion aggregates and their associated water hydrogen-bonding networks still remains a challenging problem. In this paper, a newly-invented mathematical method called persistent homology is introduced, for the first time, to quantitatively analyze the intrinsic topological properties of ion aggregation systems and hydrogen-bonding networks. The two most distinguishable properties of persistent homology analysis of assembly systems are as follows. First, it does not require a predefined bond length to construct the ion or hydrogen-bonding network. Persistent homology results are determined by the morphological structure of the data only. Second, it can directly measure the size of circles or holes in ion aggregates and hydrogen-bonding networks. To validate our model, we consider two well-studied systems, i.e., NaCl and KSCN solutions, generated from molecular dynamics simulations. They are believed to represent two morphological types of aggregation, i.e., local clusters and extended ion networks. It has been found that the two aggregation types have distinguishable topological features and can be characterized by our topological model very well. Further, we construct two types of networks, i.e., O-networks and H2O-networks, for analyzing the topological properties of hydrogen-bonding networks. It is found that for both models, KSCN systems demonstrate much more dramatic variations in their local circle structures with a concentration increase. A consistent increase of large-sized local circle structures is observed and the sizes of these circles become more and more diverse. In contrast, NaCl systems show no obvious increase of large-sized circles. Instead a consistent decline of the average size of the circle structures is observed and the sizes of these circles become more and more uniform with a concentration increase. As far as we know, these unique intrinsic topological features in ion aggregation systems have never been pointed out before. More importantly, our models can be directly used to quantitatively analyze the intrinsic topological invariants, including circles, loops, holes, and cavities, of any network-like structures, such as nanomaterials, colloidal systems, biomolecular assemblies, among others. These topological invariants cannot be described by traditional graph and network models.

Real-space identification of intermolecular bonding with atomic force microscopy.

PubMed

Zhang, Jun; Chen, Pengcheng; Yuan, Bingkai; Ji, Wei; Cheng, Zhihai; Qiu, Xiaohui

2013-11-01

We report a real-space visualization of the formation of hydrogen bonding in 8-hydroxyquinoline (8-hq) molecular assemblies on a Cu(111) substrate, using noncontact atomic force microscopy (NC-AFM). The atomically resolved molecular structures enable a precise determination of the characteristics of hydrogen bonding networks, including the bonding sites, orientations, and lengths. The observation of bond contrast was interpreted by ab initio density functional calculations, which indicated the electron density contribution from the hybridized electronic state of the hydrogen bond. Intermolecular coordination between the dehydrogenated 8-hq and Cu adatoms was also revealed by the submolecular resolution AFM characterization. The direct identification of local bonding configurations by NC-AFM would facilitate detailed investigations of intermolecular interactions in complex molecules with multiple active sites.

Rapid induction bonding of composites, plastics, and metals

NASA Technical Reports Server (NTRS)

Buckley, John D.; Fox, Robert L.

1991-01-01

The Toroid Bonding Gun is and induction heating device. It is a self contained, portable, low powered induction welding system developed for bonding or joining plastic, ceramic, or metallic parts. Structures can be bonded in a factory or in a the field. This type of equipment allows for applying heat directly to the bond lines and/or to the adhesives without heating the entire structure, supports, and fixtures of a bonding assembly. The induction heating gun originally developed for use in the fabrication of space Gangs of bonders are now used to rapidly join composite sheet and structural components. Other NASA-developed applications of this bonding technique include the joining of thermoplastic composites, thermosetting composites, metals, and combinations of these materials.

Recycling stainless steel orthodontic brackets with Er:YAG laser - An environmental scanning electron microscope and shear bond strength study.

PubMed

Chacko, Prince K; Kodoth, Jithesh; John, Jacob; Kumar, Kishore

2013-07-01

TO DETERMINE THE EFFICIENCY OF ERBIUM: Yttrium aluminum garnet (Er:YAG) laser with Environmental Scanning Electron Microscope (ESEM) and shear bond strength analysis as a method of recycling stainless steel orthodontic brackets and compare with other methods of recycling. Eighty samples of extracted premolar teeth bonded to SS brackets were tested for rebonded shear bond strength after recycling by four methods and compared with a control group of 20 samples. These 80 samples were randomized into four groups which were recycled by four methods, namely, sandblasting, thermal method, adhesive grinding by tungsten carbide bur, and Er: YAG laser method. After recycling, ESEM and shear bond strength analysis were used to analyze the efficiency of the recycling methods. ER: YAG laser group was found to be having the greatest bond strength among the recycled brackets (8.33±2.51 followed by the sandblasting at 6.12±1.12 MPa, thermal and electropolishing at 4.44±0.95 MPa, and lastly the adhesive grinding method at 3.08±1.07 MPa. The shear bond strength of Er: YAG laser group was found to be having no statistically significant difference with that of the control group (P>0.05 and had statistical signifance with sandblasting, thermal and electropolishing and adhesive grinding groups at P>0.001. ESEM analysis showed complete removal of adhesive from the brackets recycled with Er: YAG laser which mimicked that of the control group. ER: YAG laser (2940 nm) was found to be the most efficient method for recycling, followed by the sandblasting, thermal, and the tungsten carbide methods, which had the least shear bond strength value and is not fit for clinical usage.

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.

Structural diversification of the aminobicyclo[4.3.0]nonane skeleton using alkynylsilyl-derived allylic trichloroacetimidates.

PubMed

Mostafa, Mohamed A B; McMillan, Angus E; Sutherland, Andrew

2017-04-05

The amino substituted bicyclo[4.3.0]nonane is a molecular scaffold found in a wide range of natural products and medicinal agents. Despite this, synthetic methods for the general preparation of this structural motif are sparse. Here we evaluate a diastereoselective approach for the preparation of vinylsilyl derived aminobicyclo[4.3.0]nonanes using a one-pot multi-bond forming process involving a Pd(ii)-catalysed Overman rearrangement, a Ru(ii)-catalysed ring closing enyne metathesis reaction, followed by a hydrogen bonding directed Diels-Alder reaction. We show that a benzyldimethylsilyl-substituted alkene analogue is amenable to further functionalisation and the late stage generation of diverse sp 3 -rich, drug-like aminobicyclo[4.3.0]nonane scaffolds with up to six stereogenic centres.

Covalent Organic Frameworks as a Platform for Multidimensional Polymerization.

PubMed

Bisbey, Ryan P; Dichtel, William R

2017-06-28

The simultaneous polymerization and crystallization of monomers featuring directional bonding designs provides covalent organic frameworks (COFs), which are periodic polymer networks with robust covalent bonds arranged in two- or three-dimensional topologies. The range of properties characterized in COFs has rapidly expanded to include those of interest for heterogeneous catalysis, energy storage and photovoltaic devices, and proton-conducting membranes. Yet many of these applications will require materials quality, morphological control, and synthetic efficiency exceeding the capabilities of contemporary synthetic methods. This level of control will emerge from an improved fundamental understanding of COF nucleation and growth processes. More powerful characterization of structure and defects, improved syntheses guided by mechanistic understanding, and accessing diverse isolated forms, ranging from single crystals to thin films to colloidal suspensions, remain important frontier problems.

Covalent Organic Frameworks as a Platform for Multidimensional Polymerization

PubMed Central

2017-01-01

The simultaneous polymerization and crystallization of monomers featuring directional bonding designs provides covalent organic frameworks (COFs), which are periodic polymer networks with robust covalent bonds arranged in two- or three-dimensional topologies. The range of properties characterized in COFs has rapidly expanded to include those of interest for heterogeneous catalysis, energy storage and photovoltaic devices, and proton-conducting membranes. Yet many of these applications will require materials quality, morphological control, and synthetic efficiency exceeding the capabilities of contemporary synthetic methods. This level of control will emerge from an improved fundamental understanding of COF nucleation and growth processes. More powerful characterization of structure and defects, improved syntheses guided by mechanistic understanding, and accessing diverse isolated forms, ranging from single crystals to thin films to colloidal suspensions, remain important frontier problems. PMID:28691064

Application of the Covalent Bond Classification Method for the Teaching of Inorganic Chemistry

ERIC Educational Resources Information Center

Green, Malcolm L. H.; Parkin, Gerard

2014-01-01

The Covalent Bond Classification (CBC) method provides a means to classify covalent molecules according to the number and types of bonds that surround an atom of interest. This approach is based on an elementary molecular orbital analysis of the bonding involving the central atom (M), with the various interactions being classified according to the…

Metal Ion Modeling Using Classical Mechanics

PubMed Central

2017-01-01

Metal ions play significant roles in numerous fields including chemistry, geochemistry, biochemistry, and materials science. With computational tools increasingly becoming important in chemical research, methods have emerged to effectively face the challenge of modeling metal ions in the gas, aqueous, and solid phases. Herein, we review both quantum and classical modeling strategies for metal ion-containing systems that have been developed over the past few decades. This Review focuses on classical metal ion modeling based on unpolarized models (including the nonbonded, bonded, cationic dummy atom, and combined models), polarizable models (e.g., the fluctuating charge, Drude oscillator, and the induced dipole models), the angular overlap model, and valence bond-based models. Quantum mechanical studies of metal ion-containing systems at the semiempirical, ab initio, and density functional levels of theory are reviewed as well with a particular focus on how these methods inform classical modeling efforts. Finally, conclusions and future prospects and directions are offered that will further enhance the classical modeling of metal ion-containing systems. PMID:28045509

Structural, electronic and optical properties of well-known primary explosive: Mercury fulminate

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

Yedukondalu, N.; Vaitheeswaran, G., E-mail: gvsp@uohyd.ernet.in

2015-11-28

Mercury Fulminate (MF) is one of the well-known primary explosives since 17th century and it has rendered invaluable service over many years. However, the correct molecular and crystal structures are determined recently after 300 years of its discovery. In the present study, we report pressure dependent structural, elastic, electronic and optical properties of MF. Non-local correction methods have been employed to capture the weak van der Waals interactions in layered and molecular energetic MF. Among the non-local correction methods tested, optB88-vdW method works well for the investigated compound. The obtained equilibrium bulk modulus reveals that MF is softer than themore » well known primary explosives Silver Fulminate (SF), silver azide and lead azide. MF exhibits anisotropic compressibility (b > a > c) under pressure, consequently the corresponding elastic moduli decrease in the following order: C{sub 22} > C{sub 11} > C{sub 33}. The structural and mechanical properties suggest that MF is more sensitive to detonate along c-axis (similar to RDX) due to high compressibility of Hg⋯O non-bonded interactions along that axis. Electronic structure and optical properties were calculated including spin-orbit (SO) interactions using full potential linearized augmented plane wave method within recently developed Tran-Blaha modified Becke-Johnson (TB-mBJ) potential. The calculated TB-mBJ electronic structures of SF and MF show that these compounds are indirect bandgap insulators. Also, SO coupling is found to be more pronounced for 4d and 5d-states of Ag and Hg atoms of SF and MF, respectively. Partial density of states and electron charge density maps were used to describe the nature of chemical bonding. Ag—C bond is more directional than Hg—C bond which makes SF to be more unstable than MF. The effect of SO coupling on optical properties has also been studied and found to be significant for both (SF and MF) of the compounds.« less

Gapped paramagnetic state in a frustrated spin-1/2 Heisenberg antiferromagnet on the cross-striped square lattice

NASA Astrophysics Data System (ADS)

Li, P. H. Y.; Bishop, R. F.

2018-03-01

We implement the coupled cluster method to very high orders of approximation to study the spin-1/2 J1 -J2 Heisenberg model on a cross-striped square lattice. Every nearest-neighbour pair of sites on the square lattice has an isotropic antiferromagnetic exchange bond of strength J1 > 0 , while the basic square plaquettes in alternate columns have either both or neither next-nearest-neighbour (diagonal) pairs of sites connected by an equivalent frustrating bond of strength J2 ≡ αJ1 > 0 . By studying the magnetic order parameter (i.e., the average local on-site magnetization) in the range 0 ≤ α ≤ 1 of the frustration parameter we find that the quasiclassical antiferromagnetic Néel and (so-called) double Néel states form the stable ground-state phases in the respective regions α < α1ac = 0 . 46(1) and α > α1bc = 0.615(5) . The double Néel state has Néel (⋯ ↑↓↑↓ ⋯) ordering along the (column) direction parallel to the stripes of squares with both or no J2 bonds, and spins alternating in a pairwise (⋯ ↑↑↓↓↑↑↓↓ ⋯) fashion along the perpendicular (row) direction, so that the parallel pairs occur on squares with both J2 bonds present. Further explicit calculations of both the triplet spin gap and the zero-field uniform transverse magnetic susceptibility provide compelling evidence that the ground-state phase over all or most of the intermediate regime α1ac < α < α1bc is a gapped state with no discernible long-range magnetic order.

Natural abundance 17O DNP NMR provides precise O–H distances and insights into the Brønsted acidity of heterogeneous catalysts

DOE PAGES

Perras, Frederic A.; Wang, Zhuoran; Naik, Pranjali; ...

2017-05-12

Heterogeneous Brønsted acid catalysts are tremendously important in industry, particularly in catalytic cracking processes. Here we show that these Brønsted acid sites can be directly observed at natural abundance by 17O DNP surface-enhanced NMR spectroscopy (SENS). We additionally show that the O–H bond length in these catalysts can be measured with sub-picometer precision, to enable a direct structural gauge of the lability of protons in a given material, which is correlated with the pH of the zero point of charge of the material. As a result, experiments performed on materials impregnated with pyridine also allow for the direct detection ofmore » intermolecular hydrogen bonding interactions through the lengthening of O–H bonds.« less

Natural abundance 17O DNP NMR provides precise O–H distances and insights into the Brønsted acidity of heterogeneous catalysts

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

Perras, Frederic A.; Wang, Zhuoran; Naik, Pranjali

Heterogeneous Brønsted acid catalysts are tremendously important in industry, particularly in catalytic cracking processes. Here we show that these Brønsted acid sites can be directly observed at natural abundance by 17O DNP surface-enhanced NMR spectroscopy (SENS). We additionally show that the O–H bond length in these catalysts can be measured with sub-picometer precision, to enable a direct structural gauge of the lability of protons in a given material, which is correlated with the pH of the zero point of charge of the material. As a result, experiments performed on materials impregnated with pyridine also allow for the direct detection ofmore » intermolecular hydrogen bonding interactions through the lengthening of O–H bonds.« less

Photochemical bonding of epithelial cell-seeded collagen lattice to rat muscle layer for esophageal tissue engineering: a pilot study

NASA Astrophysics Data System (ADS)

Chan, Barbara P.; Sato, M.; Vacanti, Joseph P.; Kochevar, Irene E.; Redmond, Robert W.

2005-04-01

Bilayered tube structures consist of epithelial cell-seeded collagen lattice and muscle layer have been fabricated for esophageal tissue engineering. Good adhesion between layers in order to facilitate cell infiltration and neovascularization in the collagen lattice is required. Previous efforts include using other bioglues such as fibrin glue and silicone tube as the physical support. However, the former is subjected to chances of transmitting blood-born infectious disease and is time consuming while the latter requires a second surgical procedure. The current project aimed to bond the cell-seeded collagen lattice to muscle layer using photochemical bonding, which has previously been demonstrated a rapid and non-thermal procedure in bonding collagenous tissues. Rat esophageal epithelial cells were seeded on collagen lattice and together with the latissimus dorsi muscle layer, were exposed to a photosensitizer rose Bengal at the bonding surface. An argon laser was used to irradiate the approximated layers. Bonding strength was measured during the peeling test of the collagen layer from the muscle layer. Post-bonding cell viability was assessed using a modified NADH-diaphorase microassay. A pilot in vivo study was conducted by directly bonding the cell-seeded collagen layer onto the muscle flap in rats and the structures were characterized histologically. Photochemical bonding was found to significantly increase the adherence at the bonding interface without compromising the cell viability. This indicates the feasibility of using the technique to fabricate multi-layered structures in the presence of living cells. The pilot animal study demonstrated integration of the collagen lattice with the muscle layer at the bonding interface although the subsequent surgical manipulation disturbed the integration at some region. This means that an additional procedure removing the tube could be avoided if the approximation and thus the bonding are optimized. Cell infiltration and neovascularization were also evident demonstrating that direct bonding of engineered tissue structures in particular those with low processability such as collagen lattice to the host tissue is feasible.