WorldWideScience

Sample records for group cooh bonded

  1. Density functional study of hydrogen bond formation between methanol and organic molecules containing Cl, F, NH2, OH, and COOH functional groups.

    Science.gov (United States)

    Kolev, Stefan K; St Petkov, Petko; Rangelov, Miroslav A; Vayssilov, Georgi N

    2011-12-08

    Various hydrogen-bonded complexes of methanol with different proton accepting and proton donating molecules containing Cl, F, NH(2), OH, OR, and COOH functional groups have been modeled using DFT with hybrid B3LYP and M05-2X functionals. The latter functional was found to provide more accurate estimates of the structural and thermodynamic parameters of the complexes of halides, amines, and alcohols. The characteristics of these complexes are influenced not only by the principle hydrogen bond of the methanol OH with the proton acceptor heteroatom, but also by additional hydrogen bonds of a C-H moiety with methanol oxygen as a proton acceptor. The contribution of the former hydrogen bond in the total binding enthalpy increases in the order chlorides contribution of the second type of hydrogen bond increases in the reverse order. A general correlation was found between the binding enthalpy of the complex and the electrostatic potential at the hydrogen center participating in the formation of the hydrogen bond. The calculated binding enthalpies of different complexes were used to clarify which functional groups can potentially form a hydrogen bond to the 2'-OH hydroxyl group in ribose, which is strong enough to block it from participation in the intramolecular catalytic activation of the peptide bond synthesis. Such blocking could result in inhibition of the protein biosynthesis in the living cell if the corresponding group is delivered as a part of a drug molecule in the vicinity of the active site in the ribosome. According to our results, such activity can be accomplished by secondary or tertiary amines, alkoxy groups, deprotonated carboxyl groups, and aliphatic fluorides, but not by the other modeled functional groups.

  2. A theoretical study on C-COOH homolytic bond dissociation enthalpies.

    Science.gov (United States)

    Shi, Jing; Huang, Xiong-Yi; Wang, Jun-Peng; Li, Run

    2010-06-01

    The knowledge of C-COOH homolytic bond dissociation enthalpies (BDEs) is of great importance in understanding various chemical and biochemical processes involving the decarboxylation reaction. In the present study, the density functional theory (DFT method), B3P86/6-311++G(2df,2p)//B3LYP/6-31+G(d), is found to be reliable to predict the C-COOH BDE of various structurally unrelated carboxylic acids. The mean absolute deviation (MAD) and root-mean-square deviation (rmsd) of this optimal method are equal to 2.0 and 2.5 kcal/mol, respectively. With the authorized theoretical protocol in hand, an extensive C-COOH BDE scale containing over 100 carboxylic acids has been established. The availability of this body of data enabled a detailed investigation of remote substituent effect on four types of carboxylic acids, including para-substituted benzoic acid, beta-substituted cis-propenoic acid, beta-substituted trans-propenoic acid, and substituted propiolic acid. Also with the C-COOH BDE data obtained in this work, an excellent linear relationship has been found between the C-COOH BDE of carboxylic acids and the C-H BDE of their hydrocarbon analogues. After comparing the energy barrier of the Pd-catalyzed decarboxylation reaction (DeltaG(decarboxylation)++) with the related C-COOH BDE, a negative correlation between the DeltaG(decarboxylation)++ and the C-COOH BDE was found.

  3. Quantum chemical calculations of bond dissociation energies for COOH scission and electronic structure in some acids

    Institute of Scientific and Technical Information of China (English)

    Zeng Hui; Zhao Jun; Xiao Xun

    2013-01-01

    Quantum chemical calculations are performed to investigate the equilibrium C-COOH bond distances and the bond dissociation energies (BDEs) for 15 acids.These compounds are studied by utilizing the hybrid density functional theory (DFT) (B3LYP,B3PW91,B3P86,PBE1PBE) and the complete basis set (CBS-Q) method in conjunction with the 6-31 lG** basis as DFT methods have been found to have low basis sets sensitivity for small and medium molecules in our previous work.Comparisons between the computational results and the experimental values reveal that CBS-Q method,which can produce reasonable BDEs for some systems in our previous work,seems unable to predict accurate BDEs here.However,the B3P86 calculated results accord very well with the experimental values,within an average absolute error of 2.3 kcal/mol.Thus,B3P86 method is suitable for computing the reliable BDEs of C-COOH bond for carboxylic acid compounds.In addition,the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of studied compounds are estimated,based on which the relative thermal stabilities of the studied acids are also discussed.

  4. Functionalization of carbon nanotubes with -CH(n), -NH(n) fragments, -COOH and -OH groups.

    Science.gov (United States)

    Milowska, Karolina Z; Majewski, Jacek A

    2013-05-21

    We present results of extensive theoretical studies concerning stability, morphology, and band structure of single wall carbon nanotubes (CNTs) covalently functionalized by -CH(n) (for n = 2,3,4), -NH(n) (for n = 1,2,3,4), -COOH, and -OH groups. These studies are based on ab initio calculations in the framework of the density functional theory. For functionalized systems, we determine the dependence of the binding energies on the concentration of the adsorbed molecules, critical densities of adsorbed molecules, global and local changes in the morphology, and electronic structure paying particular attention to the functionalization induced changes of the band gaps. These studies reveal physical mechanisms that determine stability and electronic structure of functionalized systems and also provide valuable theoretical predictions relevant for application. In particular, we observe that functionalization of CNTs causes generally their elongation and locally sp(2) to sp(3) rehybridization in the neighborhood of chemisorbed molecules. For adsorbants making particularly strong covalent bonds with the CNTs, such as the -CH2 fragments, we observe formation of the characteristic pentagon/heptagon (5/7) defects. In systems functionalized with the -CH2, -NH4, and -OH groups, we determine critical density of molecules that could be covalently bound to the lateral surface of CNTs. Our studies show that functionalization of CNTs can be utilized for band gap engineering. Functionalization of CNTs can also lead to changes in their metallic/semiconductor character. In semiconducting CNTs, functionalizing molecules such as -CH3, -NH2, -OH, -COOH, and both -OH and -COOH, introduce "impurity" bands in the band gap of pristine CNTs. In the case of -CH3, -NH2 molecules, the induced band gaps are typically smaller than in the pure CNT and depend strongly on the concentration of adsorbants. However, functionalization of semiconducting CNTs with hydroxyl groups leads to the metallization

  5. On the viability of cyclometalated Ru(II) complexes as dyes in DSSC regulated by COOH group, a DFT study.

    Science.gov (United States)

    Wang, Jian; Bai, Fu-Quan; Xia, Bao-Hui; Feng, Lu; Zhang, Hong-Xing; Pan, Qing-Jiang

    2011-02-14

    The Ru(II) complexes [Ru(bpp)(dcbpy)Cl](+) (1), [Ru(tcbpp)(bpy)Cl](+) (2), and [Ru(tc'bpp)(bpy)Cl](+) (3) (bpp = 2,6-bis(N-pyrazolyl)pyridine, dcbpy = 4,4'-dicarboxyl-bipyridine, bpy = bipyridine, tcbpp = 4-carboxyl-2,6-bis(2-carboxyl-N-pyrazolyl)pyridine, tc'bpp = 4-carboxyl-2,6-bis(4-carboxyl-N-pyrazolyl)pyridine) are studied theoretically using density functional theory (DFT) techniques to explore their properties as dye in a solar cell. The calculated geometry structure and absorption spectrum of 1 are consistent with its experimental results. The calculation results indicate which sites the COOH groups attach to can significantly influence the electronic structure of the complex. By migrating the COOH groups from the bpy ligand in 1 to bpp ligand in 2 and 3, the nature of LUMO changes from bpy-localized to bpp dominated. The calculated low-lying absorptions at λ > 370 nm of the three complexes are categorized as metal-to-ligand charge-transfer (MLCT) transitions and the transition terminates at the orbital populated by the COOH appended ligand. The atomic spin density analysis also indicates that the ligand which is modified by the COOH groups is the ideal spot for the captured electron to situate. It can be predicted that the performance of 2 and 3 in the dye-sensitized solar cell can be enhanced as compared with 1.

  6. Unscrambling micro-solvation of -COOH and -NH groups in neat dimethyl sulfoxide: insights from (1)H-NMR spectroscopy and computational studies.

    Science.gov (United States)

    Takis, Panteleimon G; Papavasileiou, Konstantinos D; Peristeras, Loukas D; Boulougouris, Georgios C; Melissas, Vasilios S; Troganis, Anastassios N

    2017-05-31

    Dimethyl sulfoxide (DMSO) has a significant, multi-faceted role in medicine, pharmacy, and biology as well as in biophysical chemistry and catalysis. Its physical properties and impact on biomolecular structures still attract major scientific interest, especially the interactions of DMSO with biomolecular functional groups. In the present study, we shed light on the "isolated" carboxylic (-COOH) and amide (-NH) interactions in neat DMSO via(1)H NMR studies along with extensive theoretical approaches, i.e. molecular dynamics (MD) simulations, density functional theory (DFT), and ab initio calculations, applied on model compounds (i.e. acetic and benzoic acid, ethyl acetamidocyanoacetate). Both experimental and theoretical results show excellent agreement, thereby permitting the calculation of the association constants between the studied compounds and DMSO molecules. Our coupled MD simulations, DFT and ab initio calculations, and NMR spectroscopy results indicated that complex formation is entropically driven and DMSO molecules undergo multiple strong interactions with the studied molecules, particularly with the -COOH groups. The combined experimental and theoretical techniques unraveled the interactions of DMSO with the most abundant functional groups of peptides (i.e. peptide bonds, side chain and terminal carboxyl groups) in high detail, providing significant insights on the underlying thermodynamics driving these interactions. Moreover, the developed methodology for the analysis of the simulation results could serve as a template for future thermodynamic and kinetic studies of similar systems.

  7. Reaction pathways of 2-iodoacetic acid on Cu(100): coverage-dependent competition between C-I bond scission and COOH deprotonation and identification of surface intermediates.

    Science.gov (United States)

    Lin, Yi-Shiue; Lin, Jain-Shiun; Liao, Yung-Hsuan; Yang, Che-Ming; Kuo, Che-Wei; Lin, Hong-Ping; Fan, Liang-Jen; Yang, Yaw-Wen; Lin, Jong-Liang

    2010-06-01

    The chemistry of 2-iodoacetic acid on Cu(100) has been studied by a combination of reflection-absorption infrared spectroscopy (RAIRS), X-ray photoelectron spectroscopy (XPS), temperature-programmed reaction/desorption (TPR/D), and theoretical calculations based on density functional theory for the optimized intermediate structures. In the thermal decomposition of ICH(2)COOH on Cu(100) with a coverage less than a half monolayer, three surface intermediates, CH(2)COO, CH(3)COO, and CCOH, are generated and characterized spectroscopically. Based on their different thermal stabilities, the reaction pathways of ICH(2)COOH on Cu(100) at temperatures higher than 230 K are established to be ICH(2)COOH --> CH(2)COO + H + I, CH(2)COO + H --> CH(3)COO, and CH(3)COO --> CCOH. Theoretical calculations suggest that the surface CH(2)COO has the skeletal plane, with delocalized pi electrons, approximately parallel to the surface. The calculated Mulliken charges agree with the detected binding energies for the two carbon atoms in CH(2)COO on Cu(100). The CCOH derived from CH(3)COO decomposition has a CC stretching frequency at 2025 cm(-1), reflecting its triple-bond character which is consistent with the calculated CCOH structure on Cu(100). Theoretically, CCOH at the bridge and hollow sites has a similar stability and is adsorbed with the molecular axis approximately perpendicular to the surface. The TPR/D study has shown the evolution of the products of H(2), CH(4), H(2)O, CO, CO(2), CH(2)CO, and CH(3)COOH from CH(3)COO decomposition between 500 and 600 K and the formation of H(2) and CO from CCOH between 600 and 700 K. However, at a coverage near one monolayer, the major species formed at 230 and 320 K are proposed to be ICH(2)COO and CH(3)COO. CH(3)COO becomes the only species present on the surface at 400 K. That is, there are two reaction pathways of ICH(2)COOH --> ICH(2)COO + H and ICH(2)COO + H --> CH(3)COO + I (possibly via CH(2)COO), which are different from those

  8. Covalent bonding of YIGSR and RGD to PEDOT/PSS/MWCNT-COOH composite material to improve the neural interface.

    Science.gov (United States)

    Wang, Kun; Tang, Rong-Yu; Zhao, Xiao-Bo; Li, Jun-Jie; Lang, Yi-Ran; Jiang, Xiao-Xia; Sun, Hong-Ji; Lin, Qiu-Xia; Wang, Chang-Yong

    2015-11-28

    The development of coating materials for neural interfaces has been a pursued to improve the electrical, mechanical and biological performances. For these goals, a bioactive coating was developed in this work featuring a poly(3,4-ethylenedioxythiophene) (PEDOT)/carbon nanotube (CNT) composite and covalently bonded YIGSR and RGD. Its biological effect and electrical characteristics were assessed in vivo on microwire arrays (MWA). The coated electrodes exhibited a significantly higher charge storage capacity (CSC) and lower electrochemical impedance at 1 kHz which are desired to improve the stimulating and recording performances, respectively. Acute neural recording experiments revealed that coated MWA possess a higher signal/noise ratio capturing spikes undetected by uncoated electrodes. Moreover, coated MWA possessed more active sites and single units, and the noise floor of coated electrodes was lower than that of uncoated electrodes. There is little information in the literature concerning the chronic performance of bioactively modified neural interfaces in vivo. Therefore in this work, chronic in vivo tests were conducted and the PEDOT/PSS/MWCNT-polypeptide coated arrays exhibited excellent performances with the highest mean maximal amplitude from day 4 to day 12 during which the acute response severely compromised the performance of the electrodes. In brief, we developed a simple method of covalently bonding YIGSR and RGD to a PEDOT/PSS/MWCNT-COOH composite improving both the biocompatibility and electrical performance of the neural interface. Our findings suggest that YIGSR and RGD modified PEDOT/PSS/MWCNT is a promising bioactivated composite coating for neural recording and stimulating.

  9. Mass spectrometry-based sequencing of protein C-terminal peptide using α-carboxyl group-specific derivatization and COOH capturing.

    Science.gov (United States)

    Nakajima, Chihiro; Kuyama, Hiroki; Tanaka, Koichi

    2012-09-15

    An approach to mass spectrometry (MS)-based sequence analysis of selectively enriched C-terminal peptide from protein is described. This approach employs a combination of the specific derivatization of α-carboxyl group (α-COOH), enzymatic proteolysis using endoproteinase GluC, and enrichment of C-terminal peptide through the use of COOH-capturing material. Highly selective derivatization of α-COOH was achieved by a combination of specific activation of α-COOH through oxazolone chemistry and amidation using 3-aminopropyltris-(2,4,6-trimethoxyphenyl)phosphonium bromide (TMPP-propylamine). This amine component was used to simplify fragmentation in tandem mass spectrometry (MS/MS) measurement, which facilitated manual sequence interpretation. The peptides produced after GluC digestion were then treated with a COOH scavenger to enrich the C-terminal peptide that is only devoid of COOH groups, and the obtained C-terminal peptide was readily sequenced by matrix-assisted laser desorption/ionization (MALDI)-MS/MS due to the TMPP mass tag.

  10. Effects of COOH+ ion implantation on hemocompatibility of polypropylene

    Institute of Scientific and Technical Information of China (English)

    LI; Dejun(李德军); NIU; Lifang(牛丽芳)

    2002-01-01

    Carboxyl ion (COOH+) implantation was performed at 50 keV with different fluences for polypropylene. Hemocompatibility tests show that blood coagulation time and recalcification time of polypropylene were enhanced significantly with the increasing fluence. At the same time, the human endothelial cells grown on the surface of the implanted samples exhibited normal cellular growth and morphology. X-ray photoelectron spectroscopy and water contact angle analysis showed that COOH+ ion implantation rearranges chemical bonds and produces some new polar O-containing groups on the surface. The formation of polar functional groups, together with increase of roughness, induced an increase in hydrophilicity, which in turn improved the surface hemocompatibility of polypropylene.

  11. Monocarbaborane anion chemistry. [COOH], [CH2OH] and [CHO] units as functional groups on ten-vertex monocarbaborane anionic compounds.

    Science.gov (United States)

    Franken, Andreas; Carr, Michael J; Clegg, William; Kilner, Colin A; Kennedy, John D

    2004-11-01

    B(10)H(14) reacts with para-C(6)H(4)(CHO)(COOH) in aqueous KOH solution to give the [nido-6-CB(9)H(11)-6-(C(6)H(4)-para-COOH)](-) anion 1, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB(9)H(9)-2-(C(6)H(4)-para-COOH)](-) anion 2. Upon heating, anion 2 rearranges to form the [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-COOH)](-) anion 3. Similarly, B(10)H(14) with glyoxylic acid OHCCOOH in aqueous KOH gives the [arachno-6-CB(9)H(13)-6-(COOH)](-) anion 4, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB(9)H(9)-2-(COOH)](-) anion 5. Upon heating, anion 5 rearranges to give the [closo-1-CB(9)H(9)-1-(COOH)](-) anion 6. Reduction of the [COOH] anions 3 and 6 with diisobutylaluminium hydride gives the [CH(2)OH] hydroxy anions [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CH(2)OH)](-) and [closo-1-CB(9)H(9)-1-(CH(2)OH)](-) 8 respectively. The [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CH(2)OH)](-) anion 7 can also be made via isomerisation of the [closo-2-CB(9)H(9)-2-(C(6)H(4)-para-CH(2)OH)](-) anion 9, in turn obtained from the [nido-6-CB(9)H(11)-6-(C(6)H(4)-para-CH(2)OH)](-) anion 10, which is obtained from the reaction of B(10)H(14) with terephthaldicarboxaldehyde, C(6)H(4)-para-(CHO)(2), in aqueous KOH solution. Oxidation of the hydroxy anions 7 and 8 with pyridinium dichromate gives the aldehydic [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CHO)](-) anion 11 and the aldehydic [closo-1-CB(9)H(9)-1-(CHO)](-) anion 12 respectively, characterised as their 2,4-dinitrophenylhydrazone derivatives, the [closo-1-CB(9)H(9)-1-C(6)H(4)-para-CH=N-NHC(6)H(3)(NO(2))(2)](-) anion 13 and the [closo-1-CB(9)H(9)-1-CH=N-NHC(6)H(3)(NO(2))(2)](-) anion respectively.

  12. DFT study on the covalent adsorption of drug carvedilol onto COOH functionalized carbon nanotubes

    Directory of Open Access Journals (Sweden)

    M. Rahbar

    2015-09-01

    Full Text Available In this work, using quantum mechanics, the interaction of drug carvedilol with (5, 5 COOH functionalized single wall carbon nanotubes (SWNT have been studied. All of the calculations have been performed using a hybrid density functional method (B3LYP in gas and solution phases. Two possible modes of covalent interaction of carvedilol onto COOH functionalized SWNT were investigated. Quantum molecular descriptors and frontier orbital analysis in the drug-nanotube systems were studied. It was found that bonding of carvedilol to COOH functionalized carbon nanotubes through hydroxyl group is stronger than amino group.

  13. Energies of the adsorption of functional groups to calcium carbonate polymorphs: the importance of -OH and -COOH groups.

    Science.gov (United States)

    Okhrimenko, D V; Nissenbaum, J; Andersson, M P; Olsson, M H M; Stipp, S L S

    2013-09-01

    The adsorption behavior of calcium carbonate is an important factor in many processes in nature, industry, and biological systems. We determined and compared the adsorption energies for a series of small molecules of different sizes and polarities (i.e., water, several alcohols, and acetic acid) on three synthetic CaCO3 polymorphs (calcite, aragonite, and vaterite). We measured isosteric heats of adsorption from vapor adsorption isotherms for 273 < T < 293 K, and we used XRD and SEM to confirm that samples did not change phase during the experiments. Density functional calculations and molecular dynamics simulations complemented the experimental results and aided interpretation. Alcohols with molecular mass greater than that of methanol bind more strongly to the calcium carbonate polymorphs than water and acetic acid. The adsorption energies for the alcohols are typical of chemisorption and indicate alcohol displacement of water from calcium carbonate surfaces. This explains why organisms favor biomolecules that contain alcohol functional groups (-OH) to control which polymorph they use, the crystal face and orientation, and the particle shape and size in biomineralization processes. This new insight is also very useful in understanding organic molecule adsorption mechanisms in soils, sediments, and rocks, which is important for predicting the behavior of mineral-fluid interactions when the challenge is to remediate contaminated groundwater aquifers or to produce oil and gas from reservoirs.

  14. Water-COOH Composite Structure with Enhanced Hydrophobicity Formed by Water Molecules Embedded into Carboxyl-Terminated Self-Assembled Monolayers.

    Science.gov (United States)

    Guo, Pan; Tu, Yusong; Yang, Jinrong; Wang, Chunlei; Sheng, Nan; Fang, Haiping

    2015-10-30

    By combining molecular dynamics simulations and quantum mechanics calculations, we show the formation of a composite structure composed of embedded water molecules and the COOH matrix on carboxyl-terminated self-assembled monolayers (COOH SAMs) with appropriate packing densities. This composite structure with an integrated hydrogen bond network inside reduces the hydrogen bonds with the water above. This explains the seeming contradiction on the stability of the surface water on COOH SAMs observed in experiments. The existence of the composite structure at appropriate packing densities results in the two-step distribution of contact angles of water droplets on COOH SAMs, around 0° and 35°, which compares favorably to the experimental measurements of contact angles collected from forty research articles over the past 25 years. These findings provide a molecular-level understanding of water on surfaces (including surfaces on biomolecules) with hydrophilic functional groups.

  15. Water-COOH Composite Structure with Enhanced Hydrophobicity Formed by Water Molecules Embedded into Carboxyl-Terminated Self-Assembled Monolayers

    Science.gov (United States)

    Guo, Pan; Tu, Yusong; Yang, Jinrong; Wang, Chunlei; Sheng, Nan; Fang, Haiping

    2015-10-01

    By combining molecular dynamics simulations and quantum mechanics calculations, we show the formation of a composite structure composed of embedded water molecules and the COOH matrix on carboxyl-terminated self-assembled monolayers (COOH SAMs) with appropriate packing densities. This composite structure with an integrated hydrogen bond network inside reduces the hydrogen bonds with the water above. This explains the seeming contradiction on the stability of the surface water on COOH SAMs observed in experiments. The existence of the composite structure at appropriate packing densities results in the two-step distribution of contact angles of water droplets on COOH SAMs, around 0° and 35°, which compares favorably to the experimental measurements of contact angles collected from forty research articles over the past 25 years. These findings provide a molecular-level understanding of water on surfaces (including surfaces on biomolecules) with hydrophilic functional groups.

  16. Movement Synchrony Forges Social Bonds Across Group Divides

    Directory of Open Access Journals (Sweden)

    Bahar eTuncgenc

    2016-05-01

    Full Text Available Group dynamics play an important role in the social interactions of both children and adults. A large amount of research has shown that merely being allocated to arbitrarily defined groups can evoke disproportionately positive attitudes toward one’s in-group and negative attitudes toward out-groups, and that these biases emerge in early childhood. This prompts important empirical questions with far-reaching theoretical and applied significance. How robust are these inter-group biases? Can biases be mitigated by behaviors known to bond individuals and groups together? How can bonds be forged across existing group divides? To explore these questions, we examined the bonding effects of interpersonal synchrony on minimally constructed groups in a controlled experiment. In-group and out-group bonding were assessed using questionnaires administered before and after a task in which groups performed movements either synchronously or non-synchronously in a between-participants design. We also developed an implicit behavioral measure, the Island Game, in which physical proximity was used as an indirect measure of interpersonal closeness. Self-report and behavioral measures showed increased bonding between groups after synchronous movement. Bonding with the out-group was significantly higher in the condition in which movements were performed synchronously than when movements were performed non-synchronously between groups. The findings are discussed in terms of their importance for the developmental social psychology of group dynamics as well as their implications for applied intervention programs.

  17. Theoretical Study on the Activity of α-COOH and β-COOH of N-Phosphoryl Aspartic Acids

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between α-COOH and β-COOH in phosphoryl aspartic acid was studied by theoretical study (Hartree-Fock and Density Functional methods) in this paper. The intermediates Ⅱ containing five-membered ring were more stable than Ⅲ with six-membered ring. While for intermediates Ⅲ, the isomers with six-membered ring in apical-equatorial spanning arrangement were more stable than those with di-equatorial spanning arrangement. At B3LYP/6-31G** level, it was shown that transition states Ⅳ and V involving α-COOH or β-COOH group had energy barriers of ΔE = 58.67 kJ·mol-1 and 103.94 kJ·mol-1, respectively. These results were in agreement with the experimental data. So the α-COOH group was involved in form of the intramolecular penta-coordinate phosphoric-carboxylic mixed anhydride intermediates, but not β-COOH group.

  18. Enhancement of interaction of L-929 cells with functionalized graphene via COOH+ ion implantation vs. chemical method

    Science.gov (United States)

    Zhao, Meng-Li; Liu, Xiao-Qi; Cao, Ye; Li, Xi-Fei; Li, De-Jun; Sun, Xue-Liang; Gu, Han-Qing; Wan, Rong-Xin

    2016-11-01

    Low hydrophilicity of graphene is one of the major obstacles for biomaterials application. To create some hydrophilic groups on graphene is addressed this issue. Herein, COOH+ ion implantation modified graphene (COOH+/graphene) and COOH functionalized graphene were designed by physical ion implantation and chemical methods, respectively. The structure and surface properties of COOH+/graphene and COOH functionalized graphene were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and contact angle measurement. Compared with graphene, COOH+/graphene and COOH functionalized graphene revealed improvement of cytocompatibility, including in vitro cell viability and morphology. More importantly, COOH+/graphene exhibited better improvement effects than functionalized graphene. For instance, COOH+/graphene with 1 × 1018 ions/cm2 showed the best cell-viability, proliferation and stretching. This study demonstrated that ion implantation can better improve the cytocompatibility of the graphene.

  19. Selenium carboxylic acids betaine; 3,3‧,3″-selenotris(propanoic acid) betaine, Se(CH2CH2COOH)2(CH2CH2COO)

    Science.gov (United States)

    Doudin, Khalid; Törnroos, Karl W.

    2017-06-01

    Attempts to prepare [Se(CH2CH2COOH)3]+Cl- from Se(CH2CH2COOH)2 and H2Cdbnd CHCOOH in concentrated hydrochloric acid, for the corresponding sulfonium salt, led exclusively to the Se-betaine, Se(CH2CH2COOH)2(CH2CH2COO). The Se-betaine crystallises in the space group P2l/c with the cell dimensions at 223 K, a = 5.5717(1), b = 24.6358(4), c = 8.4361(1) Å, β = 104.762(1)°, V = 1119.74(3) Å3, Z = 4, Dcalc = 1.763 Mgm- 3, μ = 3.364 Mm-1. The structure refined to RI = 0.0223 for 2801 reflections with Fo > 4σ(Fo). In the crystalline state the molecule is intermolecularly linked to neighbouring molecules by a number of hydrogen bonds; a very strong carboxylic-carboxylate bond with an O⋯O distance of 2.4435(16) Å, a medium strong carboxylic-carboxylate bond with an O⋯O distance of 2.6431(16) Å and several weak O⋯H(CH2) with O⋯C distances between 3.2 and 3.3 Å. In the carboxylic group involved in the very strong hydrogen bond the O⋯H bond is antiperiplanar to the Cdbnd O bond while the Osbnd H bond is periplanar to the Cdbnd O bond in the second carboxylic group. Based upon the Csbnd O bond lengths and the elongation of the Osbnd H bond involved in the strong hydrogen bond one may describe the compound as strongly linked units of Se(CH2CH2COOH)(CH2CH2COO)2 rather than Se(CH2CH2COOH)2(CH2CH2COO). The selenium atom forms two strong intramolecular 1,5-Se⋯O contacts, with a carboxylate oxygen atom, 2.9385(12) Å, and with a carboxylic oxygen atom, 2.8979(11) Å. To allow for these contacts the two organic fragments have been forced into the periplanar conformation. The molecule is only slightly asymmetric with regard to the Csbnd Sesbnd C bond angles but is very asymmetric with regard to the torsion angles.

  20. Water adsorption isotherms on CH3-, OH-, and COOH-terminated organic surfaces at ambient conditions measured with PM-RAIRS.

    Science.gov (United States)

    Tu, Aimee; Kwag, Hye Rin; Barnette, Anna L; Kim, Seong H

    2012-10-30

    The water adsorption isotherms on methyl (CH(3))-, hydroxyl (OH)-, and carboxylic acid (COOH)-terminated alkylthiol self-assembled monolayers (SAMs) on Au were studied at room temperature and ambient pressure with polarization modulation reflection-absorption infrared spectroscopy (PM-RAIRS). PM-RAIRS analysis showed that water does not adsorb at all on the CH(3)-SAM/Au at subsaturation humidity conditions. In a dry Ar environment, the OH-SAM/Au holds at least 2 layer thick strongly bound water molecules which exhibit a broad O-H stretch vibration peak centered at ∼3360 cm(-1). The peak position implies that the strongly bound water layer on the OH SAM is more like a liquid than an ice. The additional uptake of water in humid environments is relatively weak, and the peak position changes very little. Unlike the OH-SAM/Au, the COOH-SAM/Au does not have strongly bound water layer. This seems to be due to the strong hydrogen bonding between terminal COOH groups in dry conditions. The weak interactions between water and carboxyl groups at low relative humidity (RH) and the solvation of dissociated carboxylic groups in high RH lead to a type III isotherm behavior, based on the BET categories, for water adsorption on the COOH-SAM/Au. The water spectra on the COOH-SAM at RH > 45% are centered at ∼3430 cm(-1) and very broad, indicating that the hydrogen-bonding network of water on the COOH-SAM is much different from that on the OH-SAM.

  1. Preparation and theophylline delivery applications of novel PMAA/MWCNT-COOH nanohybrid hydrogels.

    Science.gov (United States)

    Zhang, Chang-Hu; Luo, Yan-Ling; Chen, Ya-Shao; Wei, Qing-Bo; Fan, Li-Hua

    2009-01-01

    A series of nanohybrid hydrogels was designed and developed based on a hydrogen bond self-assembly of poly(methacrylic acid) (PMAA) networks and carboxyl-functionalized multi-walled carbon nanotubes (MWCNT-COOH). The nanohybrid hydrogels show low micropore densities and large mesh sizes with an increase in MWCNT-COOH content. Particularly, the hydrogels containing 10 wt% MWCNT-COOH was observed to collapse at pore walls because of large holes, which is believed to be responsible for high swelling. The ability of the MWCNT-COOH to self-associate with PMAA or water molecules via hydrogen-bonding interactions and an additional electrostatic repulsion govern both pH response of the network and drug release. Increasing pH values causes equilibrium swelling ratios and accumulative release to be elevated. On the other hand, modified mechanical behavior can be obtained under a low content of the MWCNT-COOH in that the high MWCNT-COOH filling effects the formation of PMAA gel networks. Swelling and controlled release profiles of theophylline could be modulated by changing pH values, introducing the MWCNT-COOH and adjusting the proportions of the MWCNT-COOH component.

  2. Anisotropic bond percolation by position-space renormalization group

    Science.gov (United States)

    de Oliveira, Paulo Murilo

    1982-02-01

    We present a position-space renormalization-group procedure for the anisotropic bond-percolation problem in a square lattice. We use a kind of cell which preserves the geometrical features of the whole lattice, including duality. In this manner, the whole phase diagram and the dimensionality crossover exponent (both are exactly known) are reproduced for any scaling factor.

  3. Observation of water dangling OH bonds around dissolved nonpolar groups.

    Science.gov (United States)

    Perera, P N; Fega, K R; Lawrence, C; Sundstrom, E J; Tomlinson-Phillips, J; Ben-Amotz, Dor

    2009-07-28

    We report the experimental observation of water dangling OH bonds in the hydration shells around dissolved nonpolar (hydrocarbon) groups. The results are obtained by combining vibrational (Raman) spectroscopy and multivariate curve resolution (MCR), to reveal a high-frequency OH stretch peak arising from the hydration shell around nonpolar (hydrocarbon) solute groups. The frequency and width of the observed peak is similar to that of dangling OH bonds previously detected at macroscopic air-water and oil-water interfaces. The area of the observed peak is used to quantify the number of water dangling bonds around hydrocarbon chains of different length. Molecular dynamics simulation of the vibrational spectra of water molecules in the hydration shell around neopentane and benzene reveals high-frequency OH features that closely resemble the experimentally observed dangling OH vibrational bands around neopentyl alcohol and benzyl alcohol. The red-shift of approximately 50 cm(-1) induced by aromatic solutes is similar to that previously observed upon formation of a pi-H bond (in low-temperature benzene-water clusters).

  4. Methyl [13C]glucopyranosiduronic acids: effect of COOH ionization and exocyclic structure on NMR spin-couplings.

    Science.gov (United States)

    Zhang, Wenhui; Hu, Xiaosong; Carmichael, Ian; Serianni, Anthony S

    2012-11-02

    Methyl α- and β-D-glucopyranuronides singly labeled with (13)C at C1-C6 were prepared from the corresponding (13)C-labeled methyl D-glucopyranosides, and multiple NMR J-couplings (J(HH), J(CH), and J(CC)) were measured in their protonated and ionized forms in aqueous ((2)H(2)O) solution. Solvated density functional theory (DFT) calculations of J-couplings in structurally related model compounds were performed to determine how well the calculated J-couplings matched the experimental values in saccharides bearing an ionizable substituent. Intraring J(HH) values in both uronide anomers, including (3)J(H4,H5), are unaffected by solution pD, and COOH ionization exerts little effect on J(CH) and J(CC) except for (1)J(C1,H1), (1)J(C4,H4), (1)J(C5,H5), (1)J(C5,C6), and (2)J(C3,C5), where changes of up to 5 Hz were observed. Some of these changes are associated with changes in bond lengths upon ionization; in general, better agreement between theory and experiment was observed for couplings less sensitive to exocyclic C-O bond conformation. Titration of (1)H and (13)C chemical shifts, and some J-couplings, yielded a COOH pK(a) of 3.0 ± 0.1 in both anomers. DFT calculations suggest that substituents proximal to the exocyclic COOH group (i.e., the C4-O4 bond) influence the activation barrier to C5-C6 bond rotation due to transient intramolecular H-bonding. A comparison of J-couplings in the glucopyranuronides to corresponding J-couplings in the glucopyranosides showed that more pervasive changes occur upon conversion from a COOH to a CH(2)OH substituent at C6 than from COOH ionization within the uronides. Twelve J-couplings are affected, with the largest being (1)J(C5,C6) (∼18 Hz larger in the uronides), followed by (2)J(C6,H5) (∼2.5 Hz more negative in the uronides).

  5. The effects of alcohol expectancy priming on group bonding.

    Science.gov (United States)

    Moltisanti, Allison J; Below, Maureen C; Brandon, Karen O; Goldman, Mark S

    2013-12-01

    According to alcohol expectancy theory, drinking-related information is stored in memory and, when cue activated, influences alcohol-related behavior. Priming of alcohol cues and expectancies has been shown to elicit both drinking and nonconsumptive behavior associated with alcohol consumption, such as willingness to meet with a stranger and aggression. These social influence effects have been shown to be moderated by individual differences in alcohol expectancies. In the present study, we tested whether an alcohol prime would facilitate social group bonding even in the absence of consumption, and whether such group bonding would be moderated by individually held social expectancies. One hundred twenty undergraduates (75% female) completed an alcohol expectancy measure prior to participation. Participants were primed with either alcohol or neutral beverage words and completed a collaborative group activity followed by questionnaires measuring perceived group cohesion. Several interactions were found between condition and expectancy reflecting that those in the alcohol prime condition with higher social alcohol expectancies reported greater cohesion on task-related, but not emotion-related, group measures. These findings underscore the complexity of the impact of expectancy and social behavior on drinking: the priming of alcohol expectancies may activate aspects of pro-social behavior, which may influence drinking, which in turn may feedback to positively reinforce social expectancies.

  6. Packing density of HS(CH2)(n)COOH self-assembled monolayers.

    Science.gov (United States)

    Snow, A W; Jernigan, G G; Ancona, M G

    2011-12-01

    Self-assembled monolayers (SAMs) of HS(CH(2))(n)COOH, n = 5, 10, 15 deposited from ethanol solution onto gold are prepared by five approaches, and their packing densities are evaluated by X-ray photoelectron spectroscopy (XPS) measurements. The five approaches are: (1) direct deposition; (2) acetic-acid-assisted deposition; (3) butyl-amine-assisted deposition; (4) displacement of a preformed HS(CH(2))(n)CH(3) (n = 5, 10, 15) SAMs; and (5) co-deposition with HS(CH(2))(n)CH(3) (n = 5, 10, 15). Packing density metrics are calculated from measurements of SAM and substrate photoemission intensities and their attenuations by two methods. In one case the attenuated photoemissions are expressed as a ratio relative to comparable measurements on an experimental HS(CH(2))(n)CH(3) model system. In the other case a new method is introduced where a calculated attenuation based on theoretical random coil and extended chain models is used as the reference to determine a packing density fraction. Packing densities are also correlated with the S2p(Au-bonded):Au4f peak area ratios and with shifts in the C1s binding energies. SAMs prepared by the direct deposition are a partial multilayer where a second molecular layer is physisorbed onto the SAM and not removable by solvent washing. The addition of acetic acid to the deposition solution disrupts dimer associations of HS(CH(2))(n)COOH in solution and at the surface of the monolayer and yields the most ordered monolayer with the highest density of -COOH groups. The addition of butyl amine results in a labile ammonium carbonate ion pair formation but results in a lower packing density in the SAM. The displacement of the preformed HS(CH(2))(n)CH(3) SAM and the co-deposition of HS(CH(2))(n)CH(3) with HS(CH(2))(n)COOH result in SAMs with little incorporation of the -COOH component.

  7. Predictions of the fluorine NMR chemical shifts of perfluorinated carboxylic acids, CnF(2n+1)COOH (n = 6-8).

    Science.gov (United States)

    Liu, Zizhong; Goddard, John D

    2009-12-17

    Perfluorinated carboxylic acids (PFCAs) are a class of persistent environmental pollutants. Commercially available PFCAs are mixtures of linear and branched isomers, possibly with impurities. Different isomers have different physical and chemical properties and toxicities. However, little is known about the properties and the finer details of the structures of the individual branched isomers. Full geometry optimizations for the linear n-alkane (C(6)-C(27)) PFCAs indicated that all have helical structures. The helical angle increases slightly with increasing chain length, from 16.3 degrees in C(6)F(13)COOH to 17.0 degrees in C(27)F(55)COOH. This study predicts (19)F NMR parameters for 69 linear and branched isomers of the perfluoro carboxylic acids C(6)F(13)COOH, C(7)F(15)COOH, and C(8)F(17)COOH. B3LYP-GIAO/6-31++G(d,p)//B3LYP/6-31G(d,p) was used for the NMR calculations with analysis of the chemical shifts by the natural bond orbital method. The predictions of the (19)F chemical shifts revealed the differences among the CF(3), CF(2), and CF groups. In general, the absolute values for the chemical shifts for the CF(3) group are smaller than 90 ppm, for the CF larger than 160 ppm, and for the CF(2) between 110 and 130 ppm. The chemical shifts of the branched isomers are smaller in magnitude than the linear ones. The decrease is correlated with the steric hindrance of the CF(3) groups, the more hindered the CF(3), the greater the decrease in the (19)F chemical shifts. The predicted (19)F chemical shifts are similar to those for analogous perfluoro compounds with other terminal functional groups such as -SO(3)H or -SO(3)NH(2)CH(2)CH(3).

  8. Is Group Singing Special? Health, Well-Being and Social Bonds in Community-Based Adult Education Classes Group singing, well-being and social bonds

    OpenAIRE

    Pearce, E; Launay, J.; A. Machin; Dunbar, RIM

    2016-01-01

    Evidence demonstrates that group singing improves health and well-being, but the precise mechanisms remain unknown. Given that cohesive social networks also positively influence health, we focus on the social aspects of singing, exploring whether improvements in health and well-being are mediated by stronger social bonds, both to the group as a whole (collective-bonding) and to individual classmates (relational-bonding). To do so, seven newly-formed community-based adult education classes (fo...

  9. T. thermophila group I introns that cleave amide bonds

    Science.gov (United States)

    Joyce, Gerald F. (Inventor)

    1997-01-01

    The present invention relates to nucleic acid enzymes or enzymatic RNA molecules that are capable of cleaving a variety of bonds, including phosphodiester bonds and amide bonds, in a variety of substrates. Thus, the disclosed enzymatic RNA molecules are capable of functioning as nucleases and/or peptidases. The present invention also relates to compositions containing the disclosed enzymatic RNA molecule and to methods of making, selecting, and using such enzymes and compositions.

  10. Glucose Biosensor Based on Carbon/PVC-COOH/Ferrocene Composite with Covalently Immobilized Enzyme

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    A carbon/PVC-COOH/ferrocene composite electrode used for the determination of glucose has been prepared. The ferrocene acted as mediator was incorporated into the PVC-COOH polymer and the leakage could be prevented. The presence of carboxyl groups on the electrode surface allowed immobilizing enzyme via EDC and NHS. The ratio of PVC-COOH to graphite powder (w/w) has been studied. Amperometric determination of glucose has been performed at potential of 0.30 V vs SCE. The response time was < 15 s. The linear response range was of 0.1-20 mmol/L with a detection limit of 48 μmol/L.

  11. Disulfide bond formation between the COOH-terminal domain of the beta subunits and the gamma and epsilon subunits of the Escherichia coli F1-ATPase. Structural implications and functional consequences.

    Science.gov (United States)

    Aggeler, R; Haughton, M A; Capaldi, R A

    1995-04-21

    A set of mutants of the Escherichia coli F1F0-type ATPase has been generated by site-directed mutagenesis as follows: beta E381C, beta S383C, beta E381C/epsilon S108C, and beta S383C/epsilon S108C. Treatment of ECF1 isolated from any of these mutants with CuCl2 induces disulfide bond formation. For the single mutants, beta E381C and beta S383C, a disulfide bond is formed in essentially 100% yield between a beta subunit and the gamma subunit, probably at Cys87 based on the recent structure determination of F1 (Abrahams, J. P., Leslie, A. G. W., Lutter, R., and Walker, J. E. (1994) Nature 370, 621-628). In the double mutants, two disulfide bonds are formed, again in essentially full yield, one between beta and gamma, the other between a beta and the epsilon subunit via Cys108. The same two cross-links are produced with CuCl2 treatment of ECF1F0 isolated from either of the double mutants. These results show that the parts of gamma around residue 87 (a short alpha-helix) and the epsilon subunit interact with different beta subunits. The yield of covalent linkage of beta to gamma is nucleotide dependent and highest in ATP and much lower with ADP in catalytic sites. The yield of covalent linkage of beta to epsilon is also nucleotide dependent but in this case is highest in ADP and much lower in ATP. Disulfide bond formation between either beta and gamma, or beta and epsilon inhibits the ATPase activity of the enzyme in proportion to the yield of the cross-linked product. Chemical modification of the Cys at either position 381 or 383 of the beta subunit inhibits ATPase activity in a manner that appears to be dependent on the size of the modifying reagent. These results are as expected if movements of the catalytic site-containing beta subunits relative to the gamma and epsilon subunits are an essential part of the cooperativity of the enzyme.

  12. Hydrogen-bond Specific Materials Modification in Group IV Semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Tolk, Norman H. [Vanderbilt Univ., Nashville, TN (United States); Feldman, L. C. [Vanderbilt Univ., Nashville, TN (United States); Luepke, G. [College of William and Mary, Williamsburg, VA (United States)

    2015-09-14

    Executive summary Semiconductor dielectric crystals consist of two fundamental components: lattice atoms and electrons. The former component provides a crystalline structure that can be disrupted by various defects or the presence of an interface, or by transient oscillations known as phonons. The latter component produces an energetic structure that is responsible for the optical and electronic properties of the material, and can be perturbed by lattice defects or by photo-excitation. Over the period of this project, August 15, 1999 to March 31, 2015, a persistent theme has been the elucidation of the fundamental role of defects arising from the presence of radiation damage, impurities (in particular, hydrogen), localized strain or some combination of all three. As our research effort developed and evolved, we have experienced a few title changes, which reflected this evolution. Throughout the project, ultrafast lasers usually in a pump-probe configuration provided the ideal means to perturb and study semiconductor crystals by both forms of excitation, vibrational (phonon) and electronic (photon). Moreover, we have found in the course of this research that there are many interesting and relevant scientific questions that may be explored when phonon and photon excitations are controlled separately. Our early goals were to explore the dynamics of bond-selective vibrational excitation of hydrogen from point defects and impurities in crystalline and amorphous solids, initiating an investigation into the behavior of hydrogen isotopes utilizing a variety of ultrafast characterization techniques, principally transient bleaching spectroscopy to experimentally obtain vibrational lifetimes. The initiative could be divided into three related areas: (a) investigation of the change in electronic structure of solids due to the presence of hydrogen defect centers, (b) dynamical studies of hydrogen in materials and (c) characterization and stability of metastable hydrogen

  13. Primary structure of human alpha 2-macroglobulin. IV. Primary structure of two large CNBr fragments, located in the COOH-terminal part and accounting for 337 residues

    DEFF Research Database (Denmark)

    Kristensen, Torsten; Wierzbicki, D M; Sottrup-Jensen, Lars

    1984-01-01

    The amino acid sequences have been determined for two CNBr fragments of human alpha 2-macroglobulin which, due to the presence of an uncleaved Hse-Thr bond, form an Mr = 40,000 fragment. These fragments are located in the COOH-terminal part of alpha 2-macroglobulin (CB21, residues 955-1185 and CB......, residues 1186-1291). CB21 contains one glucosamine-based carbohydrate group attached to Asn-14 and one internal disulfide bridge (Cys-102 bound to Cys-150). CB21 and CB22 account for 337 of the 1451 residues of the subunit of alpha 2-macroglobulin....

  14. Hydrogen-bond Specific Materials Modification in Group IV Semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Tolk, Norman H. [Vanderbilt Univ., Nashville, TN (United States); Feldman, L. C. [Vanderbilt Univ., Nashville, TN (United States); Luepke, G. [College of William and Mary, Williamsburg, VA (United States)

    2015-09-14

    Executive summary Semiconductor dielectric crystals consist of two fundamental components: lattice atoms and electrons. The former component provides a crystalline structure that can be disrupted by various defects or the presence of an interface, or by transient oscillations known as phonons. The latter component produces an energetic structure that is responsible for the optical and electronic properties of the material, and can be perturbed by lattice defects or by photo-excitation. Over the period of this project, August 15, 1999 to March 31, 2015, a persistent theme has been the elucidation of the fundamental role of defects arising from the presence of radiation damage, impurities (in particular, hydrogen), localized strain or some combination of all three. As our research effort developed and evolved, we have experienced a few title changes, which reflected this evolution. Throughout the project, ultrafast lasers usually in a pump-probe configuration provided the ideal means to perturb and study semiconductor crystals by both forms of excitation, vibrational (phonon) and electronic (photon). Moreover, we have found in the course of this research that there are many interesting and relevant scientific questions that may be explored when phonon and photon excitations are controlled separately. Our early goals were to explore the dynamics of bond-selective vibrational excitation of hydrogen from point defects and impurities in crystalline and amorphous solids, initiating an investigation into the behavior of hydrogen isotopes utilizing a variety of ultrafast characterization techniques, principally transient bleaching spectroscopy to experimentally obtain vibrational lifetimes. The initiative could be divided into three related areas: (a) investigation of the change in electronic structure of solids due to the presence of hydrogen defect centers, (b) dynamical studies of hydrogen in materials and (c) characterization and stability of metastable hydrogen

  15. The enhanced anticoagulation for graphene induced by COOH(+) ion implantation.

    Science.gov (United States)

    Liu, Xiaoqi; Cao, Ye; Zhao, Mengli; Deng, Jianhua; Li, Xifei; Li, Dejun

    2015-01-01

    Graphene may have attractive properties for some biomedical applications, but its potential adverse biological effects, in particular, possible modulation when it comes in contact with blood, require further investigation. Little is known about the influence of exposure to COOH(+)-implanted graphene (COOH(+)/graphene) interacting with red blood cells and platelets. In this paper, COOH(+)/graphene was prepared by modified Hummers' method and implanted by COOH(+) ions. The structure and surface chemical and physical properties of COOH(+)/graphene were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and contact angle measurement. Systematic evaluation of anticoagulation, including in vitro platelet adhesion assays and hemolytic assays, proved that COOH(+)/graphene has significant anticoagulation. In addition, at the dose of 5 × 10(17) ions/cm(2), COOH(+)/graphene responded best on platelet adhesion, aggregation, and platelet activation.

  16. Influence of Reversibly Associating Side Group Bond Strength on Viscoelastic Properties of Polymer Melts

    Science.gov (United States)

    Lewis, Christopher; Stewart, Kathleen; Anthamatten, Mitchell

    2013-03-01

    Reversible hydrogen-bonding between side-groups of linear polymers can sharply influence a material's dynamic mechanical behavior, giving rise to valuable shape memory and self-healing properties. Here, we investigate how bond-strength affects the bulk rheological behavior of functional poly(n-butyl acrylate) (PBA) melts. A series of random copolymers containing three different reversibly bonding groups (aminopyridine, carboxylic acid, and ureidopyrimidinone) were synthesized to systematically vary the side-group hydrogen bond strength (~26, 40, 70 kJ/mol). The materials' volumetric hydrogen-bond energy densities can be tuned by adjusting the side-group composition. By comparing the viscoelastic behavior of materials containing an equivalent bond energy density, with different bonding groups, the efficacy and cooperativity of reversible binding can be directly examined. Melt rheology results are interpreted using a state-of-ease model that assumes continuous mechanical equilibrium between applied stress and resistive stresses of entropic origin arising from a network of reversible bonds. The authors acknowledge support from funding provided by the National Science Foundation under Grant DMR-0906627

  17. Novel Position-Space Renormalization Group for Bond Directed Percolation in Two Dimensions

    OpenAIRE

    KAYA, H.; Erzan, A.

    1998-01-01

    A new position-space renormalization group approach is investigated for bond directed percolation in two dimensions. The threshold value for the bond occupation probabilities is found to be $p_c=0.6443$. Correlation length exponents on time (parallel) and space (transverse) directions are found to be $\

  18. DFT studies of COOH tip-functionalized zigzag and armchair single wall carbon nanotubes.

    Science.gov (United States)

    Chełmecka, Elżbieta; Pasterny, Karol; Kupka, Teobald; Stobiński, Leszek

    2012-05-01

    Structure and energy calculations of pristine and COOH-modified model single wall carbon nanotubes (SWCNTs) of different length were performed at B3LYP/6-31G* level of theory. From 1 to 9 COOH groups were added at the end of the nanotube. The differences in structure and energetics of partially and fully functionalized SWCNTs at one end of the nanotube are observed. Up to nine COOH groups could be added at one end of (9,0) zigzag SWCNT in case of full functionalization. However, for (5,5) armchair SWCNT, the full functionalization was impossible due to steric crowding and rim deformation. The dependence of substituent attachment energy on the number of substituents at the carbon nanotube rim was observed.

  19. Selectivity of peptide bond dissociation on excitation of a core electron: Effects of a phenyl group

    Science.gov (United States)

    Tsai, Cheng-Cheng; Chen, Jien-Lian; Hu, Wei-Ping; Lin, Yi-Shiue; Lin, Huei-Ru; Lee, Tsai-Yun; Lee, Yuan T.; Ni, Chi-Kung; Liu, Chen-Lin

    2016-09-01

    The selective dissociation of a peptide bond upon excitation of a core electron in acetanilide and N-benzylacetamide was investigated. The total-ion-yield near-edge X-ray absorption fine structure spectra were recorded and compared with the predictions from time-dependent density functional theory. The branching ratios for the dissociation of a peptide bond are observed as 16-34% which is quite significant. This study explores the core-excitation, the X-ray photodissociation pathways, and the theoretical explanation of the NEXAFS spectra of organic molecules containing both a peptide bond and a phenyl group.

  20. Novel position-space renormalization group for bond directed percolation in two dimensions

    Science.gov (United States)

    Kaya, Hüseyin; Erzan, Ayşe

    A new position-space renormalization group approach is investigated for bond directed percolation in two dimensions. The threshold value for the bond occupation probabilities is found to be pc=0.6443. Correlation length exponents on time (parallel) and space (transverse) directions are found to be ν∥=1.719 and ν⊥=1.076, respectively, which are in very good agreement with the best-known series expansion results.

  1. Continuum in the X-Z---Y weak bonds: Z= main group elements.

    Science.gov (United States)

    Joy, Jyothish; Jose, Anex; Jemmis, Eluvathingal D

    2016-01-15

    The Continuum in the variation of the X-Z bond length change from blue-shifting to red-shifting through zero- shifting in the X-Z---Y complex is inevitable. This has been analyzed by ab-initio molecular orbital calculations using Z= Hydrogen, Halogens, Chalcogens, and Pnicogens as prototypical examples. Our analysis revealed that, the competition between negative hyperconjugation within the donor (X-Z) molecule and Charge Transfer (CT) from the acceptor (Y) molecule is the primary reason for the X-Z bond length change. Here, we report that, the proper tuning of X- and Y-group for a particular Z- can change the blue-shifting nature of X-Z bond to zero-shifting and further to red-shifting. This observation led to the proposal of a continuum in the variation of the X-Z bond length during the formation of X-Z---Y complex. The varying number of orbitals and electrons available around the Z-atom differentiates various classes of weak interactions and leads to interactions dramatically different from the H-Bond. Our explanations based on the model of anti-bonding orbitals can be transferred from one class of weak interactions to another. We further take the idea of continuum to the nature of chemical bonding in general.

  2. A facile photo-induced synthesis of COOH functionalized meso-macroporous carbon films and their excellent sensing capability for aromatic amines.

    Science.gov (United States)

    Jia, Lichao; Mane, Gurudas P; Anand, Chokkalingam; Dhawale, Dattatray S; Ji, Qingmin; Ariga, Katsuhiko; Vinu, Ajayan

    2012-09-18

    A simple photo-induced approach is developed for the preparation of COOH functionalized meso-macroporous carbon films with tunable pores without using any inorganic mesoporous silica templates, which show excellent sensing selectivity for aniline and the selectivity can be enhanced upon increasing COOH functional groups.

  3. Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes

    Science.gov (United States)

    Li, Yang; Tu, Xingchen; Wang, Minglang; Wang, Hao; Sanvito, Stefano; Hou, Shimin

    2014-11-01

    The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds.

  4. Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes

    KAUST Repository

    Li, Yang

    2014-11-07

    © 2014 AIP Publishing LLC. The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green\\'s function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds.

  5. Photo-Crosslinkable Shape-Memory Elastomers Containing Hydrogen-Bonding Side-Groups

    Science.gov (United States)

    Li, Jiahui; Lewis, Christopher; Anthamatten, Mitchell

    2010-03-01

    Lightly crosslinked poly(butyl acrylate) networks containing self-complementary hydrogen bonding side-groups (e.g. ureidopyrimidinones) can exhibit unique shape-memory effects. Conventional free-radical solution polymerization of monomer mixtures offers a simple approach to achieving these networks, but presents the following limitations: (i) the H-bonding side- group content is limited by its solubility; (ii) prepared networks can only be studied in their crosslinked form; and (iii) upon solvent removal, intrinsic stress is generated making shape-memory responses difficult to interpret. Here, photo-polymerization of linear prepolymers is reported as an approach to overcome these limitations. A series of linear poly (butyl acrylate)s containing light-sensitive benzophenone side- groups and H-bonding side-groups were prepared using free radical polymerization. These pre-polymers can be fully characterized in solution (NMR, GPC). Moreover, following solvent removal, they can be molded into any desired shape and subsequently photo-crosslinked to form shape-memory elastomers. The impact of H-bonding side-group content and the benzophenone side-group content on the mechanical properties of the photo-crosslinked polymer will be discussed. A constitutive model is also developed to interpret the mechanical response of these shape-memory elastomers.

  6. Using amino acids for the chromatofocusing of metal ions on silica with bonded tetraethylenepentamine groups

    Science.gov (United States)

    Ivanov, A. V.

    2014-09-01

    Amino acid-based eluents are used for the chromatofocusing of metal ions on Tetren-SiO2 chelating sorbent (silica with bonded tetraethylenepentamine groups) for the first time. The smoothest quasilinear pH gradients form for eluents based on glutamic and aspartic acids. The separation of Mn2+, Cr3+, Co2+, Ni2+, and Cu2+ is achieved.

  7. Coulombic amino group-metal bonding: adsorption of adenine on Cu110.

    Science.gov (United States)

    Preuss, M; Schmidt, W G; Bechstedt, F

    2005-06-17

    The interaction between molecular amino groups and metal surfaces is analyzed from first-principles calculations using the adsorption of adenine on Cu110 as a model case. The amino group nitrogens are found to adsorb on top of the surface copper atoms. However, the bonding clearly cannot be explained in terms of covalent interactions. Instead, we find it to be largely determined by mutual polarization and Coulomb interaction between substrate and adsorbate.

  8. Synthesis and Structure of [Cu(OH)2(H2O)2(4-C5H4N-COOH)2

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The hydrothermal reaction of isonicotinic acid (4-C5H4N-COOH), Cu(ClO4)2·6H2O and water at 170°C gave the title compound, [Cu(OH)2(H2O)2(4-C5H4N- COOH)2] (1), which was analyzed by single-crystal X-ray diffraction. The complex crystallizes in triclinic space group P ī with unit cell parameters: a = 6.337(2), b = 6.894(3), c = 9.178(3)?. ( = 99.40(3), ( = 105.26(3), ( = 108.17(5)°, V = 354.1(2) ?3, Z = 1, C12H16CuN2O8, Mr = 379.81, Dc = 1.791 Mg/m3, F(000) = 197, ((MoK() = 1.589 mm-1. The final R and wR are 0.068 and 0.170 for 1249 observed reflections with I ≥ 2σ(I). The central copper ion is in a distorted octahedron geometry completed by two nitrogen atoms from carboxylic ligand, two oxygen atoms from hydroxyl groups and two oxygen atoms from coordinated water molecules. The intermolecular hydrogen bonding leads to the formation of a three-dimensional supramolecular structure.

  9. Organic chemistry. Functionalization of C(sp3)-H bonds using a transient directing group.

    Science.gov (United States)

    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.

  10. Self-assembly of hydrogen-bonded two-dimensional quasicrystals

    Science.gov (United States)

    Wasio, Natalie A.; Quardokus, Rebecca C.; Forrest, Ryan P.; Lent, Craig S.; Corcelli, Steven A.; Christie, John A.; Henderson, Kenneth W.; Kandel, S. Alex

    2014-03-01

    The process of molecular self-assembly on solid surfaces is essentially one of crystallization in two dimensions, and the structures that result depend on the interplay between intermolecular forces and the interaction between adsorbates and the underlying substrate. Because a single hydrogen bond typically has an energy between 15 and 35 kilojoules per mole, hydrogen bonding can be a strong driver of molecular assembly; this is apparent from the dominant role of hydrogen bonding in nucleic-acid base pairing, as well as in the secondary structure of proteins. Carboxylic acid functional groups, which provide two hydrogen bonds, are particularly promising and reliable in creating and maintaining surface order, and self-assembled monolayers of benzoic acids produce structure that depends on the number and relative placement of carboxylic acid groups. Here we use scanning tunnelling microscopy to study self-assembled monolayers of ferrocenecarboxylic acid (FcCOOH), and find that, rather than producing dimeric or linear structures typical of carboxylic acids, FcCOOH forms highly unusual cyclic hydrogen-bonded pentamers, which combine with simultaneously formed FcCOOH dimers to form two-dimensional quasicrystallites that exhibit local five-fold symmetry and maintain translational and rotational order (without periodicity) for distances of more than 400 ångströms.

  11. Graft polymerization of styrene initiated by covalently bonded peroxide groups on silica.

    Science.gov (United States)

    Bachmann, Stefan; Wang, Hongyu; Albert, Klaus; Partch, Richard

    2007-05-01

    The graft polymerization of styrene initiated by immobilized peroxide groups was investigated. Three different types of modification reactions were used to introduce peroxide groups which are directly attached onto the surface of two different silica supports. Silanol groups were chlorinated using thionyl chloride or tetrachlorosilane. In another reaction pathway 1,3,5-benzenetricarbonyl chloride enabled the introduction of free acid chloride residues bonded onto the surface of silica. tert-Butyl hydroperoxide (TBHP) was used to transform the chlorosilyl and the acid chloride groups into peroxide residues. In a further reaction step the covalently bonded peroxides initiated the polymerization of styrene to form grafted polystyrene directly attached onto the silica support. Solid-state 13C CP/MAS NMR spectroscopy, and thermogravimetric and scanning electron microscope measurements enabled a clear structure and property elucidation of the different bonded phases. The highest amount of grafted polystyrene was achieved employing the acid chloride synthesis pathway with silica-gel, whereas modification of spherical silica only led to minor amounts of grafted polymer. The results contribute to the evolving need to understand particle surface modifications and may have positive impact on development of new HPLC stationary phases for improved elutant resolution.

  12. Desolvation penalty for burying hydrogen-bonded peptide groups in protein folding.

    Science.gov (United States)

    Baldwin, Robert L

    2010-12-16

    A novel analysis of the enthalpy of protein unfolding is proposed and used to test for a desolvation penalty when hydrogen-bonded peptide groups are desolvated via folding. The unfolding enthalpy has three components, (1) the change when peptide hydrogen bonds are broken and the exposed -CO and -NH groups are solvated, (2) the change when protein-protein van der Waals interactions are broken and replaced by protein-water van der Waals interactions, and (3) the change produced by the hydrophobic interaction when nonpolar groups in the protein interior (represented as a liquid hydrocarbon) are transferred to water. A key feature of the analysis is that the enthalpy change from the hydrophobic interaction goes through 0 at 22 °C according to the liquid hydrocarbon model. Protein unfolding enthalpies are smaller at 22 °C than the enthalpy change for unfolding an alanine peptide helix. Data in the literature indicate that the van der Waals contribution to the unfolding enthalpy is considerably larger than the unfolding enthalpy itself at 22 °C, and therefore, a sizable desolvation penalty is predicted. Such a desolvation penalty was predicted earlier from electrostatic calculations of a stabilizing interaction between water and the hydrogen-bonded peptide group.

  13. Group Classification of a General Bond-Option Pricing Equation of Mathematical Finance

    Directory of Open Access Journals (Sweden)

    Tanki Motsepa

    2014-01-01

    Full Text Available We carry out group classification of a general bond-option pricing equation. We show that the equation admits a three-dimensional equivalence Lie algebra. We also show that some of the values of the constants which result from group classification give us well-known models in mathematics of finance such as Black-Scholes, Vasicek, and Cox-Ingersoll-Ross. For all such values of these arbitrary constants we obtain Lie point symmetries. Symmetry reductions are then obtained and group invariant solutions are constructed for some cases.

  14. Tuning in to others: Exploring relational and collective bonding in singing and non-singing groups over time

    OpenAIRE

    Pearce, E; Mac Carron, P.; Launay, J.; Dunbar, RIM

    2016-01-01

    Evidence demonstrates that group singing improves health and well-being, but the precise mechanisms remain unknown. Given that cohesive social networks also positively influence health, we focus on the social aspects of singing, exploring whether improvements in health and well-being are mediated by stronger social bonds, both to the group as a whole (collective-bonding) and to individual classmates (relational-bonding). To do so, seven newly-formed community-based adult education classes (fo...

  15. Room temperature atomic layerlike deposition of ZnS on organic thin films: Role of substrate functional groups and precursors

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Zhiwei; Walker, Amy V., E-mail: amy.walker@utdallas.edu [Department of Materials Science and Engineering, University of Texas at Dallas, RL10, 800 W. Campbell Rd., Richardson, Texas 75080 (United States)

    2015-09-15

    The room temperature atomic layerlike deposition (ALLD) of ZnS on functionalized self-assembled monolayers (SAMs) was investigated, using diethyl zinc (DEZ) and in situ generated H{sub 2}S as reactants. Depositions on SAMs with three different terminal groups, –CH{sub 3,} –OH, and –COOH, were studied. It was found that the reaction of DEZ with the SAM terminal group is critical in determining the film growth rate. Little or no deposition is observed on –CH{sub 3} terminated SAMs because DEZ does not react with the methyl terminal group. ZnS does deposit on both –OH and –COOH terminated SAMs, but the grow rate on –COOH terminated SAMs is ∼10% lower per cycle than on –OH terminated SAMs. DEZ reacts with the hydroxyl group on –OH terminated SAMs, while on –COOH terminated SAMs it reacts with both the hydroxyl and carbonyl bonds of the terminal groups. The carbonyl reaction is found to lead to the formation of ketones rather than deposition of ZnS, lowering the growth rate on –COOH terminated SAMs. SIMS spectra show that both –OH and –COOH terminated SAMs are covered by the deposited ZnS layer after five ALLD cycles. In contrast to ZnO ALLD where the composition of the film differs for the first few layers on –COOH and –OH terminated SAMs, the deposited film composition is the same for both –COOH and –OH terminated SAMs. The deposited film is found to be Zn-rich, suggesting that the reaction of H{sub 2}S with the Zn-surface adduct may be incomplete.

  16. Generalization of Weber's adiabatic bond charge model to amorphous group IV semiconductors

    Science.gov (United States)

    Winer, K.; Wooten, F.

    1984-11-01

    The generalization of Weber's adiabatic bond charge model to amorphous group IV semiconductors is described. Methods of relaxing the coordinates to their equilibrium configuration and of calculating the dynamical matrix for the phonon spectra are given. Particular emphasis is given to the optimization of the Coulomb subroutines required in this model. Estimates of computation time are included for the calculation of equilibrium configuration on a Cray computer.

  17. Dichlorostannylene complexes of group 10 metals, a unique bonding mode stabilized by bridging 2-pyridyldiphenylphosphine ligands

    NARCIS (Netherlands)

    Cabon, Y.; Kleijn, H.; Siegler, M. A.; Spek, A.L.; Klein Gebbink, R.J.M.; Deelman, B.J.

    2010-01-01

    The reaction of tin dichloride with catalytically-relevant group 10 metal precursors [M(Cl)(X)(2-PyPPh2)2] (M = Ni, Pd, Pt; 2-PyPPh2 = 2-pyridyldiphenylphosphine; X = Cl, Me) provides easy access to unprecedented cationic dichlorostannylene complexes [M(X)(2-PyPPh2)2(SnCl2)]+ where the M–Sn bond is

  18. [Cd3(H2O)3((O3PCH2)2NH-CH2C6H4-COOH)2].11H2O: a layered cadmium phosphonate with reversible dehydration/hydration properties.

    Science.gov (United States)

    Bauer, Sebastian; Marrot, Jérôme; Devic, Thomas; Férey, Gérard; Stock, Norbert

    2007-11-12

    In a recent systematic study on the influence of the reaction temperature on the structure formation in the system CdCl2/H(HO3PCH2)2NH-CH2C6H4-COOH (H5L) /NaOH, [Cd3(H2O)3((O3PCH2)2NH-CH2C6H4-COOH)2].11H2O was obtained as a microcrystalline compound. We have now been able to elucidate the structure from single-crystal data: triclinic, P; a=5.4503(9), b=12.880(2), and c=16.417(3) A; alpha=67.841(6) degrees, beta=80.633(6) degrees, gamma=87.688(8) degrees, V=1052.9(3) A3; Z=1; R1=0.1143, R2=0.2108 (all data); 0.0705, 0.1823 ((I>2sigmaI)). The structure of [Cd3(H2O)3((O3PCH2)2NH-CH2C6H4-COOH)2].11H2O is built up of cadmium phosphonate layers connected by water-mediated hydrogen bonds between aryl-carboxylic acid groups and water molecules coordinated to Cd2+ ions of adjacent layers (C-OH...H2O...H2O-Cd2+). The title compound was characterized by IR spectroscopy and energy dispersive X-ray, elemental, and thermogravimetric analyses. Furthermore, temperature-dependent X-ray diffraction data are presented. [Cd3(H2O)3((O3PCH2)2NH-CH2C6H4-COOH)2].11H2O can be reversibly dehydrated, and mechanical stress and grinding in the presence of water leads to the intercalation of additional water molecules.

  19. Head rubbing and licking reinforce social bonds in a group of captive African lions, Panthera leo.

    Directory of Open Access Journals (Sweden)

    Tomoyuki Matoba

    Full Text Available Many social animals have a species-specific repertoire of affiliative behaviours that characterise individualised relationships within a group. To date, however, quantitative studies on intragroup affiliative behaviours in social carnivores have been limited. Here, we investigated the social functions of the two most commonly observed affiliative behaviours in captive African lions (Panthera leo: head rubbing and licking. We conducted behavioural observations on a captive group of lions composed of 7 males and 14 females, and tested hypotheses regarding three social functions: tension reduction, social bonding, and social status expression. Disproportionately frequent male-male and female-to-male head rubbing was observed, while more than 95% of all licking interactions occurred in female-female dyads. In accordance with the social bond hypothesis, and in disagreement with the social status expression hypothesis, both head rubbing and licking interactions were reciprocal. After controlling for spatial association, the dyadic frequency of head rubbing was negatively correlated with age difference while licking was positively correlated with relatedness. Group reunion after daily separation did not affect the frequencies of the affiliative behaviours, which was in disagreement with the predictions from the tension reduction hypothesis. These results support the social bond hypothesis for the functions of head rubbing and licking. Different patterns of affiliative behaviour between the sexes may reflect differences in the relationship quality in each sex or the differential predisposition to licking due to its original function in offspring care.

  20. Probing the bonding of CO to heteronuclear group 4 metal-nickel clusters by photoelectron spectroscopy.

    Science.gov (United States)

    Zou, Jinghan; Xie, Hua; Yuan, Qinqin; Zhang, Jumei; Dai, Dongxu; Fan, Hongjun; Tang, Zichao; Jiang, Ling

    2017-04-12

    A series of heterobinuclear group 4 metal-nickel carbonyls MNi(CO)n(-) (M = Ti, Zr, Hf; n = 3-7) has been generated via a laser vaporization supersonic cluster source and characterized by mass-selected photoelectron velocity-map imaging spectroscopy. Quantum chemical calculations have been carried out to elucidate the geometric and electronic structures and support the spectral assignments. The n = 3 cluster is determined to be capable of simultaneously accommodating three different types of CO bonds (i.e., side-on-bonded, bridging, and terminal modes), resulting in a MNi[η(2)(μ2-C, O)](μ-CO)(CO)(-) structure, which represents the smallest metal carbonyl with the involvement of all the main modes of metal-CO coordination to date. The building block of three bridging CO molecules is favored at n = 4, the structure of which persists up to n = 7. The additional CO ligands are bonded terminally to the metal atoms. The present findings provide important new insight into the structure and bonding mechanisms of CO molecules with heteronuclear transition metals, which would have important implications for understanding chemisorbed CO molecules on alloy surfaces.

  1. Influence of concentration and position of carboxyl groups on the electronic properties of single-walled carbon nanotubes.

    Science.gov (United States)

    Lara, Ivi Valentini; Zanella, Ivana; de Souza Filho, Antonio Gomes; Fagan, Solange Binotto

    2014-10-21

    The effects of attaching COOH groups at different sites and in various concentrations on electronic and structural properties of (8,0) single-walled carbon nanotubes (SWNT) were investigated using ab initio calculations. The binding energies and the charge transfers between the COOH functional groups and the tube were calculated for several configurations and a novel feature in the electronic structure of these groups was observed. The electronic character of these systems can be modulated by playing with the concentration and the position of the carboxyl groups bonded on the tube wall. The carboxyl groups bound to different carbon atom sub-lattices are more hybridized than those bound in the same one. These results suggested that SWNT-COOH systems are a playground for engineering electronic properties through a proper chemical functionalization which exploit both the attachment site and concentration of functional groups.

  2. Pigment epithelial-derived factor gene loaded novel COOH-PEG-PLGA-COOH nanoparticles promoted tumor suppression by systemic administration.

    Science.gov (United States)

    Yu, Ting; Xu, Bei; He, Lili; Xia, Shan; Chen, Yan; Zeng, Jun; Liu, Yongmei; Li, Shuangzhi; Tan, Xiaoyue; Ren, Ke; Yao, Shaohua; Song, Xiangrong

    2016-01-01

    Anti-angiogenesis has been proposed as an effective therapeutic strategy for cancer treatment. Pigment epithelium-derived factor (PEDF) is one of the most powerful endogenous anti-angiogenic reagents discovered to date and PEDF gene therapy has been recognized as a promising treatment option for various tumors. There is an urgent need to develop a safe and valid vector for its systemic delivery. Herein, a novel gene delivery system based on the newly synthesized copolymer COOH-PEG-PLGA-COOH (CPPC) was developed in this study, which was probably capable of overcoming the disadvantages of viral vectors and cationic lipids/polymers-based nonviral carriers. PEDF gene loaded CPPC nanoparticles (D-NPs) were fabricated by a modified double-emulsion water-in-oil-in-water (W/O/W) solvent evaporation method. D-NPs with uniform spherical shape had relatively high drug loading (~1.6%), probably because the introduced carboxyl group in poly (D,L-lactide-co-glycolide) terminal enhanced the interaction of copolymer with the PEDF gene complexes. An excellent in vitro antitumor effect was found in both C26 and A549 cells treated by D-NPs, in which PEDF levels were dramatically elevated due to the successful transfection of PEDF gene. D-NPs also showed a strong inhibitory effect on proliferation of human umbilical vein endothelial cells in vitro and inhibited the tumor-induced angiogenesis in vivo by an alginate-encapsulated tumor cell assay. Further in vivo antitumor investigation, carried out in a C26 subcutaneous tumor model by intravenous injection, demonstrated that D-NPs could achieve a significant antitumor activity with sharply reduced microvessel density and significantly promoted tumor cell apoptosis. Additionally, the in vitro hemolysis analysis and in vivo serological and biochemical analysis revealed that D-NPs had no obvious toxicity. All the data indicated that the novel CPPC nanoparticles were ideal vectors for the systemic delivery of PEDF gene and might be widely

  3. 2,2‧,2″-Thiotris(acetic acid) betaine, S(CH2COOH)2(CH2COO), and 2,2‧,2″-selenotris(acetic acid) betaine, Se(CH2COOH)2(CH2COO)

    Science.gov (United States)

    Doudin, Khalid; Törnroos, Karl W.

    2017-04-01

    The title compounds, X(CH2COOH)2(CH2COO), X = S, 1, and X = Se, 2, have been characterised by FTIR, NMR and MS and by their crystal structures at 123(2) K. The FTIR spectra show two major peaks, at 1396 and 1731 cm-1 in 1 and at 1390 and 1721 cm-1 in 2. The 77Se NMR signal of 2 at 325.5 ppm is 83.4 ppm downfield from the signal of Se(CH2COOH)2 indicating a substantial selenonium character of 2. The two compounds are isostructural and have a pyramidal configuration. The C-X-C bond angles range from 99.29 to 103.14° in 1 and from 97.56 to 99.87° in 2. The Xsbnd Csbnd Cdbnd O torsion angles for the three substituents are most different; one of the carboxylic acid groups attains the anti-conformation with rather short S⋯O(H) and Se⋯O(H) distances, 2.744 and 2.750 Å, the other acid group is synclinal and with longer S⋯Odbnd C and Se⋯Odbnd C distances, 3.063 and 3.090 Å, whereas the carboxylate group is in the Xsbnd Csbnd C plane with X⋯Osbnd C distances of 2.869 and 2.908 Å in 1 and 2. The presence of these strong X⋯O interactions is suggested to be the cause for the very low Bronsted basicity of this class of betaines preventing salts of the corresponding acids, the presently unknown [X(CH2COOH)3]+ - cations, to be isolated. The molecules are linked together with two fairly strong but different hydrogen bonds to the carboxylate oxygen atoms with O⋯O distances of 2.493 and 2.580 Å in 1 and 2.489 and 2.581 Å in 2 and with one X⋯Odbnd C contact, 3.244 Å in 1 and 3.209 Å in 2. The carbonyl oxygen atoms do not participate significantly in intermolecular hydrogen bonding and there are no contacts between the heteroatoms.

  4. Chemical analyses of hydroxyapatite formation on SAM surfaces modified with COOH, NH(2), CH(3), and OH functions.

    Science.gov (United States)

    Hirata, Isao; Akamatsu, Mai; Fujii, Eri; Poolthong, Suchit; Okazaki, Masayuki

    2010-08-01

    Hydroxyapatite formation was examined at the surface of self-assembled monolayers (SAMs) modified with four functional groups, -COOH, -NH(2), -CH(3), and -OH. For COOH-SAM and NH(2)-SAM, scanning electron spectroscopic observation showed that flake-like sheet crystals covered the whole wafer and small broccoli-like crystals were observed occasionally on the flake-like crystal base layer. For CH(3)-SAM and OH-SAM, no flake-like sheet crystals were observed; broccoli-like crystals were observed in a dispersed manner for CH(3)-SAM, but in localized spots for OH-SAM. X-ray diffraction patterns showed a strong apatite pattern oriented toward the c-axis direction for COOH-SAM. ESCA analysis revealed distinct Ca, P, O peaks for COOH-, NH(2)-, CH(3)-, and OH-SAM. Surface plasmon resonance (SPR) analysis indicated that during the supply of supersaturated calcium phosphate solution, the deposition of precipitates increased monotonically with time for COOH-SAM, increased slightly for NH(2)-SAM, but little increase in deposition was detected for CH(3)-SAM and OH-SAM.

  5. Oxo-group-14-element bond formation in binuclear uranium(V) Pacman complexes.

    Science.gov (United States)

    Jones, Guy M; Arnold, Polly L; Love, Jason B

    2013-07-29

    Simple and versatile routes to the functionalization of uranyl-derived U(V)-oxo groups are presented. The oxo-lithiated, binuclear uranium(V)-oxo complexes [{(py)3LiOUO}2(L)] and [{(py)3LiOUO}(OUOSiMe3)(L)] were prepared by the direct combination of the uranyl(VI) silylamide "ate" complex [Li(py)2][(OUO)(N")3] (N" = N(SiMe3)2) with the polypyrrolic macrocycle H4L or the mononuclear uranyl (VI) Pacman complex [UO2(py)(H2L)], respectively. These oxo-metalated complexes display distinct U-O single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo-stannylated complexes [{(R3Sn)OUO}2(L)] (R = nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium-oxo-group exchange occurred in reactions with [TiCl(OiPr)3] to form U-O-C bonds [{(py)3LiOUO}(OUOiPr)(L)] and [(iPrOUO)2(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements.

  6. The influence of boron doped nanodiamonds on hydrogen bonds in suspensions of protic solvents

    Science.gov (United States)

    Vervald, Alexey M.; Ekimov, Evgeny A.; Kudryavtsev, Oleg S.; Vlasov, Igor I.; Dolenko, Tatiana A.

    2016-04-01

    This work presents the results of study of the influence of BDND on hydrogen bonds of protonic solvents. In addition, the comparative analysis of the interactions of BDND and DND-COOH with solvents molecules was carried out. The analysis of temperature dependences of the quantitative characteristics of the stretching bands of OH groups of the solvents and the suspensions of NDs has shown that the BDND and DND differently weaken the hydrogen bonds in water and in water-ethanol solution with 70 vol. % ethanol content. In water-ethanol solution with 20 vol. % of ethanol the both NDs practically does not change the network of hydrogen bonds.

  7. Combustion Pathways of the Alkylated Heteroaromatics: Bond Dissociation Enthalpies and Alkyl Group Fragmentations

    Science.gov (United States)

    Hayes, Carrigan J.; Hadad, Christopher M.

    2009-04-01

    The bond dissociation enthalpies (BDEs) of the alkyl groups of the alkyl-substituted heterocycles have been studied and compiled using DFT methodology, with the intent of modeling the larger heterocyclic functionalities found in coal. DFT results were calibrated against CBS-QB3 calculations, and qualitative trends were reproduced between these methods. Loss of hydrogen at the benzylic position provided the most favorable route to radical formation, for both the azabenzenes and five-membered heterocycles. The ethyl derivatives had lower BDE values than the methyl derivatives due to increased stabilization of the corresponding radicals. Calculated spin densities correlated well with bond dissociation enthalpies for these compounds, while geometric effects were minimal with respect to the heterocycles themselves. Temperature effects on the bond dissociation enthalpies were minor, ranging by about 5 kcal/mol from 298 to 2000 K; the free energies of reaction dropped significantly over the same range due to entropic effects. Monocyclic heteroaromatic rings were seen to replicate the chemistry of multicyclic heteroaromatic systems.

  8. Confinement effects in π-bonded chains at group IV semiconductor (111) surfaces.

    Science.gov (United States)

    Bonanni, B; Bussetti, G; Violante, A; Chiaradia, P; Goletti, C

    2013-12-04

    The degree of 1D character of surface chains at group IV (111)-2 × 1 reconstructed surfaces is established by surface sensitive optical spectroscopy. Optical experiments on a diamond C(111)-2 × 1 surface show that the absorption peak related to dangling-bond transitions exhibits a marked blueshift upon oxygen exposure of the clean surface. Such behaviour is analogous to that observed on a clean Si(111)-2 × 1 surface. For both surfaces the experimental finding is interpreted in terms of quantum confinement of surface electrons in quasi-one-dimensional π-bonded chains, whose length decreases with oxygen uptake. A different behaviour is observed in Ge(111)-2 × 1, where only a very slight blueshift of the surface-state optical transition is detected upon oxidation. The almost negligible blueshift in Ge(111)-2 × 1 is consistent with a significant coupling between the π-bonded chains resulting in a much less pronounced one-dimensional character of Ge(111)-2 × 1 surface electrons compared to diamond and silicon reconstructed surfaces.

  9. NMR properties of hydrogen-bonded glycine cluster in gas phase

    Science.gov (United States)

    Carvalho, Jorge R.; da Silva, Arnaldo Machado; Ghosh, Angsula; Chaudhuri, Puspitapallab

    2016-11-01

    Density Functional Theory (DFT) calculations have been performed to study the effect of the hydrogen bond formation on the Nuclear Magnetic Resonance (NMR) parameters of hydrogen-bonded clusters of glycine molecules in gas-phase. DFT predicted isotropic chemical shifts of H, C, N and O of the isolated glycine with respect to standard reference materials are in reasonable agreement with available experimental data. The variations of isotropic and anisotropic chemical shifts for all atoms constituting these clusters containing up to four glycine molecules have been investigated systematically employing gradient corrected hybrid B3LYP functional with three different types of extended basis sets. The clusters are mainly stabilized by a network of strong hydrogen bonds among the carboxylic (COOH) groups of glycine monomers. The formation of hydrogen bond influences the molecular structure of the clusters significantly which, on the other hand, gets reflected in the variations of NMR properties. The carbon (C) atom of the sbnd COOH group, the bridging hydrogen (H) and the proton-donor oxygen (O) atom of the Osbnd H bond suffer downfield shift due to the formation of hydrogen bond. The hydrogen bond lengths and the structural complexity of the clusters are found to vary with the number of participating monomers. A direct correlation between the hydrogen bond length and isotropic chemical shift of the bridging hydrogen is observed in all cases. The individual variations of the principal axis elements in chemical shift tensor provide additional insight about the different nature of the monomers within the cluster.

  10. Average bond energies between boron and elements of the fourth, fifth, sixth, and seventh groups of the periodic table

    Science.gov (United States)

    Altshuller, Aubrey P

    1955-01-01

    The average bond energies D(gm)(B-Z) for boron-containing molecules have been calculated by the Pauling geometric-mean equation. These calculated bond energies are compared with the average bond energies D(exp)(B-Z) obtained from experimental data. The higher values of D(exp)(B-Z) in comparison with D(gm)(B-Z) when Z is an element in the fifth, sixth, or seventh periodic group may be attributed to resonance stabilization or double-bond character.

  11. Network cohesion, group size and neocortex size in female-bonded Old World primates.

    Science.gov (United States)

    Lehmann, Julia; Dunbar, R I M

    2009-12-22

    Most primates are intensely social and spend a large amount of time servicing social relationships. In this study, we use social network analysis to examine the relationship between primate group size, total brain size, neocortex ratio and several social network metrics concerned with network cohesion. Using female grooming networks from a number of Old World monkey species, we found that neocortex size was a better predictor of network characteristics than endocranial volumes. We further found that when we controlled for group size, neocortex ratio was negatively correlated with network density, connectivity, relative clan size and proportional clan membership, while there was no effect of neocortex ratio on change in connectivity following the removal of the most central female in the network. Thus, in species with larger neocortex ratios, females generally live in more fragmented networks, belong to smaller grooming clans and are members of relatively fewer clans despite living in a closely bonded group. However, even though groups are more fragmented to begin with among species with larger neocortices, the removal of the most central individual does cause groups to fall apart, suggesting that social complexity may ultimately involve the management of highly fragmented social groups while at the same time maintaining overall social cohesion. These results emphasize a need for more detailed brain data on a wider sample of primate species.

  12. Pigment epithelial-derived factor gene loaded novel COOH-PEG-PLGA-COOH nanoparticles promoted tumor suppression by systemic administration

    Directory of Open Access Journals (Sweden)

    Yu T

    2016-02-01

    Full Text Available Ting Yu,1,* Bei Xu,1,* Lili He,2 Shan Xia,3 Yan Chen,1 Jun Zeng,1 Yongmei Liu,1 Shuangzhi Li,1 Xiaoyue Tan,4 Ke Ren,1 Shaohua Yao,1 Xiangrong Song1 1State Key Laboratory of Biotherapy and Cancer Center, West China Hospital, Sichuan University, and Collaborative Innovation Center for Biotherapy, 2College of Chemistry and Environment Protection Engineering, Southwest University for Nationalities, 3Central Laboratory, Science Education Department, Chengdu Normal University, Chengdu, Sichuan, 4Department of Pathology/Collaborative Innovation Center of Biotherapy, Medical School of Nankai University, Tianjin, People’s Republic of China *These authors contributed equally to this work Abstract: Anti-angiogenesis has been proposed as an effective therapeutic strategy for cancer treatment. Pigment epithelium-derived factor (PEDF is one of the most powerful endogenous anti-angiogenic reagents discovered to date and PEDF gene therapy has been recognized as a promising treatment option for various tumors. There is an urgent need to develop a safe and valid vector for its systemic delivery. Herein, a novel gene delivery system based on the newly synthesized copolymer COOH-PEG-PLGA-COOH (CPPC was developed in this study, which was probably capable of overcoming the disadvantages of viral vectors and cationic lipids/polymers-based nonviral carriers. PEDF gene loaded CPPC nanoparticles (D-NPs were fabricated by a modified double-emulsion water-in-oil-in-water (W/O/W solvent evaporation method. D-NPs with uniform spherical shape had relatively high drug loading (~1.6%, probably because the introduced carboxyl group in poly (D,L-lactide-co-glycolide terminal enhanced the interaction of copolymer with the PEDF gene complexes. An excellent in vitro antitumor effect was found in both C26 and A549 cells treated by D-NPs, in which PEDF levels were dramatically elevated due to the successful transfection of PEDF gene. D-NPs also showed a strong inhibitory effect on

  13. Graphene Oxide Catalyzed C-H Bond Activation: The Importance Oxygen Functional Groups for Biaryl Construction

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Yongjun; Tang, Pei; Zhou, Hu; Zhang, Wei; Yang, Hanjun; Yan, Ning; Hu, Gang; Mei, Donghai; Wang, Jianguo; Ma, Ding

    2016-02-24

    A heterogeneous, inexpensive and environment-friendly carbon catalytic system was developed for the C-H bond arylation of benzene resulting in the subsequent formation of biaryl compounds. The oxygen-containing groups on these graphene oxide sheets play an essential role in the observed catalytic activity. The catalytic results of model compounds and DFT calculations show that these functional groups promote this reaction by stabilization and activation of K ions at the same time of facilitating the leaving of I. And further mechanisms studies show that it is the charge induced capabilities of oxygen groups connected to specific carbon skeleton together with the giant π-reaction platform provided by the π-domain of graphene that played the vital roles in the observed excellent catalytic activity. D. Mei acknowledges the support from the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory.

  14. Intermolecular charge flux as the origin of infrared intensity enhancement upon halogen-bond formation of the peptide group

    Science.gov (United States)

    Torii, Hajime

    2010-07-01

    The changes in the vibrational properties of the peptide group upon formation of O⋯X and N⋯X halogen bonds are studied theoretically. Calculations are carried out for complexes of N-methylacetamide (NMA), a well known model molecule of the peptide group, with halogen-containing molecules. For comparison, calculations are also carried out for some NMA-water hydrogen-bonding complexes. It is shown that the infrared (IR) intensity of the amide I mode of the peptide group is enhanced significantly (up to about 520 km mol-1 or 2.6 times) upon CO⋯X halogen-bond formation, in spite of rather modest magnitudes of the intermolecular electric field and of the changes in the CO bond length and in the amide I vibrational frequency as compared with the cases of the CO⋯H(D) hydrogen bonding. From the analysis of the changes in the dipole derivative and in the electronic structure, it is shown that this IR intensity enhancement arises from the intermolecular charge flux. For the N⋯X halogen bonding complexes, some characteristic changes in the vibrational properties are seen, among which the IR intensity enhancement of the ND out-of-plane wagging mode is most notable. The reason why such large IR intensity enhancements are seen for these particular vibrational modes is examined.

  15. Monogamy, strongly bonded groups, and the evolution of human social structure.

    Science.gov (United States)

    Chapais, Bernard

    2013-01-01

    Human social evolution has most often been treated in a piecemeal fashion, with studies focusing on the evolution of specific components of human society such as pair-bonding, cooperative hunting, male provisioning, grandmothering, cooperative breeding, food sharing, male competition, male violence, sexual coercion, territoriality, and between-group conflicts. Evolutionary models about any one of those components are usually concerned with two categories of questions, one relating to the origins of the component and the other to its impact on the evolution of human cognition and social life. Remarkably few studies have been concerned with the evolution of the entity that integrates all components, the human social system itself. That social system has as its core feature human social structure, which I define here as the common denominator of all human societies in terms of group composition, mating system, residence patterns, and kinship structures. The paucity of information on the evolution of human social structure poses substantial problems because that information is useful, if not essential, to assess both the origins and impact of any particular aspect of human society.

  16. Compression and pressure-induced amorphization of Co(OH)2 characterized by infrared vibrational spectroscopy

    Science.gov (United States)

    Nguyen, Jeffrey H.; Kruger, Michael B.; Jeanloz, Raymond

    1994-02-01

    The infrared-active (A2u) O-H vibration of Co(OH)2 decreases in frequency under hydrostatic compression to 51 GPa at 290 K. Similarly, the bond anharmonicity, determined from the ν1-->ν2 absorption-band difference, increases by more than a factor of 2 between 0 and 20 GPa. Both changes are attributed to an increase in the O-H bond length due to enhanced hydrogen bonding under pressure. The full width at half maximum (FWHM) of the fundamental absorption band increases abruptly by ~100 cm-1 at 11.2 (+/-0.3) GPa, and continues to increase at a rate of ~3.3 cm-1/GPa up to 36 GPa. Above 36 (+/-2) GPa and below the onset of amorphization, the FWHM changes at a slower rate, 0.8 (+/-0.1) cm-1/GPa. The abrupt change in FWHM is reversible on decompression, and is interpreted in terms of a pressure-induced crystal-to-glass transition exhibiting a small hysteresis compared to similar compounds. The rapid variation in FWHM above the transition pressure suggests that the amorphous structure is continuously modified between 11.3 and 36 GPa.

  17. Is group singing special? Health, well-being and social bonds in community-based adult education classes.

    Science.gov (United States)

    Pearce, Eiluned; Launay, Jacques; Machin, Anna; Dunbar, Robin I M

    Evidence demonstrates that group singing improves health and well-being, but the precise mechanisms remain unknown. Given that cohesive social networks also positively influence health, we focus on the social aspects of singing, exploring whether improvements in health and well-being are mediated by stronger social bonds, both to the group as a whole (collective-bonding) and to individual classmates (relational-bonding). To do so, seven newly-formed community-based adult education classes (four singing, N=84, and three comparison classes studying creative writing or crafts, N=51) were followed over seven months. Self-report questionnaire data on mental and physical health, well-being, and social bonding were collected at Months 1, 3 and 7. We demonstrate that physical and mental health and satisfaction with life significantly improved over time in both conditions. Path analysis did not show any indirect effects via social bonding of Condition on health and well-being. However, higher collective-bonding at timepoint 3 significantly predicted increased flourishing, reduced anxiety and improved physical health independently of baseline levels. In contrast, relational-bonding showed no such effects, suggesting that it is feeling part of a group that particularly yields health and well-being benefits. Moreover, these results indicate that singing may not improve health and well-being more than other types of activities. Nonetheless, these findings encourage further work to refine our understanding of the social aspects of community-based adult education classes in promoting health, well-being and community cohesion.

  18. Ethanol electrooxidation in alkaline medium on electrochemically synthesized Co(OH)2/Au composite

    Science.gov (United States)

    Babu, Sreejith P.; Elumalai, Perumal

    2017-01-01

    Gold (Au), cobalt hydroxide (Co(OH)2) and different Co(OH)2/Au compositions were electro-deposited onto stainless steel by a potentiodynamic method from the respective metal-ion solutions. The deposits were characterized by x-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transformed infra-red spectroscopy (FT-IR). The XRD and IR data confirmed that the deposits were Au, α-Co(OH)2 or Co(OH)2/Au composites. The SEM observations confirmed that the morphology of the Au was spherical, while the α-Co(OH)2 was flakey with pores. The morphology of the Co(OH)2/Au composites consisted of highly agglomerated Au grains distributed on the Co(OH)2 matrix. The electrocatalytic activity of each of the Au, Co(OH)2 and Co(OH)2/Au-composite electrodes towards ethanol electrooxidation in an alkaline medium was investigated by cyclic voltammetry and chronoamperometry. It turned out that the Co(OH)2/Au-composite electrodes exhibited superior catalytic activity for ethanol electrooxidation compared with the pristine Au or Co(OH)2 electrodes. A peak current density as high as 25 mA cm‑2 was exhibited by the Co(OH)2/ Au composite while the Au and Co(OH)2 showed only 0.9 and 13 mA cm‑2, respectively. The enhanced conductivity of the Co(OH)2/Au matrix due to the presence of Au, as well as the combined catalytic activity, seemed to be responsible for the superior performance of the Co(OH)2/Au-composite electrodes.

  19. The hydrogen bond stabilizing effect in enammonium salts of captodative aminoalkenes containing a carbonyl group

    Science.gov (United States)

    Fedorov, S. V.; Rulev, A. Yu; Chipanina, N. N.; Sherstyannikova, L. V.; Turchaninov, V. K.

    2004-03-01

    Enhanced stability of enammonium salts of captodative carbonyl-containing aminoalkenes as compared to the salts of simple enamines is discussed on the basis of 1H and 13C NMR, IR, UV spectroscopy and the results quantum chemical calculations. Stabilization of the N-protonated form of captodative aminoalkenes is due to either intramolecular (NH +⋯OC) or intermolecular (NH +⋯Solv or NH +⋯X -) hydrogen bonding, whereas the C-protonated form is destabilized due to umpolung of the carbon-carbon double bond. The formation of bifurcated (three-centered) hydrogen bond between the enammonium cation and the solvent is demonstrated. The three-centered solvate complex is characterized by nonclassical dependence of the chemical shift of the bridging hydrogen atom from the proton-acceptor power of the solvent.

  20. Effects of designed sulfhydryl groups and disulfide bonds into soybean proglycinin on its structural stability and heat-induced gelation.

    Science.gov (United States)

    Adachi, Motoyasu; Chunying, Ho; Utsumi, Shigeru

    2004-09-08

    The gel-forming ability of glycinin is one of soybean's most important functional properties. The proglycinin A1aB1b homotrimer was engineered to introduce sulfhydryl groups and disulfide bonds, and their effects on the structural stability and the heat-induced gelation were evaluated. On the basis of the crystal structure, five mutants were designed and prepared: R161C and F163C forming an interprotomer disulfide bond with the inherent free cysteine residue of Cys377, N116C/P248C forming a new intraprotomer disulfide bond, and N116C and P248C introducing a new sulfhydryl group. Mutants of R161C, F163C, and N116C/P248C formed a new disulfide bond as expected. N116C/P248C was significantly more stable than the wild type against chemical and thermal denaturation and more resistant to alpha-chymotrypsin digestion, whereas F163C showed significantly increased thermal stability. All mutants exhibited greater hardness of heat-induced gels than wild type, and in particular, N116C/P248C gave the hardest gel. This result indicates that it is possible to increase hardness of glycinin gel by introduction of cysteine residues using protein engineering.

  1. Elucidation of hydroxyl groups-antioxidant relationship in mono- and dihydroxyflavones based on O-H bond dissociation enthalpies.

    Science.gov (United States)

    Treesuwan, Witcha; Suramitr, Songwut; Hannongbua, Supa

    2015-06-01

    Radical scavenging potential is the key to anti-oxidation of hydroxyflavones which generally found in fruits and vegetables. The objective of this work was to investigate the influence of hydroxyl group on the O-H bond dissociation enthalpies (BDE) from a series of mono- and dihydroxyflavones. Calculation at the B3LYP/6-31G(d,p) level reveals the important roles of an additional one hydroxyl group to boost the BDE of hydroxyflavones that were a stabilization of the generated radicals through attractive H-bond interactions, an ortho- and para-dihydroxyl effect, and a presence of the 3-OH in dihydroxyflavones. On the other hand, the meta-dihydroxyl effect and range-hydroxyl effect especially associated with the either 5-OH or 8-OH promoted greater BDE. Results did not only confirm that dihydroxyflavones had lower BDE than monohydroxyflavones but also suggest the selective potent hydroxyflavone molecules that are the 6'-hydroxyflavone (for monohydroxyflavone) and the 5',6'-, 7,8- and 3',4'-dihydroxyflavone which the corresponding radical preferable generated at C6'-O•, C8-O• and C4'-O•, respectively. Electron distribution was limited only over the two connected rings of hydroxyflavones while the expansion distribution into C-ring could be enhanced if the radical was formed especially for the 2',3'- and 5',6'dihydroxyflavone radicals. The delocalized bonds were strengthened after radical was generated. However the 5-O• in 5,6-dihydroxyflavone and the 3-O• in 3,6'-dihydroxyflavone increased the bond order at C4-O11 which might interrupt the conjugated delocalized bonds at the keto group.

  2. Aryl-NHC-group 13 trimethyl complexes: structural, stability and bonding insights

    KAUST Repository

    Wu, Melissa M.

    2016-12-14

    Treatment of aromatic N-substituted N-heterocyclic carbenes (NHCs) with trimethyl-gallium and -indium yielded the new Lewis acid-base adducts, IMes·GaMe3 (1), SIMes·GaMe3 (2), IPr·GaMe3 (3), SIPr·GaMe3 (4), IMes·InMe3 (5), SIMes·InMe3 (6), IPr·InMe3 (7), and SIPr·InMe3 (8), with all complexes being identified by X-ray diffraction, IR, and multinuclear NMR analyses. Complex stability was found to be largely dependent on the nature of the constituent NHC ligands. Percent buried volume (%VBur) and topographic steric map analyses were employed to quantify and elucidate the observed trends. Additionally, a detailed bond snapping energy (BSE) decomposition analysis focusing on both steric and orbital interactions of the M-NHC bond (M = Al, Ga and In) has been performed.

  3. Conversion of a disulfide bond into a thioacetal group during echinomycin biosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Hotta, Kinya; Keegan, Ronan M.; Ranganathan, Soumya; Fang, Minyi; Bibby, Jaclyn; Winn, Martyn D.; Sato, Michio; Lian, Mingzhu; Watanabe, Kenji; Rigden, Daniel J.; Kim, Chu-Young (Liverpool); (Daresbury); (NU Singapore); (Shizuoka); (RAL)

    2013-12-02

    Echinomycin is a nonribosomal depsipeptide natural product with a range of interesting bioactivities that make it an important target for drug discovery and development. It contains a thioacetal bridge, a unique chemical motif derived from the disulfide bond of its precursor antibiotic triostin A by the action of an S-adenosyl-L-methionine-dependent methyltransferase, Ecm18. The crystal structure of Ecm18 in complex with its reaction products S-adenosyl-L-homocysteine and echinomycin was determined at 1.50 Å resolution. Phasing was achieved using a new molecular replacement package called AMPLE, which automatically derives search models from structure predictions based on ab initio protein modelling. Structural analysis indicates that a combination of proximity effects, medium effects, and catalysis by strain drives the unique transformation of the disulfide bond into the thioacetal linkage.

  4. 46 CFR Appendix F to Subpart C of... - Optional Rider for Additional NVOCC Financial Responsibility for Group Bonds [Optional Rider to...

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 9 2010-10-01 2010-10-01 false Optional Rider for Additional NVOCC Financial...—Optional Rider for Additional NVOCC Financial Responsibility for Group Bonds FMC-69A, OMB No. 3072-0018 (04/06/04) Optional Rider for Additional NVOCC Financial Responsibility for Group Bonds RIDER...

  5. Atomic force microscopy measurements reveal multiple bonds between Helicobacter pylori blood group antigen binding adhesin and Lewis b ligand.

    Science.gov (United States)

    Parreira, P; Shi, Q; Magalhaes, A; Reis, C A; Bugaytsova, J; Borén, T; Leckband, D; Martins, M C L

    2014-12-01

    The strength of binding between the Helicobacter pylori blood group antigen-binding adhesin (BabA) and its cognate glycan receptor, the Lewis b blood group antigen (Le(b)), was measured by means of atomic force microscopy. High-resolution measurements of rupture forces between single receptor-ligand pairs were performed between the purified BabA and immobilized Le(b) structures on self-assembled monolayers. Dynamic force spectroscopy revealed two similar but statistically different bond populations. These findings suggest that the BabA may form different adhesive attachments to the gastric mucosa in ways that enhance the efficiency and stability of bacterial adhesion.

  6. Carbodiimide/NHS derivatization of COOH-terminated SAMs: activation or byproduct formation?

    Science.gov (United States)

    Palazon, Francisco; Benavides, Cindy Montenegro; Léonard, Didier; Souteyrand, Éliane; Chevolot, Yann; Cloarec, Jean-Pierre

    2014-04-29

    COOH-terminated self-assembled monolayers (SAMs) are widely used in biosensor technology to bind different amine-containing biomolecules. A covalent amide bond, however, can be achieved only if the carboxylic acids are activated. This activation process usually consists of forming an N-hydroxysuccinimidyl ester (NHS-ester) by consecutively reacting carboxylic acids with a carbodiimide and NHS. Though many papers report using this method,1-8 the experimental conditions vary greatly between them and chemical characterization at this stage is often omitted. Evidence of an efficient activation is therefore rarely shown. Furthermore, recent publications9-11 have highlighted the complexity of this process, with the possible formation of different byproducts. In this paper, we have conducted a study on NHS activation under different conditions with chemical characterization by polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). Our results indicate that the nature of the solvent and carbodiimide and the reactant concentrations play crucial roles in activation kinetics and efficiency.

  7. Functional-Group-Tolerant, Silver-Catalyzed N-N Bond Formation by Nitrene Transfer to Amines.

    Science.gov (United States)

    Maestre, Lourdes; Dorel, Ruth; Pablo, Óscar; Escofet, Imma; Sameera, W M C; Álvarez, Eleuterio; Maseras, Feliu; Díaz-Requejo, M Mar; Echavarren, Antonio M; Pérez, Pedro J

    2017-02-15

    Silver(I) promotes the highly chemoselective N-amidation of tertiary amines under catalytic conditions to form aminimides by nitrene transfer from PhI═NTs. Remarkably, this transformation proceeds in a selective manner in the presence of olefins and other functional groups without formation of the commonly observed aziridines or C-H insertion products. The methodology can be applied not only to rather simple tertiary amines but also to complex natural molecules such as brucine or quinine, where the products derived from N-N bond formation were exclusively formed. Theoretical mechanistic studies have shown that this selective N-amidation reaction proceeds through triplet silver nitrenes.

  8. Studies of the binding mode of TXNHCH2COOH with calf thymus DNA by spectroscopic methods

    Science.gov (United States)

    Ataci, Nese; Arsu, Nergis

    2016-12-01

    In this study, a thioxanthone derivative named 2-(9-oxo-9H-thioxanthen-2ylamino) acetic acid (TX-NHCH2COOH) was used to investigate small molecule and DNA binding interactions. Absorption and fluorescence emission spectroscopy were used and melting studies were used to explain the binding mode of TXNHCH2COOH-DNA. Intrinsic binding constant Kb TXNHCH2COOH was found 6 × 105 M- 1from UV-Vis absorption spectroscopy. Fluorescence emmision intensity increased by adding ct-DNA to the TXNHCH2COOH and KI quenching experiments resulted with low Ksv value. Additionally, 3.7 °C increase for Tm was observed. The observed quenching of EB and ct-DNA complex and increase viscosity values of ct-DNA by addition of TXNHCH2COOH was determined. All those results indicate that TXNHCH2COOH can intercalate into DNA base pairs. Fluorescence microscopy helped to display imaging of the TXNHCH2COOH-DNA solution.

  9. Hydrogen-bond stabilized columnar discotic benzenetrisamides with pendant triphenylene groups

    NARCIS (Netherlands)

    Paraschiv, I.; Lange, de K.; Giesbers, M.; Lagen, van B.; Grozema, F.C.; Abellon, R.D.; Siebbeles, L.D.A.; Sudhölter, E.J.R.; Zuilhof, H.; Marcelis, A.T.M.

    2008-01-01

    series of 1,3,5-benzenetrisamide derivatives with three hexaalkoxytriphenylene pendant groups were prepared, in which the triphenylene groups are connected to the central 1,3,5-benzenetrisamide core through a flexible spacer. The length of this spacer, as well as the size of the ortho-substituent at

  10. Control of the intermolecular photodimerization of anthracene derivatives by hydrogen bonding of urea groups in dilute solution.

    Science.gov (United States)

    Matsumoto, Hisato; Nishimura, Yoshinobu; Arai, Tatsuo

    2016-08-04

    The photodimerization reaction of anthracene derivatives was performed by capitalizing on intermolecular hydrogen bonds. Anthracene derivatives that can control the dimerization reaction depending on the substitution site were designed by using two anthryl moieties and one urea group, referred to as N,N'-dianthracen-n-ylurea, nDAU (n = 1, 2 and 9), which are symmetrically substituted by 1-anthryl, 2-anthryl and 9-anthryl groups, respectively. We investigated the excimer emission and photodimerization reaction of these anthracene-urea derivatives using absorption, emission, and (1)H NMR spectroscopy along with fluorescence decay measurements. All derivatives showed a concentration dependence of their fluorescence spectra and multiple fluorescence lifetime components even at 10(-6) M. Significantly, 9DAU resulted in an intermolecular photodimerization reaction. These differences in photoreactivity of nDAU may depend on variations in the overlap of the intermolecularly associated anthracene rings of nDAU by hydrogen bonding between intermolecular urea moieties. Furthermore, the dimerization quantum yield of 9DAU was reduced by the addition of tetrabutylammonium acetate (TBAAc). Consequently, we revealed that the substitution site and the addition of TBAAc affected the dimerization reaction of anthracene-urea derivatives.

  11. 25 years of N-heterocyclic carbenes: activation of both main-group element-element bonds and NHCs themselves.

    Science.gov (United States)

    Würtemberger-Pietsch, Sabrina; Radius, Udo; Marder, Todd B

    2016-04-14

    N-Heterocyclic carbenes (NHCs) are widely used ligands and reagents in modern inorganic synthesis as well as in homogeneous catalysis and organocatalysis. However, NHCs are not always innocent bystanders. In the last few years, more and more examples were reported of reactions of NHCs with main-group elements which resulted in modification of the NHC. Many of these reactions lead to ring expansion and the formation of six-membered heterocyclic rings involving insertion of the heteroatom into the C-N bond and migration of hydrides, phenyl groups or boron-containing fragments. Furthermore, a few related NHC rearrangements were observed some decades ago. In this Perspective, we summarise the history of NHC ring expansion reactions from the 1960s till the present.

  12. New Anti-Corrosive Coatings with Resin-Bonded Polyaniline and Related Electroactive Groups

    Science.gov (United States)

    Weil, Edward D.

    1997-01-01

    It is already known that polyaniline (an electroactive polymer) functions as a corrosion inhibitor for steel and in view of the fact that it is known to perform in the presence of hydrochloric acid, it has been considered likely that it may be useful to NASA for protecting launch structures at KSC which are exposed to not only continual ocean-side salt spray but also to hydrochloric acid at the times that solid-fuel boosters are fired. The currently used zinc-rich silicate-bonded coating is not wholly protective against the hydrochloric acid. Water pollution from zinc salts is another concern. Other earlier and concurrent NASA sponsored projects have been focussed on polyaniline specifically. Our project, administered for NASA by Dr. K. Thompson of KSC and these more-specifically polyaniline-related projects are included in a CRADA coordinated by Dr. F. Via of Akzo Nobel. A parallel project at Polytechnic under Prof K. Levon concentrated more specifically on polyaniline with various dopants. Our exploratory project reported herein was aimed at broadening the range of such corrosion inhibitors, to give protective paint compounders a wider latitude for adding corrosion inhibitors having polyaniline-like performance, and thus we diverged in several probing directions from polyaniline. Our working hypothesis was that physical variants of polyaniline, such as supported formulations on pigments or carriers, and chemical variants of polyaniline, including those having no electroconductive character, may have enhanced anticorrosion activity. We also hypothesized that small (non-polymeric) molecules having structures related to those occurring in polyaniline, may be active as corrosion inhibitors. We did preliminary testing, using an ASTM salt spray method at a nearby commercial paint testing laboratory. Our most interesting findings were that a non-electroconductive meta-isomer of polyaniline showed some corrosion activity, suggesting that the features of the polyaniline

  13. Role of PHD fingers and COOH-terminal 30 amino acids in AIRE transactivation activity.

    Science.gov (United States)

    Meloni, Alessandra; Incani, Federica; Corda, Denise; Cao, Antonio; Rosatelli, Maria Cristina

    2008-02-01

    Autoimmune polyendocrinopathy-candidiasis-ectodermal dystrophy (APECED) is a rare autosomic autoimmune disease resulting from the defective function of a gene codifying for a transcription factor named autoimmune regulation (AIRE). The AIRE protein contains several domains among which two PHD fingers involved in the transcriptional activation. We investigated the function of the two PHD finger domains and the COOH terminal portion of AIRE by using several mutated constructs transfected in mammalian cells and a luciferase reporter assay. The results predict that the second PHD as well as the COOH terminal regions have marked transactivational properties. The COOH terminal region contains the fourth LXXLL and the PXXPXP motifs which play a critical role in mediating the transactivation capacity of the AIRE protein. Our study provides a definition of the role of the PHD fingers in transactivation and identifies a new transactivation domain of the AIRE protein localized in the COOH terminal region.

  14. Hydrothermal synthesis of porous Co(OH)2 nanoflake array film and its supercapacitor application

    Indian Academy of Sciences (India)

    Z Chen; Y Chen; C Zuo; S Zhou; A G Xiao; A X Pan

    2013-04-01

    Porous -Co(OH)2 nanoflake array film is prepared by a facile hydrothermal synthesis method. The -Co(OH)2 nanoflake array film exhibits a highly porous net-like structure composed of interconnected nanoflakes with a thickness of 15 nm. The pseudo-capacitive behaviour of the Co(OH)2 nanoflake array film is investigated by cyclic voltammograms (CV) and galvanostatic charge–discharge tests in 2MKOH. The -Co(OH)2 nanoflake array film exhibits high capacitances of 1017 F g-1 at 2Ag-1 and 890 F g-1 at 40Ag-1 as well as rather good cycling stability for supercapacitor application. The porous architecture is responsible for the enhancement of the electrochemical properties because it provides fast ion and electron transfer, large reaction surface area and good strain accommodation.

  15. Comparison between alkalimetal and group 11 transition metal halide and hydride tetramers: molecular structure and bonding.

    Science.gov (United States)

    El-Hamdi, Majid; Solà, Miquel; Frenking, Gernot; Poater, Jordi

    2013-08-22

    A comparison between alkalimetal (M = Li, Na, K, and Rb) and group 11 transition metal (M = Cu, Ag, and Au) (MX)4 tetramers with X = H, F, Cl, Br, and I has been carried out by means of the Amsterdam Density Functional software using density functional theory at the BP86/QZ4P level of theory and including relativistic effects through the ZORA approximation. We have obtained that, in the case of alkalimetals, the cubic isomer of Td geometry is more stable than the ring structure with D4h symmetry, whereas in the case of group 11 transition metal tetramers, the isomer with D4h symmetry (or D2d symmetry) is more stable than the Td form. To better understand the results obtained we have made energy decomposition analyses of the tetramerization energies. The results show that in alkalimetal halide and hydride tetramers, the cubic geometry is the most stable because the larger Pauli repulsion energies are compensated by the attractive electrostatic and orbital interaction terms. In the case of group 11 transition metal tetramers, the D4h/D2d geometry is more stable than the Td one due to the reduction of electrostatic stabilization and the dominant effect of the Pauli repulsion.

  16. The protein kinase D1 COOH terminus: marker or regulator of enzyme activity?

    Science.gov (United States)

    Qiu, Weihua; Zhang, Fan; Steinberg, Susan F

    2014-10-01

    Protein kinase D1 (PKD1) is a Ser/Thr kinase implicated in a wide variety of cellular responses. PKD1 activation is generally attributed to a PKC-dependent pathway that leads to phosphorylation of the activation loop at Ser(744)/Ser(748). This modification increases catalytic activity, including that toward an autophosphorylation site (Ser(916)) in a postsynaptic density-95/disks large/zonula occludens-1 (PDZ)-binding motif at the extreme COOH terminus. However, there is growing evidence that PKD1 activation can also result from a PKC-independent autocatalytic reaction at Ser(744)/Ser(748) and that certain stimuli increase in PKD1 phosphorylation at Ser(744)/S(748) without an increase in autophosphorylation at Ser(916). This study exposes a mechanism that results in a discrepancy between PKD1 COOH-terminal autocatalytic activity and activity toward other substrates. We show that PKD1 constructs harboring COOH-terminal epitope tags display high levels of in vitro activation loop autocatalytic activity and activity toward syntide-2 (a peptide substrate), but no Ser(916) autocatalytic activity. Cell-based studies show that the COOH-terminal tag, adjacent to PKD1's PDZ1-binding motif, does not grossly influence PKD1 partitioning between soluble and particulate fractions in resting cells or PKD1 translocation to the particulate fraction following treatment with PMA. However, a COOH-terminal tag that confers a high level of activation loop autocatalytic activity decreases the PKC requirement for agonist-dependent PKD1 activation in cells. The recognition that COOH-terminal tags alter PKD1's pharmacological profile is important from a technical standpoint. The altered dynamics and activation mechanisms for COOH-terminal-tagged PKD1 enzymes also could model the signaling properties of localized pools of enzyme anchored through the COOH terminus to PDZ domain-containing scaffolding proteins.

  17. Selective hydrogenolysis of C-O bonds using the interaction of the catalyst surface and OH groups.

    Science.gov (United States)

    Tomishige, Keiichi; Nakagawa, Yoshinao; Tamura, Masazumi

    2014-01-01

    Hydrogenolysis of C-O bonds is becoming more and more important for the production of biomass-derived chemicals. Since substrates originated from biomass usually have high oxygen content and various kinds of C-O bonds, selective hydrogenolysis is required. Rhenium or molybdenum oxide modified rhodium and iridium metal catalysts (Rh-ReO(x), Rh-MoO(x), and Ir-ReO(x)) have been reported to be effective for selective hydrogenolysis. This review introduces the catalytic performance and reaction kinetics of Rh-ReO(x), Rh-MoO(x), and Ir-ReO(x) in the hydrogenolysis of various substrates, where selectivity is especially characteristic. Based the model structure of the catalysts and the reaction mechanism, the role of the oxide components is to make the interaction between the OH groups in the substrates and the catalyst surface, and the role of metal components is to dissociate hydrogen molecule heterolytically to give hydride and proton.

  18. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock

    2014-08-01

    Full Text Available Estimating the early parent–child bonding relationship can be valuable in research and practice. Retrospective dimensional measures of parental bonding provide a means for assessing the experience of the early parent–child relationship. However, combinations of dimensional scores may provide information that is not readily captured with a dimensional approach. This study was designed to assess the presence of homogeneous groups in the population with similar profiles on parental bonding dimensions. Using a short version of the Parental Bonding Instrument (PBI, three parental bonding dimensions (care, authoritarianism, and overprotection were used to assess the presence of unobserved groups in the population using latent profile analysis. The class solutions were regressed on 23 covariates (demographics, parental psychopathology, loss events, and childhood contextual factors to assess the validity of the class solution. The results indicated four distinct profiles of parental bonding for fathers as well as mothers. Parental bonding profiles were significantly associated with a broad range of covariates. This person-centered approach to parental bonding has broad utility in future research which takes into account the effect of parent–child bonding, especially with regard to “affectionless control” style parenting.

  19. Structure, bonding and energetics of N-heterocyclic carbene (NHC) stabilized low oxidation state group 2 (Be, Mg, Ca, Sr and Ba) metal complexes: A theoretical study

    Indian Academy of Sciences (India)

    Ashim Baishya; V Rao Mundlapati; Sharanappa Nembenna; Himansu S Biswal

    2014-11-01

    A series of N-heterocyclic carbene stabilized low oxidation state group 2 metal halide and hydrides with metal-metal bonds ([L(X) M-M(X) L]; L = NHC ((CHNH)2C:), M = Be, Mg, Ca, Sr and Ba, and X = Cl or H) has been studied by computational methods. The main objective of this study is to predict whether it is possible to stabilize neutral ligated low oxidation state alkaline-earth metal complexes with metal-metal bonds. The homolytic metal-metal Bond Dissociation Energy (BDE) calculation, Natural Bond Orbital (NBO) and Energy Decomposition Analyses (EDA) on density functional theory (DFT) optimized [L(X)M-M(X)L] complexes revealed that they are as stable as their -diketiminate, guanidinate and -diimine counterparts. The optimized structures of the complexes are in trans-linear geometries. The bond order analyses such as Wiberg Bond Indices (WBI) and Fuzzi Bond Order (FBO) confirm the existence of single bond between two metal atoms, and it is covalent in nature.

  20. Exchanging Alkyl Groups through Unstrained C-C Bond Cleavage in the Presence of a Copper Catalyst.

    Science.gov (United States)

    Wada, Masaru; Noda, Yushi; Nishikata, Takashi

    2017-04-05

    Although numerous reports exist on strained C-C bond cleavage reactions in aryl substitutions, the cleavage methodology for unstrained C-C bonds in alkylation reactions has not yet been established. We found that unstrained allylic C-C bonds can be cleaved using α-radicals to form C(sp(3) )-C(sp(3) ) bonds in the presence of a copper catalyst. In this reaction, the property of leaving and loading radicals is very important for radical fragmentations. In this paper, we investigated the effects of these properties in cleavage reactions for unstrained C-C bonds.

  1. Dancing multiplicity states supported by a carboxylated group in dicopper structures bonded to O2

    KAUST Repository

    Poater, Albert

    2013-01-29

    The present study pretends to assign the correct multiplicity state to dinuclear copper complexes when interacting with free molecular oxygen. Recently, the formation of a bridge butterfly μ-η2: η2-peroxo dicopper core structure stabilized by the direct interaction of the counterion, a carboxylate group that allows the double bridge linking both metal-centre atoms, was characterized by crystallography. This system was assigned as a diradical singlet with Ms = 0. However, after new calculations it has turned out to be triplet (Ms = 1) despite the stabilization for this latter multiplicity state is not high. Here, the factors that contribute to make this structure display a multiplicity different with respect to the previously expected diradical singlet are described. In the present theoretical study, the roles of the αSp ligand constraints and the counterion are unravelled. On the other hand, the relative stability between the butterfly μ-η2: η2-peroxo structure and the isomeric bis(μ-oxo) species is also on discussion. Despite the relative stabilities of all these either structural or electronic isomeric species are supposed to depend on the computational method, which is a difficulty to reach a definite conclusion about the nature of the active species, all DFT methods using either pure or not pure DFT functionals here reach the same conclusion, favoring the triplet as the ground state for the butterfly μ-η2: η2-peroxo dicopper core structure, and the bis(μ-oxo) species when removing the benzoate counterion. © Springer-Verlag Berlin Heidelberg 2013.

  2. Hydrogen-bond acidity of OH groups in various molecular environments (phenols, alcohols, steroid derivatives, and amino acids structures): experimental measurements and density functional theory calculations.

    Science.gov (United States)

    Graton, Jérôme; Besseau, François; Brossard, Anne-Marie; Charpentier, Eloïse; Deroche, Arnaud; Le Questel, Jean-Yves

    2013-12-12

    The hydrogen-bond (H-bond) donating strengths of a series of 36 hydroxylic H-bond donors (HBDs) with N-methylpyrrolidinone have been measured in CCl4 solution by FTIR spectrometry. These data allow the definition of a H-bond acidity scale named pKAHY covering almost three pK units, corresponding to 16 kJ mol(-1). These results are supplemented by equilibrium constants determined in CH2Cl2 for one-third of the data set to study compounds showing a poor solubility in CCl4. A systematic comparison of these experimental results with theoretical data computed in the gas phase using DFT (density functional theory) calculations has also been carried out. Quantum electrostatic parameters appear to accurately describe the H-bond acidity of the hydroxyl group, whereas partial atomic charges according to the Merz-Singh-Kollman and CHelpG schemes are not suitable for this purpose. A substantial decrease of the H-bond acidity of the OH group is pointed out when the hydroxyl moiety is involved in intramolecular H-bond interactions. In such situations, the interactions are further characterized through AIM and NBO analyses, which respectively allow localizing the corresponding bond critical point and the quantification of a significant charge transfer from the available lone pair to the σ*OH antibonding orbital. Eventually, the H-bond ability of the hydroxyl groups of steroid derivatives and of lateral chains of amino acids are evaluated on the basis of experimental and/or theoretical data.

  3. Synchrotron radiation based STXM analysis and micro-XRF mapping of differential expression of extracellular thiol groups by Acidithiobacillus ferrooxidans grown on Fe(2+) and S(0).

    Science.gov (United States)

    Xia, Jin-Lan; Liu, Hong-Chang; Nie, Zhen-Yuan; Peng, An-An; Zhen, Xiang-Jun; Yang, Yun; Zhang, Xiu-Li

    2013-09-01

    The differential expression of extracellular thiol groups by Acidithiobacillus ferrooxidans grown on substrates Fe(2+) and S(0) was investigated by using synchrotron radiation based scanning transmission X-ray microscopy (STXM) imaging and microbeam X-ray fluorescence (μ-XRF) mapping. The extracellular thiol groups (SH) were first alkylated by iodoacetic acid forming Protein-SCH2COOH and then the P-SCH2COOH was marked by calcium ions forming P-SCH2COOCa. The STXM imaging and μ-XRF mapping of SH were based on analysis of SCH2COO-bonded Ca(2+). The results indicated that the thiol group content of A. ferrooxidans grown on S(0) is 3.88 times to that on Fe(2+). Combined with selective labeling of SH by Ca(2+), the STXM imaging and μ-XRF mapping provided an in situ and rapid analysis of differential expression of extracellular thiol groups.

  4. Non-additivity of Methyl Group in the Single-electron Lithium Bond of H3C…Li-H Complex

    Institute of Scientific and Technical Information of China (English)

    Zhi-feng Li; Xiao-ning Shi; Yan-zhi Liu; Hui-an Tang; Jun-yan Zhang

    2009-01-01

    The non-additivity of the methyl groups in the single-electron lithium bond was investigated using ab initio calculations at the B3LYP/6-311++G** and UMP2/6-311++G** levels. The strength of the interaction in the H3C…LiH, H3CH2C… LiH, (H3C)2HC… LiH, and (H3C)3C… LiH complexes was analyzed in term of the geometries, energies, frequency shifts, stabilization energies, charges, and topological parameters. It is shown that (H3C)3C radical with LiH forms the strongest single-electron lithium bond, followed by (H3C)2HC radical, then H3CH2.C radical, and H3C radical forms the weakest single-electron lithium bond. A positive non-additivity is present among methyl groups. Natural bond orbital and atoms in molecules analyses were used to estimate such conclusions. Furthermore, there are few linear/nonlinear relationships in the system and the interaction mode of single-electron Li-bond is different from the single-electron H-bond and single-electron halogen bond.

  5. Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C-N Bond Formation from Nonactivated Aliphatic Carboxylic Acids.

    Science.gov (United States)

    Liu, Zhao-Jing; Lu, Xi; Wang, Guan; Li, Lei; Jiang, Wei-Tao; Wang, Yu-Dong; Xiao, Bin; Fu, Yao

    2016-08-03

    Copper-catalyzed directed decarboxylative amination of nonactivated aliphatic carboxylic acids is described. This intramolecular C-N bond formation reaction provides efficient access to the synthesis of pyrrolidine and piperidine derivatives as well as the modification of complex natural products. Moreover, this reaction presents excellent site-selectivity in the C-N bond formation step through the use of directing group. Our work can be considered as a big step toward controllable radical decarboxylative carbon-heteroatom cross-coupling.

  6. Surprising Impact of Remote Groups on the Folding-Unfolding and Dimer-Chain Equilibria of Bifunctionl H-Bonding Unimers

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Rui; Cheng, Shuang; Baker, Erin Shammel; Smith, Richard D.; Zeng, Xiao Cheng; Gong, Bing

    2016-01-28

    Oligoamide 1, consisting of two H-bonding units linked by a trimethylene linker, was previously found to form a very stable, folded dimer. In this work, replacing the side chains and end groups of 1 led to derivatives that show the surprising impact of end groups on the folding and dimer-chain equilibria of the resultant molecules.

  7. Molecular interactions of different size AuNP-COOH nanoparticles with human fibrinogen.

    Science.gov (United States)

    Deng, Jun; Sun, Mingcong; Zhu, Jiyu; Gao, Changyou

    2013-09-01

    Protein adsorption influences greatly the performance of materials used in biotechnology and biomedicine. The binding of fibrinogen (Fg) to nanoparticles (NPs) can result in protein unfolding and exposure of cryptic epitopes that subsequently interact with cell surface receptors. The response and its degree are dependent on the size, charge, and concentration of the NPs. In this study the binding kinetics of human Fg to negatively charged 11-mercaptoundecanoic acid-functionalized gold nanoparticles (AuNPs-COOH) ranging from 5.6 to 64.5 nm were examined. The larger NPs bound Fg with a larger number of proteins per square unit and a higher dissociation rate (Kd'), but with decreased affinity. By contrast, the 5.6 nm AuNPs-COOH behaved in a cooperative manner for Fg adsorption. In the presence of excess Fg, only the 64.5 nm AuNPs-COOH showed severe aggregation, whose degree was alleviated in a dilute Fg solution. The Fg is adsorbed through a side-on configuration and both side-on and end-on configurations on the smaller (5.6 and 14.2 nm) and 31.5 nm AuNPs-COOH, respectively. It also retains the native conformation. By contrast, on the 64.5 nm AuNPs-COOH the Fg adopts the end-on configuration and loses most of the secondary structure.

  8. Morphological and mechanical characterization of composite calcite/SWCNT-COOH single crystals.

    Science.gov (United States)

    Calvaresi, Matteo; Falini, Giuseppe; Pasquini, Luca; Reggi, Michela; Fermani, Simona; Gazzadi, Gian Carlo; Frabboni, Stefano; Zerbetto, Francesco

    2013-08-01

    A growing number of classes of organic (macro)molecular materials have been trapped into inorganic crystalline hosts, such as calcite single crystals, without significantly disrupting their crystalline lattices. Inclusion of an organic phase plays a key role in enhancing the mechanical properties of the crystals, which are believed to share structural features with biogenic minerals. Here we report the synthesis and mechanical characterization of composite calcite/SWCNT-COOH single crystals. Once entrapped into the crystals SWCNT-COOH appeared both as aggregates of entangled bundles and nanoropes. Their observation was possible only after crystal etching, fracture or FIB (focused ion beam) cross-sectioning. SWCNT-COOHs occupied a small volume fraction and were randomly distributed into the host crystal. They did not strongly affect the crystal morphology. However, although the Young's modulus of composite calcite/SWCNT-COOH single crystals was similar to that of pure calcite their hardness increased by about 20%. Thus, SWCNT-COOHs provide an obstacle against the dislocation-mediated propagation of plastic deformation in the crystalline slip systems, in analogy with the well-known hardness increase in fiber-reinforced composites.

  9. Chronic use of the immunomodulating tripeptide feG-COOH in experimental feline asthma.

    Science.gov (United States)

    Eberhardt, Jason M; DeClue, Amy E; Reinero, Carol R

    2009-12-15

    We have previously documented that a single dose of feG-COOH prior to allergen challenge significantly decreased eosinophilic airway inflammation in cats with experimental asthma, but did not result in complete resolution of airway inflammation. This study was undertaken to determine if a chronic (2 weeks) course of feG-COOH in experimentally asthmatic cats would induce complete remission of airway inflammation and clinical signs of asthma. Experimental asthma was induced using Bermuda grass allergen (BGA) and cats were randomly selected to receive either feG-COOH (1mg/kg, PO) or saline for 2 weeks, followed by a 2-week washout period. Cats then received the alternate treatment. Aerosol challenge with BGA was performed weekly throughout the study and bronchoalveolar lavage fluid (BALF) and blood were collected prior to and after each of the 2-week treatment periods. Regular use of feG-COOH had no significant effect on airway inflammation, BALF and plasma TNF bioactivity or a clinical sign compared to placebo. Regular use of feG-COOH can thus not be recommended as the sole therapy for feline allergic asthma.

  10. Molecular interactions of different size AuNP-COOH nanoparticles with human fibrinogen

    Science.gov (United States)

    Deng, Jun; Sun, Mingcong; Zhu, Jiyu; Gao, Changyou

    2013-08-01

    Protein adsorption influences greatly the performance of materials used in biotechnology and biomedicine. The binding of fibrinogen (Fg) to nanoparticles (NPs) can result in protein unfolding and exposure of cryptic epitopes that subsequently interact with cell surface receptors. The response and its degree are dependent on the size, charge, and concentration of the NPs. In this study the binding kinetics of human Fg to negatively charged 11-mercaptoundecanoic acid-functionalized gold nanoparticles (AuNPs-COOH) ranging from 5.6 to 64.5 nm were examined. The larger NPs bound Fg with a larger number of proteins per square unit and a higher dissociation rate (Kd'), but with decreased affinity. By contrast, the 5.6 nm AuNPs-COOH behaved in a cooperative manner for Fg adsorption. In the presence of excess Fg, only the 64.5 nm AuNPs-COOH showed severe aggregation, whose degree was alleviated in a dilute Fg solution. The Fg is adsorbed through a side-on configuration and both side-on and end-on configurations on the smaller (5.6 and 14.2 nm) and 31.5 nm AuNPs-COOH, respectively. It also retains the native conformation. By contrast, on the 64.5 nm AuNPs-COOH the Fg adopts the end-on configuration and loses most of the secondary structure.

  11. Engagement of CF3 group in N-H···F-C hydrogen bond in the solution state: NMR spectroscopy and MD simulation studies.

    Science.gov (United States)

    Chaudhari, Sachin Rama; Mogurampelly, Santosh; Suryaprakash, N

    2013-01-31

    Unambiguous evidence for the engagement of CF(3) group in N-H···F-C hydrogen bond in a low polarity solvent, the first observation of its kind, is reported. The presence of such weak molecular interactions in the solution state is convincingly established by one and two-dimensional (1)H, (19)F, and natural abundant (15)N NMR spectroscopic studies. The strong and direct evidence is derived by the observation of through-space couplings, such as, (1h)J(FH), (1h)J(FN), and (2h)J(FF), where the spin polarization is transmitted through hydrogen bond. In an interesting example of a molecule containing two CF(3) groups getting simultaneously involved in hydrogen bond, where hydrogen bond mediated couplings are not reflected in the NMR spectrum, (19)F-(19)F NOESY experiment yielded confirmatory evidence. Significant deviations in the strengths of (1)J(NH), variable temperature, and the solvent induced perturbations yielded additional support. The NMR results are corroborated by both DFT calculations and MD simulations, where the quantitative information on different ways of involvement of fluorine in two and three centered hydrogen bonds, their percentage of occurrences, and geometries have been obtained. The hydrogen bond interaction energies have also been calculated.

  12. Fabrication of hierarchical -Co(OH)2 microspheres via hydrothermal process

    Indian Academy of Sciences (India)

    Guang Sheng Cao; Xiao Juan Zhang; Ling Su

    2011-07-01

    Hierarchical -Co(OH)2 microspheres with 20–50 m diameter assembled from nanoplate building blocks were successfully fabricated via a hydrothermal process in the presence of a cation surfactant cetyltrimethylammonium bromide (CTAB). The products are characterized in detail by multiform techniques: X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis. The effect of CTAB and pH value on the -Co(OH)2 morphology was also investigated. When pH value is maintained at 9, an appropriate added amount of CTAB (3 g) is the crucial prerequisite for the formation of this interesting morphology. In this experiment, pH value of the solution and the cation surfactant CTAB together results in the formation of hierarchical -Co(OH)2 microsphere structures assembled from nanoplates.

  13. Preparation of a Novel COOH Ion Implantation Sensor and Its Application

    Institute of Scientific and Technical Information of China (English)

    GAO,Dong-Mei; ZHAO,Dan-Ling; HU,Jing-Bo; LI,Qi-Long

    2008-01-01

    A novel ion implantation sensor (DNA/COOH/ITO) based on DNA immobilization in COOH/ITO probe was manufactured for the first time. The surface morphologies of the electrodes were characterized by X-ray photoelectron spectroscopy (XPS), field-emission-scanning electron microscopy (FSEM) and electrochemical methods. In a 0.5 mol/L PBS solution, a sensitive oxidation peak of DNA on the COOH/ITO electrode was obtained by voltammetry. The electrochemical behavior of DNA was studied. And the oxidative peak potential of DNA was +0.400 V (vs.Ag/AgCl). Its peak current was proportional to the concentration of DNA over the range of 1.0×10-8-1.0 ×10-6 mol/L with a detection limit of 5.0×10-9 mol/L (about 0.5 ng/mL). This sensor was applied to the direct detection of DNA samples.

  14. Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Wei [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Jiang, Ning [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Schwarz, W. H. Eugen [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Physical and Theoretical Chemistry, University of Siegen, Siegen 57068 Germany; Yang, Ping [Theoretical Division, Los Alamos National Laboratory, Los Alamos New Mexico 87545 USA; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA; Li, Jun [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA

    2017-07-11

    The geometric and electronic ground-state structures of six MS4 molecules (M = group-8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density-functional and correlated wave-function approaches. The MS4 species are compared to analogous MO4 species recently investi-gated (Inorg. Chem. 2016, 55: 4616). Metal oxidation state (MOS) of high value VIII appears in low- spin singlet Td geometric species (Os,Hs)S4 and (Ru,Os,Hs)O4, whereas low MOS=II appears in high- spin septet D2d species Fe(S2)2 and (slightly excited) metastable Fe(O2)2. The ground states of all other molecules have intermediate MOS values, containing S2-, S22-, S21- (and resp. O2--, O1-, O22-, O21-) ligands, bonded by ionic, covalent and correlative contributions.

  15. Carbon-carbon bond formation involving reactions of alkynes with group 9 metals (Ir, Rh, Co): preparation of conjugated olefins.

    Science.gov (United States)

    Chin, Chong Shik; Won, Gyongshik; Chong, Daesung; Kim, Mieock; Lee, Hyungeui

    2002-04-01

    Stable alkynyl complexes of iridium(III) (L(n)Ir-triple bond-R) that are prepared from the reactions of terminal alkynes readily undergo the intramolecular C-C bond-forming reactions between the alkynyl and adjacent hydrocarbyl ligands to yield conjugated olefins. These reactions are initiated by electrophiles (H(+), Me(+)) that attack the beta carbon of the alkynyl ligand to increase the electrophilicity of the alpha carbon of the alkynyl ligand. The C-C bond is then formed between the alpha carbons of the alkynyl and adjacent hydrocarbyl ligands.

  16. Effect of pressure on methylated glycine derivatives: relative roles of hydrogen bonds and steric repulsion of methyl groups.

    Science.gov (United States)

    Kapustin, Eugene A; Minkov, Vasily S; Boldyreva, Elena V

    2014-06-01

    Infinite head-to-tail chains of zwitterions present in the crystals of all amino acids are known to be preserved even after structural phase transitions. In order to understand the role of the N-H...O hydrogen bonds linking zwitterions in these chains in structural rearrangements, the crystal structures of the N-methyl derivatives of glycine (N-methylglycine, or sarcosine, with two donors for hydrogen bonding; two polymorphs of N,N-dimethylglycine, DMG-I and DMG-II, with one donor for hydrogen bond; and N,N,N-trimethylglycine, or betaine, with no hydrogen bonds) were studied at different pressures. Methylation has not only excluded the formation of selected hydrogen bonds, but also introduced bulky mobile fragments into the structure. The effects of pressure on the systems of the series were compared with respect to distorting and switching over hydrogen bonds and inducing reorientation of the methylated fragments. Phase transitions with fragmentation of the single crystals into fine powder were observed for partially methylated N-methyl- and N,N-dimethylglycine, whereas the structural changes in betaine were continuous with some peculiar features in the 1.4-2.9 GPa pressure range and accompanied by splitting of the crystals into several large fragments. Structural rearrangements in sarcosine and betaine were strongly dependent on the rate of pressure variation: the higher the rate of increasing pressure, the lower the pressure at which the phase transition occurred.

  17. Sphingolipid-dependent fusion of Semliki Forest virus with cholesterol-containing liposomes requires both the 3-hydroxyl group and the double bond of the sphingolipid backbone

    DEFF Research Database (Denmark)

    Corver, J; Moesby, Lise; Erukulla, R K;

    1995-01-01

    , we demonstrate that sphingolipid-dependent fusion of SFV with cholesterol-containing liposomes exhibits remarkable molecular specificity, the 3-hydroxyl group and the 4,5-trans carbon-carbon double bond of the sphingosine backbone being critical for the sphingolipid to mediate the process...

  18. Atmospheric chemistry of CF3COOH. Kinetics of the reaction with OH radicals

    DEFF Research Database (Denmark)

    Møgelberg, T.E.; Nielsen, O.J.; Sehested, J.;

    1994-01-01

    Two different experimental techniques were used to study the kinetics of the reaction of OH radicals with trifluoroacetic acid, CF3COOH. Using a pulse radiolysis absolute rate technique, rate constants at 315 and 348 K were determined to be (1.6 +/- 0.4) x 10(-13) and (1.5 +/- 0.2) x 10(-13) cm3...

  19. MATE1 has an external COOH terminus, consistent with a 13-helix topology.

    Science.gov (United States)

    Zhang, Xiaohong; Wright, Stephen H

    2009-08-01

    The mammalian members of the Multidrug And Toxin Extruder family, i.e., MATE1 and MATE2-K, are suspected of mediating the luminal step in renal secretion of organic cations. The 1,000+ prokaryotic/fungal/plant MATE family members are predicted to have 12 transmembrane helices (TMHs), whereas MATE1/2-K appear to have an additional (13th) COOH-terminal helix. Here, we determined whether rabbit MATE1 has an external COOH terminus, consistent with the presence of 13 TMHs. A V5 epitope tag at the COOH terminus of MATE1 was freely accessible to external V5 antibody, whereas tags at the NH(2) terminus, or at sites of truncation within the long cytoplasmic loop between predicted TMHs 12 and 13, were only accessible to the V5 antibody following permeabilization of the membrane. The truncated mutants that lacked TMH13 still retained transport activity, indicating that the terminal helix was not necessary for transport function. Cells that expressed a mutant lacking only TMH13 displayed similar K(t) and J(max) values to those of the full-length protein, although when normalized to protein expressed at the plasma membrane, the transport rate of the mutant was COOH terminus was freely accessible to maleimide biotin. These data are consistent with a mammalian MATE topology that includes 13 TMHs and indicate that the terminal TMH, although not necessary for transport function, may influence the turnover characteristics of the transporter.

  20. Hydrogen atoms in acetylsalicylic acid (Aspirin): the librating methyl group and probing the potential well in the hydrogen-bonded dimer

    Science.gov (United States)

    Wilson, Chick C.

    2001-02-01

    The structure of acetylsalicylic acid (2-(acetoyloxy)benzoic acid; Aspirin) has been studied by variable temperature single crystal neutron diffraction. The usual large torsional librational motion of the terminal methyl group is observed and its temperature dependence analysed using a simple model for the potential, yielding the force constant and barrier height for this motion. In addition, asymmetry of the scattering density of the proton involved in the hydrogen bond forming the carboxylic acid dimer motif is observed at temperatures above 200 K. This asymmetry is discussed in terms of its possible implications for the shape of the hydrogen bonding potential well.

  1. Exploring the intermediates of photochemical CO2 reduction: reaction of Re(dmb)(CO)3 COOH with CO2.

    Science.gov (United States)

    Agarwal, Jay; Sanders, Brian C; Fujita, Etsuko; Schaefer, Henry F; Harrop, Todd C; Muckerman, James T

    2012-07-11

    We have investigated the reaction of Re(dmb)(CO)(3)COOH with CO(2) using density functional theory, and propose a mechanism for the production of CO. This mechanism supports the role of Re(dmb)(CO)(3)COOH as a key intermediate in the formation of CO. Our new experimental work supports the proposed scheme.

  2. The Escherichia coli subtilase cytotoxin A subunit specifically cleaves cell-surface GRP78 protein and abolishes COOH-terminal-dependent signaling.

    Science.gov (United States)

    Ray, Rupa; de Ridder, Gustaaf G; Eu, Jerry P; Paton, Adrienne W; Paton, James C; Pizzo, Salvatore V

    2012-09-21

    GRP78, a molecular chaperone with critical endoplasmic reticulum functions, is aberrantly expressed on the surface of cancer cells, including prostate and melanoma. Here it functions as a pro-proliferative and anti-apoptotic signaling receptor via NH(2)-terminal domain ligation. Auto-antibodies to this domain may appear in cancer patient serum where they are a poor prognostic indicator. Conversely, GRP78 COOH-terminal domain ligation is pro-apoptotic and anti-proliferative. There is no method to disrupt cell-surface GRP78 without compromising the total GRP78 pool, making it difficult to study cell-surface GRP78 function. We studied six cell lines representing three cancer types. One cell line per group expresses high levels of cell-surface GRP78, and the other expresses low levels (human hepatoma: Hep3B and HepG2; human prostate cancer: PC3 and 1-LN; murine melanoma: B16F0 and B16F1). We investigated the effect of Escherichia coli subtilase cytoxin catalytic subunit (SubA) on GRP78. We report that SubA specifically cleaves cell-surface GRP78 on HepG2, 1-LN, and B16F1 cells without affecting intracellular GRP78. B16F0 cells (GRP78(low)) have lower amounts of cleaved cell-surface GRP78. SubA has no effect on Hep3B and PC3 cells. The predicted 28-kDa GRP78 COOH-terminal fragment is released into the culture medium by SubA treatment, and COOH-terminal domain signal transduction is abrogated, whereas pro-proliferative signaling mediated through NH(2)-terminal domain ligation is unaffected. These experiments clarify cell-surface GRP78 topology and demonstrate that the COOH-terminal domain is necessary for pro-apoptotic signal transduction occurring upon COOH-terminal antibody ligation. SubA is a powerful tool to specifically probe the functions of cell-surface GRP78.

  3. Hydrogen-bonded clusters of ferrocenecarboxylic acid on Au(111).

    Science.gov (United States)

    Quardokus, Rebecca C; Wasio, Natalie A; Christie, John A; Henderson, Kenneth W; Forrest, Ryan P; Lent, Craig S; Corcelli, Steven A; Kandel, S Alex

    2014-09-14

    Self-assembled monolayers of ferrocenecarboxylic acid (FcCOOH) contain two fundamental units, both stabilized by intermolecular hydrogen bonding: dimers and cyclic five-membered catemers. At surface coverages below a full monolayer, however, there is a significantly more varied structure that includes double-row clusters containing two to twelve FcCOOH molecules. Statistical analysis shows a distribution of cluster sizes that is sharply peaked compared to a binomial distribution. This rules out simple nucleation-and-growth mechanisms of cluster formation, and strongly suggests that clusters are formed in solution and collapse into rows when deposited on the Au(111) surface.

  4. Is THC-COOH-glucuronide a useful marker for Tetrahydrocannabinol (THC) in DUID cases?

    DEFF Research Database (Denmark)

    Telving, Rasmus; Hasselstrøm, Jørgen Bo; Andreasen, Mette Findal

    Is THC-COOH-glucuronide a useful marker for Tetrahydrocannabinol (THC) in DUID cases? Retrospective data analysis on UPLC-HR-TOFMS data files from 2 years of DUID cases. Telving R.(rt@forens.au.dk)*, Hasselstrøm J.B., Andreasen M.F. Department of Forensic Medicine, Aarhus University (Denmark......). Introduction The physical and chemical nature of THC makes it difficult to include in traditional screening procedures along with other common legal and illegal drugs. Development of multi-component toxicological screening procedures that include THC is therefore a challenge but also highly desirable in high...... throughput laboratories. Aims The aim of the present study was to evaluate the detection of THC indirectly by detecting the presence of THC-COOH-glucuronide in whole blood from individuals suspected of driving under the influence of drugs (DUID). We will compare existing data from THC screening...

  5. Formation of amide bonds without a condensation agent and implications for origin of life.

    Science.gov (United States)

    Keller, M; Blöchl, E; Wächtershäuser, G; Stetter, K O

    1994-04-28

    Amide bonds are of central importance for biochemistry; in the guise of peptide bonds, they form the backbone of proteins. The formation of amide bonds without the assistance of enzymes poses a major challenge for theories of the origin of life. Enzyme-free formation of amide bonds between amino acids has been demonstrated in the presence of condensing agents such as cyanamide. Here we report the formation of amide bonds in aqueous solution in the absence of any condensing agent. We find that the formation of pyrite (FeS2) from FeS and H2S can provide the driving force for reductive acetylation of amino acids with mercaptoacetic acid (HSCH2COOH). The redox energy of pyrite formation permits the activation of the carboxylic acid group, which is converted to a species that reacts readily with amines. This process provides support for the chemo-autotrophic theory for the origin of life, in which pyrite formation supplies the energy source for the first autocatalytic reproduction cycle.

  6. Zero-Coupon bond pricing模型的最优系统与群不变解%An optimal system and group-invariant solutions of the Zero-Coupon bond pricing models

    Institute of Scientific and Technical Information of China (English)

    张颖; 高雯

    2009-01-01

    Lie group theory is applied to differential equations occurring as mathematical models in financial problems. The Zero-Coupon bond pricing models are studied. Its one-parameter Lie point symmetries and corresponding group of adjoint representations are obtained. An optimal system of one-dimensional subalgebra is derived and used to construct distinct families of special closed-form solutions of the equation.%将李群理论用于金融问题中出现的数学模型的微分方程,研究了Zero-Coupon bond pricing模型.求出了该模型的单参数李点对称及它相应的群伴随表达式,由此求得该模型允许的一维李群的子代数的最优系统并且利用最优系统构造该模型相应的微分方程的一些特殊的不同类的闭解.

  7. Intriguing Influence of -COOH-Driven Intermolecular Aggregation and Acid-Base Interactions with N,N-Dimethylformamide on the Second-Order Nonlinear-Optical Response of 5,15 Push-Pull Diarylzinc(II) Porphyrinates.

    Science.gov (United States)

    Orbelli Biroli, Alessio; Tessore, Francesca; Righetto, Stefania; Forni, Alessandra; Macchioni, Alceo; Rocchigiani, Luca; Pizzotti, Maddalena; Di Carlo, Gabriele

    2017-06-05

    A series of 5,15 push-pull meso-diarylzinc(II) porphyrinates, carrying one or two -COOH or -COOCH3 acceptor groups and a -OCH3 or a -N(CH3)2 donor group, show in N,N-dimethylformamide and CHCl3 solutions a negative and solvent-dependent second-order nonlinear-optical (NLO) response measured by the electric-field-induced second-harmonic generation (EFISH) technique, different from the structurally related zinc(II) porphyrinate carrying a -N(CH3)2 donor group and a -NO2 acceptor group, where a still solvent-dependent but positive EFISH second-order response was previously reported. Moreover, when a -N(CH3)2 donor group and a -COOH acceptor group are part of a sterically hindered 2,12 push-pull β-pyrrolic-substituted tetraarylzinc(II) porphyrinate, the EFISH response is positive and solvent-independent. In order to rationalize these rather intriguing series of observations, EFISH measurements have been integrated by electronic absorption and IR spectroscopic investigations and by density functional theory (DFT) and coupled-perturbed DFT theoretical and (1)H pulsed-gradient spin-echo NMR investigations, which prompt that the significant concentration effects and the strong influence of the solvent nature on the NLO response are originated by a complex whole of different aggregation processes induced by the -COOH group.

  8. Identification and characterization of functionally important elements in the multidrug resistance protein 1 COOH-terminal region.

    Science.gov (United States)

    Westlake, Christopher J; Payen, Lea; Gao, Mian; Cole, Susan P C; Deeley, Roger G

    2004-12-17

    The ATP binding cassette (ABC) transporter, multidrug resistance protein 1 (MRP1/ABCC1), transports a broad spectrum of conjugated and unconjugated compounds, including natural product chemotherapeutic agents. In this study, we have investigated the importance of the COOH-terminal region of MRP1 for transport activity and basolateral plasma membrane trafficking. The COOH-terminal regions of some ABCC proteins have been implicated in protein trafficking, but the function of this region of MRP1 has not been defined. In contrast to results obtained with other ABCC proteins, we found that the COOH-proximal 30 amino acids of MRP1 can be removed without affecting trafficking to basolateral membranes. However, the truncated protein is inactive. Furthermore, removal of as few as 4 COOH-terminal amino acids profoundly decreases transport activity. Although amino acid sequence conservation of the COOH-terminal regions of ABC proteins is low, secondary structure predictions indicate that they consist of a broadly conserved helix-sheet-sheet-helix-helix structure. Consistent with a conservation of secondary and tertiary structure, MRP1 hybrids containing the COOH-terminal regions of either the homologous MRP2 or the distantly related P-glycoprotein were fully active and trafficked normally. Using mutated proteins, we have identified structural elements containing five conserved hydrophobic amino acids that are required for activity. We show that these are important for binding and hydrolysis of ATP by nucleotide binding domain 2. Based on crystal structures of several ABC proteins, we suggest that the conserved amino acids may stabilize a helical bundle formed by the COOH-terminal three helices and may contribute to interactions between the COOH-terminal region and the protein's two nucleotide binding domains.

  9. Thrombin-cleaved COOH(-) terminal osteopontin peptide binds with cyclophilin C to CD147 in murine breast cancer cells.

    Science.gov (United States)

    Mi, Zhiyong; Oliver, Tim; Guo, Hongtao; Gao, Chengjiang; Kuo, Paul C

    2007-05-01

    Osteopontin is a glycoprotein that has been linked to metastatic function in breast, lung, and prostate cancers. However, the mechanism by which osteopontin acts to induce metastatic properties is largely unknown. One intriguing feature of osteopontin is the presence of a conserved thrombin cleavage site that is COOH-terminal from a well-characterized RGD domain. Although the COOH-terminal fragment may bind to cell surface CD44 receptors, little is known about the COOH-terminal osteopontin fragment. In the current study, we use the murine mammary epithelial tumor cell lines 4T1 and 4T07; these cells are thioguanine-resistant sublines derived from the parental population of 410.4 cells from Balb/cfC3H mice. Using flow cytometry and Forster resonance energy transfer, we show that the COOH-terminal fragment of osteopontin binds with another marker of metastatic function (cyclophilin C or rotamase) to the CD147 cell surface glycoprotein (also known as extracellular matrix metalloproteinase inducer), to activate Akt1/2 and matrix metalloproteinase-2. In in vitro assays, thrombin cleavage of osteopontin to generate short COOH-terminal osteopontin in the presence of cyclophilin C increases migration and invasion of both 4T07 and 4T1 cells. This interaction between osteopontin peptide and cyclophilin C has not been previously described but assigns a heretofore unknown function for the thrombin-cleaved osteopontin COOH-terminal fragment.

  10. Aerobic dehydrogenative α-diarylation of benzyl ketones with aromatics through carbon-carbon bond cleavage.

    Science.gov (United States)

    More, Nagnath Yadav; Jeganmohan, Masilamani

    2014-02-01

    Substituted benzyl ketones reacted with aromatics in the presence of K2S2O8 in CF3COOH at room temperature, yielding α-diaryl benzyl ketones through a carbon-carbon bond cleavage. In the reaction, two new carbon-carbon bonds were formed and one carbon-carbon bond was cleaved. It is very interesting that two different nucleophiles such as benzyl ketones and aromatics were coupled together without metal, which is unusual in organic synthesis.

  11. CoPc(COOH)_8-SA/mCS双极膜的制备及表征%Preparation and Characterization of CoPc(COOH)_8-SA/mCS Bipolar Membranes

    Institute of Scientific and Technical Information of China (English)

    陈日耀; 陈震; 郑曦; 陈晓; 黄彩霞

    2009-01-01

    分别用Fe~(3+)离子和戊二醛作为交联剂对海藻酸钠(SA)阳膜层和壳聚糖(CS)阴膜层进行改性,制备了八羧基钴酞菁.海藻酸钠/改性壳聚糖(CoPc(COOH)_8SA/mCS)双极膜(BPM).在海藻酸钠阳膜层中添加八羧基钻酞菁以提高阳膜的离子交换容量,促进中间层水的解离.用傅立叶红外(FT-IR)光谱、扫描电镜(SEM)等方法对制备的双极膜进行了表征.实验结果表明,经八羧基钻酞菁改性后,阳离子交换膜层的离子交换容最、H+离子透过率均获得提高.与Fe~(3+)离子改性或二茂铁离子改性的mSA/mCS双极膜相比,CoPc(COOH)_8-SA/mCS双极膜的交流阻抗、电阻压降(IR降)和溶胀度降低.当电流密度高达105 mA·cm~(-2)时,CoPc(COOH)_8-SM/mCS双极膜的IR降仅为0.7V.%A sodium alginate (SA) cation layer was modified by cobalt octocarboxyphthalocyanine (CoPc(COOH)_8) to improve its ion exchange capacity and to promote water splitting at the interlayer. The CoPc(COOH)_8-SA and chitosan (CS) were then modified using Fe~(3+) and glutaraldehyde as linking reagents to prepare CoPc(COOH)_8-SA/mCS bipolar membranes (BPMs). FT-IR spectra and SEM were used to characterize CoPc(COOH)_8-SA/mCS BPMs. Experimental results showed that the ion exchange capacity and hydrogen ion transmigration rate of the CoPc(COOH)_8-SA cation exchange membrane had increased. By comparison to the mSA/mCS BPM that was modified by Fe~(3+) or ferrocene, the AC impedance, IR drop and the swelling degree of the CoPc(COOH)_8-SA/mCS BPMs all decreased. The IR drop of the CoPc(COOH)_8-SA/mCS BPM was only 0.7 V at a higher current density of 105 mA·cm~(-2).

  12. Ring Opening Metathesis Polymerization of Norbornene and Derivatives by the Triply Bonded Ditungsten Complex Na[W2(µ-Cl3Cl4(THF2]·(THF3

    Directory of Open Access Journals (Sweden)

    Georgios Floros

    2012-11-01

    Full Text Available In this study, the reactions of the bimetallic compound Na[W2(µ-Cl3Cl4(THF2]·(THF3 (1, (W 3 W6+, a'2e'4 with norbornene (NBE and some of its derivatives (5-X-2-NBE; X = COOH (NBE–COOH, OH (NBE–OH, CN (NBE–CN, COOMe (NBE–COOMe, CH=CH2 (VNBE; norbornadiene (NBD are described. Complex 1 contains a tungsten–tungsten triple bond, bearing three halide bridges and two labile THF ligands, in a cisoidal relationship along the metal–metal axis. The complex was found to be a highly efficient room temperature homogeneous and heterogeneous unicomponent initiator for the catalytic ring opening metathesis polymerization (ROMP of most substrates. NBE provides polynorbornene (PNBE of high molecular weight (Mw in high yields, soluble in organic solvents. The reaction proceeds with high cis-stereoselectivity (80%–86% cis, independently of the reaction conditions. Strongly coordinating pendant groups (–COOH, –OH, –CN deactivate 1, whereas substrates bearing softer ones (–COOMe, –CH=CH2 are quantitatively polymerized. NBD gives quantitatively insoluble PNBD. The polymers have been characterized by 1H, 13C NMR and Size Exclusion Chromatography (SEC. Monitoring the reactions in situ by 1H NMR (1/NBD or NBE provides direct evidence of the metathetical nature of the polymerization with the observation of the active tungsten alkylidene propagating polymeric chains. Mechanistic aspects of the reactions are discussed.

  13. The role of multiple hydrogen-bonding groups in specific alcohol binding sites in proteins: insights from structural studies of LUSH.

    Science.gov (United States)

    Thode, Anna B; Kruse, Schoen W; Nix, Jay C; Jones, David N M

    2008-03-07

    It is now generally accepted that many of the physiological effects of alcohol consumption are a direct result of binding to specific sites in neuronal proteins such as ion channels or other components of neuronal signaling cascades. Binding to these targets generally occurs in water-filled pockets and leads to alterations in protein structure and dynamics. However, the precise interactions required to confer alcohol sensitivity to a particular protein remain undefined. Using information from the previously solved crystal structures of the Drosophila melanogaster protein LUSH in complexes with short-chain alcohols, we have designed and tested the effects of specific amino acid substitutions on alcohol binding. The effects of these substitutions, specifically S52A, T57S, and T57A, were examined using a combination of molecular dynamics, X-ray crystallography, fluorescence spectroscopy, and thermal unfolding. These studies reveal that the binding of ethanol is highly sensitive to small changes in the composition of the alcohol binding site. We find that T57 is the most critical residue for binding alcohols; the T57A substitution completely abolishes binding, while the T57S substitution differentially affects ethanol binding compared to longer-chain alcohols. The additional requirement for a potential hydrogen-bond acceptor at position 52 suggests that both the presence of multiple hydrogen-bonding groups and the identity of the hydrogen-bonding residues are critical for defining an ethanol binding site. These results provide new insights into the detailed chemistry of alcohol's interactions with proteins.

  14. Alcohol and Group Formation: A Multimodal Investigation of the Effects of Alcohol on Emotion and Social Bonding

    OpenAIRE

    Sayette, Michael A.; Creswell, Kasey G.; Dimoff, John D.; Fairbairn, Catharine E.; Cohn, Jeffrey F.; Heckman, Bryan W.; Kirchner, Thomas R.; Levine, John M.; Moreland, Richard L.

    2012-01-01

    We integrated research on emotion and on small groups to address a fundamental and enduring question facing alcohol researchers: What are the specific mechanisms that underlie the reinforcing effects of drinking? In one of the largest alcohol-administration studies yet conducted, we employed a novel group-formation paradigm to evaluate the socioemotional effects of alcohol. Seven hundred twenty social drinkers (360 male, 360 female) were assembled into groups of 3 unacquainted persons each an...

  15. Singing together or apart: The effect of competitive and cooperative singing on social bonding within and between sub-groups of a university Fraternity.

    Science.gov (United States)

    Pearce, Eiluned; Launay, Jacques; van Duijn, Max; Rotkirch, Anna; David-Barrett, Tamas; Dunbar, Robin I M

    2016-11-01

    Singing together seems to facilitate social bonding, but it is unclear whether this is true in all contexts. Here we examine the social bonding outcomes of naturalistic singing behaviour in a European university Fraternity composed of exclusive 'Cliques': recognised sub-groups of 5-20 friends who adopt a special name and identity. Singing occurs frequently in this Fraternity, both 'competitively' (contests between Cliques) and 'cooperatively' (multiple Cliques singing together). Both situations were re-created experimentally in order to explore how competitive and cooperative singing affects feelings of closeness towards others. Participants were assigned to teams of four and were asked to sing together with another team either from the same Clique or from a different Clique. Participants (N = 88) felt significantly closer to teams from different Cliques after singing with them compared to before, regardless of whether they cooperated with (singing loudly together) or competed against (trying to singing louder than) the other team. In contrast, participants reported reduced closeness with other teams from their own Clique after competing with them. These results indicate that group singing can increase closeness to less familiar individuals regardless of whether they share a common motivation, but that singing competitively may reduce closeness within a very tight-knit group.

  16. Singing together or apart: The effect of competitive and cooperative singing on social bonding within and between sub-groups of a university Fraternity

    Science.gov (United States)

    Pearce, Eiluned; Launay, Jacques; van Duijn, Max; Rotkirch, Anna; David-Barrett, Tamas; Dunbar, Robin I M

    2016-01-01

    Singing together seems to facilitate social bonding, but it is unclear whether this is true in all contexts. Here we examine the social bonding outcomes of naturalistic singing behaviour in a European university Fraternity composed of exclusive ‘Cliques’: recognised sub-groups of 5-20 friends who adopt a special name and identity. Singing occurs frequently in this Fraternity, both ‘competitively’ (contests between Cliques) and ‘cooperatively’ (multiple Cliques singing together). Both situations were re-created experimentally in order to explore how competitive and cooperative singing affects feelings of closeness towards others. Participants were assigned to teams of four and were asked to sing together with another team either from the same Clique or from a different Clique. Participants (N = 88) felt significantly closer to teams from different Cliques after singing with them compared to before, regardless of whether they cooperated with (singing loudly together) or competed against (trying to singing louder than) the other team. In contrast, participants reported reduced closeness with other teams from their own Clique after competing with them. These results indicate that group singing can increase closeness to less familiar individuals regardless of whether they share a common motivation, but that singing competitively may reduce closeness within a very tight-knit group. PMID:27777494

  17. Arrangement of type IV collagen on NH₂ and COOH functionalized surfaces.

    Science.gov (United States)

    Coelho, Nuno Miranda; González-García, Cristina; Salmerón-Sánchez, Manuel; Altankov, George

    2011-12-01

    Apart from the paradigm that cell-biomaterials interaction depends on the adsorption of soluble adhesive proteins we anticipate that upon distinct conditions also other, less soluble ECM proteins such as collagens, associate with the biomaterials interface with consequences for cellular response that might be of significant bioengineering interest. Using atomic force microscopy (AFM) we seek to follow the nanoscale behavior of adsorbed type IV collagen (Col IV)--a unique multifunctional matrix protein involved in the organization of basement membranes (BMs) including vascular ones. We have previously shown that substratum wettability significantly affects Col IV adsorption pattern, and in turn alters endothelial cells interaction. Here we introduce two new model surfaces based on self-assembled monolayers (SAMs), a positively charged -NH(2) , and negatively charged -COOH surface, to learn more about their particular effect on Col IV behavior. AFM studies revealed distinct pattern of Col IV assembly onto the two SAMs resembling different aspects of network-like structure or aggregates (suggesting altered protein conformation). Moreover, the amount of adsorbed FITC-labeled Col IV was quantified and showed about twice more protein on NH(2) substrata. Human umbilical vein endothelial cells attached less efficiently to Col IV adsorbed on negatively charged COOH surface judged by altered cell spreading, focal adhesions formation, and actin cytoskeleton development. Immunofluorescence studies also revealed better Col IV recognition by both α(1) and α(2) integrins on positively charged NH(2) substrata resulting in higher phosphorylated focal adhesion kinase recruitment in the focal adhesion complexes. On COOH surface, no integrin clustering was observed. Taken altogether these results, point to the possibility that combined NH(2) and Col IV functionalization may support endothelization of cardiovascular implants.

  18. Alkali recovery using PVA/SiO2 cation exchange membranes with different -COOH contents.

    Science.gov (United States)

    Hao, Jianwen; Gong, Ming; Wu, Yonghui; Wu, Cuiming; Luo, Jingyi; Xu, Tongwen

    2013-01-15

    By changing -COOH content in poly(acrylic acid-co-methacryloxypropyl trimethoxy silane (poly(AA-co-γ-MPS)), a series of PVA/SiO(2) cation exchange membranes are prepared from sol-gel process of poly(AA-co-γ-MPS) in presence of poly(vinyl alcohol) (PVA). The membranes have the initial decomposition temperature (IDT) values of 236-274 °C. The tensile strength (TS) ranges from 17.4 MPa to 44.4 MPa. The dimensional stability in length (DS-length) is in the range of 10%-25%, and the DS-area is in the range of 21%-56% in 65 °C water. The water content (W(R)) ranges from 61.2% to 81.7%, the ion exchange capacity (IEC) ranges from 1.69 mmol/g to 1.90 mmol/g. Effects of -COOH content on diffusion dialysis (DD) performance also are investigated for their potential applications. The membranes are tested for recovering NaOH from the mixture of NaOH/Na(2)WO(4) at 25 - 45 °C. The dialysis coefficients of NaOH (U(OH)) are in the range of 0.006-0.032 m/h, which are higher than those of the previous membranes (U(OH): 0.0015 m/h, at 25 °C). The selectivity (S) can reach up to 36.2. The DD performances have been correlated with the membrane structure, especially the continuous arrangement of -COOH in poly(AA-co-γ-MPS) chain.

  19. Bonds to the homeland: Patterns and determinants of women's transnational travel frequency among three immigrant groups in Germany.

    Science.gov (United States)

    Iarmolenko, Svitlana; Titzmann, Peter F; Silbereisen, Rainer K

    2016-04-01

    Technology developments have changed immigrants' adaptation patterns in modern societies, allowing immigrants to sustain dense, complex connections with homeland while adjusting in the host country, a new phenomenon termed transnationalism. As empirical studies on immigrant transnationalism are still scarce, the purpose of this study was to investigate mean levels and determinants of a core component of transnationalism-transnational travel. Hypotheses were based on context of exiting homeland, living conditions in Germany and demographic and sociocultural variables. Transnational travel behaviour was assessed as frequency of return trips in three immigrant groups in Germany: ethnic Germans, Russian Jews and Turks. Interviews were conducted with 894 women participants from these groups. Results showed substantial transnational travel behaviour in all groups with Turks reporting higher levels than ethnic Germans and Russian Jews. Interindividual differences in transnational travel within groups were also examined. Results indicated similarities (e.g. network size in home country related positively to transnational travel frequency in all groups) and group-specific associations (e.g. co-ethnic identifying related positively to transnational travel frequency among Turks, but negatively for the other groups). Our study highlights the need for a new understanding of immigration and emphasises the consideration of group-specific mechanisms in transnational travel behaviour. © 2015 International Union of Psychological Science.

  20. Interaction between anions and cationic metal complexes containing tridentate ligands with exo-C-H groups: complex stability and hydrogen bonding.

    Science.gov (United States)

    Martínez-García, Héctor; Morales, Dolores; Pérez, Julio; Puerto, Marcos; del Río, Ignacio

    2014-05-05

    [Re(CO)3 ([9]aneS3 )][BAr'4 ] (1), prepared by reaction of ReBr(CO)5 , 1,4,7-trithiacyclononane ([9]aneS3 ) and NaBAr'4 , forms stable, soluble supramolecular adducts with chloride (2), bromide, methanosulfonate (3) and fluoride (4) anions. These new species were characterized by IR, NMR spectroscopy and, for 2 and 3, also by X-ray diffraction. The results of the solid state structure determinations indicate the formation of CH⋅⋅⋅X hydrogen bonds between the anion (X) and the exo-CH groups of the [9]aneS3 ligand, in accord with the relatively large shifts found by (1) H NMR spectroscopy in dichloromethane solution for those hydrogens. The stability of the chloride adduct contrasts with the lability of the [9]aneS3 ligand in allyldicarbonyl molybdenum complexes recently studied by us. With fluoride, in dichloromethane solution, a second, minor neutral dimeric species 5 is formed in addition to 4. In 4, the deprotonation of a CH group of the [9]aneS3 ligand, accompanied by CS bond cleavage and dimerization, afforded 5, featuring bridging thiolates. Compounds [Mo(η(3) -methallyl)(CO)2 (TpyN)][BAr'4 ] (6) and [Mo(η(3) -methallyl)(CO)2 (TpyCH)][BAr'4 ] (7) were synthesized by the reactions of [MoCl(η(3) -methallyl)(CO)2 (NCMe)2 ], NaBAr'4 and tris(2-pyridyl)amine (TpyN) or tris(2-pyridyl)methane (TpyCH) respectively, and characterized by IR and (1) H and (13) C NMR spectroscopy in solution, and by X-ray diffraction in the solid state. Compound 6 undergoes facile substitution of one of the 2-pyridyl groups by chloride, bromide, and methanosulfonate anions. Stable supramolecular adducts were formed between 7 and chloride, bromide, iodide, nitrate, and perrhenate anions. The solid state structures of these adducts (12-16) were determined by X-ray diffraction. Binding constants in dichloromethane were calculated from (1) H NMR titration data for all the new supramolecular adducts. The signal of the bridgehead CH group is the one that undergoes a

  1. Layered Ni(OH)2-Co(OH)2 films prepared by electrodeposition as charge storage electrodes for hybrid supercapacitors

    Science.gov (United States)

    Nguyen, Tuyen; Boudard, Michel; Carmezim, M. João; Montemor, M. Fátima

    2017-01-01

    Consecutive layers of Ni(OH)2 and Co(OH)2 were electrodeposited on stainless steel current collectors for preparing charge storage electrodes of high specific capacity with potential application in hybrid supercapacitors. Different electrodes were prepared consisting on films of Ni(OH)2, Co(OH)2, Ni1/2Co1/2(OH)2 and layered films of Ni(OH)2 on Co(OH)2 and Co(OH)2 on Ni(OH)2 to highlight the advantages of the new architecture. The microscopy studies revealed the formation of nanosheets in the Co(OH)2 films and of particles agglomerates in the Ni(OH)2 films. Important morphological changes were observed in the double hydroxides films and layered films. Film growth by electrodeposition was governed by instantaneous nucleation mechanism. The new architecture composed of Ni(OH)2 on Co(OH)2 displayed a redox response characterized by the presence of two peaks in the cyclic voltammograms, arising from redox reactions of the metallic species present in the layered film. These electrodes revealed a specific capacity of 762 C g−1 at the specific current of 1 A g−1. The hybrid cell using Ni(OH)2 on Co(OH)2 as positive electrode and carbon nanofoam paper as negative electrode display specific energies of 101.3 W h g−1 and 37.8 W h g−1 at specific powers of 0.2 W g−1 and 2.45 W g−1, respectively. PMID:28051143

  2. Layered Ni(OH)2-Co(OH)2 films prepared by electrodeposition as charge storage electrodes for hybrid supercapacitors.

    Science.gov (United States)

    Nguyen, Tuyen; Boudard, Michel; Carmezim, M João; Montemor, M Fátima

    2017-01-04

    Consecutive layers of Ni(OH)2 and Co(OH)2 were electrodeposited on stainless steel current collectors for preparing charge storage electrodes of high specific capacity with potential application in hybrid supercapacitors. Different electrodes were prepared consisting on films of Ni(OH)2, Co(OH)2, Ni1/2Co1/2(OH)2 and layered films of Ni(OH)2 on Co(OH)2 and Co(OH)2 on Ni(OH)2 to highlight the advantages of the new architecture. The microscopy studies revealed the formation of nanosheets in the Co(OH)2 films and of particles agglomerates in the Ni(OH)2 films. Important morphological changes were observed in the double hydroxides films and layered films. Film growth by electrodeposition was governed by instantaneous nucleation mechanism. The new architecture composed of Ni(OH)2 on Co(OH)2 displayed a redox response characterized by the presence of two peaks in the cyclic voltammograms, arising from redox reactions of the metallic species present in the layered film. These electrodes revealed a specific capacity of 762 C g(-1) at the specific current of 1 A g(-1). The hybrid cell using Ni(OH)2 on Co(OH)2 as positive electrode and carbon nanofoam paper as negative electrode display specific energies of 101.3 W h g(-1) and 37.8 W h g(-1) at specific powers of 0.2 W g(-1) and 2.45 W g(-1), respectively.

  3. Phase behaviors and self-assembly properties of two catanionic surfactant systems: C(8)F(17)COOH/TTAOH/H(2)O and C(8)H(17)COOH/TTAOH/H(2)O.

    Science.gov (United States)

    Zhang, Juan; Song, Aixin; Li, Zhibo; Xu, Guiying; Hao, Jingcheng

    2010-10-21

    Two fatty acids, perfluorononanoic acid (C(8)F(17)COOH) and nonanoic acid (C(8)H(17)COOH), were mixed with a cationic hydrocarbon surfactant, tetradecyltrimethylammonium hydroxide (TTAOH), in aqueous solutions for comparative investigation. Phase behaviors of the two systems are quite different because of the special properties of the fluorocarbon chains. For the C(8)H(17)COOH/TTAOH/H(2)O system, a single L(α) phase region with phase transition from planar lamellar phase (L(αl) phase) to vesicle phase (L(αv) phase) was observed. For the C(8)F(17)COOH/TTAOH/H(2)O system, two single phases consisting of vesicles were obtained at room temperature. One is a high viscoelastic gel phase consisting of vesicles with crystalline state bialyers at the C(8)F(17)COOH-rich side, which was confirmed by freeze-fracture transmission electron microscope (FF-TEM) and differential scanning calorimetry (DSC) measurements. With the increase of TTAOH proportion, another vesicle phase consisting of liquid state bilayers was observed after the two-phase region. The fluorosurfactant systems prefer to form vesicle bilayers than the corresponding hydrocarbon ones because of the rigid structure, the stronger hydrophobicity, and the larger volume of fluorocarbon chains.

  4. H-bond length dependence of the distortion in acid tetrahedron groups H nAsO 4 ( n=1-3)

    Science.gov (United States)

    Ichikawa, Mizuhiko

    1988-07-01

    The H-bond length O⋯O dependence of the distortions of the AsO 4 tetrahedra of acid arsenate groups H nAsO 4 ( n=1-3) have been studied by examining the correlations of the As sbnd O bond lengths, OAsO angles, O sbnd O lengths and Baur's distortion indices (DI) with O⋯O and comparing them with those of the corresponding H nPO 4 groups previously reported. The behavior of the O⋯O dependence of the AsO 4 distortion is analogous to that of PO 4 distortion as a whole, that is (a) all DI increase with increasing O⋯O, and correspondingly some of the individual or average As sbnd O lengths, OAsO angles and O sbnd O lengths correlate with O⋯O consistently; (b) the overall mean values of As sbnd O, OAsO and O sbnd O are reasonably constant in each H nAsO 4 type, most notably in the case of OAsO. The dependence of the PO 4 distortion on O⋯O can be described approximately by a model in which the P atom shifts away from the centroid of the regular tetrahedral framework, but the O⋯O dependence of the AsO 4 distortion is more complicated.

  5. Analysis of the biomineralization process on SWNT-COOH and F-SWNT films

    Energy Technology Data Exchange (ETDEWEB)

    Armentano, Ilaria [Materials Engineering Centre, UdR INSTM, NIPLAB, University of Perugia, Terni (Italy)], E-mail: Ilaria.armentano@lnl.infn.it; Alvarez-Perez, Marco Antonio; Carmona-Rodriguez, Bruno [Laboratorio de Biologia Celular y Molecular, Facultad de Odontologia, Universidad Nacional Autonoma de Mexico, Mexico D. F. (Mexico); Gutierrez-Ospina, Ivan [Universidad Autonoma Metropolitana, Xochimilco, Mexico D. F. (Mexico); Kenny, Jose Maria [Materials Engineering Centre, UdR INSTM, NIPLAB, University of Perugia, Terni (Italy); Arzate, Higinio [Laboratorio de Biologia Celular y Molecular, Facultad de Odontologia, Universidad Nacional Autonoma de Mexico, Mexico D. F. (Mexico)

    2008-12-01

    In vitro biomineralization process was investigated on functionalized single wall nanotube (SWNT) films. The films were prepared by solvent casting method by using carboxylated and fluorinated nanotubes. SWNT films were characterized by means of electron microscopy, contact angle measurements and optical absorption. The in vitro assays were performed on cultured human alveolar bone-derived cells (HABDC) to determine the capabilities of carboxylated single-walled nanotubes (SWNTs-COOH) and fluorinated single-walled nanotubes (F-SWNTs) to promote the deposit of mineral-like tissue. The results showed that the cellular response of HABDC in secreting a mineralized extracellular matrix and their consequent mineralization is dependent on the degree of functionalization of the SWNTs. Differences were found related to the kind of sidewall functionalization. Both structures promoted hydroxyapatite formation, however, calcium uptake on SWNTs-COOH increased and it was related to crystal density. From our results, it is possible to infer that CNT functionalization opens a path to future developments in new bone graft materials and techniques.

  6. Preparation, characterization and evaluation of breviscapine lipid emulsions coated with monooleate-PEG-COOH.

    Science.gov (United States)

    Xiong, Fei; Xiong, Chen; Yao, Juan; Chen, Xinmei; Gu, Ning

    2011-12-15

    Series of monooleate-modified PEG with active carboxylic terminus on the other end (MO-PEG-COOH) were used to modify the lipid emulsions surface to prepare a sterically stabilized lipid emulsions for carrying Traditional Chinese Medicine - breviscapine. Based on the research of relationship between polymer structure and prolonged circulation activity, we developed an optimized formulation and a technological method to prepare the sterile and stable MO-PEG(10,000)-COOH (Bre-LE-PEG(10,000)) coated breviscapine lipid emulsions (Bre-LE) for intravenous administration. Follow the optimum preparation, the average particle size, polydispersity index, zeta potential, Ke value and content of final product were determined to be (207.1±8.5)nm, 0.197±0.005, (-33.6±2.0)mV, (21.1±2.3)% and (95.0±1.8)% respectively (n=3). The characteristics, stability and safety of Bre-LE-PEG(10,000) were also studied with Bre-LE as a control. Increased plasma concentration by surface modification of the lipid emulsions may enhance the pharmacological activity of breviscapine to promote blood circulation.

  7. An electronic nose for amine detection based on polymer/SWNT-COOH nanocomposite.

    Science.gov (United States)

    Lorwongtragooll, Panida; Wisitsoraat, Anurat; Kerdcharoen, Teerakiat

    2011-12-01

    An electronic nose (e-nose) system based on polymer/carboxylic-functionalized single-walled carbon nanotubes (SWNT-COOH) was developed for sensing various volatile amines. The SWNT-COOH dispersed in the matrix of different polymers; namely, polyvinyl chloride (PVC), cumene terminated polystyrene-co-maleic anhydride (cumene-PSMA), poly(styrenecomaleic acid) partial isobutyl/methyl mixed ester (PSE), and polyvinylpyrrolidon (PVP), were deposited on interdigitated gold electrodes to make the gas sensors. The response of these sensors to volatile amines was studied by both static and dynamic flow measurements. It was found that all sensors exhibited behaviors corresponding to Plateau-Bretano-Stevens law (R2 = 0.81 to 0.99) as the response to volatile amines. Real-world application was demonstrated by applying this e-nose to monitor the odor of sun-dried snakeskin gourami that was pre-processed by salting-preservation. This electronic nose can discriminate sun-dried fish odors with different stored days using a simple pattern recognition based on the principal component analysis (PCA).

  8. Bridging of partially negative atoms by hydrogen bonds from main-chain NH groups in proteins: The crown motif.

    Science.gov (United States)

    Leader, David P; Milner-White, E James

    2015-11-01

    The backbone NH groups of proteins can form N1N3-bridges to δ-ve or anionic acceptor atoms when the tripeptide in which they occur orients them appropriately, as in the RL and LR nest motifs, which have dihedral angles 1,2-αR αL and 1,2-αL αR , respectively. We searched a protein database for structures with backbone N1N3-bridging to anionic atoms of the polypeptide chain and found that RL and LR nests together accounted for 92% of examples found (88% RL nests, 4% LR nests). Almost all the remaining 8% of N1N3-bridges were found within a third tripeptide motif which has not been described previously. We term this a "crown," because of the disposition of the tripeptide CO groups relative to the three NH groups and the acceptor oxygen anion, and the crown together with its bridged anion we term a "crown bridge." At position 2 of these structures the dihedral angles have a tight αR distribution, but at position 1 they have a wider distribution, with ϕ and ψ values generally being lower than those at position 1. Over half of crown bridges involve the backbone CO group three residues N-terminal to the tripeptide, the remainder being to other main-chain or side-chain carbonyl groups. As with nests, bridging of crowns to oxygen atoms within ligands was observed, as was bridging to the sulfur atom of an iron-sulfur cluster. This latter property may be of significance for protein evolution.

  9. Cysteine analogs with a free thiol group promote fertilization by reducing disulfide bonds in the zona pellucida of mice.

    Science.gov (United States)

    Takeo, Toru; Horikoshi, Yuka; Nakao, Satohiro; Sakoh, Kazuhito; Ishizuka, Yuta; Tsutsumi, Aki; Fukumoto, Kiyoko; Kondo, Tomoko; Haruguchi, Yukie; Takeshita, Yumi; Nakamuta, Yuko; Tsuchiyama, Shuuji; Nakagata, Naomi

    2015-04-01

    Archives of cryopreserved sperm harvested from genetically engineered mice, in mouse resource centers, are a readily accessible genetic resource for the scientific community. We previously reported that exposure of oocytes to reduced glutathione (GSH) greatly improves the fertilization rate of frozen-thawed mouse sperm. Application of GSH to in vitro fertilization techniques is widely accepted as a standard protocol to produce sufficient numbers of mice from cryopreserved sperm. However, the detailed mechanism of the enhancement of fertilization mediated by GSH in vitro is not fully understood. Here we focused on the chemical by determining the effects of its amino acid constituents and cysteine analogs on the fertilization of oocytes by frozen-thawed sperm. Furthermore, we determined the stability of these compounds in aqueous solution. We show here that l-cysteine (l-Cys), d-cysteine (d-Cys), or N-acetyl-l-cysteine (NAC) increased the rate of fertilization when added to the medium but did not adversely affect embryo development in vitro or in vivo. The levels of thiol groups of proteins in the zona pellucida (ZP) and the expansion of the ZP were increased by l-Cys, d-Cys, and NAC. These effects were abrogated by the methylation of the thiol group of l-Cys. NAC was the most stable of these compounds in the fertilization medium at 4°C. These results suggest that the thiol groups of cysteine analogs markedly enhance the fertilization rate of mouse oocytes.

  10. Effects of Bonding Types and Functional Groups on CO 2 Capture using Novel Multiphase Systems of Liquid-like Nanoparticle Organic Hybrid Materials

    KAUST Repository

    Lin, Kun-Yi Andrew

    2011-08-01

    Novel liquid-like nanoparticle organic hybrid materials (NOHMs) which possess unique features including negligible vapor pressure and a high degree of tunability were synthesized and their physical and chemical properties as well as CO 2 capture capacities were investigated. NOHMs can be classified based on the synthesis methods involving different bonding types, the existence of linkers, and the addition of task-specific functional groups including amines for CO 2 capture. As a canopy of polymeric chains was grafted onto the nanoparticle cores, the thermal stability of the resulting NOHMs was improved. In order to isolate the entropy effect during CO 2 capture, NOHMs were first prepared using polymers that do not contain functional groups with strong chemical affinity toward CO 2. However, it was found that even ether groups on the polymeric canopy contributed to CO 2 capture in NOHMs via Lewis acid-base interactions, although this effect was insignificant compared to the effect of task-specific functional groups such as amine. In all cases, a higher partial pressure of CO 2 was more favorable for CO 2 capture, while a higher temperature caused an adverse effect. Multicyclic CO 2 capture tests confirmed superior recyclability of NOHMs and NOHMs also showed a higher selectivity toward CO 2 over N 2O, O 2 and N 2. © 2011 American Chemical Society.

  11. Effects of bonding types and functional groups on CO2 capture using novel multiphase systems of liquid-like nanoparticle organic hybrid materials.

    Science.gov (United States)

    Lin, Kun-Yi Andrew; Park, Ah-Hyung Alissa

    2011-08-01

    Novel liquid-like nanoparticle organic hybrid materials (NOHMs) which possess unique features including negligible vapor pressure and a high degree of tunability were synthesized and their physical and chemical properties as well as CO(2) capture capacities were investigated. NOHMs can be classified based on the synthesis methods involving different bonding types, the existence of linkers, and the addition of task-specific functional groups including amines for CO(2) capture. As a canopy of polymeric chains was grafted onto the nanoparticle cores, the thermal stability of the resulting NOHMs was improved. In order to isolate the entropy effect during CO(2) capture, NOHMs were first prepared using polymers that do not contain functional groups with strong chemical affinity toward CO(2). However, it was found that even ether groups on the polymeric canopy contributed to CO(2) capture in NOHMs via Lewis acid-base interactions, although this effect was insignificant compared to the effect of task-specific functional groups such as amine. In all cases, a higher partial pressure of CO(2) was more favorable for CO(2) capture, while a higher temperature caused an adverse effect. Multicyclic CO(2) capture tests confirmed superior recyclability of NOHMs and NOHMs also showed a higher selectivity toward CO(2) over N(2)O, O(2) and N(2).

  12. AQP4 plasma membrane trafficking or channel gating is not significantly modulated by phosphorylation at COOH-terminal serine residues

    DEFF Research Database (Denmark)

    Assentoft, Mette; Larsen, Brian R; Olesen, Emma T B;

    2014-01-01

    . Phosphorylation of aquaporins can regulate plasma membrane localization and, possibly, the unit water permeability via gating of the AQP channel itself. In vivo phosphorylation of six serine residues in the COOH terminus of AQP4 has been detected by mass spectrometry: Ser(276), Ser(285), Ser(315), Ser(316), Ser...... heterologous expression in Xenopus laevis oocytes (along with serine-to-aspartate mutants of the same residues to mimic a phosphorylation). None of the mutant AQP4 constructs displayed alterations in the unit water permeability. Thus phosphorylation of six different serine residues in the COOH terminus of AQP4...

  13. Reduction of unsaturated compounds under interstellar conditions: chemoselective reduction of C≡C and C=C bonds over C=O functional group

    Science.gov (United States)

    Jonusas, Mindaugas; Guillemin, Jean-Claude; Krim, Lahouari

    2017-07-01

    The knowledge of the H-addition reactions on unsaturated organic molecules bearing a triple or a double carbon-carbon bond such as propargyl or allyl alcohols and a CO functional group such as propynal, propenal or propanal may play an important role in the understanding of the chemical complexity of the interstellar medium. Why different aldehydes like methanal, ethanal, propynal and propanal are present in dense molecular clouds while the only alcohol detected in those cold regions is methanol? In addition, ethanol has only been detected in hot molecular cores. Are those saturated and unsaturated aldehyde and alcohol species chemically linked in molecular clouds through solid phase H-addition surface reactions or are they formed through different chemical routes? To answer such questions, we have investigated a hydrogenation study of saturated and unsaturated aldehydes and alcohols at 10 K. We prove through this experimental study that while pure unsaturated alcohol ices bombarded by H atoms lead to the formation of the corresponding fully or partially saturated alcohols, surface H-addition reactions on unsaturated aldehyde ices exclusively lead to the formation of fully saturated aldehyde. Such results show that in addition to a chemoselective reduction of C≡C and C=C bonds over the C=O group, there is no link between aldehydes and their corresponding alcohols in reactions involving H atoms in dense molecular clouds. Consequently, this could be one of the reasons why some aldehydes such as propanal are abundant in dense molecular clouds in contrast to the non-detection of alcohol species larger than methanol.

  14. Surface chemistry of boron-doped SiO{sub 2} CVD: Enhanced uptake of tetraethyl orthosilicate by hydroxyl groups bonded to boron

    Energy Technology Data Exchange (ETDEWEB)

    Bartram, M.E.; Moffat, H.K.

    1993-12-31

    Insight into how dopants can enhance deposition rates has been obtained by comparing reactivities of tetraethyl orthosilicate (TEOS, Si(OCH{sub 2}CH{sub 3}){sub 4}) with silanol and boranol groups on SiO{sub 2}. This comparison is relevant for boron-doped SiO{sub 2} film growth from TEOS and trimethyl borate (TMB, B(OCH{sub 3}){sub 3}) sources since boranols and silanols are expected to be present on surface during the (CVD). A silica substrate having coadsorbed deuterated silanols (SIOD) and boranols (BOD) was reacted with TEOS in a cold-wall reactor in the mTorr pressure regime at 1000K. Reactions were followed with Fourier transform infrared spectroscopy. Use of deuterated hydroxyls allowed consumption of hydroxyls by TEOS chemisorption to be distinguished from concurrent formation of SIOH and BOH that results from TEOS decomposition. It was found that TEOS reacts with BOD at twice the rate observed for SIOD demonstrating that hydroxyl groups bonded to boron increase the rate of TEOS chemisorption. Surface ethoxy groups produced by chemisorption of TEOS decompose at a slower rate in the presence of TMB decomposition products. Possible dependencies on reactor geometries and other deposition conditions may determine which of these two competing effects will control deposition rates. This may explain (in part) why the rate enhancement effect is not always observed in boron-doped SiO{sub 2} CVD processes.

  15. Preparation and Characterization of CuPc(COOH)_8-SA/CuTAPc-CS Bipolar Membrane%CuPc(COOH)_8-SA/CuTAPc-CS双极膜的制备及表征

    Institute of Scientific and Technical Information of China (English)

    陈日耀; 陈震; 郑曦; 陈晓; 倪世茂; 尤春满

    2010-01-01

    分别用八羧基铜酞菁[CuPc(COOH)_8]和四氨基铜酞菁(CuTAPc)改性海藻酸钠(SA)阳膜层和壳聚糖(CS)阴膜层,制备了CuPc(COOH)_8-SA/CuTAPc-CS双极膜.实验结果表明,经八羧基铜酞菁和四氨基铜酞菁改性后,促进了双极膜中间层水的解离,增大了阳离子交换膜层和阴离子交换膜层的离子交换容量及H~+和OH~-的透过率.与Fe~(3+)改性的Fe-SA/mCS双极膜相比,CuPc(COOH)_8-SA/CuTAPc-CS双极膜的阻抗、电阻压降(即IR降)和溶胀度降低.当电流密度高达120 mA/cm~2时,CuPc(COOH)_8-SA/CuTAPc-CS双极膜的IR降仅为0.9 V.

  16. In situ observation of C60(C(COOH)2)2 interacting with living cells using fluorescence microscopy

    Institute of Scientific and Technical Information of China (English)

    YE Chang; ZHAO Yuliang; CHAI Zhifang; FANG Xiaohong; HAN Dong; CHEN Long; WANG Chen; WEI Taotao; CHEN Chunying; CHEN Zhen; MENG Huan; XING Li; JIANG Yaxin; YUAN Hui; XING Gengmei; ZHAO Feng

    2006-01-01

    The interactions between nanoparticles and living cells were investigated by an imaging technique of fluorescence microscopy. For this purpose, the C60 derivative C60(C(COOH)2)2, a therapeutic agent for degeneration diseases of central nervous system, was synthesized, purified and characterized. Its interaction with the living cell and penetration of the cellular membrane were in situ studied using the real time imaging technique, and its potential cytotoxicity was also examined by flow cytometry. The results indicate that C60(C(COOH)2)2 can easily enter cells, and is mainly located in cytoplasm by fluorescein labeling. Furthermore, C60(C(COOH)2)2 can carry the molecule that cannot cross cellular membranes into cells, because fluorescein compound itself cannot enter the cell or adhere to membrane. At concentrations ranging from 1×10?2 to 1×102 mg/L, C60(C(COOH)2)2 does not show any detectable cytotoxicity.

  17. Thermochemical Properties and Bond Dissociation Energies for Fluorinated Methanol, CH3-xFxOH, and Fluorinated Methyl Hydroperoxides, CH3-xFxOOH: Group Additivity.

    Science.gov (United States)

    Wang, Heng; Bozzelli, Joseph W

    2016-09-08

    Oxygenated fluorocarbons are routinely found in sampling of environmental soils and waters as a result of the widespread use of fluoro and chlorofluoro carbons as heat transfer fluids, inert materials, polymers, fire retardants and solvents; the influence of these chemicals on the environment is a growing concern. The thermochemical properties of these species are needed for understanding their stability and reactions in the environment and in thermal process. Structures and thermochemical properties on the mono- to trifluoromethanol, CH3-xFxOH, and fluoromethyl hydroperoxide, CH3-xFxOOH (1 ≤ x ≤ 3), are determined by CBS-QB3, CBS-APNO, and G4 calculations. Entropy, S°298, and heat capacities, Cp(T)'s (300 ≤ T/K ≤ 1500) from vibration, translation, and external rotation contributions are calculated on the basis of the vibration frequencies and structures obtained from the B3LYP/6-31+G(d,p) density functional method. Potential barriers for the internal rotations are also calculated from this method and used to calculate hindered rotor contributions to S°298 and Cp(T)'s using direct integration over energy levels of the internal rotational potentials. Standard enthalpies of formation, ΔfH°298 (units in kcal mol(-1)) are CH2FOOH (-83.7), CHF2OOH (-138.1), CF3OOH (-193.6), CH2FOO(•) (-44.9), CHF2OO(•) (-99.6), CF3OO(•) (-153.8), CH2FOH (-101.9), CHF2OH (-161.6), CF3OH (-218.1), CH2FO(•) (-49.1), CHF2O(•) (-97.8), CF3O(•) (-150.5), CH2F(•) (-7.6), CHF2(•) (-58.8), and CF3(•) (-112.6). Bond dissociation energies for the R-OOH, RO-OH, ROO-H, R-OO(•), RO-O(•), R-OH, RO-H, R-O(•), and R-H bonds are determined and compared with methyl hydroperoxide to observe the trends from added fluoro substitutions. Enthalpy of formation for the fluoro-hydrocarbon oxygen groups C/F/H2/O, C/F2/H/O, C/F3/O, are derived from the above fluorinated methanol and fluorinated hydroperoxide species for use in Benson's Group Additivity. It was determined that

  18. Fourier transform infrared spectroscopic study of the kinetics of a first-order phase transition in tridecanoic acid CH3(CH2)11COOH

    Science.gov (United States)

    Marikhin, V. A.; Myasnikova, L. P.; Radovanova, E. I.; Volchek, B. Z.; Medvedeva, D. A.

    2017-02-01

    The structural changes in crystalline lamella cores of tridecanoic acid CH3(CH2)11COOH during heating in the range from the temperature T 1 = 13.5°C to T 2 > T m = 41.6°C have been investigated using Fourier transform infrared spectroscopy. The behavior of the bands of rocking (in the region of 720 cm-1) and bending (in the region of 1470 cm-1) vibrations of CH2 groups in tridecanoic acid methylene segments has been analyzed. It has been shown that, in the first-order phase transition region ( T s-s 36°C) within a narrow temperature range (Δ T 1 ≤ 1 K), there is a gradual transformation of the initial triclinic subcell into the hexagonal subcell. The mechanism of this transition has been considered in terms of the theory of diffuse first-order phase transitions.

  19. Influence of nanotube content on the mechanical and thermo-mechanical behaviour of –COOH functionalized MWNTs/epoxy composites

    Indian Academy of Sciences (India)

    S SAHA; S BAL

    2017-09-01

    Functionalized multi-wall carbon nanotubes (MWNTs) with carboxylic acid group (–COOH) have been utilizedfor the preparation of epoxy nanocomposites. Composites were synthesized using three different wt% (0.5, 0.75 and 1) ofMWNTs via the solution mixing technique followed by ultrasonication. Mechanical and thermo-mechanical properties ofthe fabricated composites have been experimented for the suitability of this material in a variety of structural applications.The flexural modulus, strength, hardness, impact strength and storage modulus increased upon increasing MWNTs contents.Best results have been observed in nanocomposites with 0.75 wt% nanotubes loading, which showed 101, 166 and 61%enhancement in the flexural modulus, hardness and storage modulus, respectively, compared to neat epoxy. Achievementof uniform dispersion and hence formation of improved interface between nanotubes and epoxy was the reason behindthe maximum enhancement at this wt%, which is further evidenced by the fracture surface morphology obtained frommicroscopical investigations.

  20. Modifying the NH2 and COOH termini of aquaporin-5: effects on localization in polarized epithelial cells.

    Science.gov (United States)

    Wellner, Robert B; Hong, Sohee; Cotrim, Ana P; Swaim, William D; Baum, Bruce J

    2005-01-01

    To reengineer polarized epithelial cell functions directly in situ, or ex vivo in the fabrication of an artificial organ, it is necessary to understand mechanisms that account for polarized membrane sorting. We have used the aquaporins (AQPs), a family of homotetrameric water channel proteins, as model membrane proteins for this purpose. AQP monomers contain six transmembrane-spanning domains linked by five interconnecting loops, with the NH2 and COOH termini residing in the cytosol. AQP5 is localized in the apical membranes of several different epithelia in vivo, and in stably transfected MDCK-II cells grown as a polarized monolayer. We wished to identify a structural region(s) within rat AQP5 (rAQP5) important for apical localization, and to study the MDCK-II cell localization of rAQP5s modified in either their NH2 or COOH terminus. We show that the NH2- terminal region does not play a major role in apical localization as deletion of the NH2 terminus produced a modified rAQP5 construct (AQP5-NT(del)) that was stably expressed and localized primarily to the apical membranes of MDCK-II cells. Attachment of a FLAG epitope to the NH2 terminus of AQP5 (AQP5(flag) construct) also did not perturb apical localization. In addition, we found that the exchange of NH2-terminal regions between rAQP5 and human AQP1 (hAQP1; a nonpolarized AQP isoform) produced a modified rAQP5 construct (AQP5-1NT) and a modified hAQP1 construct (AQP1-5NT), each of which localized as the parental AQP (apically, and to both apical and basolateral membranes, respectively). In contrast, we found that deletion of the COOH terminus resulted in a modified rAQP5 construct (AQP5-CT(del)) that was unstably expressed and localized to intracellular site(s) in MDCK-II cells. Substitution of the COOH terminus of AQP1 with the COOH terminus of AQP5 also produced a construct (AQP1-5CT) transiently expressed in intracellular compartment(s). However, substitution of the COOH terminus of rAQP5 with the COOH

  1. Cytotoxic and adhesion-associated response of NIH-3T3 fibroblasts to COOH-functionalized multi-walled carbon nanotubes.

    Science.gov (United States)

    Zhao, Peipei; Chen, Lusi; Shao, Han; Zhang, Yongnu; Sun, Yuqiao; Ke, Yu; Ramakrishna, Seeram; He, Liumin; Xue, Wei

    2016-02-29

    As novel, promising, man-made nanomaterials with extraordinary properties, carbon nanotubes have been attracting massive attention in regenerative medicine. However, published reports on their potential cytotoxic effects are not concordant and are even conflicting. In the current study, the cytotoxic effects of carboxyl-modified multi-walled carbon nanotubes (COOH-MWCNTs), as well as their influences on the cell adhesion of NIH-3T3 fibroblasts, were thoroughly investigated. Live/dead cell viability assay and cell counting kit-8 assay both indicated that the viability of the NIH-3T3 cells exposed to COOH-MWCNTs in the culture medium was dependent on the latter's concentration. Cell viability increased at COOH-MWCNT concentrations below 50 μg ml(-1) and then decreased with increasing concentration. Scanning electron microscopy and immunofluorescent staining of the NIH-3T3 cells revealed that the cells were well adherent to the substrate after exposure to the COOH-MWCNTs for 48 h. Western blot demonstrated that COOH-MWCNT exposure enhanced the expression of adhesion-associated proteins compared with normal cells, peaking at an intermediate concentration. Our study showed that the cytotoxicity of COOH-MWCNTs, as well as their effects on NIH-3T3 fibroblast adhesion, was dose dependent. Therefore, COOH-MWCNT concentrations in the cell culture medium should be considered in the biomedical application of COOH-MWCNTs.

  2. The amide C-N bond of isatins as the directing group and the internal oxidant in Ru-catalyzed C-H activation and annulation reactions: access to 8-amido isocoumarins.

    Science.gov (United States)

    Kaishap, Partha Pratim; Sarma, Bipul; Gogoi, Sanjib

    2016-07-28

    The N-O, N-N and O-O bonds are the frequently used internally oxidative directing groups used in various redox-neutral coupling reactions. The sole use of the C-N bond as the oxidizing directing group was reported recently by Li X. and co-workers for the Rh(iii)-catalyzed C-H activation of phenacyl ammonium salts. Herein, we report the use of the amide C-N bond of isatins as the oxidizing directing group for the Ru(ii)-catalyzed redox-neutral C-H activation and annulation reactions with alkynes which afford 8-amido isocoumarins. The reaction also features excellent regioselectivity with alkyl aryl substituted alkynes.

  3. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  4. NMR investigation on isotope effect of glycinium phosphite H sub 3 NCH sub 2 COOH centre dot H sub 2 PO sub 3

    CERN Document Server

    Ishibashi, T

    2003-01-01

    The motions of the phosphite anions and glycinium cations in H sub 3 NCH sub 2 COOH centre dot H sub 2 PO sub 3 (GPI) and its deuterated analogue (DGPI) were investigated by sup 1 H, sup 1 sup 3 C and sup 3 sup 1 P spin-lattice relaxation times T sub 1. For both GPI and DGPI, T sub 1 's of the sup 1 H, sup 1 sup 3 C and sup 3 sup 1 P nuclei reflect the amino rotation, methylene libration and motion of the phosphite anions, respectively. Activation energies obtained from T sub 1 's of sup 1 H, sup 1 sup 3 C and sup 3 sup 1 P nuclei are 28.6(2), 26.0(4) and 26.2(4) kJ/mol for GPI and are 34.9(6), 27(1), 47(2) kJ/mol for DGPI, respectively. The deuterium substitution increases E sub a for the motion influenced by the hydrogen bonding. In all the observed motions, correlation times of DGPI are larger than those of GPI. (author)

  5. Unusual C-C bond cleavage in the formation of amine-bis(phenoxy) group 4 benzyl complexes: Mechanism of formation and application to stereospecific polymerization

    KAUST Repository

    Gowda, Ravikumar R.

    2014-08-11

    Group 4 tetrabenzyl compounds MBn4 (M = Zr, Ti), upon protonolysis with an equimolar amount of the tetradentate amine-tris(phenol) ligand N[(2,4-tBu2C6H2(CH 2)OH]3 in toluene from -30 to 25 °C, unexpectedly lead to amine-bis(phenoxy) dibenzyl complexes, BnCH2N[(2,4- tBu2C6H2(CH2)O] 2MBn2 (M = Zr (1), Ti (2)) in 80% (1) and 75% (2) yields. This reaction involves an apparent cleavage of the >NCH2-ArOH bond (loss of the phenol in the ligand) and formation of the >NCH 2-CH2Bn bond (gain of the benzyl group in the ligand). Structural characterization of 1 by X-ray diffraction analysis confirms that the complex formed is a bis(benzyl) complex of Zr coordinated by a newly derived tridentate amine-bis(phenoxy) ligand arranged in a mer configuration in the solid state. The abstractive activation of 1 and 2 with B(C6F 5)3·THF in CD2Cl2 at room temperature generates the corresponding benzyl cations {BnCH2N[(2,4- tBu2C6H2(CH2)O] 2MBn(THF)}+[BnB(C6F5) 3]- (M = Zr (3), Ti, (4)). These cationic complexes, along with their analogues derived from (imino)phenoxy tri- and dibenzyl complexes, [(2,6-iPr2C6H3)N=C(3,5- tBu2C6H2)O]ZrBn3 (5) and [2,4-Br2C6H2(O)(6-CH2(NC 5H9))CH2N=CH(2-adamantyl-4-MeC 6H2O)]ZrBn2 (6), have been found to effectively polymerize the biomass-derived renewable β-methyl-α-methylene- γ-butyrolactone (βMMBL) at room temperature into the highly stereoregular polymer PβMMBL with an isotacticity up to 99% mm. A combined experimental and DFT study has yielded a mechanistic pathway for the observed unusual C-C bond cleavage in the present protonolysis reaction between ZrBn4 and N[(2,4-tBu2C 6H2(CH2)OH]3 for the formation of complex 1, which involves the benzyl radical and the Zr(III) species, resulting from thermal and photochemical decomposition of ZrBn4, followed by a series of reaction sequences consisting of protonolysis, tautomerization, H-transfer, oxidation, elimination, and radical coupling. © 2014 American Chemical Society.

  6. Interaction of modified tail-anchored proteins with liposomes: effect of extensions of hydrophilic segment at the COOH-terminus of holo-cytochromes b₅.

    Science.gov (United States)

    Sakamoto, Yoichi; Miura, Masahiro; Takeuchi, Fusako; Park, Sam-Yong; Tsubaki, Motonari

    2012-03-01

    A group of membrane proteins having a single COOH-terminal hydrophobic domain capable of post-translational insertion into lipid bilayer is known as tail-anchored (TA) proteins. To clarify the insertion mechanism of the TA-domain of human cytochrome b(5) (Hcytb5) into ER membranes, we produced and purified various membrane-bound forms of Hcytb5 with their heme b-bound, in which various truncated forms of NH(2)-terminal bovine opsin sequence were appended at the COOH-terminus of the native form. We analyzed the integration of the TA-domains of these forms onto protein-free liposomes. The integration occurred efficiently even in the presence of a small amount of sodium cholate and, once incorporated, such proteoliposomes were very stable. The mode of the integration was further analyzed by treatment of the proteoliposomes with trypsin either on the extravesicular side or on the luminal side. LC-MS analyses of the trypsin digests obtained from the proteoliposomes indicated that most of the C-terminal hydrophilic segment of the native Hcytb5 were exposed towards the lumen of the vesicles and, further, a significant part of the population of the extended C-terminal hydrophilic segments of the modified Hcytb5 were exposed in the lumen as well, suggesting efficient translocation ability of the TA-domain without any assistance from other protein factors. Present results opened a route for the use of the C-terminal TA-domain as a convenient tool for the transport of proteins as well as short peptides into artificial liposomes.

  7. 新型PMAA/MWCNT-COOH杂合水凝胶的合成与茶碱释放%Preparation of Novel PMAA/MWCNT-COOH Hybrid Hydrogel and Theophylline Releasing

    Institute of Scientific and Technical Information of China (English)

    张常虎

    2012-01-01

    A series of nanohybrid hydrogels were designed and developed based on a hydrogen bond self-assembly of poly( methacylic acid) networks CPMAA) and carboxyl-functionalized muiti-walled carbon nanotubes (MWCNT-COOH). The structure, morphology and mechanical performance of nanohybrid hydrogels were obtained through FT-IR,ESEM,TEM,DMA, etc. The results show that MWCNT-COOH caused the swelling rate to be significantly higher than pure PMAA hydrogel. The nanohybnd hydrogels showed low mtcropore densities and larger mesh sizes with an increase in MWCNT-COOH contents, which govern the pH response to some extent. Increasing pH values caused equilibrium swelling ratios and accumulative release to be elevated. Swelling was enhanced sharply and mechanical properties distinctly declined. Theophylline was used as a model drug for the release studies to observe the effect of different MWCNT-COOH concentrations and pH values on drug release, which was released fast, to the equilibrium for about 8h with the circumstance of human intestinal tract, but emissed slow in model gastric juice. So PMAA/MWCNT-COOH hybrid hydrogel was a potential carrier of controlling drug release materials.%通过甲基丙烯酸(MAA)的原位自由基交联聚合反应制备了一系列新型pH敏感的聚甲基丙烯酸/羧基化多壁碳纳米管(PMAA/MWCNT-COOH)杂合水凝胶.利用红外光谱分析仪(FT-IR)、环境扫描电镜(ESEM)、动态粘弹谱仪(MDA)等对杂合水凝胶的结构、形态和力学性能进行表征.结果表明,MWCNT-COOH的引入,使杂合水凝胶的溶胀速率明显高于纯PMAA水凝胶;在溶胀状态下的力学性能测试表明,水凝胶弹性、回复性能等达到了软组织材料的要求.掺杂不同含量的碳纳米管和改变不同pH环境会影响永凝胶的溶胀行为,改变网孔密度和孔径大小,决定在载、释药物过程中起到重要作用.以茶碱为模拟药物对凝胶载、释药物的研究发现,茶碱在肠道

  8. 原位法P3HT-COOH/CdS纳米复合材料的制备与表征%In-Situ Synthesis and Characterization of P3HT-COOH/CdS Nanocomposites

    Institute of Scientific and Technical Information of China (English)

    马海红; 高红; 周正发; 徐卫兵; 任凤梅

    2015-01-01

    以二水乙酸镉(Cd(OOCCH3)2·2H2O)为镉源,硫粉(S)为硫源,二氯苯(DCB)和二甲基亚砜(DMSO)为混合溶剂,末端羧基化聚-3-己基噻吩(P3 HT-COOH)为模板,原位法合成了P3HT-COOH/CdS纳米复合材料;并利用核磁共振氢谱、傅里叶变换红外光谱、X射线衍射、透射电子显微镜、紫外-可见光谱和荧光光谱等分析测试方法对其组成、形貌、光电性能等进行了表征.研究了不同反应温度及S/Cd摩尔比对复合材料形貌及光电性能的影响.实验结果表明,所合成的CdS纳米粒子均匀分布在P3HT-COOH/CdS复合材料中;CdS的尺寸和分布不仅受温度影响,还很大程度上受S/Cd摩尔比的影响;P3HT-COOH/CdS纳米复合材料有较强的荧光淬灭,表明CdS与P3HT-COOH之间有电荷转移.

  9. A conserved hydrogen-bond network in the catalytic centre of animal glutaminyl cyclases is critical for catalysis.

    Science.gov (United States)

    Huang, Kai-Fa; Wang, Yu-Ruei; Chang, En-Cheng; Chou, Tsung-Lin; Wang, Andrew H-J

    2008-04-01

    QCs (glutaminyl cyclases; glutaminyl-peptide cyclotransferases, EC 2.3.2.5) catalyse N-terminal pyroglutamate formation in numerous bioactive peptides and proteins. The enzymes were reported to be involved in several pathological conditions such as amyloidotic disease, osteoporosis, rheumatoid arthritis and melanoma. The crystal structure of human QC revealed an unusual H-bond (hydrogen-bond) network in the active site, formed by several highly conserved residues (Ser(160), Glu(201), Asp(248), Asp(305) and His(319)), within which Glu(201) and Asp(248) were found to bind to substrate. In the present study we combined steady-state enzyme kinetic and X-ray structural analyses of 11 single-mutation human QCs to investigate the roles of the H-bond network in catalysis. Our results showed that disrupting one or both of the central H-bonds, i.e., Glu(201)...Asp(305) and Asp(248)...Asp(305), reduced the steady-state catalysis dramatically. The roles of these two COOH...COOH bonds on catalysis could be partly replaced by COOH...water bonds, but not by COOH...CONH(2) bonds, reminiscent of the low-barrier Asp...Asp H-bond in the active site of pepsin-like aspartic peptidases. Mutations on Asp(305), a residue located at the centre of the H-bond network, raised the K(m) value of the enzyme by 4.4-19-fold, but decreased the k(cat) value by 79-2842-fold, indicating that Asp(305) primarily plays a catalytic role. In addition, results from mutational studies on Ser(160) and His(319) suggest that these two residues might help to stabilize the conformations of Asp(248) and Asp(305) respectively. These data allow us to propose an essential proton transfer between Glu(201), Asp(305) and Asp(248) during the catalysis by animal QCs.

  10. Bond strength of direct and indirect bonded brackets after thermocycling.

    Science.gov (United States)

    Daub, Jacob; Berzins, David W; Linn, Brandon James; Bradley, Thomas Gerard

    2006-03-01

    Thermocycling simulates the temperature dynamics in the oral environment. With direct bonding, thermocycling reduces the bond strength of orthodontic adhesives to tooth structure. The purpose of this study was to evaluate the shear bond strengths (SBS) of one direct and two indirect bonding methods/adhesives after thermocycling. Sixty human premolars were divided into three groups. Teeth in group 1 were bonded directly with Transbond XT. Teeth in group 2 were indirect bonded with Transbond XT/Sondhi Rapid Set, which is chemically cured. Teeth in group 3 were indirect bonded with Enlight LV/Orthosolo and light cured. Each sample was thermocycled between 5 degrees C and 55 degrees C for 500 cycles. Mean SBS in groups 1, 2, and 3 were not statistically significantly different (13.6 +/- 2.9, 12.3 +/- 3.0, and 11.6 +/- 3.2 MPa, respectively; P > .05). However, when these values were compared with the results of a previous study using the same protocol, but without thermocycling, the SBS was reduced significantly (P = .001). Weibull analysis further showed that group 3 had the lowest bonding survival rate at the minimum clinically acceptable bond-strength range. The Adhesive Remnant Index was also determined, and group 2 had a significantly (P bond failures at the resin/enamel interface.

  11. Synthesis and classical pathway Complement inhibitory activity of C7-functionalized filifolinol derivatives, inspired in K-76 COOH.

    Science.gov (United States)

    Larghi, Enrique L; Operto, María A; Torres, Rene; Kaufman, Teodoro S

    2012-09-01

    A series of carboxylic acids carrying various functionalization on C-7 of their common 3H-spiro[benzofuran-2,1'-cyclohexane] skeleton were synthesized from filifolinol, as analogs of the natural Complement inhibitor K-76 COOH. In order to probe the relevance of the C-7 functionalization on their bioactivity, the ability of the analogs to inhibit Complement activation through the classical pathway was determined. The observed results suggest that functionalization of C-7 can modulate the inhibitory activity of the tested compounds. The 7-trifluoromethyl derivative was the compound with the lowest IC(50) value among the tested analogs (IC(50) = 100 μM), being more potent than K-76 COOH (IC(50) = 570 μM).

  12. Charge-Assisted Hydrogen-Bonded Networks of NH4+ and [Co(NH36]3+ with the New Linker Anion of 4-Phosphono-Biphenyl-4′-Carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Christian Heering

    2016-02-01

    Full Text Available The new linker molecule 4-phosphono-biphenyl-4′-carboxylic acid (H2O3P-(C6H42-COOH, H3BPPA has been structurally elucidated in hydrogen-bonded networks with the ammonium cation NH4(H2BPPA(H3BPPA (1 and the hexaamminecobalt(III cation [Co(NH36](BPPA·4H2O (2. The protic O-H and N-H hydrogen atoms were found and refined in the low-temperature single-crystal X-ray structures. The hydrogen bonds in both structures are so-called charge-assisted; that is, the H-bond donor and/or acceptor carry positive and/or negative ionic charges, respectively. The H-bonded network in 1 consists of one formally mono-deprotonated 4-phosphonato-biphenyl-4′-carboxylic acid group; that is, a H2BPPA− anion and a neutral H3BPPA molecule, which together form a 3D hydrogen-bonded network. However, an almost symmetric resonance-assisted hydrogen bond (RAHB bond [O···H = 1.17 (3 and 1.26 (3 Å, O···H···O = 180 (3°] signals charge delocalization between the formal H2BPPA− anion and the formally neutral H3BPPA molecule. Hence, the anion in 1 is better formulated as [H2BPPA···H···H2BPPA]−. In the H-bonded network of 2 the 4-phosphonato-biphenyl-4′-carboxylic acid is triply deprotonated, BPPA3−. The [Co(NH36]3+ cation is embedded between H-bond acceptor groups, –COO− and –PO3− and H2O molecules. The incorporation of sixteen H2O molecules per unit cell makes 2 an analogue of the well-studied guanidinium sulfonate frameworks.

  13. PAMAM-COOH的合成、表征及对超细纤维合成革卫生性能的影响%Synthesis and characterization of PAMAM-COOH and its effect on sanitary properties of microfiber synthetic leather

    Institute of Scientific and Technical Information of China (English)

    任龙芳; 王娜; 陈婷; 王学川

    2014-01-01

    分别采用盐酸和乙醛酸对0.5代聚酰胺-胺(G0.5 PAMAM)和1代聚酰胺-胺(G1 PAMAM)进行改性,得到了0.5代端羧基的树枝状大分子(G0.5 PAMAM-COOH)和1.0代端羧基的树枝状大分子(G1 PAMAM-COOH).采用单因素实验优化了乙醛酸改性 G1 PAMAM 的反应条件,即n(G1 PAMAM)∶n (乙醛酸)为1∶12,反应温度为35℃,反应时间为2 h.采用G0.5 PAMAM-COOH和G1 PAMAM-COOH 对超细纤维合成革基布进行改性,结果表明,改性后基布的透水汽性分别提高了26.97%和34.59%.SEM 显示改性后基布纤维松散程度增加,孔隙变大.水接触角测试表明改性后基布上的亲水基团增多,经 G0.5 PAMAM-COOH 与 G1 PAMMA-COOH 改性的基布,其渗水时间较之未改性基布分别缩短了71.74%和78.26%,表明超细纤维合成革基布的卫生性能得到改善.%G0.5 PAMAM-COOH and G1 PAMAM-COOH were prepared by modifying G0.5 PAMAM and G1 PAMAM with hydrochloric acid and aldehyde acid respectively.The modifying conditions of G1 PAMAM with glyoxalic acid were optimized by single-factor experiment.The n(G1 PAMAM)∶n(aldehyde acid)was 1∶12, the reaction temperature was 35 ℃ and the reaction time was 2 h.The G0.5 PAMAM-COOH and G1 PAM-AM-COOH were used to modify polyamide microfiber synthetic leather base.The results showed that the wa-ter vapor permeability of microfiber synthetic leather base increased by 26.97% and 34.59%.The SEM images of the modified base showed that the microfiber became loose and the pore became big.The water contact angle test revealed that the hydrophilic groups increased.Compared to unmodified base,the water penetration time of bases modified by G0.5 PAMAM-COOH and G1 PAMAM-COOH shortened by 71.74% and 78.26%.These showed that the sanitary properties of microfiber synthetic leather were greatly improved.

  14. Immunohistochemical localization of the NH(2)-terminal and COOH-terminal fragments of dentin sialoprotein in mouse teeth.

    Science.gov (United States)

    Yuan, Guohua; Yang, Guobin; Song, Guangtai; Chen, Zhi; Chen, Shuo

    2012-08-01

    Dentin sialoprotein (DSP) is a major non-collagenous protein in dentin. Mutation studies in human, along with gene knockout and transgenic experiments in mice, have confirmed the critical role of DSP for dentin formation. Our previous study reported that DSP is processed into fragments in mouse odontoblast-like cells. In order to gain insights into the function of DSP fragments, we further evaluated the expression pattern of DSP in the mouse odontoblast-like cells using immunohistochemistry and western blot assay with antibodies against the NH(2)-terminal and COOH-terminal regions of DSP. Then, the distribution profiles of the DSP NH(2)-terminal and COOH-terminal fragments and osteopontin (OPN) were investigated in mouse teeth at different ages by immunohistochemistry. In the odontoblast-like cells, multiple low molecular weight DSP fragments were detected, suggesting that part of the DSP protein was processed in the odontoblast-like cells. In mouse first lower molars, immunoreactions for anti-DSP-NH(2) antibody were intense in the predentin matrix but weak in mineralized dentin; in contrast, for anti-DSP-COOH antibody, strong immunoreactions were found in mineralized dentin, in particular dentinal tubules but weak in predentin. Therefore, DSP NH(2)-terminal and COOH-terminal fragments from odontoblasts were secreted to different parts of teeth, suggesting that they may play distinct roles in dentinogenesis. Meanwhile, both DSP antibodies showed weak staining in reactionary dentin (RD), whereas osteopontin (OPN) was clearly positive in RD. Therefore, DSP may be less crucial for RD formation than OPN.

  15. Co(OH2 nanosheet-decorated graphene–CNT composite for supercapacitors of high energy density

    Directory of Open Access Journals (Sweden)

    Qian Cheng

    2014-01-01

    Full Text Available A composite of graphene and carbon nanotubes has been synthesized and characterized for application as supercapacitor electrodes. By coating the nanostructured active material of Co(OH2 onto one electrode, the asymmetric supercapacitor has exhibited a high specific capacitance of 310 F g−1, energy density of 172 Wh kg−1 and maximum power density of 198 kW kg−1 in ionic liquid electrolyte EMI-TFSI.

  16. Bond strength with custom base indirect bonding techniques.

    Science.gov (United States)

    Klocke, Arndt; Shi, Jianmin; Kahl-Nieke, Bärbel; Bismayer, Ulrich

    2003-04-01

    Different types of adhesives for indirect bonding techniques have been introduced recently. But there is limited information regarding bond strength with these new materials. In this in vitro investigation, stainless steel brackets were bonded to 100 permanent bovine incisors using the Thomas technique, the modified Thomas technique, and light-cured direct bonding for a control group. The following five groups of 20 teeth each were formed: (1) modified Thomas technique with thermally cured base composite (Therma Cure) and chemically cured sealant (Maximum Cure), (2) Thomas technique with thermally cured base composite (Therma Cure) and chemically cured sealant (Custom I Q), (3) Thomas technique with light-cured base composite (Transbond XT) and chemically cured sealant (Sondhi Rapid Set), (4) modified Thomas technique with chemically cured base adhesive (Phase II) and chemically cured sealant (Maximum Cure), and (5) control group directly bonded with light-cured adhesive (Transbond XT). Mean bond strengths in groups 3, 4, and 5 were 14.99 +/- 2.85, 15.41 +/- 3.21, and 13.88 +/- 2.33 MPa, respectively, and these groups were not significantly different from each other. Groups 1 (mean bond strength 7.28 +/- 4.88 MPa) and 2 (mean bond strength 7.07 +/- 4.11 MPa) showed significantly lower bond strengths than groups 3, 4, and 5 and a higher probability of bond failure. Both the original (group 2) and the modified (group 1) Thomas technique were able to achieve bond strengths comparable to the light-cured direct bonded control group.

  17. Treatment of TiO2 with COOH-functionalized germanium nanoparticles to enhance the photocurrent of dye-sensitized solar cells.

    Science.gov (United States)

    Kim, Chang-Ho; Ha, Eun-Sung; Baik, Hionsuck; Kim, Kang-Jin

    2011-03-01

    A dye-sensitized solar cell (DSSC) containing a TiO(2) film treated with COOH-functionalized germanium nanoparticles (Ge-COOH Nps) exhibited a higher short-circuit photocurrent density (J(sc); 15.4 mA cm(-2)) compared to the corresponding untreated DSSC (13.4 mA cm(-2)) using N719 and a 12 μm thick TiO(2) film at 100 mW cm(-2). The amount of N719 attached to the treated TiO(2) film was 21% greater than that attached to the untreated TiO(2) film. Enhancement of the J(sc) value by 15% was attributed mostly to an intramolecular charge transfer from N719 attached to the Ge-COOH Nps to the TiO(2) conduction band through the Ge-COOH Nps.

  18. Preparation of mesoporous SiO2@azobenzene-COOH chemoselective nanoprobes for comprehensive mapping of amino metabolites in human serum.

    Science.gov (United States)

    Li, Hua; Qin, Qian; Qiao, Lizhen; Shi, Xianzhe; Xu, Guowang

    2015-06-30

    A novel type of mesoporous SiO2@H4/D4 tagged azobenzene-COOH chemoselective nanoprobe was developed for comprehensive mapping of amino metabolites in complex biological samples with high specificity and sensitivity.

  19. Temperature profiles of three types CNTs (SWCNT, MWCNT and MWCNT-COOH) loaded environmental matrices generated from a microwave induced heating quantification method

    Data.gov (United States)

    U.S. Environmental Protection Agency — Relationships of temperature and CNT mass (SWCNT, MWCNT, MWCNT-COOH) were developed for three environmental matrices (sand, soil and sludge) spiked with known...

  20. Mechanistic Insights on C-O and C-C Bond Activation and Hydrogen Insertion during Acetic Acid Hydrogenation Catalyzed by Ruthenium Clusters in Aqueous Medium

    Energy Technology Data Exchange (ETDEWEB)

    Shangguan, Junnan; Olarte, Mariefel V.; Chin, Ya-Huei [Cathy

    2016-06-07

    Catalytic pathways for acetic acid (CH3COOH) and hydrogen (H2) reactions on dispersed Ru clusters in the aqueous medium and the associated kinetic requirements for C-O and C-C bond cleavages and hydrogen insertion are established from rate and isotopic assessments. CH3COOH reacts with H2 in steps that either retain its carbon backbone and lead to ethanol, ethyl acetate, and ethane (47-95 %, 1-23 %, and 2-17 % carbon selectivities, respectively) or break its C-C bond and form methane (1-43 % carbon selectivities) at moderate temperatures (413-523 K) and H2 pressures (10-60 bar, 298 K). Initial CH3COOH activation is the kinetically relevant step, during which CH3C(O)-OH bond cleaves on a metal site pair at Ru cluster surfaces nearly saturated with adsorbed hydroxyl (OH*) and acetate (CH3COO*) intermediates, forming an adsorbed acetyl (CH3CO*) and hydroxyl (OH*) species. Acetic acid turnover rates increase proportionally with both H2 (10-60 bar) and CH3COOH concentrations at low CH3COOH concentrations (<0.83 M), but decrease from first to zero order as the CH3COOH concentration and the CH3COO* coverages increase and the vacant Ru sites concomitantly decrease. Beyond the initial CH3C(O)-OH bond activation, sequential H-insertions on the surface acetyl species (CH3CO*) lead to C2 products and their derivative (ethanol, ethane, and ethyl acetate) and the competitive C-C bond cleavage of CH3CO* causes the eventual methane formation. The instantaneous carbon selectivities towards C2 species (ethanol, ethane, and ethyl acetate) increase linearly with the concentration of proton-type Hδ+ (derived from carboxylic acid dissociation) and chemisorbed H*. The selectivities towards C2 products decrease with increasing temperature, because of higher observed barriers for C-C bond cleavage than H-insertion. This study offers an interpretation of mechanism and energetics and provides kinetic evidence of carboxylic acid assisted proton-type hydrogen (Hδ+) shuffling during H

  1. Hydrogen-bonded clusters of 1, 1'-ferrocenedicarboxylic acid on Au(111) are initially formed in solution.

    Science.gov (United States)

    Quardokus, Rebecca C; Wasio, Natalie A; Brown, Ryan D; Christie, John A; Henderson, Kenneth W; Forrest, Ryan P; Lent, Craig S; Corcelli, Steven A; Kandel, S Alex

    2015-03-14

    Low-temperature scanning tunneling microscopy is used to observe self-assembled structures of ferrocenedicarboxylic acid (Fc(COOH)2) on the Au(111) surface. The surface is prepared by pulse-deposition of Fc(COOH)2 dissolved in methanol, and the solvent is evaporated before imaging. While the rows of hydrogen-bonded dimers that are common for carboxylic acid species are observed, the majority of adsorbed Fc(COOH)2 is instead found in six-molecule clusters with a well-defined and chiral geometry. The coverage and distribution of these clusters are consistent with a random sequential adsorption model, showing that solution-phase species are determinative of adsorbate distribution for this system under these reaction conditions.

  2. The NH2-terminal and COOH-terminal fragments of dentin matrix protein 1 (DMP1) localize differently in the compartments of dentin and growth plate of bone.

    Science.gov (United States)

    Maciejewska, Izabela; Cowan, Cameron; Svoboda, Kathy; Butler, William T; D'Souza, Rena; Qin, Chunlin

    2009-02-01

    Multiple studies have shown that dentin matrix protein 1 (DMP1) is essential for bone and dentin mineralization. After post-translational proteolytic cleavage, DMP1 exists within the extracellular matrix of bone and dentin as an NH2-terminal fragment, a COOH-terminal fragment, and the proteoglycan form of the NH2-terminal fragment (DMP1-PG). To begin to assess the biological function of each fragment, we evaluated the distribution of both fragments in the rat tooth and bone using antibodies specific to the NH2-terminal and COOH-terminal regions of DMP1 and confocal microscopy. In rat first molar organs, the NH2-terminal fragment localized to predentin, whereas the COOH-terminal fragment was mainly restricted to mineralized dentin. In the growth plate of bone, the NH2-terminal fragment appeared in the proliferation and hypertrophic zones, whereas the COOH-terminal fragment occupied the ossification zone. Forster resonance energy transfer analysis showed colocalization of both fragments of DMP1 in odontoblasts and predentin, as well as hypertrophic chondrocytes within the growth plates of bone. The biochemical analysis of bovine teeth showed that predentin is rich in DMP1-PG, whereas mineralized dentin primarily contains the COOH-terminal fragment. We conclude that the differential patterns of expression of NH2-terminal and COOH-terminal fragments of DMP1 reflect their potentially distinct roles in the biomineralization of dentin and bone matrices.

  3. Differential roles of the COOH termini of AAA subunits of PA700 (19 S regulator) in asymmetric assembly and activation of the 26 S proteasome.

    Science.gov (United States)

    Gillette, Thomas G; Kumar, Brajesh; Thompson, David; Slaughter, Clive A; DeMartino, George N

    2008-11-14

    The 26 S proteasome is an energy-dependent protease that degrades proteins modified with polyubiquitin chains. It is assembled from two multi-protein subcomplexes: a protease (20 S proteasome) and an ATPase regulatory complex (PA700 or 19 S regulatory particle) that contains six different AAA family subunits (Rpt1 to -6). Here we show that binding of PA700 to the 20 S proteasome is mediated by the COOH termini of two (Rpt2 and Rpt5) of the six Rpt subunits that constitute the interaction surface between the subcomplexes. COOH-terminal peptides of either Rpt2 or Rpt5 bind to the 20 S proteasome and activate hydrolysis of short peptide substrates. Simultaneous binding of both COOH-terminal peptides had additive effects on peptide substrate hydrolysis, suggesting that they bind to distinct sites on the proteasome. In contrast, only the Rpt5 peptide activated hydrolysis of protein substrates. Nevertheless, the COOH-terminal peptide of Rpt2 greatly enhanced this effect, suggesting that proteasome activation is a multistate process. Rpt2 and Rpt5 COOH-terminal peptides cross-linked to different but specific subunits of the 20 S proteasome. These results reveal critical roles of COOH termini of Rpt subunits of PA700 in the assembly and activation of eukaryotic 26 S proteasome. Moreover, they support a model in which Rpt subunits bind to dedicated sites on the proteasome and play specific, nonequivalent roles in the asymmetric assembly and activation of the 26 S proteasome.

  4. The COOH-terminal domain of the JIL-1 histone H3S10 kinase interacts with histone H3 and is required for correct targeting to chromatin.

    Science.gov (United States)

    Bao, Xiaomin; Cai, Weili; Deng, Huai; Zhang, Weiguo; Krencik, Robert; Girton, Jack; Johansen, Jørgen; Johansen, Kristen M

    2008-11-21

    The JIL-1 histone H3S10 kinase in Drosophila localizes specifically to euchromatic interband regions of polytene chromosomes and is enriched 2-fold on the male X chromosome. JIL-1 can be divided into four main domains including an NH(2)-terminal domain, two separate kinase domains, and a COOH-terminal domain. Our results demonstrate that the COOH-terminal domain of JIL-1 is necessary and sufficient for correct chromosome targeting to autosomes but that both COOH- and NH(2)-terminal sequences are necessary for enrichment on the male X chromosome. We furthermore show that a small 53-amino acid region within the COOH-terminal domain can interact with the tail region of histone H3, suggesting that this interaction is necessary for the correct chromatin targeting of the JIL-1 kinase. Interestingly, our data indicate that the COOH-terminal domain alone is sufficient to rescue JIL-1 null mutant polytene chromosome defects including those of the male X chromosome. Nonetheless, we also found that a truncated JIL-1 protein which was without the COOH-terminal domain but retained histone H3S10 kinase activity was able to rescue autosome as well as partially rescue male X polytene chromosome morphology. Taken together these findings indicate that JIL-1 may participate in regulating chromatin structure by multiple and partially redundant mechanisms.

  5. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen,and Zhejiang and Guangdong provinces to issue bonds for the first time.How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the Shanghai Securities Journal.Edited excerpts follow.

  6. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen, and Zhejiang and Guangdong provinces to issue bonds for the first time. How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the ShanghaiSecuritiesJournal. Edited excerpts follow:

  7. Shear bond strength of two resin cements to human root dentin using three dentin bonding agents.

    Science.gov (United States)

    Gogos, C; Stavrianos, C; Kolokouris, I; Economides, N; Papadoyannis, I

    2007-01-01

    This study compared the bond strength of two resin cements to human root dentin when used with three bonding agents. The materials used were Rely X ARC and Perma Cem, two one-bottle bonding agents (Single Bond, Bond-1) and one self-etching bonding agent (Clearfil SE Bond). The dentin was obtained from single rooted human teeth, and the specimens were treated with either 15% EDTA or 37% phosphoric acid to remove the smear layer, except in groups where the self-etching bonding agent was used. The resin cements were placed on dentin surfaces with the use of bonding agents. Shear bond strength (SBS) was tested using a single plane shear test assembly. The dentin specimens were divided into 10 groups. Eight groups were pre-treated with EDTA or phosphoric acid to remove the smear layer, followed by a bonding agent (Bond-1 or Single Bond) and resin cement (Rely X or Perma Cem). In the two remaining groups, the smear layer was left intact, and the two resins cements were used in combination with the self-etching bonding agent (Clearfil SE Bond). No statistically significant differences were observed among the eight groups treated with one-bottle bonding agents. The mean bond strengths of the two groups treated with the self-etching bonding agent did not differ significantly from each other but were both significantly greater than the bond strengths of all the other groups. The results of this study also showed that EDTA can be used as an alternative to phosphoric acid in bonding procedures for resin cements. However, the bond strengths of resin cements, in combination with a self-etching bonding agent, were significantly greater than those of the same cements when used with one-bottle bonding agents.

  8. A sequence upstream of canonical PDZ-binding motif within CFTR COOH-terminus enhances NHERF1 interaction.

    Science.gov (United States)

    Sharma, Neeraj; LaRusch, Jessica; Sosnay, Patrick R; Gottschalk, Laura B; Lopez, Andrea P; Pellicore, Matthew J; Evans, Taylor; Davis, Emily; Atalar, Melis; Na, Chan-Hyun; Rosson, Gedge D; Belchis, Deborah; Milewski, Michal; Pandey, Akhilesh; Cutting, Garry R

    2016-12-01

    The development of cystic fibrosis transmembrane conductance regulator (CFTR) targeted therapy for cystic fibrosis has generated interest in maximizing membrane residence of mutant forms of CFTR by manipulating interactions with scaffold proteins, such as sodium/hydrogen exchange regulatory factor-1 (NHERF1). In this study, we explored whether COOH-terminal sequences in CFTR beyond the PDZ-binding motif influence its interaction with NHERF1. NHERF1 displayed minimal self-association in blot overlays (NHERF1, Kd = 1,382 ± 61.1 nM) at concentrations well above physiological levels, estimated at 240 nM from RNA-sequencing and 260 nM by liquid chromatography tandem mass spectrometry in sweat gland, a key site of CFTR function in vivo. However, NHERF1 oligomerized at considerably lower concentrations (10 nM) in the presence of the last 111 amino acids of CFTR (20 nM) in blot overlays and cross-linking assays and in coimmunoprecipitations using differently tagged versions of NHERF1. Deletion and alanine mutagenesis revealed that a six-amino acid sequence (1417)EENKVR(1422) and the terminal (1478)TRL(1480) (PDZ-binding motif) in the COOH-terminus were essential for the enhanced oligomerization of NHERF1. Full-length CFTR stably expressed in Madin-Darby canine kidney epithelial cells fostered NHERF1 oligomerization that was substantially reduced (∼5-fold) on alanine substitution of EEN, KVR, or EENKVR residues or deletion of the TRL motif. Confocal fluorescent microscopy revealed that the EENKVR and TRL sequences contribute to preferential localization of CFTR to the apical membrane. Together, these results indicate that COOH-terminal sequences mediate enhanced NHERF1 interaction and facilitate the localization of CFTR, a property that could be manipulated to stabilize mutant forms of CFTR at the apical surface to maximize the effect of CFTR-targeted therapeutics.

  9. A highly conserved motif at the COOH terminus dictates endoplasmic reticulum exit and cell surface expression of NKCC2.

    Science.gov (United States)

    Zaarour, Nancy; Demaretz, Sylvie; Defontaine, Nadia; Mordasini, David; Laghmani, Kamel

    2009-08-01

    Mutations in the apically located Na(+)-K(+)-2Cl(-) co-transporter, NKCC2, lead to type I Bartter syndrome, a life-threatening kidney disorder, yet the mechanisms underlying the regulation of mutated NKCC2 proteins in renal cells have not been investigated. Here, we identified a trihydrophobic motif in the distal COOH terminus of NKCC2 that was required for endoplasmic reticulum (ER) exit and surface expression of the co-transporter. Indeed, microscopic confocal imaging showed that a naturally occurring mutation depriving NKCC2 of its distal COOH-terminal region results in the absence of cell surface expression. Biotinylation assays revealed that lack of cell surface expression was associated with abolition of mature complex-glycosylated NKCC2. Pulse-chase analysis demonstrated that the absence of mature protein was not caused by reduced synthesis or increased rates of degradation of mutant co-transporters. Co-immunolocalization experiments revealed that these mutants co-localized with the ER marker protein-disulfide isomerase, demonstrating that they are retained in the ER. Cell treatment with proteasome or lysosome inhibitors failed to restore the loss of complex-glycosylated NKCC2, further eliminating the possibility that mutant co-transporters were processed by the Golgi apparatus. Serial truncation of the NKCC2 COOH terminus, followed by site-directed mutagenesis, identified hydrophobic residues (1081)LLV(1083) as an ER exit signal necessary for maturation of NKCC2. Mutation of (1081)LLV(1083) to AAA within the context of the full-length protein prevented NKCC2 ER exit independently of the expression system. This trihydrophobic motif is highly conserved in the COOH-terminal tails of all members of the cation-chloride co-transporter family, and thus may function as a common motif mediating their transport from the ER to the cell surface. Taken together, these data are consistent with a model whereby naturally occurring premature terminations that interfere with

  10. Trends in Homolytic Bond Dissociation Energies of Five- and Six-Coordinate Hydrides of Group 9 Transition Metals: Co, Rh, Ir.

    Science.gov (United States)

    Glezakou, Vassiliki-Alexandra; Rousseau, Roger; Elbert, Stephen T; Franz, James A

    2017-03-09

    The homolytic bond dissociation energies of a series of five- and six-coordinate mono- and dihydride complexes of the type HM(diphosphine)2 and [H2M(diphosphine)2](+) (where M = Co, Rh, and Ir) are calculated and compared with experimental values. This work probes the relationship between the homolytic bond dissociation energies (HMBDEs) of these complexes in these two different coordination environments and formal oxidation states. The results of these calculations and previous experimental observations suggest that for M = Rh the HMBDE of the five-coordinate HM(diphosphine)2 species are 0-2 kcal/mol larger than the HMBDE of the corresponding six-coordinate [H2M(diphosphine)2](+) species. For M = Ir the bond energies of the five- and six-coordinate complexes are nearly the same and for M = Co the six-coordinate species are 1-5 kcal/mol less than the corresponding five-coordinate species. Simplified models of large and complicated ligands seem to capture the essential trends and give very good estimates of these thermodynamic properties compared with experimentally available data that are difficult to obtain.

  11. The Study on the Interaction between DNA and CdS-COOH-EcoRI Complex%DNA与CdS-COOH-EcoRI复合物相互作用的研究

    Institute of Scientific and Technical Information of China (English)

    黄梅; 叶树虹; 宋永海

    2014-01-01

    采用荧光光谱、原子力显微镜、琼脂糖凝胶电泳等技术探究CdS-COOH-EcoRI复合物与DNA的相互作用.研究发现,小粒径的CdS-COOH-EcoRI复合物与DNA除了有特异性结合,还发生非特异性结合.DNA相对浓度比较大以及恒温孵育时间较短时,以特异性结合为主;而随着DNA相对浓度的减小以及恒温孵育时间的延长,会伴有非特异性结合.Ca2+存在时,可以通过延长孵育时间“激活”酶切反应,使得DNA被剪切.因此可以通过改变DNA相对浓度和孵育时间来调控EcoRI对DNA的剪切.

  12. The Lifetimes of Nitriles (-C*N) and Acids (-COOH) during Ultraviolet Photolysis and Their Survival in Space

    Science.gov (United States)

    Bernstein, Max P.; Ashbourn, Samantha; Sandford, Scott A.; Allamandola, Louis J.

    2003-01-01

    Nitriles are one of the most common classes of molecules observed in the gas phase in space, with over a dozen having been positively identified in interstellar and circumstellar environments through the detection of their rotational transitions. Acids, in contrast, are much less common. In this paper we present laboratory data comparing the stability of two structurally related acid-nitrile pairs to ultraviolet (UV) photolytic destruction: acetic acid vs. acetonitrile (CH3-COOH vs. CH3-CN) and glycine vs. aminoacetonitrile (H2N-CH2-COOH vs. H2N-CH2-CN). We find that the nitriles are destroyed ten and five times more slowly (respectively) by UV photolysis than are the corresponding acids. This suggests that whatever their relative formation rates, acids may be less abundant than nitriles in interstellar environments in part because they are more rapidly destroyed by photolysis. The results of this infrared (IR) spectral matrix isolation study indicate that during the lifetime of a typical interstellar cloud, even in its darkest regions, a population of acids in the gas phase will likely be diminished by at least half. Since aminoacetonitrile is a precursor to the amino acid glycine, and far more stable, presolar aminoacetonitrile may be a contributor to the deuterium enriched glycine detected in meteorites. It would clearly be informative to search for aminoacetonitrile (the nitrile corresponding to glycine) in the regions where the amino acid glycine has been reported.

  13. Advanced oxidation (H₂O₂ and/or UV) of functionalized carbon nanotubes (CNT-OH and CNT-COOH) and its influence on the stabilization of CNTs in water and tannic acid solution.

    Science.gov (United States)

    Czech, Bożena; Oleszczuk, Patryk; Wiącek, Agnieszka

    2015-05-01

    The properties of carbon nanotubes (CNTs) functionalized with -OH and -COOH groups during simulated water treatment with H2O2 and/or UV were tested. There following properties of CNTs were investigated: specific surface area, elemental composition (CHN), dynamic light scattering, Raman spectroscopy, X-ray photoelectron spectroscopy and changes in the CNTs structure were observed using transmission electron microscopy. Treatment of CNTs with H2O2 and/or UV affected their properties. This effect, however, was different depending on the functionalization of CNTs and also on the factor used (UV and/or H2O2). H2O2 plays a key role as a factor modifying the surface of CNT-OHs, whereas the properties of CNT-COOHs were most affected by UV rays. A shortening of the nanotubes, exfoliation, the opening of their ends, and changes in the surface charge were observed as a result of the action of UV and/or H2O2. The changes in observed parameters may influence the stability of the aqueous suspensions of CNTs.

  14. Effect of geometric deformation of tetrahedral bonding on the vibrational properties of Group-IV semiconductors: Si in the BC-8 structure

    Energy Technology Data Exchange (ETDEWEB)

    Goldberg, A.; El-Batanouny, M.; Wooten, F.

    1982-12-15

    The phonon dispersion curves and phonon density of states for silicon in the BC-8 structure have been calculated with the use of Weber's adiabatic-bond-charge model. All parameters were scaled in an unambiguous physical manner from Weber's values for silicon in the diamond structure. The frequency values at GAMMA agree to within 10% of those values available from Raman spectroscopy. The GAMMA/sub 1//sup -/ mode is compatible with a transformation from the BC-8 structure to the wurtzite structure, a transformation that takes place upon heating the BC-8 polymorph.

  15. Effect of geometric deformation of tetrahedral bonding on the vibrational properties of Group-IV semiconductors: Si in the BC-8 structure

    Science.gov (United States)

    Goldberg, A.; El-Batanouny, M.; Wooten, F.

    1982-12-01

    The phonon dispersion curves and phonon density of states for silicon in the BC-8 structure have been calculated with the use of Weber's adiabatic-bond-charge model. All parameters were scaled in an unambiguous physical manner from Weber's values for silicon in the diamond structure. The frequency values at Γ agree to within 10% of those values available from Raman spectroscopy. The Γ-1 mode is compatible with a transformation from the BC-8 structure to the wurtzite structure, a transformation that takes place upon heating the BC-8 polymorph.

  16. Copper-catalyzed domino synthesis of 2-imino-1H-imidazol-5(2H)-ones and quinoxalines involving C-C bond cleavage with a 1,3-dicarbonyl unit as a leaving group.

    Science.gov (United States)

    Yang, Yan; Ni, Fan; Shu, Wen-Ming; Wu, An-Xin

    2014-09-08

    Although 2-imino-1H-imidazol-5(2H)-ones have important biological activities in metabolism, their synthesis has rarely been investigated. Quinoxalines as "privileged scaffolds" in medicinal chemistry have been extensively investigated, but the development of novel and efficient synthetic methods remains very attractive. Herein, we have developed two copper-catalyzed domino reactions for the synthesis of 2-imino-1H-imidazol-5(2H)-ones and quinoxalines involving CC bond-cleavage with a 1,3-dicarbonyl unit as a leaving group. The domino sequence for the synthesis of 2-imino-1H-imidazol-5(2H)-ones includes aza-Michael addition, intramolecular cyclization, CC bond-cleavage, 1,2-rearrangement, and aerobic dehydrogenation reaction, whereas the domino sequence for the synthesis of quinoxalines includes aza-Michael addition, intramolecular cyclization, elimination reaction, and CC bond-cleavage reaction. The two domino reactions have significant advantages including high efficiency, mild reaction conditions, and high tolerance of various functional groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. The description and validation of a computationally-Efficient CH4-CO-OH (ECCOHv1.01 chemistry module for 3-D model applications

    Directory of Open Access Journals (Sweden)

    Y. F. Elshorbany

    2015-11-01

    Full Text Available We present the Efficient CH4-CO-OH chemistry module (ECCOH that allows for the simulation of the methane, carbon monoxide and hydroxyl radical (CH4-CO-OH system, within a chemistry climate model, carbon cycle model, or earth system model. The computational efficiency of the module allows many multi-decadal sensitivity simulations of the CH4-CO-OH system, which primarily determines the global atmospheric oxidizing capacity. This capability is important for capturing the nonlinear feedbacks of the CH4-CO-OH system and understanding the perturbations to methane, CO and OH and the concomitant impacts on climate. We implemented the ECCOH chemistry module into the NASA GEOS-5 Atmospheric Global Circulation Model (AGCM, performed multiple sensitivity simulations of the CH4-CO-OH system over two decades, and evaluated the model output with surface and satellite datasets of methane and CO. The favorable comparison of output from the ECCOH chemistry module (as configured in the GEOS-5 AGCM with observations demonstrates the fidelity of the module for use in scientific research.

  18. Bone Marrow Stem Cells Response to Collagen/Single-Wall Carbon Nanotubes-COOHs Nanocomposite Films with Transforming Growth Factor Beta 1.

    Science.gov (United States)

    Wang, Jianhua; He, Chaolong; Cheng, Niangmei; Yang, Qiu; Chen, Mingmao; You, Lijun; Zhang, Qiqing

    2015-07-01

    Single-wall carbon nanotubes (SWNTs) have attractive biochemical properties such as strong cell adhesion and protein absorption, which are very useful for a cell cultivation scaffold. In this study, collagen/SWNT-COOHs nanocomposite films composed of regenerated fish collagen and SWNT-COOHs (0, 0.5, 1.0 and 2.0 weight percent) were prepared by mixing solubilized pepsin-soluble collagen with solutions of SWNT-COOHs. Morphological observation by SEM indicated the homogenous dispersion of SWNT-COOHs in the collagen matrix. The application of FTIR confirmed that the process we applied to prepare the composites did not destroy the native structures of collagen and composites were crosslinked by D-ribose. The biocompatibility was evaluated in vitro using SD rat bone marrow stem cells (BMSCs). Compared with films without transforming growth factor beta 1 (TGF-β1), films with TGF-β1 had superior performance on promotion of cell growth. Compared with pure collagen film with TGF-β1, SWNT-containing films might promote cellular functions by adsorbing more growth factors. In conclusion, the study suggested that the collagen/SWNT-COOHs nanocomposite films with TGF-β1 were expected to be useful scaffolds in cartilage tissue engineering.

  19. Bridging silyl groups in sigma-bond metathesis and [1, 2] shifts. An experimental and computational study of the reaction between cerium metallocenes and MeOSiMe3

    Energy Technology Data Exchange (ETDEWEB)

    Werkema, Evan; Yahia, Ahmed; Maron, Laurent; Eisenstein, Odile; Andersen, Richard

    2010-04-21

    The reaction of Cp'2CeH (Cp' = 1,2,4-(Me3C)3C5H2 ) with MeOSiMe3 gives Cp'2CeOMe and HSiMe3 and the reaction of the metallacycle, Cp'[(Me3C)2C5H2C(Me) 2CH2]Ce, with MeOSiMe3 yields Cp'2CeOCH2SiMe3, formed from hypothetical Cp'2CeCH2OSiMe3 by a [1, 2] shift also known as a silyl-Wittig rearrangement. Although both cerium products are alkoxides, they are formed by different pathways. DFT calculations on the reaction of the model metallocene, Cp2CeH, and MeOSiMe3 show that the lowest energy pathway is a H for OMe exchange at Ce that occurs by way of a sigma-bond metathesis transition state as SiMe3 exchanges partners. The formation of Cp2CeOCH2SiMe3 occurs by way of a low activation barrier [1, 2]shift of the SiMe3 group in Cp2CeCH2OSiMe3. Calculations on a model metallacycle, Cp[C5H4C(Me)2CH2]Ce, show that the metallacycle favors CH bond activation over sigma-bond metathesis involving the transfer of the SiMe3 group in good agreement with experiment. The sigma-bond metathesis involving the transfer of SiMe3 and the [1, 2]shift of SiMe3 reactions have in common a pentacoordinate silicon at the transition states. A molecular orbital analysis illustrates the connection between these two Si-O bond cleavage reactions and traces the reason why they occur for a silyl but not for an alkyl group to the difference in energy required to form a pentacoordinate silicon or carbon atom in the transition state. This difference clearly distinguishes a silyl from an alkyl group as shown in the study of"Pyrolysis of Tetramethylsilane Yielding Free d-orbitals by Seyferth and Pudvin in ChemTech 1981, 11, 230-233".

  20. Bridging silyl groups in sigma-bond metathesis and [1, 2] shifts. An experimental and computational study of the reaction between cerium metallocenes and MeOSiMe3

    Energy Technology Data Exchange (ETDEWEB)

    Werkema, Evan; Yahia, Ahmed; Maron, Laurent; Eisenstein, Odile; Andersen, Richard

    2010-04-21

    The reaction of Cp'2CeH (Cp' = 1,2,4-(Me3C)3C5H2 ) with MeOSiMe3 gives Cp'2CeOMe and HSiMe3 and the reaction of the metallacycle, Cp'[(Me3C)2C5H2C(Me) 2CH2]Ce, with MeOSiMe3 yields Cp'2CeOCH2SiMe3, formed from hypothetical Cp'2CeCH2OSiMe3 by a [1, 2] shift also known as a silyl-Wittig rearrangement. Although both cerium products are alkoxides, they are formed by different pathways. DFT calculations on the reaction of the model metallocene, Cp2CeH, and MeOSiMe3 show that the lowest energy pathway is a H for OMe exchange at Ce that occurs by way of a sigma-bond metathesis transition state as SiMe3 exchanges partners. The formation of Cp2CeOCH2SiMe3 occurs by way of a low activation barrier [1, 2]shift of the SiMe3 group in Cp2CeCH2OSiMe3. Calculations on a model metallacycle, Cp[C5H4C(Me)2CH2]Ce, show that the metallacycle favors CH bond activation over sigma-bond metathesis involving the transfer of the SiMe3 group in good agreement with experiment. The sigma-bond metathesis involving the transfer of SiMe3 and the [1, 2]shift of SiMe3 reactions have in common a pentacoordinate silicon at the transition states. A molecular orbital analysis illustrates the connection between these two Si-O bond cleavage reactions and traces the reason why they occur for a silyl but not for an alkyl group to the difference in energy required to form a pentacoordinate silicon or carbon atom in the transition state. This difference clearly distinguishes a silyl from an alkyl group as shown in the study of"Pyrolysis of Tetramethylsilane Yielding Free d-orbitals by Seyferth and Pudvin in ChemTech 1981, 11, 230-233".

  1. Bis(alkyl) rare-earth complexes coordinated by bulky tridentate amidinate ligands bearing pendant Ph2P[double bond, length as m-dash]O and Ph2P[double bond, length as m-dash]NR groups. Synthesis, structures and catalytic activity in stereospecific isoprene polymerization.

    Science.gov (United States)

    Rad'kova, Natalia Yu; Tolpygin, Aleksei O; Rad'kov, Vasily Yu; Khamaletdinova, Nadia M; Cherkasov, Anton V; Fukin, Georgi K; Trifonov, Alexander A

    2016-11-22

    A series of new tridentate amidines 2-[Ph2P[double bond, length as m-dash]X]C6H4NHC(tBu)[double bond, length as m-dash]N(2,6-R2C6H3) (X = O, R = iPr (1); X = S, R = Me (2); X = NPh, R = Me (3); X = N(2,6-Me2C6H3), R = Me (4)) bearing various types of donor Ph2P[double bond, length as m-dash]X groups in a pendant chain was synthesized. Bis(alkyl) complexes {2-[Ph2P[double bond, length as m-dash]X]C6H4NC(tBu)N(2,6-R2C6H3)}Ln(CH2SiMe3)2 (Ln = Y, X = O, R = iPr (5); Ln = Er, X = O, R = iPr (6); Ln = Lu, X = O, R = iPr (7); Ln = Y, X = NPh, R = Me (8); Ln = Lu, X = NPh, R = Me (9); Ln = Lu, X = N(2,6-Me2C6H3), R = Me (10)) were prepared using alkane elimination reactions of 1, 3 and 4 with Ln(CH2SiMe3)3(THF)2 (Ln = Y, Er, Lu) in toluene and were isolated in 45 (5), 62 (6), 56 (7), 65 (8), 60 (9), and 60 (10) % yields respectively. The X-ray diffraction studies showed that complexes 6-8 are solvent free and feature intramolecular coordination of the P[double bond, length as m-dash]X (X = O, NPh) group to the lanthanide ions. The ternary systems 5-10/borate/AlR3 (borate = [PhNHMe2][B(C6F5)4], [Ph3C][B(C6F5)4], AlR3 = AliBu3, AliBu2H; molar ratio = 1/1/10 or 1/1/1, toluene) proved to be active in isoprene polymerization and enable complete conversion of 1000-10 000 equivalents of the monomer into a polymer at 25 °C within 0.5-24 h affording polyisoprenes with polydispersities Mw/Mn = 1.22-3.18. A comparative study of the catalytic performance of the bis(alkyl) complexes coordinated by tridentate amidinate ligands containing different pendant donor groups demonstrated that replacement of the Ph2P[double bond, length as m-dash]O group by Ph2P[double bond, length as m-dash]NPh leads to a switch of stereoselectivity in isoprene polymerization from cis-1,4 (up to 98.5%) to trans-1,4 (up to 84.8%). And conversely introduction of methyl substituents in the 2,6 positions of the phenyl group of the Ph2P[double bond, length as m-dash]NPh fragment allows us to restore the 1,4-cis

  2. Effect of diamond bur cutting efficacy on dentin bond strengths of different bonding systems

    Directory of Open Access Journals (Sweden)

    Shirani F.

    2009-03-01

    Full Text Available "nBackground and Aim: As composite-dentin bond strength is affected by cavity preparation and the bond strength of composite resin to new and used bur prepared dentin has not yet been evaluated, this study evaluated the effects of cutting dentin with different cutting efficacy (new and used of burs on composite-dentin shear bond strength using self-etching primer bonding system and total etching bonding system. "nMaterials and Methods: Sixty caries free human 3rd molar were sectioned in occlosal surface to expose dentin, then polished with silicon carbide paper and randomly divided into four groups. Each group was prepared in a depth of 0.5mm of dentin, using new diamond bur, or used diamond bur. To change into a used bur, each new rough diamond bur had to work on bovine enamel for 30 minutes, under a load of 150g. Then, each group was bonded, using a total etch adhesive (single Bond or a self etch adhesive (clearfil SE Bond So there were 4 groups : 1-SE Bond, New bur; 2-SE Bond , used bur; 3-Single Bond , New bur ; 4-Single Bond, used bur. Similar composite capsules(Filtek Z250 were bonded to dentin surface and cured. specimens were stored in physiologic saline for 48h at 370 c , then put under shearing load to define composite - dentin shear bond strength. Results were interpreted via statistical analysis (T-test & two - way variance. "nResults: Shear bond strength of each group was as follows: 1-(27.3Mpa, 2-(33.5Mpa, 3-(16.9Mpa 4-(19.3Mpa. Statistical analysis proved that shear bond strength of used diamond bur prepared groups (2,4 was more than new diamond bur prepared ones (1,3. This statistical difference, specially, was seen between SE Bond groups (1,2 but not between single Bond groups (3,4. Also, shear bond strength of (SE Bond bonded groups (1,2 were more significantly than (single Bond bonded ones (3,4. "nConclusion: This study show that Bur cutting efficiency influences composite - dentin shear bond strength especially when the

  3. Preparation of Targeted Pegylated Adenoviral Vectors From Plga-cooh and Targeting Study in Vitro%靶向包载经PEG修饰的重组腺病毒PLGA造影剂的制备及其体外寻靶实验

    Institute of Scientific and Technical Information of China (English)

    叶鸣; 王志刚; 李兴升; 冉海涛; 骆杰

    2012-01-01

    Objective To prepare a kind of targeted PEG-ADV-loaded PLGA-COOH covalently binding with monoclonal antibody and investigate its affinity for Human umbilical vein endothelial cell (HUVEC) in vitro. Methods Targeted PLGA-COOH were prepared by combining PLGA-COOH with anti-E-selectin monoclonal antibody using l-ethyl-3-( 3-dimethylaminopropvl) carbodi-imide hydrochloride ( EDC) and N-hydroxysuccinimide (NHS) mediated cross linking agents. The characteristic of targeting to HUVEC and served non-targeted PLGA-COOH as the control group were valued. Results In the targeting study in vitro, it was shown that many targeted PLGA-COOH ultrasound contrast agents conjugated with HUVEC tightly. Conclusions Targeted PEG-ADV-loaded PLGA-COOH were prepared successfully and can bind to HUVEC effectively in vitro.%目的 采用共价结合的方法制备靶向包载经PEG修饰的重组腺病毒PLGA- COOH造影剂,并考察其体外寻靶能力.方法 采用碳二亚胺法将包载经PEG修饰的重组腺病毒PLGA-COOH造影剂与抗体共价结合,制备靶向高分子超声造影剂,检测该造影剂一般特性及体外寻靶能力.结果 体外寻靶实验显示,该靶向超声造影剂与普通包载经PEG修饰的重组腺病毒PLGA COOH造影剂对照能聚集并牢固结合到人脐静脉血管内皮细胞表面.结论 成功制备出靶向包载经PEG修饰的重组腺病毒PLGA-COOH造影剂,该靶向造影剂在体外具有较强的特异性寻靶结合能力.

  4. Effect of ortho-SR groups on O-H bond strength and H-atom donating ability of phenols: a possible role for the Tyr-Cys link in galactose oxidase active site?

    Science.gov (United States)

    Amorati, Riccardo; Catarzi, Francesca; Menichetti, Stefano; Pedulli, Gian Franco; Viglianisi, Caterina

    2008-01-09

    Rotation about the Ar-S bond in ortho-(alkylthio)phenols strongly affects the bond dissociation enthalpy (BDE) and the reactivity of the OH group. Newly synthesized sulfur containing heterocycles 3 and 4, where the -SR group is almost coplanar with the phenolic ring, are characterized by unusually low BDE(O-H) values (79.6 and 79.2 kcal/mol, respectively) and by much higher reactivities toward peroxyl radicals than the ortho-methylthio derivative 1 (82.0 kcal/mol). The importance of the intramolecular hydrogen bond (IHB) in determining the BDE(O-H) was demonstrated by FT-IR experiments, which showed that in heterocycles 3 and 4 the IHB between the phenolic OH group and the S atom is much weaker than that present in 1. Since the IHB can be formed only if the -SR group adopts an out-of-plane geometry, this interaction is possible only in the methylthio derivative 1 and not in 3 and 4. The additive contribution to the phenolic BDE(O-H) of the -SR substituent therefore varies from -3.1 to +2.8 kcal/mol for the in-plane and out-of-plane conformations, respectively. These results may be relevant to understanding the role of the tyrosine-cysteine link in the active site of galactose oxidase, an important enzyme that catalyzes the two-electron aerobic oxidation of primary alcohols to aldehydes. The switching of the ortho -SR substituent between perpendicular and planar conformations may account for the catalytic efficiency of this enzyme.

  5. Hydrogen bonds and electrostatic interactions in the 1:1 complex of DABCO di-betaine with squaric acid: Crystallographic, theoretical and spectroscopic studies

    Science.gov (United States)

    Barczyński, P.; Dega-Szafran, Z.; Katrusiak, A.; Szafran, M.

    2012-06-01

    The molecular structure of the 1:1 complex of DABCO di-betaine (1,4-dicarboxymethyl-1,4-diazabicyclo[2.2.2]octane inner salt) with squaric acid (1) has been characterized by single-crystal X-ray diffraction, infrared spectroscopy and DFT calculations. Crystals 1 are monoclinic, space group P21/c. One proton of squaric acid is transferred to one of the carboxylate groups of DABCO di-betaine. The mono-protonated DABCO di-betaine cation is further engaged in the COOH⋯OOC hydrogen bond of 2.526(2) Å with the neighboring cations, linking them into a zigzag chain. The hydrogen squarate anion interacts with the oxygen atom of the carboxylate group of DABCO di-betaine cation, through the Osbnd H⋯Odbnd C hydrogen bonds of 2.600(2) Å. The structures of monomer 1a, dimer 2 and cation 3 have been optimized at the B3LYP/6-31G(d,p) level of theory. The FTIR spectrum is consistent with the X-ray results. The second-derivative spectrum of 1 and calculated frequencies for the optimized structure 1a are used to explain the frequencies in the experimental FTIR spectrum.

  6. New inhibitors of the complement system inspired in K76-COOH. A SAR study of filifolinol derivatives through modifications of the C3' position.

    Science.gov (United States)

    Larghi, Enrique L; Operto, María A; Torres, Rene; Kaufman, Teodoro S

    2009-11-01

    A new series of tricyclic carboxylic acids with a 3H-spiro[benzofuran-2,10-cyclohexane] skeleton were synthesized from filifolinol, as analogs of the natural complement inhibitor K76-COOH. Their complement inhibitory activity was determined aiming to probe the importance of structural characteristics of the alicyclic part of K76-COOH. The presence and stereochemistry of O- and N-functionalities on C3' of the filifolinol derivatives are relevant for biological activity. The IC50 values of the most potent compounds were comparable or surpassed the activity of K76-COOH. The results also suggest that the diol moiety of the natural product may be useful for improving compound solubility.

  7. Syntheses and crystal structures of two ionic liquids with halogen-bonding groups: 4,5-dibromo- and 4,5-diiodo-1-butyl-3-methylimidazolium trifluoromethanesulfonates

    Science.gov (United States)

    Mukai, Tomohiro; Nishikawa, Keiko

    2010-05-01

    We have prepared and characterized two novel Lewis acidic ionic liquids, 4,5-dibromo- and 4,5-diiodo-1-butyl-3-methylimidazolium trifluoromethanesulfonates, using differential scanning calorimetry and single-crystal X-ray analysis. The effect of the halogen species on the phase transition behaviour and the cation-anion interacting geometry was investigated. The minor difference in chemical structure strongly affects the melting point, glass transition temperature and crystal structure because of the different halogen-bonding strength and linearity between C-Br⋯O and C-I⋯O. Both the salts melt above room temperature, but the fused salts show glass-forming property and poor crystallizability.

  8. Mutational analysis of bacteriophage T4 RNA ligase 1. Different functional groups are required for the nucleotidyl transfer and phosphodiester bond formation steps of the ligation reaction.

    Science.gov (United States)

    Wang, Li Kai; Ho, C Kiong; Pei, Yi; Shuman, Stewart

    2003-08-08

    T4 RNA ligase 1 (Rnl1) exemplifies an ATP-dependent RNA ligase family that includes fungal tRNA ligase (Trl1) and a putative baculovirus RNA ligase. Rnl1 acts via a covalent enzyme-AMP intermediate generated by attack of Lys-99 N zeta on the alpha phosphorus of ATP. Mutation of Lys-99 abolishes ligase activity. Here we tested the effects of alanine mutations at 19 conserved positions in Rnl1 and thereby identified 9 new residues essential for ligase activity: Arg-54, Lys-75, Phe-77, Gly-102, Lys-119, Glu-227, Gly-228, Lys-240, and Lys-242. Seven of the essential residues are located within counterparts of conserved nucleotidyltransferase motifs I (99KEDG102), Ia (118SK119), IV (227EGYVA231), and V (238HFKIK242) that comprise the active sites of DNA ligases, RNA capping enzymes, and T4 RNA ligase 2. Three other essential residues, Arg-54, Lys-75 and Phe-77, are located upstream of the AMP attachment site within a conserved domain unique to the Rnl1-like ligase family. We infer a shared evolutionary history and active site architecture in Rnl1 (a tRNA repair enzyme) and Trl1 (a tRNA splicing enzyme). We determined structure-activity relationships via conservative substitutions and examined mutational effects on the isolated steps of Rnl1 adenylylation (step 1) and phosphodiester bond formation (step 3). Lys-75, Lys-240, and Lys-242 were found to be essential for step 1 and overall ligation of 5'-phosphorylated RNA but not for phosphodiester bond formation. These results suggest that the composition of the Rnl1 active site is different during steps 1 and 3. Mutations at Arg-54 and Lys-119 abolished the overall RNA ligation reaction without affecting steps 1 and 3. Arg-54 and Lys-119 are thereby implicated as specific catalysts of the RNA adenylation reaction (step 2) of the ligation pathway.

  9. Effect of moisture, saliva, and blood contamination on the shear bond strength of brackets bonded with a conventional bonding system and self-etched bonding system

    Science.gov (United States)

    Prasad, Mandava; Mohamed, Shamil; Nayak, Krishna; Shetty, Sharath Kumar; Talapaneni, Ashok Kumar

    2014-01-01

    Background: The success of bonding brackets to enamel with resin bonding systems is negatively affected by contamination with oral fluids such as blood and saliva. The new self-etch primer systems combine conditioning and priming agents into a single application, making the procedure more cost effective. Objective: The purpose of the study was to investigate the effect of moisture, saliva and blood contamination on shear bond strength of orthodontic brackets bonded with conventional bonding system and self-etch bonding system. Materials and Methods: Each system was examined under four enamel surface conditions (dry, water, saliva, and blood), and 80 human teeth were divided into two groups with four subgroups each of 10 according to enamel surface condition. Group 1 used conventional bonding system and Group 2 used self-etched bonding system. Subgroups 1a and 2a under dry enamel surface conditions; Subgroups 1b and 2b under moist enamel surface condition; Subgroups 3a and 3b under saliva enamel surface condition and Subgroup 4a and 4b under blood enamel surface condition. Brackets were bonded, and all the samples were then submitted to a shear bond test with a universal testing machine with a cross head speed of 1mm/sec. Results: The results showed that the contamination reduced the shear bond strength of all groups. In self-etch bonding system water and saliva had significantly higher bond strength when compared to other groups. Conclusion: It was concluded that the blood contamination showed lowest bond strength from both bonding systems. Self-etch bonding system resulted in higher bond strength than conventional bonding system under all conditions except the dry enamel surface. PMID:24678210

  10. Arg333 and Arg334 in the COOH terminus of the human P2Y1 receptor are crucial for Gq coupling.

    Science.gov (United States)

    Ding, Zhongren; Tuluc, Florin; Bandivadekar, Kavita R; Zhang, Lili; Jin, Jianguo; Kunapuli, Satya P

    2005-03-01

    The P2Y(1) ADP receptor activates G(q) and causes increases in intracellular Ca(2+) concentration through stimulation of PLC. In this study, we investigated the role of the amino acid residues in the COOH terminus of the human P2Y(1) receptor in G(q) activation. Stimulation of Chinese hamster ovary (CHO-K1) cells stably expressing the wild-type human P2Y(1) receptor (P2Y(1)-WT cells), P2Y(1)-DeltaR340-L373, or P2Y(1)-DeltaD356-L373 with 2-methylthio-ADP (2-MeSADP) caused inositol phosphate production. In contrast, cells expressing P2Y(1)-DeltaT330-L373, a mutant lacking the entire COOH terminus, completely lost their response to 2-MeSADP. Similar data were obtained by using these cell lines and measuring Ca(2+) mobilization upon stimulation with 2-MeSADP, indicating that the 10 amino acids (330TFRRRLSRAT339) in the COOH terminus of the human P2Y(1) receptor are essential for G(q) coupling. Radioligand binding demonstrated that both the P2Y(1)-WT and P2Y(1)-DeltaT330-L373-expressing cells have almost equal binding of [(3)H]MRS2279, a P2Y(1) receptor antagonist, indicating that COOH-terminal truncation did not drastically affect the conformation of the receptor. CHO-K1 cells expressing a chimeric P2Y(12) receptor with the P2Y(1) COOH terminus failed to elicit G(q) functional responses, indicating that the P2Y(1) COOH terminus is essential but not sufficient for G(q) activation. Finally, cells expressing a double-mutant P2Y(1) receptor (R333A/R334A) in the conserved BBXXB region of the COOH terminus of the G(q)-activating P2Y receptors completely lost their functional ability to activate G(q). We conclude that the two arginine residues (R333R334) in the COOH terminus of the human P2Y(1) receptor are essential for G(q) coupling.

  11. Formaldehyde mediated proton-transport catalysis in the ketene-water radical cation CH2C(O)OH2+

    Science.gov (United States)

    Lee, Richard; Ruttink, Paul J. A.; Burgers, Peter C.; Terlouw, Johan K.

    2006-09-01

    Previous studies have shown that the solitary ketene-water ion CH2C(O)OH2+ (1) does not isomerize into CH2C(OH)2+ (2), its more stable hydrogen shift isomer. Tandem mass spectrometry based collision experiments reveal that this isomerization does take place in the CH2O loss from low-energy 1,3-dihydroxyacetone ions (HOCH2)2CO+. A mechanistic analysis using the CBS-QB3 model chemistry shows that such molecular ions rearrange into hydrogen-bridged radical cations [CH2C(O)O(H)-H...OCH2]+ in which the CH2O molecule catalyzes the transformation 1 --> 2 prior to dissociation. The barrier for the unassisted reaction, 29 kcal mol-1, is reduced to a mere 0.6 kcal mol-1 for the catalysed transformation. Formaldehyde is an efficient catalyst because its proton affinity meets the criterion for facile proton-transport catalysis.

  12. Synthesis and structure of ruthenium(IV) complexes featuring N-heterocyclic ligands with an N-H group as the hydrogen-bond donor: hydrogen interactions in solution and in the solid state.

    Science.gov (United States)

    Díez, Josefina; Gimeno, José; Merino, Isabel; Rubio, Eduardo; Suárez, Francisco J

    2011-06-06

    The synthesis and characterization of novel ruthenium(IV) complexes [Ru(η(3):η(3)-C(10)H(16))Cl(2)L] [L = 3-methylpyrazole (2b), 3,5-dimethylpyrazole (2c), 3-methyl-5-phenylpyrazole (2d), 2-(1H-pyrazol-5-yl)phenol (2e), 6-azauracile (3), and 1H-indazol-3-ol (4)] are reported. Complex 2e is converted to the chelated complex [Ru(η(3):η(3)-C(10)H(16))Cl(κ(2)-N,O-2-(1H-pyrazol-3-yl)phenoxy)] (5) by treatment with an excess of NaOH. All of the ligands feature N-H, O-H, or C═O as the potential hydrogen-bonding group. The structures of complexes 2a-2c, 2e, 3, and 5 in the solid state have been determined by X-ray diffraction. Complexes 2a-2c and 3, which contain the pyrazole N-H group, exhibit intra- and intermolecular hydrogen bonds with chloride ligands [N-H···Cl distances (Å): intramolecular, 2.30-2.78; intermolecular, 2.59-2.77]. Complexes 2e and 3 bearing respectively O-H and C═O groups also feature N-H···O interactions [intramolecular (2e), 2.27 Å; intermolecular (3), 2.00 Å]. Chelated complex 5, lacking the O-H group, only shows an intramolecular N-H···Cl hydrogen bonding of 2.42 Å. The structure of complex 3, which turns out to be a dimer in the solid state through a double intermolecular N-H···O hydrogen bonding, has also been investigated in solution (CD(2)Cl(2)) by NMR diffusion studies. Diffusion-ordered spectroscopy experiments reveal an equilibrium between monomer and dimer species in solution whose extension depends on the temperature, concentration, and coordinating properties of the solvent. Preliminary catalytic studies show that complex 3 is highly active in the redox isomerization of the allylic alcohols in an aqueous medium under very mild reaction conditions (35 °C) and in the absence of a base.

  13. AQP4 plasma membrane trafficking or channel gating is not significantly modulated by phosphorylation at COOH-terminal serine residues.

    Science.gov (United States)

    Assentoft, Mette; Larsen, Brian R; Olesen, Emma T B; Fenton, Robert A; MacAulay, Nanna

    2014-11-15

    Aquaporin 4 (AQP4) is the predominant water channel in the mammalian brain and is mainly expressed in the perivascular glial endfeet at the brain-blood interface. AQP4 serves as a water entry site during brain edema formation, and regulation of AQP4 may therefore be of therapeutic interest. Phosphorylation of aquaporins can regulate plasma membrane localization and, possibly, the unit water permeability via gating of the AQP channel itself. In vivo phosphorylation of six serine residues in the COOH terminus of AQP4 has been detected by mass spectrometry: Ser(276), Ser(285), Ser(315), Ser(316), Ser(321), and Ser(322). To address the role of these phosphorylation sites for AQP4 function, serine-to-alanine mutants were created to abolish the phosphorylation sites. All mutants were detected at the plasma membrane of transfected C6 cells, with the fraction of the total cellular AQP4 expressed at the plasma membrane of transfected C6 cells being similar between the wild-type (WT) and mutant forms of AQP4. Activation of protein kinases A, C, and G in primary astrocytic cultures did not affect the plasma membrane abundance of AQP4. The unit water permeability was determined for the mutant AQP4s upon heterologous expression in Xenopus laevis oocytes (along with serine-to-aspartate mutants of the same residues to mimic a phosphorylation). None of the mutant AQP4 constructs displayed alterations in the unit water permeability. Thus phosphorylation of six different serine residues in the COOH terminus of AQP4 appears not to be required for proper plasma membrane localization of AQP4 or to act as a molecular switch to gate the water channel.

  14. Comparative study of polymer containing beta-cyclodextrin and -COOH for adsorption toward aniline, 1-naphthylamine and methylene blue.

    Science.gov (United States)

    Zhao, Dong; Zhao, Liang; Zhu, Cheng-Shen; Shen, Xiangyu; Zhang, Xiaozhuan; Sha, Baofeng

    2009-11-15

    Three different polymers P1, P2 and P3 (P1 containing both beta-CD and -COOH, P2 containing beta-CD and P3 containing -COOH) were synthesized and applied to adsorption toward aniline, 1-naphthylamine and methylene blue. The concentrations (C) before and after adsorption were determined and the adsorption capacities (q) of P1, P2 and P3 were calculated. The maximum adsorption capacities (q(max)) toward aniline: q(max) (P1)=104 micromol g(-1), q(max) (P2)=14.9 micromol g(-1) and q(max) (P3)=53.1 micromol g(-1); toward 1-naphthylamine: q(max) (P1)=184 micromol g(-1), q(max) (P2)=53.8 micromol g(-1) and q(max) (P3)=125 micromol g(-1); toward methylene blue: q(max) (P1)=200 micromol g(-1), q(max) (P2)=12.7 micromol g(-1) and q(max) (P3)=215 micromol g(-1). P1 exhibited remarkable adsorption toward all the three adsorbates. P2 was almost equal to P1 in adsorption toward methylene blue, but was less efficient than P1 in adsorption toward aniline and 1-naphthylamine. P3 also exhibited considerable adsorption toward aniline and 1-naphthylamine, but was inefficient toward methylene blue. P1 was obtained from nontoxic materials and through environment friendly procedures, so it was potentially an efficient and green adsorbent for water purification.

  15. Uptake of CF3COOH in Upper Tropospheric Sulfate Particles: Effects of Fluorination on the Accommodation of Oxygenated Organic Vapors.

    Science.gov (United States)

    Sulbaek Andersen, M. P.; Nielsen, O. J.; Michelsen, R. R.; Iraci, L. T.

    2005-12-01

    Recognition of the adverse impact of chlorofluorocarbon (CFC) release into the atmosphere has led to an international effort to replace CFCs with environmentally acceptable alternatives. Laboratory studies indicate that some of these, including HFC-134a, degrade to yield trifluoroacetyl halides of the form CF3C(O)X. Hydrolysis of trifluoroacetyl halides in cloud water is expected to form trifluoroacetic acid (TFA). Although TFA is produced in aqueous phase chemistry, is highly soluble and also partitions into the water phase, the evaporation of cloud droplets can relocate TFA to the gas phase where it can react with OH radicals. Still this reaction is slow and can only account for to account for fog water will act as a sink for atmospheric TFA, an accurate knowledge of the Henry's law coefficient is required to assess gas/liquid partitioning in upper tropospheric sulfate aerosols, where the temperature and liquid phase pH is much lower. The purpose of this work is to evaluate the role of upper tropospheric sulfate aerosols as a potential sink for TFA, and more generally, the effects of fluorine substitution on uptake of organic compounds into upper tropospheric aerosols. We have measured the solubility of gaseous acetic acid (CH3C(O)OH), and TFA (CF3C(O)OH) in cold sulfuric acid solutions over ranges of temperature (210-245 K) and acid composition (40-75 wt% H2SO4). The determining factors in the accumulation of organic material into sulfate particles in the UT/LS are discussed and the possibility of upper tropospheric sulfate aerosols to act as a global sink for TFA is evaluated.

  16. COOH-terminal deletion of HBx gene is a frequent event in HBV-associated hepatocellular carcinoma

    Institute of Scientific and Technical Information of China (English)

    Xiao-Hong Liu; Jing Lin; Shu-Hui Zhang; Shun-Min Zhang; Mark A Feitelson; Heng-Jun Gao; Ming-Hua Zhu

    2008-01-01

    AIM:To investigate the hepatitis B virus (HBV) x gene (HBx) state in the tissues of HBV-related hepatocellular carcinoma (HCC) in Chinese patients and whether there were particular HBx mutations.METHODS:HBx gene was amplified and direct sequencing was used in genomic DNA samples from 20HCC and corresponding non-cancerous liver tissues from HBsAg-positive patients.HBV DNA integration and HBx deleted mutation were validated in 45 HCC patients at different stages by Southern blot analysis and polymerase chain reaction methods.RESULTS:The frequencies of HBx point mutations were significantly lower in HCC than their corresponding non-cancerous liver tissues (11/19 vs 18/19,P = 0.019).In contrast,deletions in HBx gene were significantly higher in HCC than their non-cancerous liver tissues (16/19 vs 4/19,P<0.001).The deletion of HBx COOH-terminal was detected in 14 HCC tissues.A specific integration of HBx at 17p13 locus was also found in 8 of 16 HCC,and all of them also exhibited full-length HBx deletions.Integrated or integrated coexistence with replicated pattern was obtained in 45.5% (20145)-56.8% (25145)tumors and 40.9% (18/45)-52.3% (23/45) non-tumor tissues.CONCLUSION:HBx deletion,especially the COOH-terminal deletion of HBx is a frequent event in HBV-associated HCC tissues in China.HBV integration had also taken place in partial HCC tissues.This supporting the hypothesis that deletion and probably integrated forms of the HBx gene may be implicated in liver carcinogenesis.

  17. Quantum Confinement in Hydrogen Bond

    CERN Document Server

    Santos, Carlos da Silva dos; Ricotta, Regina Maria

    2015-01-01

    In this work, the quantum confinement effect is proposed as the cause of the displacement of the vibrational spectrum of molecular groups that involve hydrogen bonds. In this approach the hydrogen bond imposes a space barrier to hydrogen and constrains its oscillatory motion. We studied the vibrational transitions through the Morse potential, for the NH and OH molecular groups inside macromolecules in situation of confinement (when hydrogen bonding is formed) and non-confinement (when there is no hydrogen bonding). The energies were obtained through the variational method with the trial wave functions obtained from Supersymmetric Quantum Mechanics (SQM) formalism. The results indicate that it is possible to distinguish the emission peaks related to the existence of the hydrogen bonds. These analytical results were satisfactorily compared with experimental results obtained from infrared spectroscopy.

  18. 八羧基铜酞菁修饰海藻酸钠阳膜层制备CuPc(COOH)_8-SA/mCS双极膜及其表征%Preparation and Characterization of CuPc(COOH)_8-SA/mCS Bipolar Membrane Modified by Copper Octocarboxyphthalocyanine in Cation Layer

    Institute of Scientific and Technical Information of China (English)

    陈日耀; 陈震; 郑曦; 陈晓; 张娟灵

    2009-01-01

    In this paper,the sodium alginate(SA)cation layer was modified by copper octocarboxyphthalocyanine (CuPc(COOH)_8),then the CuPc(COOH)_8-SA and chitosan(CS)were modified by Fe~(3+)and ghtaraldehyde as linking reagents to prepare CuPc(COOH)-8-SA/mCS bipolar membrane(BPM).The FTIR and SEM were used to characterize the CuPc(COOH)_8-SMmCS BPM.The CuPc(COOH)-8 can promote water splitting at the interlayer of the CuPc (COOH)_8-SA/mCS BPM.For comparison with the CuPc(COOH)_8-SA/mCS BPM,the mSA/mCS BPMs modified by Fe~(3+)and ferrocene were prepared.The experimental results showed that the ion exchange capacity and hydrogen ion transmigration rate of the CuPc(COOH)_8-SA cation exchange membrane were increased.In comparison with the mSA/mCS BPM modified by Fe~(3+)or ferrocene,the membrane impedance,IR drop and swelling degree of the CuPc(COOH)_8-SA/mCS BPM were decreased.The BPM was stable in an acid solution(c_(H~+)<8 mol·L~(-1).%在海藻酸钠(SA)中添加八羧基铜酞菁(CuPc(COOH)_8),并分别用Fe~(3+)离子和戊二醛作为交联剂对海藻酸钠一八羧基铜酞菁阳膜层和壳聚糖(CS)阴膜层进行改性,制备了八羧基铜酞菁-海藻酸钠/改性壳聚糖双极膜(CuPe(COOH)_8-SA/BPM).在海藻酸钠中添加八羧基铜酞菁以促进中间层中水的解离.用FTIR、SEM等对制备的CuPc(COOH)_8-SMmCS双极膜进行了表征.作为比对,制备了Fe~(3+)离子改性的Fe-SA/mCS双极膜和二茂铁(Fc)离子改性的Fc-SA/mCS双极膜.实验结果表明,CuPc(COOH)8-SA阳离子交换膜的离子交换容量、H+离子透过率均获得提高.与Fe~(3+)离子改性或二茂铁离子改性的mSA/mCS双极膜相比,CuPc(COOH)_8-SA/mCS双极膜的阻抗、电阻压降(IR降)和溶胀度降低,在H+离子浓度低于8 mol·L~(-1)的酸溶液中具有稳定的工作性能.

  19. Direct C-C Coupling of CO2 and the Methyl Group from CH4 Activation through Facile Insertion of CO2 into Zn-CH3 σ-Bond.

    Science.gov (United States)

    Zhao, Yuntao; Cui, Chaonan; Han, Jinyu; Wang, Hua; Zhu, Xinli; Ge, Qingfeng

    2016-08-17

    Conversion of CO2 and CH4 to value-added products will contribute to alleviating the green-house gas effect but is a challenge both scientifically and practically. Stabilization of the methyl group through CH4 activation and facile CO2 insertion ensure the realization of C-C coupling. In the present study, we demonstrate the ready C-C coupling reaction on a Zn-doped ceria catalyst. The detailed mechanism of this direct C-C coupling reaction was examined based on the results from density functional theory calculations. The results show that the Zn dopant stabilizes the methyl group by forming a Zn-C bond, thus hindering subsequent dehydrogenation of CH4. CO2 can be inserted into the Zn-C bond in an activated bent configuration, with the transition state in the form of a three-centered Zn-C-C moiety and an activation barrier of 0.51 eV. The C-C coupling reaction resulted in the acetate species, which could desorb as acetic acid by combining with a surface proton. The formation of acetic acid from CO2 and CH4 is a reaction with 100% atom economy, and the implementation of the reaction on a heterogeneous catalyst is of great importance to the utilization of the greenhouse gases. We tested other possible dopants including Al, Ga, Cd, In, and Ni and found a positive correlation between the activation barrier of C-C coupling and the electronegativity of the dopant, although C-H bond activation is likely the dominant reaction on the Ni-doped ceria catalyst.

  20. Selective Reductive Removal of Ester and Amide Groups from Arenes and Heteroarenes through Nickel-Catalyzed C−O and C−N Bond Activation

    KAUST Repository

    Yue, Huifeng

    2017-03-21

    An inexpensive nickel(II) catalyst and a hydrosilane were used for the efficient reductive defunctionalization of aryl and heteroaryl esters through a decarbonylative pathway. This versatile method could be used for the removal of ester and amide functional groups from various organic molecules. Moreover, a scale-up experiment and a synthetic application based on the use of a removable carboxylic acid directing group highlight the usefulness of this reaction.

  1. Evaluation of bond strength of brackets using various indirect bonding techniques

    Directory of Open Access Journals (Sweden)

    Piyush Bolya

    2017-01-01

    Full Text Available Introduction: Accurate bracket placement has been always an area of interest for all orthodontists. Different types of adhesives for indirect bonding techniques have been introduced recently. However, there is limited information regarding bond strength with these new materials. The aim of this study is to compare and evaluate the bond strength in various indirect bonding techniques when using different primers and adhesives. Materials and Methods: In this in vitro investigation, brackets were bonded to fifty extracted premolars which were divided into five groups (A–E of ten each. Results: The overall comparison of all the techniques produced comparable mean bond strengths that were well within the clinically acceptable range. Group D produced the highest bond strength in comparison to other groups followed by Group E, B, C, and A. Conclusion: In the present study, all the groups have shown shear bond strength of more than 7.8 MPa. Hence, all the five techniques are suitable for clinical use.

  2. Plasma COOH-Terminal Proendothelin-1 A marker of fatal cardiovascular events, all-cause mortality, and new-onset albuminuria in type 2 diabetes? (ZODIAC-29)

    NARCIS (Netherlands)

    Drion, Iefke; Kleefstra, Nanne; Landman, Gijs W. D.; Alkhalaf, Alaa; Struck, Joachim; Groenier, Klaas H.; Bakker, Stephan J. L.; Bilo, Henk J. G.

    2012-01-01

    OBJECTIVE-The aim of this study was to investigate the association between plasma COOH-terminal proendothelin-1 (CT-proET-1) and fatal cardiovascular events, all-cause mortality, and new-onset albuminuria in patients with type 2 diabetes. RESEARCH DESIGN AND METHODS-A total of 1,225 patients with ty

  3. Quantification of 11-Carboxy-Delta-9-Tetrahydrocannabinol (THC-COOH) in Meconium Using Gas Chromatography/Mass Spectrometry (GC/MS).

    Science.gov (United States)

    Peat, Judy; Davis, Brehon; Frazee, Clint; Garg, Uttam

    2016-01-01

    Maternal substance abuse is an ongoing concern and detecting drug use during pregnancy is an important component of neonatal care when drug abuse is suspected. Meconium is the preferred specimen for drug testing because it is easier to collect than neonatal urine and it provides a much broader time frame of drug exposure. We describe a method for quantifying 11-carboxy-delta-9-tetrahydrocannabinol (THC-COOH) in meconium. After adding a labeled internal standard (THC-COOH D9) and acetonitrile, samples are sonicated to release both free and conjugated THC-COOH. The acetonitrile/aqueous layer is removed and mixed with a strong base to hydrolyze the conjugated THC-COOH. The samples are then extracted with an organic solvent mixture as part of a sample "cleanup." The organic solvent layer is discarded and the remaining aqueous sample is acidified. Following extraction with a second organic mixture, the organic layer is removed and concentrated to dryness. The resulting residue is converted to a trimethylsilyl (TMS) derivative and analyzed using gas chromatography/mass spectrometry (GC/MS) in selective ion monitoring (SIM) mode.

  4. Self-assembly of NH₂-(α,L-lysine)₅-COOH and SDS into nanodiscs or nanoribbons regulated by pH.

    Science.gov (United States)

    Zhang, S; Yang, S; Zang, J; Yang, R; Zhao, G; Xu, C

    2014-09-01

    NH2-(α,l-lysine)5-COOH and SDS can self-assemble into nanodiscs or nanoribbons. We show that pH can regulate not only the diameter of nanodiscs but also the conversion between nanodiscs and nanoribbons. This system can be used as two different templates for fabricating platinum nanowires and nanodiscs.

  5. Formaldehyde mediated proton-transport catalysis in the ketene-water radical cation CH2=C(=O)OH2•+

    NARCIS (Netherlands)

    Lee, R.; Ruttink, P.J.A.; Burgers, P.C.; Terlouw, J.K.

    2006-01-01

    Previous studies have shown that the solitary ketene-water ion CH2=C(=O)OH2+ (1) does not isomerize into CH2=C(OH)2+ (2), its more stable hydrogen shift isomer. Tandem mass spectrometry based collision experiments reveal that this isomerization does take place in the CH2=O loss from low-energy 1,3-d

  6. Synthesis and Characterization of 8-Yttrium(III-Containing 81-Tungsto-8-Arsenate(III, [Y8(CH3COO(H2O18(As2W19O684(W2O62(WO4]43−

    Directory of Open Access Journals (Sweden)

    Masooma Ibrahim

    2015-06-01

    Full Text Available The 8-yttrium(III-containing 81-tungsto-8-arsenate(III [Y8(CH3COO(H2O18(As2W19O684(W2O62(WO4]43− (1 has been synthesized in a one-pot reaction of yttrium(III ions with [B-α-AsW9O33]9− in 1 M NaOAc/HOAc buffer at pH 4.8. Polyanion 1 is composed of four {As2W19O68} units, two {W2O10} fragments, one {WO6} group, and eight YIII ions. The hydrated cesium-sodium salt of 1 (CsNa-1 was characterized in the solid-state by single-crystal XRD, FT-IR spectroscopy, thermogravimetric and elemental analyses.

  7. Evaluation of uptake, cytotoxicity and inflammatory effects in respiratory cells exposed to pristine and -OH and -COOH functionalized multi-wall carbon nanotubes.

    Science.gov (United States)

    Ursini, Cinzia Lucia; Maiello, Raffaele; Ciervo, Aureliano; Fresegna, Anna Maria; Buresti, Giuliana; Superti, Fabiana; Marchetti, Magda; Iavicoli, Sergio; Cavallo, Delia

    2016-03-01

    Toxic effects were reported for pristine-multi-wall carbon nanotubes (p-MWCNTs) while the role of the functionalization on MWCNT-induced toxicity is not yet well defined. We evaluated on human alveolar (A549) epithelial cells and normal bronchial (BEAS-2B) cells exposed to p-MWCNTs, MWCNTs-OH and MWCNTs-COOH: uptake by TEM, cell viability by different assays, membrane damage by the LDH assay and cytokine release by ELISA. The aims of the present study were to: (i) confirm MWCNT cytotoxicity mechanisms hypothesized in our previous studies; (ii) identify the most reliable viability assay to screen MWCNT toxicity; and (iii) to test our model to clarify the role of functionalization on MWCNT-induced toxicity. In A549 cells, p-MWCNTs and MWCNTs-OH were localized free in the cytoplasm and inside vacuoles whereas MWCNTs-COOH were confined inside filled cytoplasmic vesicles. WST-1 and Trypan blue assays showed in A549 cells a similar slight viability reduction for all MWCNTs whereas in BEAS-2B cells WST1 showed a high viability reduction at the highest concentrations, particularly for MWCNTs-COOH. The MTT assay showed a false cytotoxicity as a result of MWCNTs-interference. Pristine and MWCNTs-COOH induced membrane damage, particularly in BEAS-2B cells. MWCNTs-COOH induced interleukin-6 (IL-6) and IL-8 release in A549 cells whereas p-MWCNTs induced IL-8 release in BEAS-2B cells. MWCNTs intracellular localization in A549 cells confirms the toxicity mechanisms previously hypothesized, with p-MWCNTs disrupting the membrane and vesicle-confined MWCNTs-COOH inducing inflammation. WST-1 was more reliable than MTT to test MWCNT-toxicity. BEAS-2B cells were more susceptible then A549 cells, particularly to MWCNT-COOH cytotoxicity. Our results confirm the toxicity of p-MWCNTs and demonstrate, also for the two kinds of tested functionalized MWCNTs toxic effects with a different mechanism of action.

  8. Direct oxidative arylation of aryl C - H bonds with aryl boronic acids via pd catalysis directed by the N,N-dimethylaminomethyl group.

    Science.gov (United States)

    Zhang, Ji-Cheng; Shi, Jiang-Ling; Wang, Bi-Qin; Hu, Ping; Zhao, Ke-Qing; Shi, Zhang-Jie

    2015-04-01

    Biaryl skeletons were directly constructed via palladium-catalyzed ortho-arylation of N,N-dimethyl benzylamine with aryl boronic acids with high efficiency and high regioselectivity under open-flask conditions. The N,N-dimethylaminomethyl group was first applied as a directing group in such an oxidative coupling. Various substrates proved to be efficient coupling partners, furnishing the corresponding ortho-monoarylated or -diarylated arenes in moderate to good yields under mild conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Controlling the Conformational Energy of a Phenyl Group by Tuning the Strength of a Nonclassical CH···O Hydrogen Bond: The Case of 5-Phenyl-1,3-dioxane.

    Science.gov (United States)

    Bailey, William F; Lambert, Kyle M; Stempel, Zachary D; Wiberg, Kenneth B; Mercado, Brandon Q

    2016-12-16

    Anancomeric 5-phenyl-1,3-dioxanes provide a unique opportunity to study factors that control conformation. Whereas one might expect an axial phenyl group at C(5) of 1,3-dioxane to adopt a conformation similar to that in axial phenylcyclohexane, a series of studies including X-ray crystallography, NOE measurements, and DFT calculations demonstrate that the phenyl prefers to lie over the dioxane ring in order to position an ortho-hydrogen to participate in a stabilizing, nonclassical CH···O hydrogen bond with a ring oxygen of the dioxane. Acid-catalyzed equilibration of a series of anancomeric 2-tert-butyl-5-aryl-1,3-dioxane isomers demonstrates that remote substituents on the phenyl ring affect the conformational energy of a 5-aryl-1,3-dioxane: electron-withdrawing substituents decrease the conformational energy of the aryl group, while electron-donating substituents increase the conformational energy of the group. This effect is correlated in a very linear way to Hammett substituent parameters. In short, the strength of the CH···O hydrogen bond may be tuned in a predictable way in response to the electron-withdrawing or electron-donating ability of substituents positioned remotely on the aryl ring. This effect may be profound: a 3,5-bis-CF3 phenyl group at C(5) in 1,3-dioxane displays a pronounced preference for the axial orientation. The results are relevant to broader conformational issues involving heterocyclic systems bearing aryl substituents.

  10. Investigation of the interfacial bonding in composite propellants. 1,3,5-Trisubstituted isocyanurates as universal bonding agents

    Directory of Open Access Journals (Sweden)

    GORDANA S. USCUMLIC

    2006-05-01

    Full Text Available A series of 1,3,5-trisubstituted isocyanurates (substituents: CH2CH2OH, CH2CH=CH2 and CH2CH2COOH was synthesized according to a modified literature procedure. Experimental investigations included modification of the synthetic procedure in terms of the starting materials, solvents, temperature, isolation techniques, as well as purification and identification of the products. All the synthesized isocyanurates were identified by their melting point and FTIR, 1H NMR and UV spectroscopic data. Fourier transform infrared spectrophotometry was also used to study the interaction between ammonium perchlorate, hydroxyl terminated poly(butadiene, carboxyl terminated poly(butadiene, poly(butadiene-co-acrylonitrile, poly(propylene ether, cyclotrimethylenetrinitramine and the compounds synthesized in this work, which can serve as bonding agents. The results show that tris(2-hydroxyethylisocyanurate is a universal bonding agent for the ammonium perchlorate/carboxyl terminated poly(butadiene/cyclotrimethylenetrinitramine composite propellant system.

  11. COOH-terminal isoleucine of lysosome-associated membrane protein-1 is optimal for its efficient targeting to dense secondary lysosomes.

    Science.gov (United States)

    Akasaki, Kenji; Suenobu, Michihisa; Mukaida, Maki; Michihara, Akihiro; Wada, Ikuo

    2010-12-01

    Lysosome-associated membrane protein-1 (LAMP-1) consists of a highly glycosylated luminal domain, a single-transmembrane domain and a short cytoplasmic tail that possesses a lysosome-targeting signal (GYQTI(382)) at the COOH terminus. It is hypothesized that the COOH-terminal isoleucine, I(382), could be substituted with any other bulky hydrophobic amino acid residue for LAMP-1 to exclusively localize in lysosomes. In order to test this hypothesis, we compared subcellular distribution of four substitution mutants with phenylalanine, leucine, methionine and valine at the COOH-terminus (termed I382F, I382L, I382M and I382V, respectively) with that of wild-type (WT)-LAMP-1. Double-labelled immunofluorescence analyses showed that these substitution mutants were localized as significantly to late endocytic organelles as WT-LAMP-1. However, the quantitative subcellular fractionation study revealed different distribution of WT-LAMP-1 and these four COOH-terminal mutants in late endosomes and dense secondary lysosomes. WT-LAMP-1 was accumulated three to six times more in the dense lysosomal fraction than the four mutants. The level of WT-LAMP-1 in late endosomal fraction was comparable to those of I382F, I382M and I382V. Conversely, I382L in the late endosomal fraction was approximately three times more abundant than WT-LAMP-1. These findings define the presence of isoleucine residue at the COOH-terminus of LAMP-1 as critical in governing its efficient delivery to secondary lysosomes and its ratio of lysosomes to late endosomes.

  12. Ligation of cancer cell surface GRP78 with antibodies directed against its COOH-terminal domain up-regulates p53 activity and promotes apoptosis.

    Science.gov (United States)

    Misra, Uma Kant; Mowery, Yvonne; Kaczowka, Steven; Pizzo, Salvatore Vincent

    2009-05-01

    Binding of activated α(2)-macroglobulin to GRP78 on the surface of human prostate cancer cells promotes proliferation by activating signaling cascades. Autoantibodies directed against the activated α(2)-macroglobulin binding site in the NH(2)-terminal domain of GRP78 are receptor agonists, and their presence in the sera of cancer patients is a poor prognostic indicator. We now show that antibodies directed against the GRP78 COOH-terminal domain inhibit [(3)H]thymidine uptake and cellular proliferation while promoting apoptosis as measured by DNA fragmentation, Annexin V assay, and clonogenic assay. These antibodies are receptor antagonists blocking autophosphorylation and activation of GRP78. Using 1-LN and DU145 prostate cancer cell lines and A375 melanoma cells, which express GRP78 on their cell surface, we show that antibodies directed against the COOH-terminal domain of GRP78 up-regulate the tumor suppressor protein p53. By contrast, antibody directed against the NH(2)-terminal domain of GRP78 shows negligible effects on p53 expression. PC-3 prostate cancer cells, which do not express GRP78 on their cell surface, are refractory to the effects of anti-GRP78 antibodies directed against either the COOH- or NH(2)-terminal domains. However, overexpression of GRP78 in PC-3 cells causes translocation of GRP78 to the cell surface and promotes apoptosis when these cells are treated with antibody directed against its COOH-terminal domain. Silencing GRP78 or p53 expression by RNA interference significantly blocked the increase in p53 induced by antibodies. Antibodies directed against the COOH-terminal domain may play a therapeutic role in cancer patients whose tumors trigger the production of autoantibodies directed against the NH(2)-terminal domain of GRP78.

  13. COOH-terminal collagen Q (COLQ) mutants causing human deficiency of endplate acetylcholinesterase impair the interaction of ColQ with proteins of the basal lamina.

    Science.gov (United States)

    Arredondo, Juan; Lara, Marian; Ng, Fiona; Gochez, Danielle A; Lee, Diana C; Logia, Stephanie P; Nguyen, Joanna; Maselli, Ricardo A

    2014-05-01

    Collagen Q (ColQ) is a key multidomain functional protein of the neuromuscular junction (NMJ), crucial for anchoring acetylcholinesterase (AChE) to the basal lamina (BL) and accumulating AChE at the NMJ. The attachment of AChE to the BL is primarily accomplished by the binding of the ColQ collagen domain to the heparan sulfate proteoglycan perlecan and the COOH-terminus to the muscle-specific receptor tyrosine kinase (MuSK), which in turn plays a fundamental role in the development and maintenance of the NMJ. Yet, the precise mechanism by which ColQ anchors AChE at the NMJ remains unknown. We identified five novel mutations at the COOH-terminus of ColQ in seven patients from five families affected with endplate (EP) AChE deficiency. We found that the mutations do not affect the assembly of ColQ with AChE to form asymmetric forms of AChE or impair the interaction of ColQ with perlecan. By contrast, all mutations impair in varied degree the interaction of ColQ with MuSK as well as basement membrane extract (BME) that have no detectable MuSK. Our data confirm that the interaction of ColQ to perlecan and MuSK is crucial for anchoring AChE to the NMJ. In addition, the identified COOH-terminal mutants not only reduce the interaction of ColQ with MuSK, but also diminish the interaction of ColQ with BME. These findings suggest that the impaired attachment of COOH-terminal mutants causing EP AChE deficiency is in part independent of MuSK, and that the COOH-terminus of ColQ may interact with other proteins at the BL.

  14. Bioorganometallic Chemistry, Part 15. A novel molecular recognition process of host, trans-[Cp*Rh({eta}{sup 1}(N3)-1-methylcytosine)({mu}-OH)]{sub 2} (OTf){sub 2}, with l-aromatic amino acid guests: selective hydrogen bonding to the {mu}-OH groups and the 1-methylcytosine ligands

    Energy Technology Data Exchange (ETDEWEB)

    Elduque, Anabel; Carmona, Daniel; Oro, Luis; Eisenstein, Miriam; Fish, Richard H.

    2002-11-01

    The {sup 1}H-NMR and computer docking experiments have elucidated a novel molecular recognition process of host, trans-[Cp*Rh({eta}{sup 1}(Ne)-1-methylcytosine)({mu}-OH)]{sub 2}(OTf){sub 2} (1), with L-aromatic amino acids, which is predicated on a selective hydrogen bonding regime of the NH{sub 3}{sup +} of the amino acid to one of the Rh-{mu}-OH groups, as well as to a C{double_bond}O group of one of the other 1-methycytosine ligands, while the COO{sup -} H-bonds to an NH{sub 2} of the other 1-methycytosine ligand.

  15. Estanilenos: organometálicos de estanho (II σ - ligados a grupos orgânicos Stannylenes: organometallic compounds of tin (II σ-bonded to organic groups

    Directory of Open Access Journals (Sweden)

    Geraldo M. de Lima

    2010-01-01

    Full Text Available This article provides a short review of the chemistry of stannylenes and their derivatives, including the preparation, spectroscopic properties, molecular structure and reactivity of the various species. The organometallic chemistry of Sn(II is far less explored than that of its much more common Sn(IV counterpart. Organometallics of main group metals have become increasingly important in recent years, which prompted us to present an overview of the situation regarding the case of Sn(II.

  16. Water-soluble light-emitting nanoparticles prepared by non-covalent bond self-assembly of a hydroxyl group functionalized oligo(p-phenyleneethynylene) with different water-soluble polymers

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Water-soluble light-emitting nanoparticles were prepared from hydroxyl group functionalized oligos(p-phenyleneethynylene) (OHOPEL) and water-soluble polymers(PEG,PAA,and PG) by non-covalent bond self-assembly.Their structure and optoelectronic properties were investigated through dynamic light scattering(DLS) ,UV and PL spectroscopy.The optical properties of OHOPEL-based water-soluble nanoparticles exhibited the same properties as that found in OHOPEL films,indicating the existence of interchain-aggregation of OHOPELs in the nanoparticles.OHOPEL-based nanoparticles prepared from conjugated oligomers show smaller size and lower dispersity than nanoparticles from conjugated polymers,which means that the structures of water-soluble nanoparticles are linked to the conjugated length.Furthermore,the OHOPEL/PG and OHOPEL/PAA systems produced smaller particles and lower polydispersity than the OHOPEL/PEG system,indicating that there may exist influence of the strength of non-covalent bonds on the size and degree of dispersity of the nanoparticles.

  17. Composite Bonding to Stainless Steel Crowns Using a New Universal Bonding and Single-Bottle Systems

    Directory of Open Access Journals (Sweden)

    Mohammad Ali Hattan

    2013-01-01

    Full Text Available Aim. The aim of this study is to evaluate the shear bond strength of nanocomposite to stainless steel crowns using a new universal bonding system. Material and Methods. Eighty (80 stainless steel crowns (SSCs were divided into four groups (20 each. Packable nanocomposite was bonded to the lingual surface of the crowns in the following methods: Group A without adhesive (control group, Group B using a new universal adhesive system (Scotchbond Universal Adhesive, 3M ESPE, Seefeld, Germany, and Group C and Group D using two different brands of single-bottle adhesive systems. Shear bond strengths were calculated and the types of failure also were recorded. Results. The shear strength of Group B was significantly greater than that of other groups. No significant differences were found between the shear bond strengths of Groups C and D. The control group had significantly lower shear bond strength ( to composite than the groups that utilized bonding agents. Conclusion. Composites bonding to stainless steel crowns using the new universal bonding agent (Scotchbond Universal Adhesive, 3M ESPE, Seefeld, Germany show significantly greater shear bond strengths and fewer adhesive failures when compared to traditional single-bottle systems.

  18. Applications of Bis(1-R-imidazol-2-yl)disulfides and Diselenides as Ligands for Main Group and Transition Metals: κ2-[N,N] Coordination, S-S Bond Cleavage and S-S/E-E (E = S, Se) Bond Metathesis Reactions

    Science.gov (United States)

    Figueroa, Joshua S.; Yurkerwich, Kevin; Melnick, Jonathan; Buccella, Daniela; Parkin, Gerard

    2008-01-01

    Bis(1-R-imidazol-2-yl)disulfides, (mimR)2 (R = Ph, But), and diselenides, (seimMes)2, serve as bidentate [N,N]-donor ligands for main group and transition metals. For example, [κ2-(mimBut)2]MCl2 (M = Fe, Co, Ni, Zn), [κ2-(mimPh)2]MCl2 (M = Co, Zn), [κ2-(mimBut)2]CuX (X = Cl, I) and [κ2-(seimMes)2]MCl2 (M = Fe, Co, Ni) are obtained by treatment of (mimBut)2 or (seimMes)2 with the respective metal halide, and have been structurally characterized by X-ray diffraction. On the other hand, the zerovalent nickel complex Ni(PMe3)4 effects cleavage of the disulfide bond of (mimBut)2 to give square planar trans-Ni(PMe3)2(mimBut)2 in which the (mimBut) ligands coordinate via nitrogen rather than sulfur, a most uncommon coordination mode for this class of ligands. Although [κ2-(mimR)2]MCl2 (M = Fe, Co, Ni, Zn) are not subject to homolytic cleavage of the S-S bond because the tetravalent state is not readily accessible, the observation that [κ2-(mimPh)2]CoCl2 and [κ2-(mimBut)2]CoCl2 form an equilibrium mixture with the asymmetric disulfide [κ2-(mimPh)(mimBut)]CoCl2 indicates that S-S bond cleavage via another mechanism is possible. Likewise, metathesis between disulfide and diselenide ligands is observed in the formation of [κ2-(mimBut)(seimMes)]CoCl2 upon treatment of [κ2-(mimBut)2]CoCl2 with [κ2-(seimMes)2]CoCl2. PMID:17900186

  19. Apatite-forming ability of polymers with carboxy groups in simulated body fluid

    Energy Technology Data Exchange (ETDEWEB)

    Kawashita, M.; Nakao, M.; Kim, H.M.; Kokubo, T. [Kyoto Univ. (Japan). Dept. of Material Chemistry; Minoda, M. [Kyoto Inst. of Tech. (Japan). Dept. of Chemistry and Materials Technology; Miyamoto, T. [Matsue National Coll. of Technology (Japan); Nakamura, T. [Kyoto Univ. (Japan). Dept. of Orthopaedic Surgery

    2001-07-01

    Apatite-polymer composites with analogous structure to that of the natural bone are desired to be developed, since such composites are believed to show biological and mechanical properties similar to those of the natural bone. In the present study, apatite-forming ability of various kinds of polymers with or without carboxy (COOH) groups in simulated body fluid (SBF) was investigated. Carboxymethyl- (CM)- chitin and gellan gum gels, which have COOH groups, formed apatite on their surfaces within 3 d, when they were previously treated with saturated Ca(OH){sub 2} solution. Calcium alginate gel with COOH groups formed apatite on its surface within 7 d without the Ca(OH){sub 2}-treatment, since calcium ions are previously incorporated into the gel structure in the gel-forming process. In contrast, curdlan gel without COOH groups did not form that the COOH groups on a polymer surface are effective for the apatite nucleation and the apatite-forming ability of the polymer can be improved by incorporation of the calcium ions. In conclusion, these types of polymers are promising candidates for obtaining apatite-polymer composites with bonelike structure by a biomimetic process. (orig.)

  20. Preparation and characterization of nanocomposites based on COOH functionalized multi-walled carbon nanotubes and on poly(trimethylene terephthalate

    Directory of Open Access Journals (Sweden)

    2011-11-01

    Full Text Available Poly(trimethylene terephthalate nanocomposites containing COOH functionalized multi-walled nanotubes were synthesized with in situ polymerization method. The microstructure of the nanocomposites was studied by SEM, in terms of the dispersion state of the nanotubes and the polymer–nanotube interface. The thermal behaviour, mechanical properties and conductivity of these resultant PTT/MWCNTs nanocomposites were studied. The effect of the presence of MWCNTs on cold crystallization of PTT was monitored by dielectric spectroscopy. From thermal analysis study, it is found that the melting temperature and glass transition temperature are not significantly affected by the addition of MWCNTs. The crystallization temperature of PTT matrix is affected by the presence of CNTs. Nanocomposites have slightly higher degree of crystallinity than neat PTT and their thermo-oxidative stability is not significantly affected by the addition of MWCNTs. The study of the isothermal cold crystallization of amorphous PTT and its nanocomposites monitored by dielectric spectroscopy reveals that the presence of MWCNTs have influence on crystallization rate, especially at higher concentration (0.3 wt%. In comparison with neat PTT, the MWCNTs reinforced nanocomposites posses higher tensile strength and Young’s modulus at low MWCNTs loading (0.05–0.3 wt%. In addition, all nanocomposites show reduction of brittleness as compared to the neat PTT. The electrical percolation threshold was found between 0.3 and 0.4 wt% loading of MWCNTs.

  1. Chelation ion chromatography of alkaline earth and transition metals a using monolithic silica column with bonded N-hydroxyethyliminodiacetic acid functional groups.

    Science.gov (United States)

    McGillicuddy, Nicola; Nesterenko, Ekaterina P; Nesterenko, Pavel N; Jones, Phil; Paull, Brett

    2013-02-08

    A commercially available porous silica monolithic column (Onyx Monolithic Si, 100 mm×4.6 mm I.D.) was 'in-column' covalently functionalised with 2-hydroxyethyliminodiacetic acid (HEIDA) groups, and applied to the simultaneous and rapid separation of alkaline earth and transition metal ions, using high-performance chelation ion chromatography (HPCIC). With a 0.3mM dipicolinic acid (DPA) containing eluent, the baseline separation of various common transition and heavy metal ions and the four alkaline earth metal ions could be achieved in under 14 min with a flow rate of just 0.8 mL/min. Detection was achieved using spectrophotometric detection at 540 nm after post-column reaction (PCR) with 4-(2-pyridylazo)-resorcinol (PAR). Significant effects from variation of eluent nature, concentration and temperature upon selectivity and retention were demonstrated with the new monolithic silica chelating phase. Under optimised conditions (0.165 M LiNO(3) eluent, pH 2.5), peak efficiencies of 54,000, 60,000 and 64,000 N/m, for Zn(2+), Mn(2+) and Cd(2+), respectively, were recorded, far exceeding that previously reported for IDA based chelation ion exchange columns.

  2. Understanding Bonds - Denmark

    DEFF Research Database (Denmark)

    Rimmer, Nina Røhr

    2016-01-01

    a specified rate of interest during the life of the bond and to repay the face value of the bond (the principal) when it “matures,” or comes due. Among the types of bonds you can choose from are: Government securities, municipal bonds, corporate bonds, mortgage and asset-backed securities, federal agency...

  3. Active groups for oxidative activation of C-H bond in C{sub 2}-C{sub 5} paraffins on V-P-O catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

    1998-12-31

    For the first time in scientific literature, in our joint work with Dr. G. Ladwig in 1978 it was established phase portraite of the oxide vanadium-phosphorus system within wide range of P/V ratios from 0.5 to 3.2. Some later those data were confirmed. By investigation of the properties of individual vanadium-phosphorus phases it was also shown that the active component of such catalysts in n-butane oxidation was vanadyl pyrophosphate phase (VO){sub 2}Pr{sub 2}O{sub 7}. From then the conclusion has been evidenced by numerous publications and at present it has been out of doubt practically all over the world. It was hypothized that the unique properties of (VO){sub 2}P{sub 2}O{sub 7} in the reaction of n-butane oxidation could be explained by the presence of paired vanadyl groups and nearness of the distances between neighbouring vanadyl pairs and that between the first and fourth carbon atoms in n-butane molecule. The molecule activation occured at the latter atoms by proton abstraction. A comparison of the results on n-butane and butenes oxidation over vanadyl pyrophosphate allowed to conclude that the paraffin oxidation did not take place due to the molecule dehydrogenation process at the first stage of its conversion. Up to now, more than 100 papers related to paraffins oxidation over vanadyl pyrophosphate and the physico-chemical properties of the catalyst have been published. The process of n-butane oxidation is realized in practice. But still, the question about the nature of active sites of the catalyst and the reaction mechanism remains open and provokes further investigations. The present paper deals with our opinion about the problem and the experimental results supporting it. (orig.)

  4. Synthesis, Anti-HCV, Antioxidant and Reduction of Intracellular Reactive Oxygen Species Generation of a Chlorogenic Acid Analogue with an Amide Bond Replacing the Ester Bond

    Directory of Open Access Journals (Sweden)

    Ling-Na Wang

    2016-06-01

    Full Text Available Chlorogenic acid is a well known natural product with important bioactivities. It contains an ester bond formed between the COOH of caffeic acid and the 3-OH of quinic acid. We synthesized a chlorogenic acid analogue, 3α-caffeoylquinic acid amide, using caffeic and quinic acids as starting materials. The caffeoylquinc acid amide was found to be much more stable than chlorogenic acid and showed anti-Hepatitis C virus (anti-HCV activity with a potency similar to chlorogenic acid. The caffeoylquinc acid amide potently protected HepG2 cells against oxidative stress induced by tert-butyl hydroperoxide.

  5. Synthesis, Anti-HCV, Antioxidant and Reduction of Intracellular Reactive Oxygen Species Generation of a Chlorogenic Acid Analogue with an Amide Bond Replacing the Ester Bond

    OpenAIRE

    2016-01-01

    Chlorogenic acid is a well known natural product with important bioactivities. It contains an ester bond formed between the COOH of caffeic acid and the 3-OH of quinic acid. We synthesized a chlorogenic acid analogue, 3α-caffeoylquinic acid amide, using caffeic and quinic acids as starting materials. The caffeoylquinc acid amide was found to be much more stable than chlorogenic acid and showed anti-Hepatitis C virus (anti-HCV) activity with a potency similar to chlorogenic acid. The caffeoylq...

  6. Intramolecular hydrogen bond between 4-oxo and 3-carboxylic groups in quinolones and their analogs. Crystal structures of 7-methyl- and 6-fluoro-1,4-dihydro-4-oxocinnoline-3-carboxylic acids

    Science.gov (United States)

    Główka, Marek L.; Martynowski, Dariusz; Olczak, Andrzej; Bojarska, Joanna; Szczesio, Małgorzata; Kozłowska, Krystyna

    2003-09-01

    Crystal structures of two cinnoline analogs of quinolones and statistics on quinolones molecular forms observed in the crystal state have been determined. It has been shown that common quinolones may be divided into two main types, depending on presence of proton acceptor, usually aliphatic amine group, capable of protonation under mild conditions. Quinolones lacking amine group or having one(s) bound to an aromatic system exist at physiological pH mainly in a free acid form, in which acidic hydrogen atom is locked into an intramolecular hydrogen bond. The phenomenon enhances permeability of quinolones through lipophilic cell membranes but decreases the concentration of carboxylate form capable of specific binding with bacterial DNA. Molecular (neutral) form was observed exclusively in the crystalline state for these quinolones. The dominant forms seem different for quinolones having amine substituents with unconjugated lone pair electrons at N atom. Even in the crystalline state, they may exist also in a zwitterionic form, which was found to dominate in secondary amines crystallised at neutral pH. Our limited data suggest that position and order of amine group may play important role in controlling quinolones absorption, transport and concentration and thus their biological profile.

  7. van der Waals forces and confinement in carbon nanopores: Interaction between CH4, COOH, NH3, OH, SH and single-walled carbon nanotubes

    Science.gov (United States)

    Weck, Philippe F.; Kim, Eunja; Wang, Yifeng

    2016-05-01

    Interactions between CH4, COOH, NH3, OH, SH and armchair (n, n) (n = 4, 7, 14) and zigzag (n, 0) (n = 7, 12, 25) single-walled carbon nanotubes (SWCNTs) have been systematically investigated within the framework of dispersion-corrected density functional theory (DFT-D2). Endohedral and exohedral molecular adsorption on SWCNT walls is energetically unfavorable or weak, despite the use of C6 /r6 pairwise London-dispersion corrections. The effects of pore size and chirality on the molecule/SWCNTs interaction were also assessed. Chemisorption of COOH, NH3, OH and SH at SWCNT edge sites was examined using a H-capped (7, 0) SWCNT fragment and its impact on electrophilic, nucleophilic and radical attacks was predicted by means of Fukui functions.

  8. Role of multiple phosphorylation sites in the COOH-terminal tail of aquaporin-2 for water transport: evidence against channel gating

    DEFF Research Database (Denmark)

    Moeller, Hanne B; Macaulay, Nanna; Knepper, Mark A;

    2009-01-01

    in the COOH-terminal tail of AQP2 on protein function. When expressed in Xenopus laevis oocytes, prevention of AQP2 phosphorylation at S256A (S256A-AQP2) reduced osmotic water permeability threefold compared with wild-type (WT) AQP2-injected oocytes. In contrast, prevention of AQP2 single phosphorylation at S...... demonstrated that lack of phosphorylation at S256, S261, S264, or S269 had no effect on AQP2 unit water transport. Similarly, no effect on AQP2 unit water transport was observed for the 264D and 269D forms, indicating that phosphorylation of the COOH-terminal tail of AQP2 is not involved in gating...

  9. Reversible and irreversible higher-order cycloaddition reactions of polyolefins with a multiple-bonded heavier group 13 alkene analogue: contrasting the behavior of systems with π-π, π-π*, and π-n+ frontier molecular orbital symmetry.

    Science.gov (United States)

    Caputo, Christine A; Guo, Jing-Dong; Nagase, Shigeru; Fettinger, James C; Power, Philip P

    2012-04-25

    The heavier group 13 element alkene analogue, digallene Ar(iPr(4))GaGaAr(iPr(4)) (1) [Ar(iPr(4)) = C(6)H(3)-2,6-(C(6)H(3)-2,6-(i)Pr(2))(2)], has been shown to react readily in [n + 2] (n = 6, 4, 2 + 2) cycloaddition reactions with norbornadiene and quadricyclane, 1,3,5,7-cyclooctatetraene, 1,3-cyclopentadiene, and 1,3,5-cycloheptatriene to afford the heavier element deltacyclane species Ar(iPr(4))Ga(C(7)H(8))GaAr(iPr(4)) (2), pseudoinverse sandwiches Ar(iPr(4))Ga(C(8)H(8))GaAr(iPr(4)) (3, 3(iso)), and polycyclic compounds Ar(iPr(4))Ga(C(5)H(6))GaAr(iPr(4)) (4) and Ar(iPr(4))Ga(C(7)H(8))GaAr(iPr(4)) (5, 5(iso)), respectively, under ambient conditions. These reactions are facile and may be contrasted with other all-carbon versions, which require transition-metal catalysis or forcing conditions (temperature, pressure), or with the reactions of the corresponding heavier group 14 species Ar(iPr(4))EEAr(iPr(4)) (E = Ge, Sn), which give very different product structures. We discuss several mechanistic possibilities, including radical- and non-radical-mediated cyclization pathways. These mechanisms are consistent with the improved energetic accessibility of the LUMO of the heavier group 13 element multiple bond in comparison with that of a simple alkene or alkyne. We show that the calculated frontier molecular orbitals (FMOs) of Ar(iPr(4))GaGaAr(iPr(4)) are of π-π symmetry, allowing this molecule to engage in a wider range of reactions than permitted by the usual π-π* FMOs of C-C π bonds or the π-n(+) FMOs of heavier group 14 alkyne analogues.

  10. Experimental and computational investigation of the group 11-group 2 diatomic molecules: First determination of the AuSr and AuBa bond energies and thermodynamic stability of the copper- and silver-alkaline earth species

    Science.gov (United States)

    Ciccioli, A.; Gigli, G.; Lauricella, M.

    2012-05-01

    The dissociation energies of the intermetallic molecules AuSr and AuBa were for the first time determined by the Knudsen effusion mass spectrometry method. The two species were produced in the vapor phase equilibrated with apt mixtures of the constituent elements, and the dissociation equilibria were monitored mass-spectrometrically in the temperature range 1406-1971 K (AuSr) and 1505-1971 K (AuBa). The third-law analysis of the equilibrium data gives the following dissociation energies (D_0°, in kJ/mol): 244.4 ± 4.8 (AuSr) and 273.3 ± 6.3 (AuBa), so completing the series of D_0°s for the AuAE (AE = group 2 element) diatomics. The AuAE species were also studied computationally at the coupled cluster including single, double and perturbative triple excitation [CCSD(T)] level with basis sets of increasing zeta quality, and various complete basis set limit extrapolations were performed to calculate the dissociation energies. Furthermore, the entire series of the heteronuclear diatomic species formed from one group 11 (Cu, Ag) and one group 2 (Be, Mg, Ca, Sr, Ba) metal was studied by DFT with the hybrid meta-GGA TPSSh functional and the def2-QZVPP basis set, selected after screening a number of functional-basis set combinations using the AuAE species as benchmark. Dissociation energies, internuclear distances, vibrational frequencies, and anharmonic constants were determined for the CuAE and AgAE species and their thermal functions evaluated therefrom. On this basis, a thermodynamic evaluation of the formation of these species was carried out under various conditions.

  11. Experimental and computational investigation of the group 11-group 2 diatomic molecules: first determination of the AuSr and AuBa bond energies and thermodynamic stability of the copper- and silver-alkaline earth species.

    Science.gov (United States)

    Ciccioli, A; Gigli, G; Lauricella, M

    2012-05-14

    The dissociation energies of the intermetallic molecules AuSr and AuBa were for the first time determined by the Knudsen effusion mass spectrometry method. The two species were produced in the vapor phase equilibrated with apt mixtures of the constituent elements, and the dissociation equilibria were monitored mass-spectrometrically in the temperature range 1406-1971 K (AuSr) and 1505-1971 K (AuBa). The third-law analysis of the equilibrium data gives the following dissociation energies (D(0)°, in kJ/mol): 244.4 ± 4.8 (AuSr) and 273.3 ± 6.3 (AuBa), so completing the series of D(0)°s for the AuAE (AE = group 2 element) diatomics. The AuAE species were also studied computationally at the coupled cluster including single, double and perturbative triple excitation [CCSD(T)] level with basis sets of increasing zeta quality, and various complete basis set limit extrapolations were performed to calculate the dissociation energies. Furthermore, the entire series of the heteronuclear diatomic species formed from one group 11 (Cu, Ag) and one group 2 (Be, Mg, Ca, Sr, Ba) metal was studied by DFT with the hybrid meta-GGA TPSSh functional and the def2-QZVPP basis set, selected after screening a number of functional-basis set combinations using the AuAE species as benchmark. Dissociation energies, internuclear distances, vibrational frequencies, and anharmonic constants were determined for the CuAE and AgAE species and their thermal functions evaluated therefrom. On this basis, a thermodynamic evaluation of the formation of these species was carried out under various conditions.

  12. Differences in cytotoxic, genotoxic, and inflammatory response of bronchial and alveolar human lung epithelial cells to pristine and COOH-functionalized multiwalled carbon nanotubes.

    Science.gov (United States)

    Ursini, Cinzia Lucia; Cavallo, Delia; Fresegna, Anna Maria; Ciervo, Aureliano; Maiello, Raffaele; Buresti, Giuliana; Casciardi, Stefano; Bellucci, Stefano; Iavicoli, Sergio

    2014-01-01

    Functionalized MWCNTs are used in many commercial and biomedical applications, but their potential health effects are not well defined. We investigated and compared cytotoxic, genotoxic/oxidative, and inflammatory effects of pristine and carboxyl MWCNTs exposing human respiratory (A549 and BEAS-2B) cells to 1-40 μg/mL of CNTs for 24 h. Both MWCNTs induced low viability reduction (by WST1 assay) in A549 cells and only MWCNTs-COOH caused high viability reduction in BEAS-2B cells reaching 28.5% viability at 40 μg/mL. Both CNTs induced membrane damage (by LDH assay) with higher effects in BEAS-2B cells at the highest concentrations reaching 20% cytotoxicity at 40 μg/mL. DNA damage (by Fpg-comet assay) was induced by pristine MWCNTs in A549 cells and by both MWCNTs in BEAS-2B cells reaching for MWCNTs-COOH a tail moment of 22.2 at 40 μg/mL versus 10.2 of unexposed cells. Increases of IL-6 and IL-8 release (by ELISA) were detected in A549 cells exposed to MWCNTs-COOH from 10 μg/mL while IL-8 increased in BEAS-2B cells exposed to pristine MWCNTs at 20 and 40 μg/mL. The results show higher cytogenotoxicity of MWCNTs-COOH in bronchial and of pristine MWCNTs in alveolar cells. Different inflammatory response was also found. The findings suggest the use of in vitro models with different end points and cells to study CNT toxicity.

  13. Constitutive expression of a COOH-terminal leucine mutant of lysosome-associated membrane protein-1 causes its exclusive localization in low density intracellular vesicles.

    Science.gov (United States)

    Akasaki, Kenji; Shiotsu, Keiko; Michihara, Akihiro; Ide, Norie; Wada, Ikuo

    2014-07-01

    Lysosome-associated membrane protein-1 (LAMP-1) is a type I transmembrane protein with a short cytoplasmic tail that possesses a lysosome-targeting signal of GYQTI(382)-COOH. Wild-type (WT)-LAMP-1 was exclusively localized in high density lysosomes, and efficiency of LAMP-1's transport to lysosomes depends on its COOH-terminal amino acid residue. Among many different COOH-terminal amino acid substitution mutants of LAMP-1, a leucine-substituted mutant (I382L) displays the most efficient targeting to late endosomes and lysosomes [Akasaki et al. (2010) J. Biochem. 148: , 669-679]. In this study, we generated two human hepatoma cell lines (HepG2 cell lines) that stably express WT-LAMP-1 and I382L, and compared their intracellular distributions. The subcellular fractionation study using Percoll density gradient centrifugation revealed that WT-LAMP-1 had preferential localization in the high density secondary lysosomes where endogenous human LAMP-1 was enriched. In contrast, a major portion of I382L was located in a low density fraction. The low density fraction also contained approximately 80% of endogenous human LAMP-1 and significant amounts of endogenous β-glucuronidase and LAMP-2, which probably represents occurrence of low density lysosomes in the I382L-expressing cells. Double immunofluorescence microscopic analyses distinguished I382L-containing intracellular vesicles from endogenous LAMP-1-containing lysosomes and early endosomes. Altogether, constitutive expression of I382L causes its aberrant intracellular localization and generation of low density lysosomes, indicating that the COOH-terminal isoleucine is critical for normal localization of LAMP-1 in the dense lysosomes.

  14. Pengaruh Konsentrasi Asam Asetat (CH3COOH) Terhadap Modulus Green 300% Pada Proses Produksi Benang Karet Di PT. Industri Karet Nusantara

    OpenAIRE

    Permata Mhardela

    2009-01-01

    Konsentrasi asam asetat (CH3COOH) mempengaruhi salah satu parameter fisik benang karet yaitu modulus green 300%. Jika konsentrasi asam asetat suatu benang karet tinggi maka modulus green 300%-nya tinggi yang mengakibatkan benang karet yang dihasilkan kurang elastis dan terlalu keras dan jika konsentrasi asam asetat rendah maka modulus green 300%-nya juga semakin rendah yang mengakibatkan benang karet yang dihasilkan lunak dan mudah putus. Hubungan antara konsentrasi asam asetat dengan mo...

  15. Differences in Cytotoxic, Genotoxic, and Inflammatory Response of Bronchial and Alveolar Human Lung Epithelial Cells to Pristine and COOH-Functionalized Multiwalled Carbon Nanotubes

    Science.gov (United States)

    Fresegna, Anna Maria; Ciervo, Aureliano; Buresti, Giuliana

    2014-01-01

    Functionalized MWCNTs are used in many commercial and biomedical applications, but their potential health effects are not well defined. We investigated and compared cytotoxic, genotoxic/oxidative, and inflammatory effects of pristine and carboxyl MWCNTs exposing human respiratory (A549 and BEAS-2B) cells to 1–40 μg/mL of CNTs for 24 h. Both MWCNTs induced low viability reduction (by WST1 assay) in A549 cells and only MWCNTs-COOH caused high viability reduction in BEAS-2B cells reaching 28.5% viability at 40 μg/mL. Both CNTs induced membrane damage (by LDH assay) with higher effects in BEAS-2B cells at the highest concentrations reaching 20% cytotoxicity at 40 μg/mL. DNA damage (by Fpg-comet assay) was induced by pristine MWCNTs in A549 cells and by both MWCNTs in BEAS-2B cells reaching for MWCNTs-COOH a tail moment of 22.2 at 40 μg/mL versus 10.2 of unexposed cells. Increases of IL-6 and IL-8 release (by ELISA) were detected in A549 cells exposed to MWCNTs-COOH from 10 μg/mL while IL-8 increased in BEAS-2B cells exposed to pristine MWCNTs at 20 and 40 μg/mL. The results show higher cytogenotoxicity of MWCNTs-COOH in bronchial and of pristine MWCNTs in alveolar cells. Different inflammatory response was also found. The findings suggest the use of in vitro models with different end points and cells to study CNT toxicity. PMID:25147797

  16. Physical Nature of Hydrogen Bond

    CERN Document Server

    Zhyganiuk, I V

    2015-01-01

    The physical nature and the correct definition of hydrogen bond (H-bond) are considered.\\,\\,The influence of H-bonds on the thermodynamic, kinetic, and spectroscopic properties of water is analyzed.\\,\\,The conventional model of H-bonds as sharply directed and saturated bridges between water molecules is incompatible with the behavior of the specific volume, evaporation heat, and self-diffusion and kinematic shear viscosity coefficients of water. On the other hand, it is shown that the variation of the dipole moment of a water molecule and the frequency shift of valence vibrations of a hydroxyl group can be totally explained in the framework of the electrostatic model of H-bond.\\,\\,At the same time, the temperature dependences of the heat capacity of water in the liquid and vapor states clearly testify to the existence of weak H-bonds.\\,\\,The analysis of a water dimer shows that the contribution of weak H-bonds to its ground state energy is approximately 4--5 times lower in comparison with the energy of electr...

  17. Are Bonding Agents being Effective on the Shear Bond Strength of Orthodontic Brackets Bonded to the Composite?

    Directory of Open Access Journals (Sweden)

    Fahimeh Farzanegan

    2014-06-01

    Full Text Available Introduction: One of the clinical problems in orthodontics is the bonding of brackets tocomposite restorations. The aim of this study was to evaluate the shear bondstrength of brackets bonded to composite restorations using Excite. Methods:Forty brackets were bonded to composite surfaces, which were embedded inacrylic resin. One of the following four protocols was employed for surfacepreparation of the composite: group 1 37% phosphoric acid for 60 seconds, group2 roughening with a diamond bur plus 37% phosphoric acid for 60 seconds, group3 37% phosphoric acid for 60 seconds and the applying Excite®, group4 roughening with diamond bur plus 37% phosphoric acid for 60 seconds andapplying Excite®. Maxillary central brackets were bonded onto thecomposite prepared samples with Transbond XT. Shear Bond Strength (SBS wasmeasured by a universal testing machine. The ANOVA and Tukey test was utilizedfor data analysis. Results: There was a significant difference betweenthe four groups (P

  18. Shear bond strength of ceramic and metallic orthodontic brackets bonded with self-etching primer and conventional bonding adhesives

    Science.gov (United States)

    Arash, Valiollah; Naghipour, Fatemeh; Ravadgar, Mehdi; Karkhah, Ahmad; Barati, Mohammad Saleh

    2017-01-01

    Introduction Adult patients typically require high-quality orthodontic treatment for ceramic brackets, but some clinicians remain concerned about the bond strength of these brackets. Therefore, the aim of this study was to determine the shear bond strength and de-bonding characteristics of metallic and ceramic brackets bonded with two types of bonding agents. Methods In an experimental study done in 2013 in Babol, Iran, 120 extracted human maxillary premolar teeth were randomly divided into four groups as follows: HM group: metallic bracket/conventional bonding agent; SM group: metallic bracket/Transbond self-etching primer; HC group: ceramic bracket/conventional bonding agent; SC group: ceramic bracket/Transbond self-etching primer. Twenty-four hours after thermocycling (1000 cycle, 5 °C–55 °C), the shear bond strength values were measured. The amount of resin remaining on the tooth surface (adhesive remnant index: ARI) was determined under a stereomicroscope. Enamel detachment index was evaluated under a scanning electron microscope. To perform statistical analysis, ANOVA, Kruskal–Wallis, and Tukey post-hoc tests were applied. The level of significance was set at p ceramic brackets. In addition, self-etching primer was able to produce fewer bonds compared with the conventional technique. Many samples showed the bracket-adhesive interface failure or failure inside the adhesive. PMID:28243410

  19. Cross Shear Roll Bonding

    DEFF Research Database (Denmark)

    Bay, Niels; Bjerregaard, Henrik; Petersen, Søren. B;

    1994-01-01

    The present paper describes an investigation of roll bonding an AlZn alloy to mild steel. Application of cross shear roll bonding, where the two equal sized rolls run with different peripheral speed, is shown to give better bond strength than conventional roll bonding. Improvements of up to 20......-23% in bond strength are found and full bond strength is obtained at a reduction of 50% whereas 65% is required in case of conventional roll bonding. Pseudo cross shear roll bonding, where the cross shear effect is obtained by running two equal sized rolls with different speed, gives the same results....

  20. Quantitative analysis of 11-nor-9-carboxy-tetrahydrocannbinol (THC-COOH) in urine by LC-MS/MS following a simple filtration.

    Science.gov (United States)

    Rumpler, Marc J

    2014-04-15

    Quantification methods utilizing liquid chromatography tandem mass spectrometry (LC-MS/MS) are common in clinical and forensic toxicology laboratories and the efficiency and rapidity of such methods continues to evolve. In most cases, urine drug confirmation does not require a drug extraction and can quickly and easily be accomplished with a dilution followed by sample filtration. The report describes the validation of a simple confirmation method for 11-nor-9-carboxy-tetrahydrocannabinol (THC-COOH) and compared two types of filter extraction columns for sample clean-up. The method achieved a linear range of 10-3000ng/mL, acceptable bias (-4.7-2.6%) and precision (0.9-6.9%) and autosampler stability up to 72h. Universal filter columns offered less variable recovery over the linear range and fewer matrix interferences compared to THC-COOH specific filter columns. Authentic specimens testing positive for THC-COOH by LC-MS/MS were in good agreement with typically used GC-MS methods.

  1. Septal localization by membrane targeting sequences and a conserved sequence essential for activity at the COOH-terminus of Bacillus subtilis cardiolipin synthase.

    Science.gov (United States)

    Kusaka, Jin; Shuto, Satoshi; Imai, Yukiko; Ishikawa, Kazuki; Saito, Tomo; Natori, Kohei; Matsuoka, Satoshi; Hara, Hiroshi; Matsumoto, Kouji

    2016-04-01

    The acidic phospholipid cardiolipin (CL) is localized on polar and septal membranes and plays an important physiological role in Bacillus subtilis cells. ClsA, the enzyme responsible for CL synthesis, is also localized on septal membranes. We found that GFP fusion proteins of the enzyme with NH2-terminal and internal deletions retained septal localization. However, derivatives with deletions starting from the COOH-terminus (Leu482) ceased to localize to the septum once the deletion passed the Ile residue at 448, indicating that the sequence responsible for septal localization is confined within a short distance from the COOH-terminus. Two sequences, Ile436-Leu450 and Leu466-Leu478, are predicted to individually form an amphipathic α-helix. This configuration is known as a membrane targeting sequence (MTS) and we therefore refer to them as MTS2 and MTS1, respectively. Either one has the ability to affect septal localization, and each of these sequences by itself localizes to the septum. Membrane association of the constructs of this enzyme containing the MTSs was verified by subcellular fractionation of the cells. CL synthesis, in contrast, was abolished after deleting just the last residue, Leu482, in the COOH-terminal four amino acid residue sequence, Ser-Pro-Ile-Leu, which is highly conserved among bacterial CL synthases.

  2. The effects of C60(C(COOH)2)2-FITC on proliferation and differentiation of human mesenchymal stem cells in vitro.

    Science.gov (United States)

    Li, Juan; Song, Yan; Liu, Xiaoxiao; Zhang, Mingyi; He, Rui; Chang, Yanan; Jin, Junjiang; Xing, Geng-Mei; Zhang, Jun

    2013-10-01

    As manufactured nanoparticles, fullerene nanoparticles were used as the model to research the manufactured nanoparticles entering into cells and hence have been rapidly developed for biomedical uses. Human mesenchymal stem cells (hMSCs) have become the most widely used seeding cells in tissue engineering because they are readily obtained without ethical problems and are multipotent with regard to adipogenic, chondrogenic, and osteogenic lineages. Because of their favorable biological and cellular activities, C60 carboxyl derivatives are among the most widely studied C60 derivatives. FITC labeled C60(C(COOH)2)2 nanoparticles were charactered by FTIR, ESI-MS, XPS and DLS. The effects of C60(C(COOH)2)2-FITC on proliferation and differentiation of human mesenchymal stem cells (hMSCs) in vitro were observed. The fullerene nanoparticles are quickly internalized by the cells and they had low toxicity to proliferation of hMSCs. The C60(C(COOH)2)2 nanoparticles could promote cell proliferation, enhance osteoclast differentiation of hMSCs.

  3. Novel method for simultaneous aqueous in situ derivatization of THC and THC-COOH in human urine samples: validation and application to real samples.

    Science.gov (United States)

    Chericoni, S; Battistini, I; Dugheri, S; Pacenti, M; Giusiani, M

    2011-05-01

    The present work describes the validation of a novel aqueous in situ derivatization procedure with trimethyloxonium tetrafluoroborate (TMO) as methylating agent for the simultaneous, quantitative analysis of Δ(9)-tetrahydrocannabinol (THC) and 11-nor-Δ(9)-tetrahydrocannabinol carboxylic acid (THC-COOH) in human urine. The derivatizing agent is directly added to the urine sample and the methyl-derivatives are then recovered by liquid-liquid extraction procedure. Gas chromatography-mass spectrometry was used to detect the derivatives in selected ion monitoring mode. The limits of detection were 0.7 ng/mL for THC and 0.5 ng/mL for THC-COOH, whereas the limits of quantification were 1.9 and 0.9 ng/mL, respectively. The method has been applied to 60 real samples both positive and negative to immunochemical screening test resulting to be very useful and reliable in routine analysis of THC-COOH in human urine for toxicological and forensic purposes.

  4. COOH-terminal truncation of flightin decreases myofilament lattice organization, cross-bridge binding, and power output in Drosophila indirect flight muscle.

    Science.gov (United States)

    Tanner, Bertrand C W; Miller, Mark S; Miller, Becky M; Lekkas, Panagiotis; Irving, Thomas C; Maughan, David W; Vigoreaux, Jim O

    2011-08-01

    The indirect flight muscle (IFM) of insects is characterized by a near crystalline myofilament lattice structure that likely evolved to achieve high power output. In Drosophila IFM, the myosin rod binding protein flightin plays a crucial role in thick filament organization and sarcomere integrity. Here we investigate the extent to which the COOH terminus of flightin contributes to IFM structure and mechanical performance using transgenic Drosophila expressing a truncated flightin lacking the 44 COOH-terminal amino acids (fln(ΔC44)). Electron microscopy and X-ray diffraction measurements show decreased myofilament lattice order in the fln(ΔC44) line compared with control, a transgenic flightin-null rescued line (fln(+)). fln(ΔC44) fibers produced roughly 1/3 the oscillatory work and power of fln(+), with reduced frequencies of maximum work (123 Hz vs. 154 Hz) and power (139 Hz vs. 187 Hz) output, indicating slower myosin cycling kinetics. These reductions in work and power stem from a slower rate of cross-bridge recruitment and decreased cross-bridge binding in fln(ΔC44) fibers, although the mean duration of cross-bridge attachment was not different between both lines. The decreases in lattice order and myosin kinetics resulted in fln(ΔC44) flies being unable to beat their wings. These results indicate that the COOH terminus of flightin is necessary for normal myofilament lattice organization, thereby facilitating the cross-bridge binding required to achieve high power output for flight.

  5. Amino acid mutations in the caldesmon COOH-terminal functional domain increase force generation in bladder smooth muscle.

    Science.gov (United States)

    Deng, Maoxian; Boopathi, Ettickan; Hypolite, Joseph A; Raabe, Tobias; Chang, Shaohua; Zderic, Stephen; Wein, Alan J; Chacko, Samuel

    2013-11-15

    Caldesmon (CaD), a component of smooth muscle thin filaments, binds actin, tropomyosin, calmodulin, and myosin and inhibits actin-activated ATP hydrolysis by smooth muscle myosin. Internal deletions of the chicken CaD functional domain that spans from amino acids (aa) 718 to 731, which corresponds to aa 512-530 including the adjacent aa sequence in mouse CaD, lead to diminished CaD-induced inhibition of actin-activated ATP hydrolysis by myosin. Transgenic mice with mutations of five aa residues (Lys(523) to Gln, Val(524) to Leu, Ser(526) to Thr, Pro(527) to Cys, and Lys(529) to Ser), which encompass the ATPase inhibitory determinants located in exon 12, were generated by homologous recombination. Homozygous (-/-) animals did not develop, but heterozygous (+/-) mice carrying the expected mutations in the CaD ATPase inhibitory domain (CaD mutant) matured and reproduced normally. The peak force produced in response to KCl and electrical field stimulation by the detrusor smooth muscle from the CaD mutant was high compared with that of the wild type. CaD mutant mice revealed nonvoiding contractions during bladder filling on awake cystometry, suggesting that the CaD ATPase inhibitory domain suppresses force generation during the filling phase and this suppression is partially released by mutations in 50% of CaD in heterozygous. Our data show for the first time a functional phenotype, at the intact smooth muscle tissue and in vivo organ levels, following mutation of a functional domain at the COOH-terminal region of CaD.

  6. Effect of surface treatments and bonding agents on the bond strength of repaired composites.

    Science.gov (United States)

    Cavalcanti, Andrea Nóbrega; De Lima, Adriano Fonseca; Peris, Alessandra Rezende; Mitsui, Fabio Hiroyuki Ogata; Marchi, Giselle Maria

    2007-01-01

    An adequate repair procedure depends on high bond strength between the existing composite and the new composite. To evaluate the effect of surface treatments and bonding procedures on the bond strength of repairs performed 24 hours after composite polymerization. Composite specimens were stored in distilled water at 37 degrees C for 24 hours. Specimens were allocated into 12 groups (N=10) according to the combination of surface treatment (none, air abrasion, diamond bur) and bonding procedure (none, Single Bond after H(3)PO(4) cleansing, Clearfil SE Bond after H(3)PO(4) cleansing, Clearfil SE Bond without H(3)PO(4) cleansing). The ultimate tensile strength (UTS) of the composite was tested in nonrepaired specimens. Twenty-four hours after repair, specimens were sectioned into three slabs and trimmed to an hourglass shape (1 mm(2) area). Slabs were tested under tension and mean bond strengths analyzed with two-way analysis of variance/Tukey and Dunnett tests (alpha=5%). Two groups resulted in repair bond strengths similar to composite UTS: air abrasion combined with Clearfil SE Bond after H(3)PO(4) cleansing, and air abrasion combined with Clearfil SE Bond without H(3)PO(4) cleansing. Combinations of surface treatments and bonding procedures were not statistically different. When repair procedure was performed 24 hours after composite polymerization, different combinations of surface treatments and bonding procedures affected repair bond strength similarly. There was no statistical difference between the repair bond strength of groups air-abraded and bonded with the self-etching system and composite UTS. Only air abrasion associated with a self-etching system provided repair bond strength comparable to composite UTS.

  7. Direct bonded space maintainers.

    Science.gov (United States)

    Santos, V L; Almeida, M A; Mello, H S; Keith, O

    1993-01-01

    The aim of this study was to evaluate clinically a bonded space maintainer, which would reduce chair-side time and cost. Sixty appliances were fabricated from 0.7 mm stainless steel round wire and bonded using light-cured composite to the two teeth adjacent to the site of extraction of a posterior primary tooth. Twenty males and sixteen females (age range 5-9-years-old) were selected from the Pedodontic clinic of the State University of Rio de Janeiro. The sixty space maintainers were divided into two groups according to the site in which they were placed: a) absent first primary molar and b) absent second primary molar. Impressions and study models were obtained prior to and 6 months after bonding the appliances. During this period only 8.3% of failures were observed, most of them from occlusal or facial trauma. Student t-test did not show statistically significant alterations in the sizes of the maintained spaces during the trial period.

  8. Halogen Bonding in Hypervalent Iodine Compounds.

    Science.gov (United States)

    Catalano, Luca; Cavallo, Gabriella; Metrangolo, Pierangelo; Resnati, Giuseppe; Terraneo, Giancarlo

    Halogen bonds occur when electrophilic halogens (Lewis acids) attractively interact with donors of electron density (Lewis bases). This term is commonly used for interactions undertaken by monovalent halogen derivatives. The aim of this chapter is to show that the geometric features of the bonding pattern around iodine in its hypervalent derivatives justify the understanding of some of the longer bonds as halogen bonds. We suggest that interactions directionality in ionic and neutral λ(3)-iodane derivatives is evidence that the electron density distribution around iodine atoms is anisotropic, a region of most positive electrostatic potential exists on the extensions of the covalent bonds formed by iodine, and these positive caps affect, or even determine, the crystal packing of these derivatives. For instance, the short cation-anion contacts in ionic λ(3)-iodane and λ(5)-iodane derivatives fully match the halogen bond definition and geometrical prerequisites. The same holds for the short contacts the cation of ionic λ(3)-iodanes forms with lone-pair donors or the short contacts given by neutral λ(3)-iodanes with incoming nucleophiles. The longer and weaker bonds formed by iodine in hypervalent compounds are usually called secondary bondings and we propose that the term halogen bond can also be used. Compared to the term secondary bond, halogen bond may possibly be more descriptive of some bonding features, e.g., its directionality and the relationships between structure of interacting groups and interaction strength.

  9. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G

    2010-01-01

    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  10. Comparison of the microtensile bond strength of different composite core materials and bonding systems to a fiber post (DT Light

    Directory of Open Access Journals (Sweden)

    Lelya Sadighpour

    2013-10-01

    Full Text Available   Background and Aims: Retention and stability of the post and core system is the key factor for success of final restoration . The aim of this study was to evaluate the microtensile bond strength of the different composite core materials and bonding systems to a fiber post.   Materials and Methods: To evaluate the bond strength of the composite resins to a fiber post ( DT light post 60 posts were divided into six groups : group A: Heliomolar Flow + Seal Bond, group B: Heliomolar Flow + SE Bond , group C: Valux Plus + Seal Bond , group D: Valux Plus + SE Bond , group E: Corecem + Seal Bond, group F: Corecem + SE Bond. All samples were thermocycled for 5000 cycles (5-55 0C and cut into four bars for the microtensile bond strength test. Failure modes were identified using a stereomicroscope. Data were analysed using One-way ANOVA and Tukey HSD post hoc test (P<0.05.   Results: The interaction between composite resin materials and bonding systems were positive. The conventional hybrid composite (Valux Plus had significantly higher bond strength compared with the core specific flowable composite (Corecem when Seal Bond was applied as bonding agent (P<0.05. However, when SE Bond was utilized hybrid composite demonstrated significantly lower bond strength than that of other two groups (P<0.05.   Conclusion: The performance of a particular composite is affected by the bonding system that is applied. A single composite resin may have different bond strength when combined with different bonding system.

  11. Evaluation of shear bond strength of porcelain bonded to laser welded titanium surface and determination of mode of bond failure.

    Science.gov (United States)

    Patil, Narendra P; Dandekar, Minal; Nadiger, Ramesh K; Guttal, Satyabodh S

    2010-09-01

    The aim of this study was to evaluate the shear bond strength of porcelain to laser welded titanium surface and to determine the mode of bond failure through scanning electron microscopy (SEM) and energy dispersive spectrophotometry (EDS). Forty five cast rectangular titanium specimens with the dimension of 10 mm x 8 mm x 1 mm were tested. Thirty specimens had a perforation of 2 mm diameter in the centre. These were randomly divided into Group A and B. The perforations in the Group B specimens were repaired by laser welding using Cp Grade II titanium wire. The remaining 15 specimens were taken as control group. All the test specimens were layered with low fusing porcelain and tested for shear bond strength. The debonded specimens were subjected to SEM and EDS. Data were analysed with 1-way analysis of variance and Student's t-test for comparison among the different groups. One-way analysis of variance (ANOVA) showed no statistically significant difference in shear bond strength values at a 5% level of confidence. The mean shear bond strength values for control group, Group A and B was 8.4 +/- 0.5 Mpa, 8.1 +/- 0.4 Mpa and 8.3 +/- 0.3 Mpa respectively. SEM/EDS analysis of the specimens showed mixed and cohesive type of bond failure. Within the limitations of the study laser welding did not have any effect on the shear bond strength of porcelain bonded to titanium.

  12. Hybrid layer difference between sixth and seventh generation bonding agent

    Directory of Open Access Journals (Sweden)

    Grace Syavira Suryabrata

    2006-03-01

    Full Text Available Since etching is completed at the same stage as priming and bonding, when applying the sixth and seventh generation bonding, the exposed smear layers are constantly surrounded by primer and bonding and cannot collapse. The smear layer and the depth of penetration of resin bonding in dentinal tubules are completely integrated into hybrid layer. The purpose of this laboratory research was to study the penetration depth of two self etching adhesive. Fourteen samples of human extracted teeth were divided into two groups. Each groups consisted of seven samples, each of them was treated with sixth generation bonding agent and the other was treated with seventh generation bonding agent. The results disclosed that the penetration into dentinal tubules of seventh generation bonding agent was deeper than sixth generation bonding agent. Conclusion: bond strength will improve due to the increasing of penetration depth of resin bonding in dentinal tubules.

  13. Improving orthodontic bonding to silver amalgam.

    Science.gov (United States)

    Zachrisson, B U; Büyükyilmaz, T; Zachrisson, Y O

    1995-01-01

    Flat rectangular tabs (n = 84) prepared from lathe-cut amalgam (ANA 2000) were subjected to aluminum oxide sandblasting or roughening with a diamond bur. Mandibular incisor edgewise brackets were bonded to these tabs using: Concise (Bis-GMA resin); one of three metal-bonding adhesives, viz., Superbond C&B (4-META resin), Panavia Ex (10-MDP Bis-GMA resin) or Geristore (composite base); and Concise after application of the intermediate resins All-Bond 2 Primers A+B, or the Scotch-Bond Multi-Purpose (SBMP) system. All specimens were stored in water at 37 degrees C for 24 hours before tensile bond strength testing. Alignment and uniform loading during testing were secured by engaging a hook in a circular ring soldered onto the bracket slot before bonding. Similar control brackets (n = 12) were bonded with Concise to extracted caries-free mandibular incisors. Bond failure sites were classified by a modified ARI system. Mean tensile bond strengths in the experimental group ranged from 3.4 to 6.4 MPa--significantly weaker than the control sample (13.2 MPa). Bond failure generally occurred at the amalgam/adhesive interface. Superbond C&B created the strongest bonds to amalgam; according to ANOVA and Duncan's Multiple-Range test, they were significantly stronger than the bonds with Panavia Ex and Concise, with Geristore in between. However, the bond strength of Concise to sandblasted amalgam was comparable to the Superbond C&B bonds when coupled with an intermediate application of All-Bond 2 Primers A+B. The SBMP, on the other hand, was less effective.(ABSTRACT TRUNCATED AT 250 WORDS)

  14. Composite bonding to stainless steel crowns using a new universal bonding and single-bottle systems.

    Science.gov (United States)

    Hattan, Mohammad Ali; Pani, Sharat Chandra; Alomari, Mohammad

    2013-01-01

    Aim. The aim of this study is to evaluate the shear bond strength of nanocomposite to stainless steel crowns using a new universal bonding system. Material and Methods. Eighty (80) stainless steel crowns (SSCs) were divided into four groups (20 each). Packable nanocomposite was bonded to the lingual surface of the crowns in the following methods: Group A without adhesive (control group), Group B using a new universal adhesive system (Scotchbond Universal Adhesive, 3M ESPE, Seefeld, Germany), and Group C and Group D using two different brands of single-bottle adhesive systems. Shear bond strengths were calculated and the types of failure also were recorded. Results. The shear strength of Group B was significantly greater than that of other groups. No significant differences were found between the shear bond strengths of Groups C and D. The control group had significantly lower shear bond strength (P steel crowns using the new universal bonding agent (Scotchbond Universal Adhesive, 3M ESPE, Seefeld, Germany) show significantly greater shear bond strengths and fewer adhesive failures when compared to traditional single-bottle systems.

  15. Bond strength of repaired amalgam restorations.

    Science.gov (United States)

    Rey, Rosalia; Mondragon, Eduardo; Shen, Chiayi

    2015-01-01

    This in vitro study investigated the interfacial flexural strength (FS) of amalgam repairs and the optimal combination of repair materials and mechanical retention required for a consistent and durable repair bond. Amalgam bricks were created, each with 1 end roughened to expose a fresh surface before repair. Four groups followed separate repair protocols: group 1, bonding agent with amalgam; group 2, bonding agent with composite resin; group 3, mechanical retention (slot) with amalgam; and group 4, slot with bonding agent and amalgam. Repaired specimens were stored in artificial saliva for 1, 10, 30, 120, or 360 days before being loaded to failure in a 3-point bending test. Statistical analysis showed significant changes in median FS over time in groups 2 and 4. The effect of the repair method on the FS values after each storage period was significant for most groups except the 30-day storage groups. Amalgam-amalgam repair with adequate condensation yielded the most consistent and durable bond. An amalgam bonding agent could be beneficial when firm condensation on the repair surface cannot be achieved or when tooth structure is involved. Composite resin can be a viable option for amalgam repair in an esthetically demanding region, but proper mechanical modification of the amalgam surface and selection of the proper bonding system are essential.

  16. Comparison of Shear Bond Strengths of three resin systems for a Base Metal Alloy bonded to

    Directory of Open Access Journals (Sweden)

    Jlali H

    1999-12-01

    Full Text Available Resin-bonded fixed partial dentures (F.P.D can be used for conservative treatment of partially edentulous"npatients. There are numerous studies regarding the strength of resin composite bond to base meta! alloys. Shear bond"nstrength of three resin systems were invistigated. In this study these systems consisted of: Panavia Ex, Mirage FLC and"nMarathon V. Thirty base metal specimens were prepared from rexillium III alloy and divided into three groups. Then each"ngroup was bonded to enamel of human extracted molar teeth with these systems. All of specimens were stored in water at"n37ac for 48 hours. A shear force was applied to each specimen by the instron universal testing machine. A statistical"nevaluation of the data using one-way analysis of variance showed that there was highly significant difference (P<0.01"nbetween the bond strengths of these three groups."nThe base metal specimens bonded with panavia Ex luting agent, exhibited the highest mean bond strength. Shear bond"nstrength of the specimens bonded to enamel with Mirage F1C showed lower bond strenght than panavia EX. However, the"nlowest bond strength was obtained by the specimens bonded with Marathon V.

  17. Análise do vínculo entre grupo e professora numa aula de ciências do Ensino Fundamental Analysis of the bond between group and teacher in a basic science lesson

    Directory of Open Access Journals (Sweden)

    Marcelo Alves Barros

    2007-08-01

    Full Text Available O objetivo deste trabalho consiste em investigar a dinâmica de um grupo de aprendizagem numa aula de ciências. O grupo selecionado para a pesquisa constituiu-se de quatro alunos do II Ciclo (3ª e 4ª séries do Ensino Fundamental. Os dados foram coletados no 1º semestre de 2004, mediante gravação das aulas em vídeo, numa escola pública do município de Londrina-Paraná. O referencial teórico utilizado para análise e interpretação dos dados é de orientação psicanalítica, particularmente a Teoria do Vínculo de Pichon-Rivière. Entre os principais resultados encontrados, destacamos o vínculo estabelecido entre o grupo e a professora, o qual contribuiu para uma organização mais estável entre os membros, inclusive, com a aceitação de um aluno que se sentia excluído. Concluímos discutindo alguns aspectos relevantes a serem levados em consideração na promoção e sustentação da aprendizagem em grupo em sala de aula.The objective of this work consists in investigating the dynamics of group of learning in a science workshop. The group selected for the research consisted of four students. The data had been collected in 1º semester of 2004 through video recording of the lesson in a public school of the city of Londrina/PR. The theoretical basis for the analysis and interpretation of the data is psychoanalytical, particularly the Theory of Pichon-Rivière. From the results we identify the group-professor relationship bond established by the group as it evolved. We conclude by arguing that some aspects should be taken in consideration in the promotion and support of the learning in groups in classrooms.

  18. Effect of two different dentin desensitizers on shear bond strength of two different bonding agents to dentin: An in vitro study

    Directory of Open Access Journals (Sweden)

    Shekhar Bhatia

    2012-01-01

    Results: Statistically significant difference existed between the two bonding agents in the control groups (group 1 and 2, with Prime and Bond NT showing higher bond strength than Single Bond. No statistically significant difference existed between either control or pretreated with any desensitizer when either of the adhesive systems was used. Prime and Bond NT showed statistically higher bond strength value when teeth were pretreated with Sensodent-K™ (groups 5 and 6. No statistically significant difference in bond strength values were observed between the bonding agents when pretreated with Denshield™ desensitizer.

  19. Metal ion hydrocarbon bidentate bonding in alkyl acetates, methyl alkanoates, alcohols and 1-alkenes: a comparative study.

    Science.gov (United States)

    Burgers, Peter C; Holmes, John L; Terlouwc, Johan K

    2016-01-01

    The relative affinity of the monovalent metal ions Li(+), Na(+), Cu(+) and Ag(+) towards a series of aliphatic alkyl acetates and some selected 1-alkenes (P) was examined using the kinetic method. A detailed analysis of the dissociation characteristics of a series of mixed metal-bound dimer ions of the type P1-M(+)-P2 and the evaluated proton affinities (PAs) of the monomers shows that the affinity of the cation towards long-chain alkyl acetates and alkenes (having a chain length ≤ C4) is markedly enhanced. In line with recent studies of nitriles, alcohols and methyl alkanoates, this is attributed to a bidentate interaction of the metal ion with the functional group or double bond and the aliphatic chain. In particular, the longer chain alkyl acetates, methyl alkanoates and alcohols show a remarkably similar behaviour with respect to silver ion hydrocarbon bonding. The Ag(+) adducts of the alkyl acetates dissociate by loss of CH3COOH. This reaction becomes more pronounced at longer chain lengths, which points to metal ion bidentate formation in [Ag(+)···1-alkene] product ions having a long hydrocarbon chain. In the same vein, the heterodimers [1- hexene···Ag(+)···1-heptene] and [1- heptene···Ag(+)···1-octene] dissociate primarily into [Ag(+)···1-heptene] and [Ag(+)···1-octene] ions, respectively. Hydrocarbon bidentate formation in [Ag(+)···1-octene] also reveals itself by the reluctance of this ion to react with water in an ion trap, as opposed to [Ag(+)···1-hexene] which readily undergoes hydration.

  20. "Long-distance" H/D isotopic self-organization phenomena in scope of the infrared spectra of hydrogen-bonded terephthalic and phthalic acid crystals

    Science.gov (United States)

    Flakus, Henryk T.; Hachuła, Barbara.; Hołaj-Krzak, Jakub T.; Al-Agel, Faisal A.; Rekik, Najeh

    2017-02-01

    This paper deals with the experimental and theoretical studies of abnormal properties of terephthalic acid (TAC) and phthalic acid (PAC) crystals manifested in the H/D isotopic exchange. The widely utilized deuteration routine appeared to be insufficiently effective in the case of the h6-TAC isotopomer. In the case of the d4-TAC derivative the isotopic exchange process occurred noticeably more effectively. In contrast, both isotopomers of PAC, h6 and d4, appeared much more susceptible for deuteration. A theoretical model was elaborated describing "long-distance" dynamical co-operative interactions involving hydrogen bonds in TAC and PAC crystals. The model assumes extremely strong dynamical co-operative interactions of hydrogen bonds from the adjacent (COOH)2 cycles. This leads to an additional stabilization of h6-TAC molecular chains. The interaction energies affect the chemical equilibrium of the H/D isotopic exchange. The model predicts a differentiated influence of the H and D atoms linked to the aromatic rings on to the process. In this approach the totally-symmetric Csbnd H bond stretching vibrations and the proton stretching totally symmetric vibrations couple with the π-electronic motions. It was also shown that identical hydrogen isotope atoms, H or D, in whole TAC molecules, noticeably enlarge the energy of the dynamical co-operative interactions in the crystals, in contrast to the case of different hydrogen isotopes present in the carboxyl groups and linked to the aromatic rings. The "long-distance" dynamical co-operative interactions in PAC crystals were found of a minor importance due to the electronic properties of PAC molecules.

  1. Validated method for the simultaneous determination of Delta9-THC and Delta9-THC-COOH in oral fluid, urine and whole blood using solid-phase extraction and liquid chromatography-mass spectrometry with electrospray ionization.

    Science.gov (United States)

    Teixeira, Helena; Verstraete, Alain; Proença, Paula; Corte-Real, Francisco; Monsanto, Paula; Vieira, Duarte Nuno

    2007-08-01

    A fully validated, sensitive and specific method for the extraction and quantification of Delta(9)-tetrahydrocannabinol (THC) and 11-nor-9-carboxy-Delta(9)-THC (THC-COOH) and for the detection of 11-hydroxy-Delta(9)-THC (11-OH THC) in oral fluid, urine and whole blood is presented. Solid-phase extraction and liquid chromatography-mass spectrometry (LC-MS) technique were used, with electrospray ionization. Three ions were monitored for THC and THC-COOH and two for 11-OH THC. The compounds were quantified by selected ion recording of m/z 315.31, 329.18 and 343.16 for THC, 11-OH THC and THC-COOH, respectively, and m/z 318.27 and 346.26 for the deuterated internal standards, THC-d(3) and THC-COOH-d(3), respectively. The method proved to be precise for THC and THC-COOH both in terms of intra-day and inter-day analysis, with intra-day coefficients of variation (CV) less than 6.3, 6.6 and 6.5% for THC in saliva, urine and blood, respectively, and 6.8 and 7.7% for THC-COOH in urine and blood, respectively. Day-to-day CVs were less than 3.5, 4.9 and 11.3% for THC in saliva, urine and blood, respectively, and 6.2 and 6.4% for THC-COOH in urine and blood, respectively. Limits of detection (LOD) were 2 ng/mL for THC in oral fluid and 0.5 ng/mL for THC and THC-COOH and 20 ng/mL for 11-OH THC, in urine and blood. Calibration curves showed a linear relationship for THC and THC-COOH in all samples (r(2)>0.999) within the range investigated. The procedure presented here has high specificity, selectivity and sensitivity. It can be regarded as an alternative method to GC-MS for the confirmation of positive immunoassay test results, and can be used as a suitable analytical tool for the quantification of THC and THC-COOH in oral fluid, urine and/or blood samples.

  2. Critical roles for the COOH terminus of the Cu-ATPase ATP7B in protein stability, trans-Golgi network retention, copper sensing, and retrograde trafficking.

    Science.gov (United States)

    Braiterman, L; Nyasae, L; Leves, F; Hubbard, A L

    2011-07-01

    ATP7A and ATP7B are copper-transporting P-type ATPases that are essential to eukaryotic copper homeostasis and must traffic between intracellular compartments to carry out their functions. Previously, we identified a nine-amino acid sequence (F37-E45) in the NH(2) terminus of ATP7B that is required to retain the protein in the Golgi when copper levels are low and target it apically in polarized hepatic cells when copper levels rise. To understand further the mechanisms regulating the intracellular dynamics of ATP7B, using multiple functional assays, we characterized the protein phenotypes of 10 engineered and Wilson disease-associated mutations in the ATP7B COOH terminus in polarized hepatic cells and fibroblasts. We also examined the behavior of a chimera between ATP7B and ATP7A. Our results clearly demonstrate the importance of the COOH terminus of ATP7B in the protein's copper-responsive apical trafficking. L1373 at the end of transmembrane domain 8 is required for protein stability and Golgi retention in low copper, the trileucine motif (L1454-L1456) is required for retrograde trafficking, and the COOH terminus of ATP7B exhibits a higher sensitivity to copper than does ATP7A. Importantly, our results demonstrating that four Wilson disease-associated missense mutations behaved in a wild-type manner in all our assays, together with current information in the literature, raise the possibility that several may not be disease-causing mutations.

  3. COOH-Terminal Clustering of Autoantibody and T-Cell Determinants on the Structure of GAD65 Provide Insights Into the Molecular Basis of Autoreactivity

    Energy Technology Data Exchange (ETDEWEB)

    Fenalti, Gustavo; Hampe, Christiane S.; Arafat, Yasir; Law, Ruby H.P.; Banga, J. Paul; Mackay, Ian R.; Whisstock, James C.; Buckle, Ashley M.; Rowley, Merrill J. (UWASH); (King’s College); (Monash)

    2008-11-19

    To gain structural insights into the autoantigenic properties of GAD65 in type 1 diabetes, we analyzed experimental epitope mapping data in the context of the recently determined crystal structures of GAD65 and GAD67, to allow 'molecular positioning' of epitope sites for B- and T-cell reactivity. Data were assembled from analysis of reported effects of mutagenesis of GAD65 on its reactivity with a panel of 11 human monoclonal antibodies (mAbs), supplemented by use of recombinant Fab to cross-inhibit reactivity with GAD65 by radioimmunoprecipitation of the same mAbs. COOH-terminal region on GAD65 was the major autoantigenic site. B-cell epitopes were distributed within two separate clusters around different faces of the COOH-terminal domain. Inclusion of epitope sites in the pyridoxal phosphate- and NH{sub 2}-terminal domains was attributed to the juxtaposition of all three domains in the crystal structure. Epitope preferences of different mAbs to GAD65 aligned with different clinical expressions of type 1 diabetes. Epitopes for four of five known reactive T-cell sequences restricted by HLA DRB1*0401 were aligned to solvent-exposed regions of the GAD65 structure and colocalized within the two B-cell epitope clusters. The continuous COOH-terminal epitope region of GAD65 was structurally highly flexible and therefore differed markedly from the equivalent region of GAD67. Structural features could explain the differing antigenicity, and perhaps immunogenicity, of GAD65 versus GAD67. The proximity of B- and T-cell epitopes within the GAD65 structure suggests that antigen-antibody complexes may influence antigen processing by accessory cells and thereby T-cell reactivity.

  4. Parental Bonding and Mental Health in Adolescence.

    Science.gov (United States)

    Canetti, Laura; Bachar, Eytan; Galili-Weisstub, Esti; De-Nour, Atara Kaplan; Shalev, Arieh Y.

    1997-01-01

    Examines the relationship between parental bonding and mental health in healthy adolescents. Results, based on 847 Israeli high school students, show that those who reported high care and low control (optimal bonding) reported less distress, better general well-being, and better social support than did all other groups. (RJM)

  5. COOH-terminal association of human smooth muscle calcium channel Ca(v)1.2b with Src kinase protein binding domains: effect of nitrotyrosylation.

    Science.gov (United States)

    Kang, Minho; Ross, Gracious R; Akbarali, Hamid I

    2007-12-01

    The carboxyl terminus of the calcium channel plays an important role in the regulation of calcium entry, signal transduction, and gene expression. Potential protein-protein interaction sites within the COOH terminus of the L-type calcium channel include those for the SH3 and SH2 binding domains of c-Src kinase that regulates calcium currents in smooth muscle. In this study, we examined the binding sites involved in Src kinase-mediated phosphorylation of the human voltage-gated calcium channel (Ca(v)) 1.2b (hCav1.2b) and the effect of nitrotyrosylation. Cotransfection of human embryonic kidney (HEK)-293 cells with hCa(v)1.2b and c-Src resulted in tyrosine phosphorylation of the calcium channel, which was prevented by nitration of tyrosine residues by peroxynitrite. Whole cell calcium currents were reduced by 58 + 5% by the Src kinase inhibitor PP2 and 64 + 6% by peroxynitrite. Nitrotyrosylation prevented Src-mediated regulation of the currents. Glutathione S-transferase fusion protein of the distal COOH terminus of hCa(v)1.2b (1809-2138) bound to SH2 domain of Src following tyrosine phosphorylation, while binding to SH3 required the presence of the proline-rich motif. Site-directed mutation of Y(2134) prevented SH2 binding and resulted in reduced phosphorylation of hCa(v)1.2b. Within the distal COOH terminus, single, double, or triple mutations of Y(1837), Y(1861), and Y(2134) were constructed and expressed in HEK-293 cells. The inhibitory effects of PP2 and peroxynitrite on calcium currents were significantly reduced in the double mutant Y(1837-2134F). These data demonstrate that the COOH terminus of hCa(v)1.2b contains sites for the SH2 and SH3 binding of Src kinase. Nitrotyrosylation of these sites prevents Src kinase regulation and may be importantly involved in calcium influx regulation during inflammation.

  6. Ferroelectric TGS ((NH sub 2 CH sub 2 COOH) sub 3 centre dot H sub 2 SO sub 4) under high pressure

    CERN Document Server

    Kobayashi, Y; Furuta, H; Endo, S; Deguchi, K

    2002-01-01

    The ferroelectric transition temperature T sub c of (NH sub 2 CH sub 2 COOH) sub 3 centre dot H sub 2 SO sub 4 (TGS), which is a typical order-disorder-type ferroelectric, was determined by dielectric constant and Raman scattering measurements under high pressure. T sub c increased, passed through a maximum and then decreased slightly with increasing pressure, and then abruptly dropped at about 2.5 GPa, where a transition to a new high-pressure phase was confirmed to exist. A tentative p-T phase diagram was proposed for TGS.

  7. The effect of repeated bonding on the shear bond strength of different resin cements to enamel and dentin

    Science.gov (United States)

    Atsü, Saadet Sağlam

    2017-01-01

    PURPOSE Cementation failures of restorations are frequently observed in clinical practice. The purpose of this study is to compare the effect of initial and repeated bonding on the bond strengths of different resin cements to enamel and dentin. MATERIALS AND METHODS Ninety human maxillary central incisors were bisected longitudinally. The 180 tooth halves were divided into 2 groups (n = 90) for enamel and dentin bonding. The enamel and dentin groups were further divided into 3 groups (n = 30) for different resin cement types. Composite resin (Filtek Ultimate) cylinders (3 × 3 mm) were prepared and luted to enamel and dentin using Variolink II (Group V), RelyX ARC (Group R), or Panavia F 2.0 (Group P) resin cement. After 24 hours, initial shear bond strengths of the resin cements to enamel and dentin were measured. Using new cylinders, the specimens were de-bonded and re-bonded twice to measure the first and the second bond strengths to enamel and dentin. Failure modes and bonding interfaces were examined. Data were statistically analyzed. RESULTS Initial and repeated bond strengths to enamel were similar for all the groups. The first (15.3 ± 2.2 MPa) and second (10.4 ± 2.2 MPa) bond strengths to dentin were significantly higher in Group V (P<.0001). Second bond strengths of dentin groups were significantly lower than initial and first bond strengths to dentin (P<.0001). CONCLUSION All resin cements have similar initial and repeated bond strengths to enamel. Variolink II has the highest first and second bond strength to dentin. Bond strength to dentin decreases after the first re-bonding for all resin cements. PMID:28243393

  8. Bonding with Your Baby

    Science.gov (United States)

    ... in infant massage in your area. Breastfeeding and bottle-feeding are both natural times for bonding. Infants respond ... activities include: participating together in labor and delivery feeding ( breast or bottle ); sometimes dad forms a special bond with baby ...

  9. Tumor-associated NH2-terminal fragments are the most stable part of the adenomatous polyposis coli protein and can be regulated by interactions with COOH-terminal domains.

    Science.gov (United States)

    Li, Zhuoyu; Näthke, Inke S

    2005-06-15

    Truncation mutations in the adenomatous polyposis coli (APC) gene are responsible for familial and sporadic colorectal cancer. APC is a large, multifunctional protein involved in cell migration, proliferation, and differentiation. Dominant effects that have been attributed to the NH2-terminal fragments of APC expressed in tumors may result from loss of functions due to lack of COOH-terminal regions or gain of functions due to fewer regulatory interactions. Resolving this issue and determining how structural changes contribute to the multiple functions of the APC protein requires knowledge about the structural organization of the APC molecule. To this end, we used limited proteolysis to distinguish regions of the molecule with limited structure from those that form well-folded domains. We discovered that the NH2-terminal region of APC was most resistant to proteolytic degradation, whereas middle and COOH-terminal regions were significantly more sensitive. Binding of APC to microtubules protected COOH-terminal regions of APC against proteolysis, consistent with the idea that this region of the molecule becomes ordered when bound to microtubules. Furthermore, interactions between the NH2- and COOH-terminal domains of APC were identified in vitro and in vivo, suggesting that NH2-terminal fragments of APC may be regulated by interactions with COOH-terminal domains. Indeed, expressing COOH-terminal APC fragments in tumor cells resulted in changes in the protein interactions of endogenous NH2-terminal fragments in these cells. Thus, the dominant function of NH2-terminal APC fragments found in tumor cells could be explained by loss of this regulation in tumors where COOH-terminal domains are missing.

  10. The modified extended Hansen method to determine partial solubility parameters of drugs containing a single hydrogen bonding group and their sodium derivatives: benzoic acid/Na and ibuprofen/Na.

    Science.gov (United States)

    Bustamante, P; Pena, M A; Barra, J

    2000-01-20

    Sodium salts are often used in drug formulation but their partial solubility parameters are not available. Sodium alters the physical properties of the drug and the knowledge of these parameters would help to predict adhesion properties that cannot be estimated using the solubility parameters of the parent acid. This work tests the applicability of the modified extended Hansen method to determine partial solubility parameters of sodium salts of acidic drugs containing a single hydrogen bonding group (ibuprofen, sodium ibuprofen, benzoic acid and sodium benzoate). The method uses a regression analysis of the logarithm of the experimental mole fraction solubility of the drug against the partial solubility parameters of the solvents, using models with three and four parameters. The solubility of the drugs was determined in a set of solvents representative of several chemical classes, ranging from low to high solubility parameter values. The best results were obtained with the four parameter model for the acidic drugs and with the three parameter model for the sodium derivatives. The four parameter model includes both a Lewis-acid and a Lewis-base term. Since the Lewis acid properties of the sodium derivatives are blocked by sodium, the three parameter model is recommended for these kind of compounds. Comparison of the parameters obtained shows that sodium greatly changes the polar parameters whereas the dispersion parameter is not much affected. Consequently the total solubility parameters of the salts are larger than for the parent acids in good agreement with the larger hydrophilicity expected from the introduction of sodium. The results indicate that the modified extended Hansen method can be applied to determine the partial solubility parameters of acidic drugs and their sodium salts.

  11. Bond percolation in films

    Science.gov (United States)

    Korneta, W.; Pytel, Z.

    1988-04-01

    Bond percolation in films with simple cubic structure is considered. It is assumed that the probability of a bond being present between nearest-neighbor sites depends on the distances to surfaces. Based on the relation between the Potts model and the bond percolation model, and using the mean-field approximation, the phase diagram and profiles of the percolation probability have been obtained.

  12. Acrylic mechanical bond tests

    Energy Technology Data Exchange (ETDEWEB)

    Wouters, J.M.; Doe, P.J.

    1991-02-01

    The tensile strength of bonded acrylic is tested as a function of bond joint thickness. 0.125 in. thick bond joints were found to posses the maximum strength while the acceptable range of joints varied from 0.063 in. to almost 0.25 in. Such joints are used in the Sudbury Neutrino Observatory.

  13. Chemical bond fundamental aspects of chemical bonding

    CERN Document Server

    Frenking, Gernot

    2014-01-01

    This is the perfect complement to ""Chemical Bonding - Across the Periodic Table"" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community. The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemica

  14. Shear Bond Strengths of Different Adhesive Systems to Biodentine

    OpenAIRE

    Mesut Enes Odabaş; Mehmet Bani; Resmiye Ebru Tirali

    2013-01-01

    The aim of this study was to measure the shear bond strength of different adhesive systems to Biodentine with different time intervals. Eighty specimens of Biodentine were prepared and divided into 8 groups. After 12 minutes, 40 samples were randomly selected and divided into 4 groups of 10 each: group 1: (etch-and-rinse adhesive system) Prime & Bond NT; group 2: (2-step self-etch adhesive system) Clearfil SE Bond; group 3: (1-step self-etch adhesive systems) Clearfil S3 Bond; group 4: contro...

  15. Synthesis, Crystal Structure and Electrochemical Properties of Complex[Ni(2,2'-bipy)2(ClC6H4COO)(H2O)](ClO4)

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A new nickel(Ⅱ) coordination complex [Ni(2,2'-bipy)2(ClC6H4COO)(H2O)](ClO4) was synthesized by self-assembly reaction of m-chlorobenzoic acid, 2,2'-bipy and Ni(ClO4)2(6H2O. The crystal of the title compound belongs to monoclinic system, space group P21/n with a = 0.77764(14), b = 2.6572(5), c = 1.3637(2) nm, β = 96.456(3)°, V = 2.8000(9) nm3, Dc = 1.528 g/cm3, Z = 4, Mr = 644.10, μ(MoKα) = 0.937 mm-1, F(000) =1320, R = 0.0549 and wR = 0.1164. Structure analysis shows that the nickel(Ⅱ) ion is coordinated with four nitrogen atoms from two bipys as well as two oxygen atoms from m-chlorobenzoic acid and water, respectively, giving a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex is also presented.

  16. Acidities of closo-1-COOH-1,7-C2B10H11 and amino acids based on icosahedral carbaboranes.

    Science.gov (United States)

    Dávalos, Juan Z; González, Javier; Ramos, Rocío; Hnyk, Drahomír; Holub, Josef; Santaballa, J Arturo; Canle-L, Moisés; Oliva, Josep M

    2014-04-17

    Carborane clusters are not found in Nature and are exclusively man-made. In this work we study, both experimentally and computationally, the gas-phase acidity (measured GA = 1325 kJ·mol(-1), computed GA = 1321 kJ·mol(-1)) and liquid-phase acidity (measured pKa = 2.00, computed pKa = 1.88) of the carborane acid closo-1-COOH-1,7-C2B10H11. The experimental gas-phase acidity was determined with electrospray tandem mass spectrometry (ESI/MS), by using the extended Cooks kinetic method (EKM). Given the similar spatial requirements of the title icosahedral cage and benzene and the known importance of aminoacids as a whole, such a study is extended, within an acid-base context, to corresponding ortho, meta, and para amino acids derived from icosahedral carborane cages, 1-COOH-n-NH2-1, n-R with {R = C2B10H10, n = 2, 7, 12}, and from benzene {R = C6H4, n = 2, 3, 4}. A remarkable difference is found between the proportion of neutral versus zwitterion structures in water for glycine and the carborane derived amino acids.

  17. Label-Free Electrochemiluminescent Immunosensor for Detection of Carcinoembryonic Antigen Based on Nanocomposites of GO/MWCNTs-COOH/Au@CeO₂.

    Science.gov (United States)

    Pang, Xuehui; Li, Jianxiu; Zhao, Yongbei; Wu, Dan; Zhang, Yong; Du, Bin; Ma, Hongmin; Wei, Qin

    2015-09-01

    A high-sensitivity electrochemiluminescence (ECL) sensor was conducted to detect carcinoembryonic antigen (CEA). Nanocomposites of graphene oxide/carboxylated multiwall carbon nanotubes/gold/cerium oxide nanoparticles (GO/MWCNTs-COOH/Au@CeO2) were used as antibody carriers and sensing platforms to modify on glassy carbon electrodes (GCE). CeO2 nanoparticles were first exploited as an ECL luminescent material and the possible ECL mechanism was proposed in this work. GO/MWCNTs-COOH was used as a loading matrix for CeO2 nanoparticles because of the superior conductivity and large specific surface area. Au nanoparticles were further deposited on this matrix to attach anti-CEA and enhance the sensitivity of immunosensor. The proposed sensing platform showed excellent cathodic ECL performance and sensitive response to CEA. The effects of experimental conditions on the ECL performance were investigated. The proposed immunosensor showed the broad linear range (0.05-100 ng/mL) and the low detection limit (LOD, 0.02 ng/mL, signal-to-noise ratio = 3) according to the selected experimental conditions. The excellent analysis performance for determination of CEA in the human serum samples simplied this immunosensor displayed high sensitivity and excellent repeatability. More importantly, this conducted immunosensor broadens the use scope of CeO2 nanoparticles.

  18. 3,5,5,6,8,8-Hexamethyl-5,6,7,8-tetrahydro-2-naphthoic acid (AHTN–COOH

    Directory of Open Access Journals (Sweden)

    Irene Nehls

    2010-10-01

    Full Text Available The title compound, C17H24O2, is the product of a haloform reaction of 6-acetyl-1,1,2,4,4,7-hexamethyltetraline (AHTN. The compound is a racemic mixture with a disorder in its aliphatic ring [occupany ratio 0.683 (4:0.317 (4] due to two possible half-chair forms. The carboxylic acid unit is slightly twisted out of coplanarity with the aromatic system [dihedral angle = 29.26 (6°]. In the crystal, pairs of short classical intermolecular O—H...O hydrogen bonds link pairs of molecules around a center of symmetry.

  19. Bond strength of composite resin to pulp capping biomaterials after application of three different bonding systems.

    Science.gov (United States)

    Jaberi-Ansari, Zahra; Mahdilou, Maryam; Ahmadyar, Maryam; Asgary, Saeed

    2013-01-01

    Background and aims. Bonding of composite resin filling materials to pulp protecting agents produces an adhesive joint which is important for the quality of filling as well as success of restoration. We aimed to assess the bond strength of composite resin to three pulp capping biomaterials: Pro Root mineral trioxide aggregate (PMTA), Root MTA (RMTA) and calcium enriched mixture (CEM) cement, using three bonding systems [a total-etch (Single Bond) and two self-etch systems (Protect bond and SE Bond)]. Materials and methods. Ninety acrylic molds, each containing a 6×2-mm hole, were divided into 3 groups and filled with PMTA, RMTA and CEM cements. The samples in each experimental group were then randomly divided into 3 sub-groups; Single Bond, Protect Bond and SE Bond bonding systems were applied to the tested materials. Cylindrical forms of composite resin (Z100, 2×2 mm) were placed onto the samples and cured. Shear bond strength values were measured for 9 subgroups using a universal testing machine. Data were analyzed using two-way ANOVA. Results. The average shear bond strengths of Z100 composite resin after application of Single Bond, Protect Bond and SE Bond systems were as follows; PMTA: 5.1±2.42, 4.56±1.96 and 4.52±1.7; RMTA: 4.71±1.77, 4.31±0.56 and 4.79±1.88; and CEM cement: 4.75±1.1, 4.54±1.59 and 4.64±1.78 MPa, respectively. The type of pulp capping material, bonding system and their interacting effects did not have a significant effect on the bond strengths of composite resin to pulp capping biomaterials. Conclusion. Within the limitations of this in vitrostudy, bond strength of composite resin to two types of MTA as well as CEM cement were similar following application of the total-etch or self-etch bonding systems.

  20. Evaluation of enamel damages following orthodontic bracket debonding in fluorosed teeth bonded with adhesion promoter

    OpenAIRE

    Baherimoghadam, Tahreh; Akbarian, Sahar; Rasouli, Reza; Naseri, Navid

    2016-01-01

    Objective: To evaluate shear bond strength (SBS) of the orthodontic brackets bonded to fluorosed and nonfluorosed teeth using Light Bond with and without adhesion promoters and compare their enamel damages following debonding. Materials and Methods: In this study, 30 fluorosed (Thylstrup and Fejerskov Index = 4?5) and 30 nonfluorosed teeth were randomly distributed between two subgroups according to the bonding materials: Group 1, fluorosed teeth bonded with Light Bond; Group 2, fluorosed tee...

  1. Comparison of Shear Bond Strength of RMGI and Composite Resin for Orthodontic Bracket Bonding.

    Science.gov (United States)

    Yassaei, Soghra; Davari, Abdolrahim; Goldani Moghadam, Mahjobeh; Kamaei, Ahmad

    2014-05-01

    The aim of this study was to compare the shear bond strength (SBS) of resin modified glass ionomer (RMGI) and composite resin for bonding metal and ceramic brackets. Eighty-eight human premolars extracted for orthodontic purposes were divided into 4 groups (n=22). In groups 1 and 2, 22 metal and ceramic brackets were bonded using composite resin (Transbond XT), respectively. Twenty-two metal and ceramic brackets in groups 3 and 4, respectively were bonded using RMGI (Fuji Ortho LC, Japan). After photo polymerization, the teeth were stored in water and thermocycled (500 cycles between 5° and 55°). The SBS value of each sample was determined using a Universal Testing Machine. The amount of residual adhesive remaining on each tooth was evaluated under a stereomicroscope. Statistical analyses were done using two-way ANOVA. RMGI bonded brackets had significantly lower SBS value compared to composite resin bonded groups. No statistically significant difference was observed between metal and ceramic brackets bonded with either the RMGI or composite resin. The comparison of the adhesive remnant index (ARI) scores between the groups indicated that the bracket failure mode was significantly different among groups (Pcomposite resin. RMGIs have significantly lower SBS compared to composite resin for orthodontic bonding purposes; however the provided SBS is still within the clinically acceptable range.

  2. Preparation and cell cytotoxicity of CHI/SWCNT-COOHs%壳聚糖修饰单壁碳纳米管的制备与细胞毒性研究

    Institute of Scientific and Technical Information of China (English)

    陈乘; 王晖; 周谦; 余书勤

    2011-01-01

    Objective:To synthesis SWCNT-based CHI/SWCNT-COOHs nano-materials and evaluate its in vitro cell toxicity.Methods: Raw single walled carbon nanotubes (SWCNTs) were treated by acid oxidation to form carboxylic SWCNT-COOHs.Then, SWCNT-COOHs were employed as native carriers wrapped with low molecular weight chitosan (CHI) through electrostatic force.The CHI/SWCNT-COOHs samples were charactered by using transmission electron microscopy (TEM) and Raman spectroscopy.A549 cell viability was determined by trypan blue dye exclusion assay after being treated with nano-materials.Statistics of the single cell colonies was obtained by nutritional depletion associated with the treatment of CNTs for one week.Scanning electron microscopy was used to observe the morphology stnuctural of the red blood cell after treating with CNTs to them.Results: With high water stability, CHI/SWCNT-COOHs could greatly improve the survival rate of cells, reduce nutrient depletion, and cause no significant change in red blood cell morphology.Conclusion:CHI/SWCNT-COOHs have good stability in water, with nano-features and low cytotoxicity.%目的:制备稳定的水溶性的壳聚糖/碳纳米管(CHI/SWCNT-COOHs)纳米材料,对其表征并检测纳米材料的细胞毒性.方法:市售单壁碳纳米管(Raw SWCNTs)以强酸处理,形成残缺的羧基化单壁碳纳米管(SWCNT-COOHs),然后,低分子壳聚糖(CHI)与SWCNT-COOHs反应制备壳聚糖/碳纳米管(CHI/SWCNT-COOHs)纳米材料;运用透射电镜技术、拉曼光谱技术检测纳米材料的性状;通过台盼蓝染色计算纳米材料对A549细胞存活率的影响,计算纳米材料营养耗竭后对单细胞克隆的影响;应用扫描电镜检测其对红细胞形态的影响.结果:CHI/SWCNT-COOHs在水系中有很好的稳定性,对细胞无明显毒性,营养耗竭量减少,对红细胞形态没有显著影响.结论:CHI/SWCNT-COOHs性状稳定,具有纳米特性,细胞毒性低.

  3. Tensile Bond Strength of Metal Bracket Bonding to Glazed Ceramic Surfaces With Different Surface Conditionings

    Directory of Open Access Journals (Sweden)

    M. Imani

    2011-12-01

    Full Text Available Objective: The objective of this study was to compare the tensile bond strength of metal brackets bonding to glazed ceramic surfaces using three various surface treatments.Materials and Methods: Forty two glazed ceramic disks were assigned to three groups. In the first and second groups the specimens were etched with 9.5% hydrofluoric acid (HFA. Subsequently in first group, ceramic primer and adhesive were applied, but in second group a bonding agent alone was used. In third group, specimens were treated with 35% phosphoric acid followed by ceramic primerand adhesive application. Brackets were bonded with light cure composites. The specimens were stored in distilled water in the room temperature for 24 hours and thermocycled 500 times between 5°C and 55°C. The universal testing machine was used to test the tensile bond strength and the adhesive remenant index scores between three groups was evaluated. The data were subjected to one-way ANOVA, Tukey and Kruskal-Wallis tests respectively.Results: The tensile bond strength was 3.69±0.52 MPa forfirst group, 2.69±0.91 MPa for second group and 3.60±0.41 MPa for third group. Group II specimens showed tensile strength values significantly different from other groups (P<0.01.Conclusion: In spite of limitations in laboratory studies it may be concluded that in application of Scotch bond multipurpose plus adhesive, phosphoric acid can be used instead of HFA for bonding brackets to the glazed ceramic restorations with enough tensile bond strength.

  4. Enamel and dentin bond strength following gaseous ozone application.

    Science.gov (United States)

    Cadenaro, Milena; Delise, Chiara; Antoniollo, Francesca; Navarra, Ottavia Chiara; Di Lenarda, Roberto; Breschi, Lorenzo

    2009-08-01

    To evaluate the effects of gaseous ozone application on enamel and dentin bond strength produced by two self-etching adhesive systems. The shear bond strength test was conducted to assess adhesion on enamel (protocol 1), while the microtensile bond strength test was performed on dentin (protocol 2). Protocol 1: 96 bovine incisors were randomly divided into 4 groups, and enamel surfaces were bonded in accordance with the following treatments: (1E) ozone + Clearfil Protect Bond; (2E) Clearfil Protect Bond (control); (3E) ozone + Xeno III; (4E) Xeno III (control). Ozone gas was applied for 80 s. Shear bond strength was measured with a universal testing machine. Protocol 2: 40 noncarious human molars were selected. Middle/deep dentin was exposed and bonded in accordance with the following treatments: (1D) ozone+Clearfil Protect Bond; (2D) Clearfil Protect Bond (control); (3D) ozone+Xeno III (4D) Xeno III (control). Four-mm-thick buildups were built on the adhesives, then specimens were sectioned in accordance with the nontrimming technique. Specimens were stressed until failure occurred, and failure modes were analyzed. Shear bond and microtensile bond strength data were analyzed using two-way ANOVA and Tukey's post-hoc test. No statistical differences were found between ozone treated specimens and controls, neither on enamel nor on dentin irrespective of the tested adhesive. Clearfil Protect Bond showed higher bond strength to enamel than Xeno III, irrespective of the ozone treatment (p enamel and dentin bond strength.

  5. Bond Strength of Composite Resin to Pulp Capping Biomaterials after Application of Three Different Bonding Systems

    Directory of Open Access Journals (Sweden)

    Zahra Jaberi-Ansari

    2013-08-01

    Full Text Available Background and aims. Bonding of composite resin filling materials to pulp protecting agents produces an adhesive joint which is important for the quality of filling as well as success of restoration. We aimed to assess the bond strength of composite resin to three pulp capping biomaterials: Pro Root mineral trioxide aggregate (PMTA, Root MTA (RMTA and calcium enriched mixture (CEM cement, using three bonding systems [a total-etch (Single Bond and two self-etch systems (Protect bond and SE Bond]. Materials and methods. Ninety acrylic molds, each containing a 6×2-mm hole, were divided into 3 groups and filled with PMTA, RMTA and CEM cements. The samples in each experimental group were then randomly divided into 3 subgroups; Single Bond, Protect Bond and SE Bond bonding systems were applied to the tested materials. Cylindrical forms of composite resin (Z100, 2×2 mm were placed onto the samples and cured. Shear bond strength values were measured for 9 subgroups using a universal testing machine. Data were analyzed using two-way ANOVA. Results. The average shear bond strengths of Z100 composite resin after application of Single Bond, Protect Bond and SE Bond systems were as follows; PMTA: 5.1±2.42, 4.56±1.96 and 4.52±1.7; RMTA: 4.71±1.77, 4.31±0.56 and 4.79±1.88; and CEM cement: 4.75±1.1, 4.54±1.59 and 4.64±1.78 MPa, respectively. The type of pulp capping material, bonding system and their interacting effects did not have a significant effect on the bond strengths of composite resin to pulp capping biomaterials. Conclusion. Within the limitations of this in vitro study, bond strength of composite resin to two types of MTA as well as CEM cement were similar following application of the total-etch or self-etch bonding systems.

  6. Effects of green tea on the shear bond strength of orthodontic brackets after in-office vital bleaching.

    Science.gov (United States)

    Berger, Sandrine Bittencourt; Guiraldo, Ricardo Danil; Lopes, Murilo Baena; Oltramari-Navarro, Paula Vanessa; Fernandes, Thais Maria; Schwertner, Renata de Castro Alves; Ursi, Wagner José Silva

    2016-01-01

    The application of bleaching agents before placement of resin-bonded fixed appliances significantly, but temporarily, reduces bond strength to tooth structure. Antioxidants have been studied as a means to remove residual oxygen that compromises bonding to bleached enamel. This in vitro study evaluated whether green tea (GT) could restore the shear bond strength between bonded orthodontic brackets and bleached enamel. Six experimental groups were compared: group 1, no bleaching plus bracket bonding (positive control); group 2, bleaching with 35% hydrogen peroxide (HP) plus bracket bonding (negative control); group 3, 35% HP plus 10% sodium ascorbate (SA) plus bracket bonding; group 4, 35% HP plus 10% GT plus bracket bonding; group 5, no bleaching plus 10% SA plus bracket bonding; group 6, no bleaching plus 10% GT plus bracket bonding. Results suggested that GT, like SA, may be beneficial for bracket bonding immediately after bleaching.

  7. Hydrogen bond dynamics in bulk alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Shinokita, Keisuke; Cunha, Ana V.; Jansen, Thomas L. C.; Pshenichnikov, Maxim S., E-mail: Maxim.Pchenitchnikov@RuG.nl [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen (Netherlands)

    2015-06-07

    Hydrogen-bonded liquids play a significant role in numerous chemical and biological phenomena. In the past decade, impressive developments in multidimensional vibrational spectroscopy and combined molecular dynamics–quantum mechanical simulation have established many intriguing features of hydrogen bond dynamics in one of the fundamental solvents in nature, water. The next class of a hydrogen-bonded liquid—alcohols—has attracted much less attention. This is surprising given such important differences between water and alcohols as the imbalance between the number of hydrogen bonds, each molecule can accept (two) and donate (one) and the very presence of the hydrophobic group in alcohols. Here, we use polarization-resolved pump-probe and 2D infrared spectroscopy supported by extensive theoretical modeling to investigate hydrogen bond dynamics in methanol, ethanol, and isopropanol employing the OH stretching mode as a reporter. The sub-ps dynamics in alcohols are similar to those in water as they are determined by similar librational and hydrogen-bond stretch motions. However, lower density of hydrogen bond acceptors and donors in alcohols leads to the appearance of slow diffusion-controlled hydrogen bond exchange dynamics, which are essentially absent in water. We anticipate that the findings herein would have a potential impact on fundamental chemistry and biology as many processes in nature involve the interplay of hydrophobic and hydrophilic groups.

  8. Halogen bonds in crystal engineering: like hydrogen bonds yet different.

    Science.gov (United States)

    Mukherjee, Arijit; Tothadi, Srinu; Desiraju, Gautam R

    2014-08-19

    The halogen bond is an attractive interaction in which an electrophilic halogen atom approaches a negatively polarized species. Short halogen atom contacts in crystals have been known for around 50 years. Such contacts are found in two varieties: type I, which is symmetrical, and type II, which is bent. Both are influenced by geometric and chemical considerations. Our research group has been using halogen atom interactions as design elements in crystal engineering, for nearly 30 years. These interactions include halogen···halogen interactions (X···X) and halogen···heteroatom interactions (X···B). Many X···X and almost all X···B contacts can be classified as halogen bonds. In this Account, we illustrate examples of crystal engineering where one can build up from previous knowledge with a focus that is provided by the modern definition of the halogen bond. We also comment on the similarities and differences between halogen bonds and hydrogen bonds. These interactions are similar because the protagonist atoms-halogen and hydrogen-are both electrophilic in nature. The interactions are distinctive because the size of a halogen atom is of consequence when compared with the atomic sizes of, for example, C, N, and O, unlike that of a hydrogen atom. Conclusions may be drawn pertaining to the nature of X···X interactions from the Cambridge Structural Database (CSD). There is a clear geometric and chemical distinction between type I and type II, with only type II being halogen bonds. Cl/Br isostructurality is explained based on a geometric model. In parallel, experimental studies on 3,4-dichlorophenol and its congeners shed light on the nature of halogen···halogen interactions and reveal the chemical difference between Cl and Br. Variable temperature studies also show differences between type I and type II contacts. In terms of crystal design, halogen bonds offer a unique opportunity in the strength, atom size and interaction gradation; this may be

  9. Shear Bond Strength of Two Types of Glass Ionomer to Bleached Dentin: Effect of Delayed Bonding and Antioxidant Agent

    Science.gov (United States)

    Omrani, Ladan Ranjbar; Sabouri, Parastoo; Abbasi, Mehdi; Ahmadi, Elham; Ghavam, Maryam

    2016-01-01

    Background: Studies have shown a reduction in bond strength of composites and glass ionomer to bleached enamel and dentin. Several methods have been proposed to reverse compromised bond strength. Objective: The aim of this study was to evaluate the effect of delayed bonding and application of antioxidant agent on the bond strength of reinforced self-cured (Fuji IX) and light-cured glass ionomers (Fuji II LC) to bleached dentin. Material: Eighty extracted third molars were randomly divided into 8 groups. Buccal dentin surfaces received different treatments: Two control groups: no treatment + bonding Fuji IX or Fuji II LC. Two immediate bonding groups: bleaching + bonding Fuji IX or Fuji II LC. Two delayed bonding groups: bleaching + 7 days delay + bonding Fuji IX or Fuji II LC. Two sodium ascorbate application groups: Bleaching + application of 10% sodium ascorbate + bonding Fuji IX or Fuji II LC. All samples were tested for shear bond strength. Two-way analysis of variance (ANOVA) was used to compare the mean and standard deviations among groups, followed by the Tukey’s test for significant interaction. Results: No statistically significant difference was detected in shear bond strength of Fuji IX to bleached or normal dentin. Although a significant reduction was found shear bond strength values of Fuji II LC to bleached dentin, no significant difference was observed between no bleaching group and those treated with 10% sodium ascorbate or 7 days of delay in bonding for both types of glass ionomer. Conclusion: Bleaching had no significant effect on shear bond strength of Fuji IX to dentin; this type of GI can be used immediately after bleaching. PMID:28217187

  10. Covalent bond glued sulfur nanosheet-based cathode integration for long-cycle-life Li-S batteries.

    Science.gov (United States)

    Wang, Lei; Dong, Zhihui; Wang, Dong; Zhang, Fengxing; Jin, Jian

    2013-01-01

    High-capacity electrochemical active material-based electrodes for lithium ion batteries (LIBs), such as sulfur (S), always face the collapse of the electrode due to the big volume change during insertion of the lithium (Li) ion and therefore shorten the cycle life of the cells. Herein, a series of design from the viewpoint of both individual components and the entire cathode in lithium-sulfur (Li-S) cell was introduced aiming at addressing the issues of poor conductivity, leakage of intermediate polysulphides, and large volumetric expansion upon insertion of the Li ion. In the designed electrode, polydopamine (PD)-coated S nanosheets (NSs) were used as active materials, carboxylic acid functionalized multiwall carbon nanotube (MWCNT-COOH) as conductive additives, and poly(acrylic acid) (PAA) as binders. Far different from the traditional hydrogen bond and/or van der Waals force linked electrodes, stronger covalent bonds formed by cross-linking of PD/MWCNT-COOH and PD/PAA into amide bonds, respectively, were built throughout the whole electrode to firmly integrate all of the individual components in the electrode together. As a result, the cathode demonstrated excellent cyclic performance with a charge capacity of 640 mAh/g after 500 cycles at a current density of 1 A/g. Besides, the charge capacity decay after 500 cycles is as small as 0.021% per cycle, which represents the best capacity retention so far.

  11. The Dewar-Chatt-Duncanson model reversed Bonding analysis of group-10 complexes [(PMe3)2M-EX3] (M = Ni, Pd, Pt;; E = B, Al, Ga, In, Tl;; X = H, F, Cl, Br, I)

    National Research Council Canada - National Science Library

    Haunschild, Robin; Hillebrecht, Pierre; Goedecke, Catharina; Uhlemann, Till; Frenking, Gernot

    2009-01-01

    ...-acceptor complexes [(PMe 3 ) 2 M-EX 3 ] with X = H, F, Cl, Br, I;; E = B, Al, Ga, In, Tl; and M = Ni, Pd, Pt. The nature of the metal-ligand bond was investigated with an energy decomposition analysis...

  12. Shear bond strength evaluation of resin composite bonded to glass-ionomer cement using self-etching bonding agents with different pH: In vitro study

    Directory of Open Access Journals (Sweden)

    Deivanayagam Kandaswamy

    2012-01-01

    Full Text Available Aim: To evaluate the bonding ability of composite to unset glass-ionomer cement (GIC using different self-etching bonding systems. Materials and Methods: One hundred samples of composite bonded to unset GIC were prepared and were divided into four groups. In Group A, composite was bonded to unset GIC employing a strong (pH 1 self-etch primer was used. In Group B, intermediary strong (pH 1.4 self-etch primer was employed. In Group C and D, mild (pH 2 and (pH 2.2 self-etch primer was employed. Shear bond strength analysis was performed at a cross-head speed of 0.5 mm/min. Results: Statistical analysis performed with one way analysis of variance and Tukey′s test showed that the bond strength of composite to unset GIC was significantly higher for the mild self-etch primer group. In addition, energy dispersive x-ray (EDX analysis was used to determine the composition of various structural phases identified by FE-SEM along the GIC-bonding agent interfaces. Conclusion: Hence this present study concludes that clinically the use of mild self-etching bonding agent over unset GIC has improved bond strength compared to the use of strong and intermediate self-etching bonding agent.

  13. Bonding polycarbonate brackets to ceramic: : Effects of substrate treatment on bond strength

    NARCIS (Netherlands)

    Özcan, Mutlu; Vallittu, Pekka K.; Peltomäki, Timo; Huysmans, Marie-Charlotte; Kalk, Warner

    2004-01-01

    This study evaluated the effects of 5 different surface conditioning methods on the bond strength of polycarbonate brackets bonded to ceramic surfaces with resin based cement. Six disc-shaped ceramic specimens (feldspathic porcelain) with glazed surfaces were used for each group. The specimens were

  14. Bonding polycarbonate brackets to ceramic : Effects of substrate treatment on bond strength

    NARCIS (Netherlands)

    Özcan, Mutlu; Vallittu, Pekka K.; Peltomäki, Timo; Huysmans, Marie-Charlotte; Kalk, Warner

    2004-01-01

    This study evaluated the effects of 5 different surface conditioning methods on the bond strength of polycarbonate brackets bonded to ceramic surfaces with resin based cement. Six disc-shaped ceramic specimens (feldspathic porcelain) with glazed surfaces were used for each group. The specimens were

  15. Equilibrium CO bond lengths

    Science.gov (United States)

    Demaison, Jean; Császár, Attila G.

    2012-09-01

    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  16. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  17. Universal low-temperature MWCNT-COOH-based counter electrode and a new thiolate/disulfide electrolyte system for dye-sensitized solar cells.

    Science.gov (United States)

    Hilmi, Abdulla; Shoker, Tharallah A; Ghaddar, Tarek H

    2014-06-11

    A new thiolate/disulfide organic-based electrolyte system composed of the tetrabutylammonium salt of 2-methyl-5-trifluoromethyl-2H-[1,2,4]triazole-3-thiol (S(-)) and its oxidized form 3,3'-dithiobis(2-methyl-5-trifluoromethyl-2H-[1,2,4]triazole) (DS) has been formulated and used in dye-sensitized solar cells (DSSCs). The electrocatalytic activity of different counter electrodes (CEs) has been evaluated by means of measuring J-V curves, cyclic voltammetry, Tafel plots, and electrochemical impedance spectroscopy. A stable and low-temperature CE based on acid-functionalized multiwalled carbon nanotubes (MWCNT-COOH) was investigated with our S(-)/DS, I(-)/I3(-), T(-)/T2, and Co(II/III)-based electrolyte systems. The proposed CE showed superb electrocatalytic activity toward the regeneration of the different electrolytes. In addition, good stability of solar cell devices based on the reported electrolyte and CE was shown.

  18. Microshear bond strength evaluation of surface pretreated zirconia ceramics bonded to dentin

    Science.gov (United States)

    Anand, Shenbagakuttalam; Ebenezar, Ambrose Vedamanickam Rajesh; Anand, Nirupa; Rajkumar, Kothandaraman; Mahalaxmi, Sekar; Srinivasan, Narasimhan

    2015-01-01

    Objectives: To comparatively assess the micro shear bond strength (MSBS) of dentin bonded surface pre-treated zirconia ceramics. Materials and Methods: Zirconia blocks were sectioned into 50 cubical blocks. The blocks were further categorized into five groups (n = 10 each). Group I: No treatment was performed on zirconia samples; Group II: The zirconia samples were sand-blasted; Group III: Group II + etched with 9.8% of hydrofluoric (HF) acid for 60 s; Group IV: The sandblasted zirconia samples were selectively infiltrated with low fusing porcelain; and Group V: Group IV + etched using 9.8% HF acid gel. The zirconia specimens were then bonded to dentin samples, and the samples were tested for MSBS evaluation using universal testing machine. Results: The MSBS of all the four experimental groups shows greater value than group I. Among the experimental groups, group V and group IV do not show any statistical significant difference, whereas the mean MSBS of groups IV and V were statistically greater than group III and group II. However, groups I, II, and III do not show any statistical significant difference in mean MSBS values between them. Conclusion: Selective infiltration etching of zirconia ceramics provides the highest bond strength with resin cement. PMID:26038654

  19. Bonding to a porcelain surface: Factors affecting the shear bond strength

    Directory of Open Access Journals (Sweden)

    Shishir Singh

    2013-01-01

    Full Text Available Objectives: Bonding to porcelain veneers, crowns or restorations is a major challenge for an orthodontist. A study was undertaken wherein, the shear bond strengths of metal and ceramic brackets on porcelain were compared and the effects of debonding on the debonded surfaces were evaluated. Materials and Methods: A total of 50 acrylic duplicate samples were fabricated from a therapeutically extracted maxillary first premolar, duly prepared for metal crown with porcelain facing. The samples were divided into two equal groups for bonding of metal and ceramic brackets. The shear bond strength of the samples was measured with a universal testing machine. Results: The metal brackets showed shear bond strengths with a mean of 12.21 ± 1.4 MPa, whereas the ceramic brackets displayed shear bond strengths with a mean of 17.45 ± 2.36 MPa. Visual and scanning electron microscope examination revealed multiple failure patterns with more of porcelain fractures in the ceramic brackets group. Conclusion: Bonding of metal and ceramic brackets to porcelain can be achieved with bond strengths comparable to that when bonded to enamel surface. Porcelain fractures are more commonly associated with debonding of ceramic brackets.

  20. Human blood contains both the uncleaved precursor of anti-Mullerian hormone and a complex of the NH2- and COOH-terminal peptides.

    Science.gov (United States)

    Pankhurst, Michael W; McLennan, Ian S

    2013-11-15

    Anti-Müllerian hormone (AMH) in blood is a marker of ovarian status in women and the presence of cryptic testes in babies. Despite this, the molecular form of AMH in blood has not been verified. AMH is synthesized as an inert proprotein precursor (proAMH), which can be cleaved to yield NH2-terminal (AMHN) and COOH-terminal (AMHC) fragments, that can complex noncovalently (AMHN,C). Developing males have 10-fold more AMH than young adults. We report here that human blood is a mixture of inactive proAMH and receptor-binding AMHN,C. The AMH in the blood of boys, men, and premenopausal women was immunoprecipitated using antibodies to the NH2- and COOH-terminal peptides. The precipitated proteins were then analyzed by Western blots, using recombinant proteins as markers. The glycosylation status of AMH was verified using deglycosylating enzymes. The NH2-terminal antibody precipitated a major protein that migrated alongside rhproAMH and was detected by anti-AMHN and anti-AMHC. This antibody also precipitated significant levels of AMHN and AMHC from all participants. Antibodies specific to AMHC precipitated rhAMHC but did not precipitate AMHC from human blood. Hence, all the AMHC in human blood appears to be bound to AMHN. Both AMHN and proAMH were glycosylated, independent of age and sex. In conclusion, boys and young adults have the same form of AMH, with a significant proportion being the inactive precursor. This raises the possibility that the endocrine functions of AMH are partly controlled by its cleavage in the target organ. The presence of proAMH in blood may confound the use of AMH for diagnosis.

  1. Mechano-growth factor peptide, the COOH terminus of unprocessed insulin-like growth factor 1, has no apparent effect on myoblasts or primary muscle stem cells.

    Science.gov (United States)

    Fornaro, Mara; Hinken, Aaron C; Needle, Saul; Hu, Erding; Trendelenburg, Anne-Ulrike; Mayer, Angelika; Rosenstiel, Antonia; Chang, Calvin; Meier, Viktor; Billin, Andrew N; Becherer, J David; Brace, Arthur D; Evans, William J; Glass, David J; Russell, Alan J

    2014-01-15

    A splice form of IGF-1, IGF-1Eb, is upregulated after exercise or injury. Physiological responses have been ascribed to the 24-amino acid COOH-terminal peptide that is cleaved from the NH3-terminal 70-amino acid mature IGF-1 protein. This COOH-terminal peptide was termed "mechano-growth factor" (MGF). Activities claimed for the MGF peptide included enhancing muscle satellite cell proliferation and delaying myoblast fusion. As such, MGF could represent a promising strategy to improve muscle regeneration. Thus, at our two pharmaceutical companies, we attempted to reproduce the claimed effect of MGF peptides on human and mouse muscle myoblast proliferation and differentiation in vitro. Concentrations of peptide up to 500 ng/ml failed to increase the proliferation of C2C12 cells or primary human skeletal muscle myoblasts. In contrast, all cell types exhibited a proliferative response to mature IGF-1 or full-length IGF-1Eb. MGF also failed to inhibit the differentiation of myoblasts into myotubes. To address whether the response to MGF was lost in these tissue culture lines, we measured proliferation and differentiation of primary mouse skeletal muscle stem cells exposed to MGF. This, too, failed to demonstrate a significant effect. Finally, we tested whether MGF could alter a separate documented in vitro effect of the peptide, activation of p-ERK, but not p-Akt, in cardiac myocytes. Although a robust response to IGF-1 was observed, there were no demonstrated activating responses from the native or a stabilized MGF peptide. These results call in to question whether there is a physiological role for MGF.

  2. Interactions between hERG and KCNQ1 α-subunits are mediated by their COOH termini and modulated by cAMP.

    Science.gov (United States)

    Organ-Darling, Louise E; Vernon, Amanda N; Giovanniello, Jacqueline R; Lu, Yichun; Moshal, Karni; Roder, Karim; Li, Weiyan; Koren, Gideon

    2013-02-15

    KCNQ1 and hERG encode the voltage-gated potassium channel α-subunits of the cardiac repolarizing currents I(Ks) and I(Kr), respectively. These currents function in vivo with some redundancy to maintain appropriate action potential durations (APDs), and loss-of-function mutations in these channels manifest clinically as long QT syndrome, characterized by the prolongation of the QT interval, polymorphic ventricular tachycardia, and sudden cardiac death. Previous cellular electrophysiology experiments in transgenic rabbit cardiomyocytes and heterologous cell lines demonstrated functional downregulation of complementary repolarizing currents. Biochemical assays indicated direct, protein-protein interactions between KCNQ1 and hERG may underlie the interplay between I(Ks) and I(Kr). Our objective was to investigate hERG-KCNQ1 interactions in the intact cellular environment primarily through acceptor photobleach FRET (apFRET) experiments. We quantitatively assessed the extent of interactions based on fluorophore location and the potential regulation of interactions by physiologically relevant signals. apFRET experiments established specific hERG-KCNQ1 associations in both heterologous and primary cardiomyocytes. The largest FRET efficiency (E(f); 12.0 ± 5.2%) was seen between ion channels with GFP variants fused to the COOH termini. Acute treatment with forskolin + IBMX or a membrane-permeable cAMP analog significantly and specifically reduced the extent of hERG-KCNQ1 interactions (by 41 and 38%, respectively). Our results demonstrate direct interactions between KCNQ1 and hERG occur in both intact heterologous cells and primary cardiomyocytes and are mediated by their COOH termini. Furthermore, this interplay between channel proteins is regulated by intracellular cAMP.

  3. The extreme COOH terminus of the retinoblastoma tumor suppressor protein pRb is required for phosphorylation on Thr-373 and activation of E2F.

    Science.gov (United States)

    Gorges, Laura L; Lents, Nathan H; Baldassare, Joseph J

    2008-11-01

    The retinoblastoma protein pRb plays a pivotal role in G(1)- to S-phase cell cycle progression and is among the most frequently mutated gene products in human cancer. Although much focus has been placed on understanding how the A/B pocket and COOH-terminal domain of pRb cooperate to relieve transcriptional repression of E2F-responsive genes, comparatively little emphasis has been placed on the function of the NH(2)-terminal region of pRb and the interaction of the multiple domains of pRb in the full-length context. Using "reverse mutational analysis" of Rb(DeltaCDK) (a dominantly active repressive allele of Rb), we have previously shown that restoration of Thr-373 is sufficient to render Rb(DeltaCDK) sensitive to inactivation via cyclin-CDK phosphorylation. This suggests that the NH(2)-terminal region plays a more critical role in pRb regulation than previously thought. In the present study, we have expanded this analysis to include additional residues in the NH(2)-terminal region of pRb and further establish that the mechanism of pRb inactivation by Thr-373 phosphorylation is through the dissociation of E2F. Most surprisingly, we further have found that removal of the COOH-terminal domain of either RbDeltaCDK(+T373) or wild-type pRb yields a functional allele that cannot be inactivated by phosphorylation and is repressive of E2F activation and S-phase entry. Our data demonstrate a novel function for the NH(2)-terminal domain of pRb and the necessity for cooperation of multiple domains for proper pRb regulation.

  4. Comparison of Gold Bonding with Mercury Bonding

    NARCIS (Netherlands)

    Kraka, Elfi; Filatov, Michael; Cremer, Dieter

    2009-01-01

    Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX(+) analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation energie

  5. Comparison of Gold Bonding with Mercury Bonding

    NARCIS (Netherlands)

    Kraka, Elfi; Filatov, Michael; Cremer, Dieter

    2009-01-01

    Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX(+) analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation

  6. The dissociative bond.

    Science.gov (United States)

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  7. The samurai bond market

    OpenAIRE

    1997-01-01

    Issuance in the samurai bond market has more than tripled over the past several years. Some observers have attributed this growth to a systematic underestimation of credit risk in the market. A detailed review of credit quality, ratings differences, and initial issue pricing in the samurai bond market, however, turns up little evidence to support this concern.

  8. Dentin bond strengths of simplified adhesives: effect of dentin depth.

    Science.gov (United States)

    Lopes, Guilherme Carpena; Perdigão, Jorge; Lopes, Mariana de F; Vieira, Luiz Clovis Cardoso; Baratieri, Luiz Narciso; Monteiro, Sylvio

    2006-06-01

    The objective of this study was to compare the shear bond strength of 3 simplified adhesive systems applied on shallow vs deep dentin. For superficial dentin, 30 human molars were sectioned with a diamond saw to expose dentin immediately below the dentoenamel junction. For deep dentin, 30 molars were sectioned 3 mm below the dentoenamel junction. The teeth were mounted, polished to 600-grit, and randomly assigned to 3 groups (n=10): Single Bonda and OptiBond Solo, total-etch adhesives, and Clearfil Liner Bond 2V, a self-etching primer adhesive. Adhesives were applied, the restorative material Filtek Z250 inserted in a No. 5 gelatin capsule, and light-cured. After 24 hours in water at 37 degrees C, shear bond strength was measured with an Instron at 5 mm/min. The data were analyzed with 2-way ANOVA and Duncan's post-hoc test. The results showed the following shear bond strengths (mean +/- SD in MPa): Single Bond/superficial dentin = 22.1 +/- 2.8; Single Bond/deep dentin = 14.2 +/- 7.0; OptiBond Solo/superficial dentin = 18.9 +/- 4.1; OptiBond Solo/deep dentin = 18.4 +/- 4.8; Clearfil Liner Bond 2V/superficial dentin = 21.0 +/- 7.4; Clearfil Liner Bond 2V/deep dentin = 17.6 +/- 5.9. There were no significant differences between mean shear bond strength for the factor "adhesive system" (P>.822). The Duncan's test showed that Single Bond resulted in higher shear bond strength on superficial dentin than on deep dentin. The mean shear bond strength for Clearfil Liner Bond 2V and OptiBond Solo were not influenced by dentin depth. When data were pooled for dentin depth, deep dentin resulted in statistically lower bond strengths than superficial dentin (Pcomposition of the dentin adhesive.

  9. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael

    2015-01-01

    Corporate financing is the choice between capital generated by the corporation and capital from external investors. However, since the financial crisis shook the markets in 2007–2008, financing opportunities through the classical means of financing have decreased. As a result, corporations have...... to think in alternative ways such as issuing corporate bonds. A market for corporate bonds exists in countries such as Norway, Germany, France, the United Kingdom and the United States, while Denmark is still behind in this trend. Some large Danish corporations have instead used foreign corporate bonds...... markets. However, NASDAQ OMX has introduced the First North Bond Market in December 2012 and new regulatory framework came into place in 2014, which may contribute to a Danish based corporate bond market. The purpose of this article is to present the regulatory changes in Denmark in relation to corporate...

  10. Comparison of Shear Bond Strength between Composite Resin and Porcelain Using Different Bonding Systems

    Directory of Open Access Journals (Sweden)

    E.Yassini

    2005-03-01

    Full Text Available Statement of Problem: Ceramics as in ceramo-metallic and all ceramic tooth restorations have grown popular owing to their high tissue compatibility and esthetic advantages. Such restorations have the capability to deliver valuable services over a long period of time; however, failures under intraoral conditions are not unanticipated.Purpose: The purpose of this in-vitro study was to investigate the shear bond strength of composite resin to porcelain using different bonding system materials.Materials and Methods: In this experimental study forty porcelain blocks were prepared and randomly divided into four equal groups. The porcelain surfaces were then etched with HF for 2 minutes, washed with water for 2 minutes and treated with a silane layer. The silane treated porcelain surfaces were left for one minute and then the specimens were bonded to composite resin as follow:Group 1 (control group, hybrid composite Z100 was applied and light cured from four directions for 20 seconds. Group 2, flowable composite was applied and light cured for 20 seconds. Group 3, unfilled resin was used and photo cured for 20 seconds. Group 4,(Dentin bonding agent adhesive resin was used followed by 20 seconds photo curing.Hybrid composite resin Z100 was subsequently applied on all porcelain surfaces of groups 2, 3 and 4, and light cured for 20 seconds from four directions. Specimens were then subjected to thermocycling 1000 times. Shear bond strength was determined by a Universal testing machine. The data obtained was subjected to a one-way ANOVA test.Results: The results indicate that there is a statistically significant difference between adhesive group and the other three groups of hybrid, flowable and unfilled resin (P<0.05.Conclusion: The results from this study showed that the shear bond strength of composite resin to porcelain was significantly higher for porcelain bonded surfaces using a dentin bonding agent than that of other materials tested.

  11. Dentin-bonding agents

    Directory of Open Access Journals (Sweden)

    João Carlos Gomes

    2008-01-01

    Full Text Available New dental restorative materials have been developed to meet not only the functional demands, but esthetics as well, and in the last few years an enormous range of new materials has appeared for use in dentistry. Among them, several adhesive systems, and different operative techniques for each group materials. Therefore, is indispensable for the professional to know about the properties, characteristics, and association of these materials with the dental structures, in order to select and use them correctly. Should conventional self-etching adhesive systems be used? This question encouraged this literature review to be conducted, with the aim of comparing the conventional adhesive systems with the self-etching systems and to look for scientific data that would help professionals to choose which adhesive system to use. When compared to conventional systems, it was noted that the self-etching systems show less sensitivity to technique, especially as regards errors the operator could commit. The self-etching systems, particularly the 2-step type, have shown equivalent values of bond strength, marginal microleakage and performance, therefore, will be an option for direct composite resin restorations in posterior teeth.

  12. Shear Bond Strength of Three Orthodontic Bonding Systems on Enamel and Restorative Materials

    Science.gov (United States)

    Ebeling, Jennifer; Schauseil, Michael; Stein, Steffen; Roggendorf, Matthias; Korbmacher-Steiner, Heike

    2016-01-01

    Objective. The aim of this in vitro study was to determine the shear bond strength (SBS) and adhesive remnant index (ARI) score of two self-etching no-mix adhesives (iBond™ and Scotchbond™) on different prosthetic surfaces and enamel, in comparison with the commonly used total etch system Transbond XT™. Materials and Methods. A total of 270 surfaces (1 enamel and 8 restorative surfaces, n = 30) were randomly divided into three adhesive groups. In group 1 (control) brackets were bonded with Transbond XT primer. In the experimental groups iBond adhesive (group 2) and Scotchbond Universal adhesive (group 3) were used. The SBS was measured using a Zwicki 1120™ testing machine. The ARI and SBS were compared statistically using the Kruskal–Wallis test (P ≤ 0.05). Results. Significant differences in SBS and ARI were found between the control group and experimental groups. Conclusions. Transbond XT showed the highest SBS on human enamel. Scotchbond Universal on average provides the best bonding on all other types of surface (metal, composite, and porcelain), with no need for additional primers. It might therefore be helpful for simplifying bonding in orthodontic procedures on restorative materials in patients. If metal brackets have to be bonded to a metal surface, the use of a dual-curing resin is recommended.

  13. Comparison of shear bond strength between unfilled resin to dry enamel and dentin bonding to moist and dry enamel

    Directory of Open Access Journals (Sweden)

    Yasini E.

    2005-05-01

    Full Text Available Statement of Problem: The use of dentine bondings on enamel and dentin in total etch protocols has recently become popular. Unfilled resin is hydrophobic and dentin bonding is hydrophilic in nature. This chemical difference could be effective in enamel bonding process. Purpose: The aim of this study was to compare the shear bond strength of unfilled resin to dry enamel and dentin bonding to dry and moist enamel. Materials and Methods: In this experimental study, a total of 30 incisor teeth were used. The specimens were randomly assigned to three groups of 10. 37% phosphoric acid etchant was applied to the enamel surfaces in each group for 15 seconds, rinsed with water for 20 seconds and dried for 20 seconds with compressed air in groups one and two. After conditioning, group 1 received unfilled resin (Margin Bond, Colten and group 2 received dentin bonding (Single Bond, 3M and in group 3 after conditioning and rinsing with water, a layer of dentin bonding (Single Bond was applied on wet enamel. The enamel and dentin bonding were light cured for 20 seconds. A ring mold 3.5 mm in diameter and 2 mm height was placed over the specimens to receive the composite filling material (Z100, 3M. The composite was cured for 40 seconds. The specimens were thermocycled and shear bond strengths were determined using an Instron Universal Testing Machine. The findings were analyzed by ANOVA One-Way and Tukey HSD tests. Results: Shear bond strength of dentin bonding to dry enamel was significantly less than unfilled resin to dry enamel (P<0.05. There was no significant difference between the bond strength of dentin bonding to moist and dry enamel. In addition bond strength of dentin bonding to wet enamel was not significantly different from unfilled resin to dry enamel. Conclusion: Based on the findings of this study, it is suggested that enamel surface should remain slightly moist after etching before bonding with single bond but when using unfilled resin, the

  14. Functional groups grafted nonwoven fabrics for blood filtration-The effects of functional groups and wettability on the adhesion of leukocyte and platelet

    Energy Technology Data Exchange (ETDEWEB)

    Yang Chao [State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Cao Ye [Institute of Blood Transfusion, Chinese Academy of Medical Sciences and Peking Union Medical College, Chengdu 610081 (China); Sun Kang, E-mail: ksun@sjtu.edu.cn [State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Liu Jiaxin; Wang Hong [Institute of Blood Transfusion, Chinese Academy of Medical Sciences and Peking Union Medical College, Chengdu 610081 (China)

    2011-01-15

    In this work, the effects of grafted functional groups and surface wettability on the adhesion of leukocyte and platelet were investigated by the method of blood filtration. The filter materials, poly(butylene terephthalate) nonwoven fabrics bearing different functional groups including hydroxyl (OH), carboxyl (COOH), sulfonic acid group (SO{sub 3}H) and zwitterionic sulfobetaine group ({sup +}N((CH{sub 3}){sub 2})(CH{sub 2}){sub 3}SO{sub 3}{sup Circled-Minus }) with controllable wettability were prepared by UV radiation grafting vinyl monomers with these functional groups. Our results emphasized that both surface functional groups and surface wettability had significant effects on the adhesion of leukocyte and platelet. In the case of filter materials with the same wettability, leukocytes adhering to filter materials decreased in the order: the surface bearing OH only > the surface bearing both OH and COOH > the surface bearing sulfobetaine group > the surface bearing SO{sub 3}H, while platelets adhering to filter materials decreased as the following order: the surface bearing SO{sub 3}H > the surface bearing both OH and COOH > the surface bearing OH only > the surface bearing sulfobetaine group. As the wettability of filter materials increased, both leukocyte and platelet adhesion to filter materials declined, except that leukocyte adhesion to the surface bearing OH only remained unchanged.

  15. Diazotization of the amino acid [closo-1-CB9H8-1-COOH-6-NH3] and reactivity of the [closo-1-CB9H8-1-COO-6-N2]- anion.

    Science.gov (United States)

    Ringstrand, Bryan; Kaszynski, Piotr; Young, Victor G

    2011-03-21

    A comparative study of the reactivity of dinitrogen acids [closo-1-CB(9)H(8)-1-COOH-10-N(2)] (3[10]) and [closo-1-CB(9)H(8)-1-COOH-6-N(2)] (3[6]) was conducted by diazotization of a mixture of amino acids [closo-1-CB(9)H(8)-1-COOH-6-NH(3)] (1[6]) and [closo-1-CB(9)H(8)-1-COOH-10-NH(3)] (1[10]) with NO(+)BF(4)(-) in the presence of a heterocyclic base (pyridine, 4-methoxypyridine, 2-picoline, or quinoline). The 10-amino acid 1[10] formed an isolable stable 10-dinitrogen acid 3[10], while the 6-dinitrogen carboxylate 3[6](-) reacted in situ, giving products of N-substitution at the B6 position with the heterocyclic solvent (4[6]). The molecular and crystal structures for pyridinium acid 4[6]a were determined by X-ray crystallography. The electronic structures and reactivity of the 6-dinitrogen derivatives of the {1-CB(9)} cluster were assessed computationally at the B3LYP/6-31G(d,p) and MP2/6-31G(d,p) levels of theory and compared to those of the 10-dinitrogen, 2-dinitrogen, and 1-dinitrogen analogues.

  16. Self-assembling of Zn porphyrins on a (110) face of rutile TiO2-The anchoring role of carboxyl groups

    Science.gov (United States)

    Zajac, Lukasz; Olszowski, Piotr; Godlewski, Szymon; Bodek, Lukasz; Such, Bartosz; Jöhr, Res; Pawlak, Remy; Hinaut, Antoine; Glatzel, Thilo; Meyer, Ernst; Szymonski, Marek

    2016-08-01

    The ordering of zinc containing porphyrin molecules on surface of rutile TiO2(110)-(1×1) has been investigated using scanning tunneling microscopy (STM) in ultra-high vacuum at room temperature. It is demonstrated that a carboxylic group (COOH) has a profound impact on the immobilization of the molecules. At coverages below 0.1 monolayer only molecules equipped with the group COOH could be anchored to the surface and imaged with STM. At higher coverage both species, with and without the carboxyl substituent, assemble into ordered structures, forming complete monolayers. It is found, however, that the rhomboid unit cells of these structures exhibit differences in size.

  17. Comparative in vitro study of the shear bond strength of brackets bonded with restorative and orthodontic resins

    Directory of Open Access Journals (Sweden)

    Hassan Isber

    2011-02-01

    Full Text Available The aim of this study was to evaluate the shear bond strength of brackets bonded with different restorative systems and compare it with that afforded by an established orthodontic bonding system. Seventy human bicuspids were used, divided into five different groups with 14 teeth each. Whereas a specific orthodontic bonding resin (TransbondTM XT was used in the control group, the restorative systems Charisma, Tetric Ceram, TPH Spectrum and Z100 were used in the other four groups. Seven days after bonding the brackets to the samples, shear forces were applied under pressure in a universal testing machine. The data collected was evaluated using the ANOVA test and, when a difference was identified, the Tukey test was applied. A 5% level of significance was adopted. The mean results of the shear bond strength tests were as follows: Group 1 (Charisma, 14.98 MPa; Group 2 (Tetric Ceram, 15.16 MPa; Group 3 (TPH, 17.70 MPa; Group 4 (Z100, 13.91 MPa; and Group 5 or control group (TransbondTM XT, 17.15 MPa. No statistically significant difference was found among the groups. It was concluded that all tested resins have sufficient bond strength to be recommended for bonding orthodontic brackets.

  18. Microtensile Bond Strength of Single Bond and Adper Prompt-L-Pop Adhesives to Dentin

    Directory of Open Access Journals (Sweden)

    P. Alizadeh Oskoee

    2008-03-01

    Full Text Available Objective: The aim of this study was to evaluate the microtensile bond strength to sound and caries-affected dentin using Single Bond and Adper Prompt-L-Pop adhesives.Materials and Methods: Sixteen extracted human molars with carious lesions extended halfway through dentin were ground to expose the caries affected and the surrounding normal dentin. The samples were divided into two groups of eight samples each, including Single Bond (two-step etch and rinse and Adper Prompt-L-Pop (one step self-etch. Z-100 (3M was used for composite build-ups. The teeth were then sectioned and prepared for micro tensile bond strength test, at cross head speed of 1.5 mm/min. Data were ana-lyzed by 1- and 2-way ANOVA.Results: Bond strengths of Single Bond and Adper Prompt-L-Pop adhesives to sound den-tin were significantly higher than to the caries-affected one (P<0.001, besides, bond strength of Single Bond to dentin was generally found to be higher than Adper Prompt-L-Pop adhesive (P<0.001.The interaction effect was not significant (P=0.116Conclusion: Bond strength to caries-affected dentin was compromised when one and two step adhesives were used.

  19. A Statistical Theory for Hydrogen Bonding Networks: One Component Case

    Institute of Scientific and Technical Information of China (English)

    WANG Hai-Jun; BA Xin-Wu; ZHAO Min; LI Ze-Sheng

    2000-01-01

    The theory of reversible gelation is shown to be applicable to the hydrogen bonding system by analyzing their similarities in statistical viewpoint. The size distribution of hydrogen bonding clusters, the gelation condition and the generalized scaling law can be obtained directly. These results show that such a system can undergo phase transition process. Furthermore, a relationship between Gibbs free energy of forming hydrogen bond and conversions of groups is given. As an example, the chemical shift of OH groups is considered.

  20. Effect of ultrasonic power and bonding force on the bonding strength of copper ball bonds

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Copper wire, serving as a cost-saving alternative to gold wire, has been used in many high-end thermosonic ball bonding applications. In this paper, the bond shear force, bond shear strength, and the ball bond diameter are adopted to evaluate the bonding quality. It is concluded that the efficient ultrasonic power is needed to soften the ball to form the copper bonds with high bonding strength. However, excessive ultrasonic power would serve as a fatigue loading to weaken the bonding. Excessive or less bonding force would cause cratering in the silicon.

  1. Transmission of electronic effects through the {closo-1-CB9} and {closo-1-CB11} cages: apparent dissociation constants for series of [closo-1-CB9H8-1-COOH-10-X] and [closo-1-CB11H10-1-COOH-12-X] acids.

    Science.gov (United States)

    Pecyna, Jacek G; Ringstrand, Bryan; Kaszyński, Piotr

    2012-05-01

    The apparent ionization constants pK(a)' for series of carboxylic acids [closo-1-CB(9)H(8)-1-COOH-10-X](-) (1) and [closo-1-CB(11)H(10)-1-COOH-12-X](-) (2), where X = H, I, n-C(6)H(13), (+)NMe(3), (+)N(2), (+)SMe(2), OC(5)H(11), were measured in EtOH/H(2)O (1/1, v/v) at 24 °C. Correlation analysis of the pK(a)' values using Hammett substituent constants σ(p)(X) gave the reaction constant ρ = 0.87 ± 0.04 for series 1 and ρ = 1.00 ± 0.09 for series 2. These values are higher than for derivatives of PhCH═CHCOOH (ρ = 0.70 ± 0.09 in 55% EtOH) and correspond to 56% and 65% efficiencies in transmission of electronic effects by [closo-1-CB(9)H(10)](-) (E) and [closo-1-CB(11)H(12)](-) (F), respectively, as compared to benzene (A). Experimental results were supported with DFT calculations of relative acidity for series of acids derived from A, E, and F in aqueous medium.

  2. Transversely Compressed Bonded Joints

    DEFF Research Database (Denmark)

    Hansen, Christian Skodborg; Schmidt, Jacob Wittrup; Stang, Henrik

    2012-01-01

    The load capacity of bonded joints can be increased if transverse pressure is applied at the interface. The transverse pressure is assumed to introduce a Coulomb-friction contribution to the cohesive law for the interface. Response and load capacity for a bonded single-lap joint was derived using...... non-linear fracture mechanics. The results indicated a good correlation between theory and tests. Furthermore, the model is suggested as theoretical base for determining load capacity of bonded anchorages with transverse pressure, in externally reinforced concrete structures....

  3. An Ex-vivo Shear and tensile bond strengths of orthodontic molar tubes bonded using different techniques

    Science.gov (United States)

    Alwahadni, Ahed

    2017-01-01

    Background Molar bonding procedures need continuous improvement to be widely accepted clinically and eventually replace molar bands. Material and Methods The purpose of this study was to determine the effects of enamel micro-abrasion and silane coating of the base of molar tubes on shear and tensile bond strengths of orthodontic molar tubes. A total of 200 third molars were randomly allocated into five groups of 40 teeth as follows: group 1: molar tubes bonded to etched teeth (37% phosphoric acid gel; control group); group 2: molar tubes bonded to etched teeth (37% phosphoric acid) with the addition of silane to the base of molar tubes; group 3: molar tubes bonded to teeth pre-treated with 18% hydrochloric acid and pumice (micro-abrasion); group 4: molar tubes bonded to teeth pre-treated with microabrasion with the addition of silane to the base of molar tubes; group 5: molar tubes bonded to teeth pre-treated with microabrasion before conventional acid etching combined with the addition of silane to the base of molar tubes. The bond strength testing was performed using a computer control electromechanical universal testing machine. Results The highest mean shear and tensile bond strengths were recorded in group 5 (13.81±2.54MPa and 13.97±2.29 MPa, respectively). Micro-abrasion alone (group 3) and the combination of enamel micro-abrasion and the addition of silane (group 4) produced bond strength values comparable to the control. Conclusions Enamel surface pre-treatment (micro abrasion) before conventional acid etching combined with the addition of silane to the base of the molar tube produced the highest bond strengths among all tested groups. Key words:Molar, shear strength, tensile strength, orthodontic appliances. PMID:28298990

  4. The Positively Charged COOH-terminal Glycosaminoglycan-binding CXCL9(74-103) Peptide Inhibits CXCL8-induced Neutrophil Extravasation and Monosodium Urate Crystal-induced Gout in Mice.

    Science.gov (United States)

    Vanheule, Vincent; Janssens, Rik; Boff, Daiane; Kitic, Nikola; Berghmans, Nele; Ronsse, Isabelle; Kungl, Andreas J; Amaral, Flavio Almeida; Teixeira, Mauro Martins; Van Damme, Jo; Proost, Paul; Mortier, Anneleen

    2015-08-28

    The ELR(-)CXC chemokine CXCL9 is characterized by a long, highly positively charged COOH-terminal region, absent in most other chemokines. Several natural leukocyte- and fibroblast-derived COOH-terminally truncated CXCL9 forms missing up to 30 amino acids were identified. To investigate the role of the COOH-terminal region of CXCL9, several COOH-terminal peptides were chemically synthesized. These peptides display high affinity for glycosaminoglycans (GAGs) and compete with functional intact chemokines for GAG binding, the longest peptide (CXCL9(74-103)) being the most potent. The COOH-terminal peptide CXCL9(74-103) does not signal through or act as an antagonist for CXCR3, the G protein-coupled CXCL9 receptor, and does not influence neutrophil chemotactic activity of CXCL8 in vitro. Based on the GAG binding data, an anti-inflammatory role for CXCL9(74-103) was further evidenced in vivo. Simultaneous intravenous injection of CXCL9(74-103) with CXCL8 injection in the joint diminished CXCL8-induced neutrophil extravasation. Analogously, monosodium urate crystal-induced neutrophil migration to the tibiofemural articulation, a murine model of gout, is highly reduced by intravenous injection of CXCL9(74-103). These data show that chemokine-derived peptides with high affinity for GAGs may be used as anti-inflammatory peptides; by competing with active chemokines for binding and immobilization on GAGs, these peptides may lower chemokine presentation on the endothelium and disrupt the generation of a chemokine gradient, thereby preventing a chemokine from properly performing its chemotactic function. The CXCL9 peptide may serve as a lead molecule for further development of inhibitors of inflammation based on interference with chemokine-GAG interactions.

  5. The Effect of Temperature on Shear Bond Strength of Clearfil SE Bond and Adper Single Bond Adhesive Systems to Dentin

    Directory of Open Access Journals (Sweden)

    Hossein Nouri

    2015-03-01

    Full Text Available Statement of the Problem: Monomer viscosity and solvent evaporation can be affected by the adhesive system temperature. Higher temperature can elevate the vapor pressure in solution and penetration of adhesive in smear layer. Bonding mechanism may be influenced by the adhesive temperature. Purpose: This study aimed to evaluate the effect of pre-heating on shear bond strength of etch-and-rinse and self-etching adhesives to ground bovine dentin surfaces, at temperatures of 4˚C, 25˚C and 40˚C. Materials and Method: In this experimental study, 60 maxillary bovine incisors were randomly divided into 6 groups (n=10. The central part of labial dentin surfaces was exposed with a diamond bur and standardized smear layer was creat-ed by using silicon carbide paper (600 grit under water-coolant while the specimens were mounted in acrylic resin. Two adhesive systems, an etch-and-rinse (Adper single bond and a self-etch (Clearfil SE Bond were stored at temperatures of 4˚C, 25˚C and 40˚C for 30 minutes and were then applied on the prepared labial surface according to the manufacturer’s instructions. The composite resin (Z350 was packed in Teflon mold (5 mm in diameter on this surface and was cured. The shear bond strength (MPa was evaluated by universal testing machine (Zwick/Roell Z020, Germany at cross head speed of 1mm/min. The results were statistically analyzed by using ANOVA and Tukey tests (p< 0.05. Results: No significant difference was found between the shear bond strength of Clearfil SE Bond adhesive in different temperature and single Bond adhesive sys-tem at 25 ̊C and 40 ̊C. However, there were significant differences between 4 ̊C of Adper single bond in comparison with 25˚C and 40˚C (p= 0.0001. Conclusion: Pre-heating did not affect the shear bond strength of SE Bond, but could promote the shear bond strength of Adper Single Bond.

  6. Effect of two different dentin desensitizers on shear bond strength of two different bonding agents to dentin: an in vitro study.

    Science.gov (United States)

    Bhatia, Shekhar; Krishnaswamy, Manjunath Mysore

    2012-01-01

    The objective of the study was to compare the effect of two different desensitizers on shear bond strength of two different fifth-generation single-bottle adhesive agents on dentin surface. Sixty human premolars were taken and divided into six groups of 10 samples each. The first two groups were the control groups and were not pretreated with any desensitizer; the remaining four groups were the experimental groups and were pretreated with either Denshield™ or Sensodent-K™ desensitizer. The specimens in each group were subjected to acid etching, application of adhesive (Single Bond or Prime and Bond NT), and application of hybrid composite resin (Z-100) according to the standard protocol. The specimens were subjected to shear bond strength testing, using a Lloyds universal testing machine (EZ20), followed by stereomicroscopic evaluation of the fracture mode at the debonded interface. Statistically significant difference existed between the two bonding agents in the control groups (group 1 and 2), with Prime and Bond NT showing higher bond strength than Single Bond. No statistically significant difference existed between either control or pretreated with any desensitizer when either of the adhesive systems was used. Prime and Bond NT showed statistically higher bond strength value when teeth were pretreated with Sensodent-K™ (groups 5 and 6). No statistically significant difference in bond strength values were observed between the bonding agents when pretreated with Denshield™ desensitizer.

  7. Evaluation of shear bond strength of metallic and ceramic brackets bonded to enamel prepared with self-etching primer.

    Science.gov (United States)

    Uysal, Tancan; Ustdal, Ayca; Kurt, Gokmen

    2010-04-01

    The aim of this in vitro study was to evaluate the shear bond strength (SBS) of different metallic and ceramic bracket bonding combinations using self-etching primers (SEPs). Eighty freshly extracted human premolar teeth were randomly divided into four equal groups for bonding with ceramic or metallic brackets as follows: group 1, metallic brackets bonded with conventional acid etching; group 2, metallic brackets bonded with Transbond Plus Self-Etching primer (TPSEP); group 3, ceramic brackets bonded as per group 1; group 4, ceramic brackets bonded as per group 2. The SBS of these brackets was measured and recorded in megapascals (MPa). The adhesive remnant index (ARI) scores were determined after bracket failure. Data were analyzed with the analysis of variance, Tukey, and chi-square tests. The bond strength of group 3 (mean: 36.7 +/- 11.8 MPa) was significantly higher than group 4 (mean: 26.6 +/- 8.9 MPa; P 0.05). Compared with conventional acid etching, SEPs significantly decreased the SBS of ceramic orthodontic brackets.

  8. In-vitro comparison of the effect of different bonding strategies on the micro-shear bond strength of a silorane-based composite resin to dentin

    Science.gov (United States)

    Samimi, Pouran; Alizadeh, Vahid; Fathpour, Kamyar; Mazaheri, Hamid; Mortazavi, Vajihosadat

    2016-01-01

    Background: The current study evaluated the micro-shear bond strengths of a new low-shrinkage composite resin to dentin. Materials and Methods: In this in-vitro study, 70 extracted premolars were assigned to one of seven groups (n = 10): Group 1: OptiBond Solo Plus (Opt; Kerr); Group 2: SE Bond (SE; Kuraray); Group 3: Silorane System Adhesive (SSA; 3M ESPE); Group 4: OptiBond Solo Plus + LS Bond (Opt LS); Group 5: SE Bond + LS Bond (SE LS); Group 6: OptiBond Solo Plus (Opt Po); and Group 7: SE Bond (SE Po). Occlusal dentin was exposed and restored with Filtek LS (3M ESPE) in groups 1 to 5 and Point 4 (Kerr) in groups 6 and 7. After thermocycling (1000 cycles at 5/55΀C), micro-shear bond test was carried out to measure the bond strengths. The results were submitted to analysis of variance and post hoc Tukeytests (P composite resin (P = 0.187), between bonding agents (P = 0.06) and between composite resin and bonding agents (P = 0.894). Because P value of bonding agents was near the significance level, one-way ANOVA was used separately between the two composite groups. This analysis showed significant differences between silorane composite resin groups (P = 0.045) and Tukey test showed a significant difference between Groups 4 and 5 (P = 0.03). Conclusion: The application of total-etch and self-etch methacrylate-based adhesives with and without use of a hydrophobic resin coating resulted in acceptable bond strengths. PMID:27076826

  9. Handbook of wafer bonding

    CERN Document Server

    Ramm, Peter; Taklo, Maaike M V

    2011-01-01

    Written by an author and editor team from microsystems companies and industry-near research organizations, this handbook and reference presents dependable, first-hand information on bonding technologies.In the first part, researchers from companies and institutions around the world discuss the most reliable and reproducible technologies for the production of bonded wafers. The second part is devoted to current and emerging applications, including microresonators, biosensors and precise measuring devices.

  10. O sbnd H⋯O and O sbnd H⋯N hydrogen bonds in the complex of DABCO mono-betaine with p-hydroxybenzoic acid studied by X-ray diffraction, DFT calculations and spectroscopic methods

    Science.gov (United States)

    Barczyński, P.; Dega-Szafran, Z.; Katrusiak, A.; Szafran, M.

    2011-08-01

    DABCO mono-betaine (1,4-diazabicyclo[2.2.2]octane-1-acetate) forms a complex with p-hydroxybenzoic acid (HBA) at the 1:1 ratio. The crystals are monoclinic, space group P2 1/ m. The HBA and DABCO mono-betaine molecules are linked into infinite chains through the COOH⋯OOC and O sbnd H⋯N hydrogen bonds of 2.604(1) and 2.771(2) Å, respectively. The DABCO mono-betaine is located on a mirror plane and the HBA molecule lies on this plane. In the structure of the 1:1 complex optimized by the B3LYP/6-31G(d,p) approach, the DABCO ring has a planar conformation, while in the chains formed by two complexes, the DABCO moieties assume the propeller conformations. The FTIR spectrum shows several bands attributed to the O sbnd H, O sbnd H⋯O, O sbnd H⋯N, C dbnd O and COO stretching vibrations. 1H and 13C chemical shifts assignments were confirmed by the magnetic isotropic shielding constants, calculated by the GIAO/B3LYP/6-31G(d,p) approach.

  11. Evaluation of micro-shear bond strength of resin modified glass-ionomer to composite resins using various bonding systems

    Directory of Open Access Journals (Sweden)

    Shahin Kasraie

    2013-01-01

    Full Text Available Aim: The aim was to compare the micro-shear bond strength between composite and resin-modified glass-ionomer (RMGI by different adhesive systems. Materials and Methods: A total of 16 discs of RMGI with a diameter of 15 mm and a thickness of 2 mm were randomly divided into four groups (n = 4. Four cylinders of composite resin (z250 were bonded to the RMGI discs with Single Bond, Clearfil SE Bond and Clearfil S3 Bond in Groups 1-3, respectively. The fourth group was the control. Samples were tested by a mechanical testing machine with a strain rate of 0.5 mm/min. Failure mode was assessed under a stereo-microscope. Results: The means of micro-shear bond strength values for Groups 1-4 were 14.45, 23.49, 16.23 and 5.46 MPa, respectively. Using a bonding agent significantly increased micro-shear bond strength (P = 0.0001. Conclusion: Micro-shear bond strength of RMGI to composite increased significantly with the use of adhesive resin. The bond strength of RMGI to composite resin could vary depending upon the type of adhesive system used.

  12. Microleakage under Orthodontic Metal Brackets Bonded with Three Different Bonding Techniques with/without Thermocycling

    Directory of Open Access Journals (Sweden)

    Berahman Sabzevari

    2013-12-01

    Full Text Available Introduction: The aim of this study was to compare the microleakage of beneath the orthodontic brackets bonded with 3 different bonding techniques and evaluate the effect of thermocycling. Methods: One hundred and twenty premolars were randomly divided into 6 groups, received the following treatment: group 1: 37% phosphoric acid gel+Unite primer+Unite adhesive, group 2: 37% phosphoric acid gel+ Transbond XT primer+Transbond XT adhesive, group 3: Transbond plus Self Etching Primer (TSEP+Transbond XT adhesive. Groups 4, 5, and 6 were similar to groups 1, 2, and 3, respectively. Evaluation of microleakage was done following to thermocycling test. After bonding, the specimens were sealed with nail varnish except for 1 mm around the brackets and then stained with 0.5% basic fuchsine. The specimens were sectioned at buccolingual direction in 2 parallel planes and evaluated under a stereomicroscope to determine the amount of microleakage at bracket-adhesive and adhesive-enamel interfaces from gingival and occlusal margins. Results: Microleakage was observed in all groups, and increased significantly after thermocycling at some interfaces of Unite adhesive group and conventional etching+Transbond XT adhesive group, but the increase was not significant in any interface of TSEP group. With or without thermocycling, TSEP displayed more microleakage than other groups. In most groups, microleakage at gingival margin was significantly higher than occlusal margin. Conclusion: Thermocycling and type of bonding technique significantly affect the amount of microleakage.

  13. Shear bond strength of partial coverage restorations to dentin

    Science.gov (United States)

    Agustín-Panadero, Rubén; Alonso-Pérez-Barquero, Jorge; Fons-Font, Antonio; Solá-Ruíz, María-Fernanda

    2015-01-01

    Background When partial coverage restorations (veneers, inlays, onlays…) must be cemented to dentin, bond strength may not reach the same predictable values as to enamel. The purpose of this study was: 1. To compare, with a shear bond test, the bond strength to dentin of a total-etch and a self-etching bonding agent. 2. To determine whether creating microretention improves the bond strength to dentin. Material and Methods Two bonding agents were assayed, Optibond FL® (Kerr), two-bottle adhesive requiring acid etching, and Clearfil SE Bond® (Kuraray), two-bottle self-etching adhesive. The vestibular, lingual, distal and mesial surfaces of ten molars (n=10) were ground to remove all enamel and 40 ceramic samples were cemented with Variolink II® (Ivoclar Vivadent). Half the molar surfaces were treated to create round microretention (pits) to determine whether these could influence bond strength to dentin. The 40 molar surfaces were divided into four groups (n=10): Optibond FL (O); Clearfil SE (C); Optibond FL + microretention (OM); Clearfil SE + micro retention (CM). A shear bond test was performed and the bond failures provoked examined under an optical microscope. Results O=35.27±8.02 MPa; C=36.23±11.23 MPa; OM=28.61±6.27 MPa; CM=27.01±7.57 MPa. No statistically significant differences were found between the adhesives. Optibond FL showed less statistical dispersion than Clearfil SE. The presence of microretentions reduced bond strength values regardless of the adhesive used. Conclusions 1. Clearfil SE self-etching adhesive and Optibond FL acid-etch showed adequate bond strengths and can be recommended for bonding ceramic restorations to dentin. 2. The creation of round microretention pits compromises these adhesives’ bond strength to dentin. Key words:Adhesion to dentin, bonding agent, Optibond FL, Clearfil SE, microretention, shear bond test. PMID:26330937

  14. The pnicogen bond: its relation to hydrogen, halogen, and other noncovalent bonds.

    Science.gov (United States)

    Scheiner, Steve

    2013-02-19

    Among a wide range of noncovalent interactions, hydrogen (H) bonds are well known for their specific roles in various chemical and biological phenomena. When describing conventional hydrogen bonding, researchers use the notation AH···D (where A refers to the electron acceptor and D to the donor). However, the AH molecule engaged in a AH···D H-bond can also be pivoted around by roughly 180°, resulting in a HA···D arrangement. Even without the H atom in a bridging position, this arrangement can be attractive, as explained in this Account. The electron density donated by D transfers into a AH σ* antibonding orbital in either case: the lobe of the σ* orbital near the H atom in the H-bonding AH···D geometry, or the lobe proximate to the A atom in the HA···D case. A favorable electrostatic interaction energy between the two molecules supplements this charge transfer. When A belongs to the pnictide family of elements, which include phosphorus, arsenic, antimony, and bismuth, this type of interaction is called a pnicogen bond. This bonding interaction is somewhat analogous to the chalcogen and halogen bonds that arise when A is an element in group 16 or 17, respectively, of the periodic table. Electronegative substitutions, such as a F for a H atom opposite the electron donor atom, strengthen the pnicogen bond. For example, the binding energy in FH(2)P···NH(3) greatly exceeds that of the paradigmatic H-bonding water dimer. Surprisingly, di- or tri-halogenation does not produce any additional stabilization, in marked contrast to H-bonds. Chalcogen and halogen bonds show similar strength to the pnicogen bond for a given electron-withdrawing substituent. This insensitivity to the electron-acceptor atom distinguishes these interactions from H-bonds, in which energy depends strongly upon the identity of the proton-donor atom. As with H-bonds, pnicogen bonds can extract electron density from the lone pairs of atoms on the partner molecule, such as N, O, and

  15. Enrichment of Nanodiamond Surfaces with Carboxyl Groups for Doxorubicin Loading and Release

    Science.gov (United States)

    Astuti, Y.; Saputra, F. D.; Wuning, S.; Arnelli; Bhaduri, G.

    2017-02-01

    In their pristine state, nanodiamond crystals produced via detonation techniques containing several functional groups present on the surface including amine, amide, alcohol, carbonyl, and carboxyl. These functional groups facilitate nanodiamond to interact drugs so as to nanodiamond is potential for medical application such as drug delivery. Even though research on t he use of nanodiamond for this application has been conducted widely, research on the effect of enrichment of nanodiamond surface with carboxyl functional groups for drug loading and release has not been explored extensively. Therefore, in this paper, the effect of carboxyl-terminated nanodiamond (ND-COOH) on drug loading and release will be presented. The enrichment of nanodiamond with carboxyl groups was undertaken by treating nanodiamond with sulphuric acid and nitric acid. The results show that the doxorubicin (DOX) loading and release efficiencies of ND pristine are higher than that of ND-COOH.

  16. An in vitro Comparative Evaluation of Micro Tensile Bond Strength of Two metal bonding Resin Cements bonded to Cobalt Chromium alloy

    Science.gov (United States)

    Musani, Smita; Musani, Iqbal; Dugal, Ramandeep; Habbu, Nitin; Madanshetty, Pallavi; Virani, Danish

    2013-01-01

    Background: The purpose of this study was to evaluate and compare the micro tensile bond strength of two metal bonding resin cements to sandblasted cobalt chromium alloy. Materials & Methods: Eight, Cobalt chromium alloy blocks of dimensions 10x5x5 mm were cast, finished and polished. One of the faces of each alloy block measuring 5x5mm was sandblasted with 50 μm grit alumina particles. The alloy blocks were then cleaned in an ultrasonic cleaner for 1 min and then air dried with an air stream. The Sandblasted surfaces of the two alloy blocks were bonded together with 2 different metal bonding resin systems (Panavia F Kuraray and DTK Kleber – Bredent). The samples were divided into 2 groups (n=4). Group 1- Two Co-Cr blocks were luted with Panavia cement. Group 2- Two Co-Cr blocks were luted with DTK Kleber-Bredent cement. The bonded samples were cut with a diamond saw to prepare Microtensile bars of approximately 1mm x 1mm x 6mm. Thirty bars from each group were randomly separated into 2 subgroups (n=15) and left for 3hrs (baseline) as per manufacturer's instructions while the other group was aged for 24hrs in 370C water, prior to loading to failure under tension at a cross head speed of 1mm/min. Failure modes were determined by means of stereomicroscopy (sm). Statistical analysis was performed through one way – ANOVA. Results: Significant variation in micro-tensile bond strength was observed between the two metal bonding resin systems. Conclusion: DTK showed higher mean bond strength values than Panavia F cement both at baseline and after aging. How to cite this article: Musani S, Musani I, Dugal R, Habbu N, Madanshetty P, Virani D. An in vitro Comparative Evaluation of Micro Tensile Bond Strength of Two metal bonding Resin Cements bonded to Cobalt Chromium alloy. J Int Oral Health 2013;5(5):73-8. PMID:24324308

  17. Shear bond strength of bonding to enamel with different laser irradiation distances.

    Science.gov (United States)

    Başaran, Güvenç; Hamamcı, Nihal; Akkurt, Atılım

    2011-03-01

    The aim of this study was to investigate the shear bond strength of bonding to enamel following laser etching with the Er:YAG or Er,Cr:YSGG laser using different irradiation distances. Of 99 extracted human premolar teeth, 90 were divided equally into nine groups. In the control group (group A) the teeth were etched with 38% phosphoric acid. In the laser groups (groups B-I) the enamel surface of the teeth was laser-irradiated, groups B-E with the Er:YAG laser and groups F-I with the Er,Cr:YSGG laser at distances of 1, 2, 4 and 6 mm, respectively. The shear bond strengths were tested using a universal testing machine. The shear bond strengths associated with the Er:YAG laser at 4 and 6 mm and the Er,Cr:YSGG laser at 2, 4 and 6 mm were significantly less than the strengths obtained with the other irradiation distances (penamel in the same manner (p>0.05). This finding was confirmed by scanning electron microscopy examination. Irradiation distance did influence the strength of adhesion to enamel. The mean shear bond strengths and enamel surface etching obtained with the Er:YAG laser at 1 and 2 mm and the Er,Cr:YSGG laser at 1 mm were comparable to that obtained with acid etching.

  18. The role of functional monomers in bonding to enamel: acid-base resistant zone and bonding performance.

    Science.gov (United States)

    Li, Na; Nikaido, Toru; Takagaki, Tomohiro; Sadr, Alireza; Makishi, Patricia; Chen, Jihua; Tagami, Junji

    2010-09-01

    To investigate the effects of two functional monomers on caries-inhibition potential and bond strength of two-step self-etching adhesive systems to enamel. Clearfil SE Bond and similar experimental formulations different in the functional monomer were used. Four combinations of primer and bonding agents were evaluated: (1) Clearfil SE Bond which contains MDP in both primer and bonding (M-M); (2) Clearfil SE Bond primer and Phenyl-P in bonding (M-P); (3) Phenyl-P in primer and Clearfil SE Bond bonding (P-M); (4) Phenyl-P in primer and bonding (P-P). Ground buccal enamel surfaces of human sound premolars were treated with one of the systems and the bonded interface was exposed to an artificial demineralising solution (pH 4.5) for 4.5 h, and then 5% NaOCl with ultrasonication for 30 min. After argon-ion etching, the interfacial ultrastructure was observed using SEM. Micro-shear bond strength to enamel was measured for all groups and results were analysed using one-way ANOVA and Turkey's HSD, while failure modes were analysed by chi-square test. An acid-base resistant zone (ABRZ) was found with all adhesive systems containing MDP either in primer or bond; however, ultramorphology and crystallite arrangement in the ABRZ were different among groups. P-P was the only group devoid of this protective zone. Micro-shear bond strength in M-M was significantly higher than those in M-P, P-M and P-P, while the latter three were not different from each other. Failure modes were significantly different (penamel. Copyright 2010 Elsevier Ltd. All rights reserved.

  19. Bonding charge density from atomic perturbations.

    Science.gov (United States)

    Wang, Yi; Wang, William Yi; Chen, Long-Qing; Liu, Zi-Kui

    2015-05-15

    Charge transfer among individual atoms is the key concept in modern electronic theory of chemical bonding. In this work, we present a first-principles approach to calculating the charge transfer. Based on the effects of perturbations of an individual atom or a group of atoms on the electron charge density, we determine unambiguously the amount of electron charge associated with a particular atom or a group of atoms. We computed the topological electron loss versus gain using ethylene, graphene, MgO, and SrTiO3 as examples. Our results verify the nature of chemical bonds in these materials at the atomic level.

  20. Cigarette smoke affects bonding to dentin.

    Science.gov (United States)

    Almeida e Silva, Junio S; de Araujo, Edson Medeiro; Araujo, Elito

    2010-01-01

    This in vitro study evaluated the microtensile bond strength (muTBS) of composite resin bonded to dentin that had been contaminated by cigarette smoke. Ten extracted unerupted human third molars were used: Six molars were prepared for muTBS testing, while the other four molars were assigned to pre- and post-etching scanning electronic microscopy (SEM) analysis. The 20 specimens obtained from the 10 coronal portions were distributed into two experimental groups so that each tooth served as its own control. Group 1 underwent a daily toothbrushing simulation and exposure to a smoking simulation chamber, while Group 2 received only a daily simulated toothbrushing. Student's t-test demonstrated that Group 1 samples demonstrated significantly lower bond strength (49.58 MPa) than Group 2 samples (58.48 MPa). Pre and postetching SEM analysis revealed the presence of contaminants on the dentinal surfaces of the Group 1 specimens. It was concluded that contamination by cigarette smoke decreases the bond strength between dentin and composite resin.

  1. Ethanol-wet bonding technique may enhance the bonding performance of contemporary etch-and-rinse dental adhesives.

    Science.gov (United States)

    Li, Fang; Liu, Xiao-Yang; Zhang, Ling; Kang, Jun-Jun; Chen, Ji-Hua

    2012-04-01

    To determine whether bonds of contemporary etch-and-rinse adhesives made with ethanol-wet bonding are stronger and more durable than those made with water-wet bonding, and to explore the possible reasons for the bonding results. Flat surfaces of midcoronal dentin were made in extracted human third molars. The dentin surfaces were randomized into 6 groups according to bonding techniques (water- vs ethanol-wet bonding) and dental adhesives [Single Bond 2 (SB), Prime Bond NT (PB), and Gluma Comfort Bond (GB)]. After etching and rinsing, dentin surfaces were either left water-moist or immersed in ethanol. Following adhesive application and composite buildups, the bonded teeth were sectioned into beams for microtensile bond strength evaluation with or without NaOCl challenge. The morphology of the hybrid layer was analyzed with SEM. The wettability of water- vs. ethanol-saturated dentin was evaluated. The concentrations of non-volatile ingredients in the adhesives were compared. Compared to water-wet bonding, ethanol-wet bonding yielded similar (p > 0.05 for PB and GB) or higher (p adhesives), and produced more even hybrid layers. Moreover, ethanol-saturated dentin exhibited a lower contact angle than water-saturated specimens, and the concentrations of non-volatile ingredients of the adhesives decreased in the order of SB > GB > PB. Ethanol-wet bonding could improve the bonding efficacy of contemporary etch-and-rinse adhesives, probably due to the good wettability of ethanol-saturated dentin and the structure of the hybrid layer. Moreover, this positive effect of ethanol-wet bonding might be influenced by the composition of adhesives.

  2. Modelling longevity bonds: Analysing the Swiss Re Kortis bond

    OpenAIRE

    2015-01-01

    A key contribution to the development of the traded market for longevity risk was the issuance of the Kortis bond, the world's first longevity trend bond, by Swiss Re in 2010. We analyse the design of the Kortis bond, develop suitable mortality models to analyse its payoff and discuss the key risk factors for the bond. We also investigate how the design of the Kortis bond can be adapted and extended to further develop the market for longevity risk.

  3. Fundamentals of fiber bonding in thermally point-bonded nonwovens

    Science.gov (United States)

    Chidambaram, Aparna

    Thermal point bonding (TPB) uses heat and pressure to bond a web of fibers at discrete points imparting strength to the manufactured fabric. This process significantly reduces the strength and elongation of the bridging fibers between bond points while strengthening the web. Single fiber experiments were performed with four structurally different polypropylene fibers to analyze the inter-relationships between fiber structure, fiber properties and bonding process. Two fiber types had a low birefringence sheath or surface layer while the remaining had uniform birefringence profiles through their thickness. Bonds were formed between isolated pairs of fibers by subjecting the fibers to a calendering process and simulating TPB process conditions. The dependence of bond strength on bonding temperature and on the type of fiber used was evaluated. Fiber strengths before and after bonding were measured and compared to understand the effect of bonding on fiber strength. Additionally, bonded fiber strength was compared to the strength of single fibers which had experienced the same process conditions as the bonded pairs. This comparison estimated the effect of mechanical damage from pressing fibers together with steel rolls while creating bonds in TPB. Interfiber bond strength increased with bonding temperature for all fiber types. Fiber strength decreased with increasing bonding temperature for all fiber types except for one type of low birefringent sheath fibers. Fiber strength degradation was unavoidable at temperatures required for successful bonding. Mechanical damage from compression of fibers between rolls was an insignificant factor in this strength loss. Thermal damage during bonding was the sole significant contributor to fiber strength degradation. Fibers with low birefringence skins formed strong bonds with minimal fiber strength loss and were superior to fibers without such surface layers in TPB performance. A simple model to predict the behavior of a two-bond

  4. A form of mitofusin 2 (Mfn2) lacking the transmembrane domains and the COOH-terminal end stimulates metabolism in muscle and liver cells.

    Science.gov (United States)

    Segalés, Jessica; Paz, José C; Hernández-Alvarez, María Isabel; Sala, David; Muñoz, Juan Pablo; Noguera, Eduard; Pich, Sara; Palacín, Manuel; Enríquez, José Antonio; Zorzano, Antonio

    2013-11-15

    Mitofusin 2 (Mfn2), a protein that participates in mitochondrial fusion, is required to maintain normal mitochondrial metabolism in skeletal muscle and liver. Given that muscle Mfn2 is repressed in obese or type 2 diabetic subjects, this protein may have a potential pathophysiological role in these conditions. To evaluate whether the metabolic effects of Mfn2 can be dissociated from its function in mitochondrial dynamics, we studied a form of human Mfn2, lacking the two transmembrane domains and the COOH-terminal coiled coil (ΔMfn2). This form localized in mitochondria but did not alter mitochondrial morphology in cells or in skeletal muscle fibers. The expression of ΔMfn2 in mouse skeletal muscle stimulated glucose oxidation and enhanced respiratory control ratio, which occurred in the absence of changes in mitochondrial mass. ΔMfn2 did not stimulate mitochondrial respiration in Mfn2-deficient muscle cells. The expression of ΔMfn2 in mouse liver or in hepatoma cells stimulated gluconeogenesis. In addition, ΔMfn2 activated basal and maximal respiration both in muscle and liver cells. In all, we show that a form of Mfn2 lacking mitochondrial fusion activity stimulates mitochondrial function and enhances glucose metabolism in muscle and liver tissues. This study suggests that Mfn2 regulates metabolism independently of changes in mitochondrial morphology.

  5. Dye mPEG2 -COOH in PEG- EPO with iodine reagents%PEG-EPO中残余聚乙二醇的碘染色法

    Institute of Scientific and Technical Information of China (English)

    张雪艳; 陈智勇; 王黔川

    2006-01-01

    目的:建立检测聚乙二醇化促红细胞生成素(PEG-EPO)产品中残余聚乙二醇(mPEG2-COOH)含量的方法.方法:样品经十二烷基硫酸钠聚丙烯酰胺凝胶电泳(SDS-PAGE)后,采用碘染色法进行染色,根据染色带深浅分析样品中mPEG2-COOH的含量.结果:确定了测量PEG-EPO中检测mPEG2-COOH含量的实验条件,在本实验条件下mPEG2-COOH的检测下限约为5μg·mL-1.结论:本法便捷、重复性好,适合该mPEG2-COOH含量的检测要求.同时可运用于相关的聚乙二醇修饰蛋白质.

  6. Research on Synthesis of DADHB/PTA/SWNT-COOH Complex%DADHB/PTA/SWNT-COOH复合物合成研究

    Institute of Scientific and Technical Information of China (English)

    王峰; 宋元军; 胡桢; 黄玉东; 赵蕾; 宋波; 林宏

    2010-01-01

    通过4,6-二氨基间苯二酚(DADHP)、对苯二甲酸(PrA)和羧酸化单壁碳纳米管(SWNT-COOH,SWNT经强氧化酸处理获得)之间的络合反应,合成了用于PBO/SWNT聚合的复合物(DADHP-PTA-SWNT-COOH络合盐),并成功制备了一系列SWNT含量不同的PBO/SWNT复合材料.对SWNT-COOH、DADHP/PTMSWNT-COOH络合盐和PBO/SWNT复合材料进行傅立叶红外光谱和扫描电子显微镜表征.结果表明:经过酸处理后,SWNT获得羧基,表面极性功能基团数量增加,在聚合物基体中的分散性提高,SWNT用量为2.5%时,分散效果最佳.

  7. Facile synthesis of nitrogen-doped carbon dots from COOH-functional ionic liquid and their sensing application in selective detection of free chlorine

    Science.gov (United States)

    Wang, Congyue; Wang, Chunfeng; Sun, Dong; Li, Aoqi; Chen, Yujuan; Zhuo, Kelei

    2016-09-01

    Heteroatom doped carbon dots (CDs) possess many unique properties and have attracted increasing attention. The precursor is vital for the preparation of highly fluorescent heteroatom doped CDs. Herein, 1, 3-bis(carboxymethyl)imidazolium chloride ([Im(AH)2]Cl, a COOH-functional ionic liquid) and aminoethylethanolamine (AEEA) were firstly used as precursors to prepare nitrogen-doped carbon dots (N-CDs) by a simple one-step pyrolysis approach. The effects of reaction time, temperature, and mass ratio of precursors on the quantum yield (QY) of N-CDs were investigated. The prepared N-CDs are spherical morphology with an average diameter of 2.4 nm, and have blue fluorescence with a QY of 23.2% and excitation-dependent emission behavior. They also possess good water solubility and fluorescent stability. In addition, based on the obtained N-CDs, a sensing method of free chlorine detection in acidic water system was introduced. The proposed method has good sensitivity and selectivity to free chlorine, and exhibits a nice linear response in the concentration range from 0.2 to 22 μM with a detection limit of 0.15 μM. Furthermore, this sensing method was successfully applied to detect free chlorine of tap water with satisfactory recovery (97%-103%), suggesting it has the potential application in water quality monitoring.

  8. Shear bond strength of brackets rebonded with a fluoride-releasing and -recharging adhesive system.

    Science.gov (United States)

    Endo, Toshiya; Ozoe, Rieko; Shinkai, Koichi; Aoyagi, Makiko; Kurokawa, Hiroomi; Katoh, Yoshiroh; Shimooka, Shohachi

    2009-05-01

    To ascertain the effects of repeated bonding on the shear bond strength of orthodontic brackets bonded with a fluoride-releasing and -recharging adhesive system with a self-etching primer in comparison with two other types of adhesive system. A total of 48 premolars were collected and divided equally into three groups of 16. Each group was assigned one of three adhesive systems: Transbond XT, Transbond Plus, or a fluoride-releasing and -recharging adhesive system, Beauty Ortho Bond. Shear bond strength was measured 24 hours after bracket bonding, with the bonding/debonding procedures repeated twice after the first debonding. A universal testing machine was used to determine shear bond strengths, and bracket/adhesive failure modes were evaluated with the adhesive remnant index after each debonding. At every debonding sequence, all of these three adhesive systems had a shear bond strength of 6 MPa, which is a minimum requirement for clinical use. Transbond XT and Transbond Plus had significantly higher mean shear bond strengths than did Beauty Ortho Bond at each debonding. No significant differences in mean bond strength were observed between the three debondings in each adhesive system. Bond failure at the enamel/adhesive interface occurred more frequently in Beauty Ortho Bond than in Transbond XT or Transbond Plus. The fluoride-releasing and -recharging adhesive system with the self-etching primer (Beauty Ortho Bond) had clinically sufficient shear bond strength in repeated bracket bonding; this finding can help orthodontists to decrease the risk of damage to enamel at debonding.

  9. Synthesis and Characterization of Quaternary Complex of Sm-CH3C(CH2OH)2COOH-Phen

    Institute of Scientific and Technical Information of China (English)

    Xi Peng; Wang Lianjun; Huang Xiangan

    2005-01-01

    A new quaternary complex with 2,2-dihydroxymethyl propionic acid and 1,10-phenanthroline, Sm(CH3C(CH2OH)2COO)(NO3)2(phen), was synthesized in ethanol solution and characterized by elemental analysis, IR and solid-state 13C NMR. The result of molar electrolytic conductivity of the complex indicates that it is non-electrolyte. Solution and thermal properties of the complex further verifies that the complex and ligant are different. In addition, the analytical results also imply that the two hydroxyl groups of 2,2-dihydroxymethyl propionic acid are not involved in the coordinate reaction. This will provide a new way for producing new multifunctional polymer materials with excellent fluorescent property. The fluorescence spectra of the complex were also studied. The main fluorescence emission peak of the complex appeared at 555, 604 and 646 nm. These fluorescent emission peaks correspond to transitions from 4G5/2 to 6H5/2, 6H7/2 and 6H9/2 energy levels of samarium(Ⅲ) ion, respectively. The most intense peak is at 646 nm, which lies in the range of absorption wavelength of chlorophyll a and chlorophyll b (600~680 nm), and it is beneficial to the crops to grow up.

  10. Bonding brackets to porcelain: in vitro study

    Directory of Open Access Journals (Sweden)

    Sant'Anna Eduardo Franzotti

    2002-01-01

    Full Text Available The aim of this research was to verify, in vitro, the effect of various porcelain surface treatments on the shear strength of orthodontic brackets bonded to porcelain and the mode of fracture after debonding. Eighty-eight samples of metallic supported feldspathic porcelain were randomly divided into four groups according to their surface preparation as follows: the porcelain was maintained intact (GI, roughened with a diamond bur (GII, etched with 10% hydrofluoric acid (GIII, or sandblasted with aluminum oxide (GIV. The specimens were treated with silane (Scothprime and brackets were bonded with Concise. Each sample was subjected to a shear load at a crosshead speed of 1 mm/min and a recording was made at the point of failure. Bond strengths, adequate to withstand the application of orthodontic forces, were achieved in all groups. The Kruskal-Wallis statistical test showed no significant differences in bond strength between the groups (p>0.05. However, many more porcelain fractures occurred on deglazed porcelain. This study indicates that with the appropriate material selection, the silane/composite procedure alone may be adequate for bonding.

  11. Romanian government bond market

    Directory of Open Access Journals (Sweden)

    Cornelia POP

    2012-12-01

    Full Text Available The present paper aims to present the level of development reached by Romanian government bond market segment, as part of the country financial market. The analysis will be descriptive (the data series available for Romania are short, based on the secondary data offered by the official bodies involved in the process of issuing and trading the Romanian government bonds (Romanian Ministry of Public Finance, Romanian National Bank and Bucharest Stock Exchange, and also on secondary data provided by the Federation of European Stock Exchanges.To enhance the market credibility as a benchmark, a various combination of measures is necessary; among these measures are mentioned: the extension of the yield curve; the issuance calendars in order to improve transparency; increasing the disclosure of information on public debt issuance and statistics; holding regular meetings with dealers, institutional investors and rating agencies; introducing a system of primary dealers; establishing a repurchase (repo market in the government bond market. These measures will be discussed based on the evolution presented inside the paper.The paper conclude with the fact that, until now, the Romanian government bond market did not provide a benchmark for the domestic financial market and that further efforts are needed in order to increase the government bond market transparency and liquidity.

  12. Evaluation of the Shear Bond Strength of Composite Resin to Wet and Dry Enamel Using Dentin Bonding Agents Containing Various Solvents

    Science.gov (United States)

    Ramarao, Sathyanarayanan; John, Bindu Meera; Rajesh, Praveen; Swatha, S

    2017-01-01

    Introduction Bonding of composite resin to dentin mandates a wet substrate whereas, enamel should be dry. This may not be easily achievable in intracoronal preparations where enamel and dentin are closely placed to each other. Therefore, Dentin Bonding Agents (DBA) are recommended for enamel and dentinal bonding, where enamel is also left moist. A research question was raised if the “enamel-only” preparations will also benefit from wet enamel bonding and contemporary DBA. Aim The aim of this study was to compare the shear bond strengths of composite resin, bonded to dry and wet enamel using fifth generation DBA (etch and rinse system) containing various solvents such as ethanol/water, acetone and ethanol. Materials and Methods The crowns of 120 maxillary premolars were split into buccal and lingual halves. They were randomly allocated into four groups of DBA: Group 1-water/ethanol based, Group 2-acetone based, Group 3-ethanol based, Group 4-universal bonding agent (control group). The buccal halves and lingual halves were bonded using the wet bonding and dry bonding technique respectively. After application of the DBAs and composite resin build up, shear bond strength testing was done. Results Group 1 (ethanol/water based ESPE 3M, Adper Single Bond) showed highest bond strength of (23.15 MPa) in dry enamel. Group 2 (acetone based Denstply, Prime and Bond NT, showed equal bond strength in wet and dry enamel condition (18.87 MPa and 18.02 MPa respectively). Conclusion Dry enamel bonding and ethanol/water based etch and rinse DBA can be recommended for “enamel-only” tooth preparations. PMID:28274042

  13. Safe and Liquid Mortgage Bonds

    DEFF Research Database (Denmark)

    Dick-Nielsen, Jens; Gyntelberg, Jacob; Lund, Jesper

    This paper shows that strict match pass-through funding of covered bonds provides safe and liquid mortgage bonds. Despite a 30% drop in house prices during the 2008 global crisis Danish mortgage bonds remained as liquid as most European government bonds. The Danish pass-through system effectively...... eliminates credit risk from the investor's perspective. Similar to other safe bonds, funding liquidity becomes the main driver of mortgage bond liquidity and this creates commonality in liquidity across markets and countries. These findings have implications for how to design a robust mortgage bond system...

  14. Safe and Liquid Mortgage Bonds

    DEFF Research Database (Denmark)

    Dick-Nielsen, Jens; Gyntelberg, Jacob; Lund, Jesper

    This paper shows that strict match pass-through funding of covered bonds provides safe and liquid mortgage bonds. Despite a 30% drop in house prices during the 2008 global crisis Danish mortgage bonds remained as liquid as most European government bonds. The Danish pass-through system effectively...... eliminates credit risk from the investor's perspective. Similar to other safe bonds, funding liquidity becomes the main driver of mortgage bond liquidity and this creates commonality in liquidity across markets and countries. These findings have implications for how to design a robust mortgage bond system...

  15. Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol.

    Science.gov (United States)

    Zhao, Hailiang; Tang, Shanshan; Xu, Xiang; Du, Lin

    2016-12-30

    Amides are important atmospheric organic-nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH) with amides (formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide and N,N-dimethylacetamide) have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH-amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O-H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components.

  16. Microtensile Bond Strength of Single Bond and Adper Prompt-L-Pop Adhesives to Dentin

    OpenAIRE

    P. Alizadeh Oskoee; AA. Ajami; S. Savadi Oskoee; F. Pournaghi-Azar

    2008-01-01

    Objective: The aim of this study was to evaluate the microtensile bond strength to sound and caries-affected dentin using Single Bond and Adper Prompt-L-Pop adhesives.Materials and Methods: Sixteen extracted human molars with carious lesions extended halfway through dentin were ground to expose the caries affected and the surrounding normal dentin. The samples were divided into two groups of eight samples each, including Single Bond (two-step etch and rinse) and Adper Prompt-L-Pop (one step s...

  17. Main group multiple C-H/N-H bond activation of a diamine and isolation of a molecular dilithium zincate hydride: experimental and DFT evidence for alkali metal-zinc synergistic effects.

    Science.gov (United States)

    Campbell, Ross; Cannon, Daniel; García-Álvarez, Pablo; Kennedy, Alan R; Mulvey, Robert E; Robertson, Stuart D; Sassmannshausen, Jörg; Tuttle, Tell

    2011-08-31

    The surprising transformation of the saturated diamine (iPr)NHCH(2)CH(2)NH(iPr) to the unsaturated diazaethene [(iPr)NCH═CHN(iPr)](2-) via the synergic mixture nBuM, (tBu)(2)Zn and TMEDA (where M = Li, Na; TMEDA = N,N,N',N'-tetramethylethylenediamine) has been investigated by multinuclear NMR spectroscopic studies and DFT calculations. Several pertinent intermediary and related compounds (TMEDA)Li[(iPr)NCH(2)CH(2)NH(iPr)]Zn(tBu)(2) (3), (TMEDA)Li[(iPr)NCH(2)CH(2)CH(2)N(iPr)]Zn(tBu) (5), {(THF)Li[(iPr)NCH(2)CH(2)N(iPr)]Zn(tBu)}(2) (6), and {(TMEDA)Na[(iPr)NCH(2)CH(2)N(iPr)]Zn(tBu)}(2) (11), characterized by single-crystal X-ray diffraction, are discussed in relation to their role in the formation of (TMEDA)M[(iPr)NCH═CHN(iPr)]Zn(tBu) (M = Li, 1; Na, 10). In addition, the dilithio zincate molecular hydride [(TMEDA)Li](2)[(iPr)NCH(2)CH(2)N(iPr)]Zn(tBu)H 7 has been synthesized from the reaction of (TMEDA)Li[(iPr)NCH(2)CH(2)NH(iPr)]Zn(tBu)(2)3 with nBuLi(TMEDA) and also characterized by both X-ray crystallographic and NMR spectroscopic studies. The retention of the Li-H bond of 7 in solution was confirmed by (7)Li-(1)H HSQC experiments. Also, the (7)Li NMR spectrum of 7 in C(6)D(6) solution allowed for the rare observation of a scalar (1)J(Li-H) coupling constant of 13.3 Hz. Possible mechanisms for the transformation from diamine to diazaethene, a process involving the formal breakage of four bonds, have been determined computationally using density functional theory. The dominant mechanism, starting from (TMEDA)Li[(iPr)NCH(2)CH(2)N(iPr)]Zn(tBu) (4), involves the formation of a hydride intermediate and leads directly to the observed diazaethene product. In addition the existence of 7 in equilibrium with 4 through the dynamic association and dissociation of a (TMEDA)LiH ligand, also provides a secondary mechanism for the formation of the diazaethene. The two reaction pathways (i.e., starting from 4 or 7) are quite distinct and provide excellent examples in which the

  18. Electronic structure of planar-quasicycled organic molecules with intramolecular hydrogen bond

    Directory of Open Access Journals (Sweden)

    ALEXEI N. PANKRATOV

    2007-03-01

    Full Text Available By means of the HF/6-311G(d,p method, the electronic structure of the series of organic molecules, among which are malonaldehyde, acetylacetone, thiomalonaldehyde,’the derivatives of aniline 2-XC6H4NH2, phenol 2-XC6H4OH, benzenethiol 2-XC6H4SH (X = CHO, COOH, COO-, NO, NO2, OH, OCH3, SH, SCH3, F, Cl, Br, 8-hydroxyquinoline, 8-mercaptoquinoline, tropolone, has been studied. The intramolecular hydrogen bond (IHB has been established to lead to a local electron redistribution in quasicycle, and primarily to the electron density transfer between the direct IHB participants – from the hydrogen atom toward the proton-aceptor atom. On forming the IHB of the S–H···O type, the electron density in general decreases on the sulphohydryl hydrogen atom and increases on the sulphur atom.

  19. An in vitro study to evaluate the effect of two ethanol-based and two acetone-based dental bonding agents on the bond strength of composite to enamel treated with 10% carbamide peroxide

    Directory of Open Access Journals (Sweden)

    Deepa Basavaraj Benni

    2014-01-01

    Full Text Available Background and Objective: Carbamide peroxide bleaching has been implicated in adversely affecting the bond strength of composite to enamel. The objective of this in vitro study was to evaluate the effect of ethanol-based (Clearfil S 3 bond, Kuraray, Adper Single bond 2, 3M ESPE dental products and acetone-based (Prime and Bond NT, Dentsply, One Step, Bisco bonding agents on the shear bond strength of composite to enamel treated with 10% carbamide peroxide bleaching agent. Materials and Methods: A total of 120 extracted human noncarious permanent incisors were randomly divided into two groups (control and experimental. Experimental group specimens were subjected to a bleaching regimen with a 10% carbamide peroxide bleaching system (Opalescence; Ultradent Products Inc, South Jordan, USA. Composite resin cylinders were bonded to the specimens using four bonding agents and shear bond strength was determined with universal testing machine. Results: There was no statistically significant difference in the shear bond strength between control and experimental groups with both ethanol-based (Clearfil S 3 Bond and Adper Single Bond 2 and acetone-based bonding agent (Prime and Bond NT and One Step. Interpretation and Conclusion: The adverse effect of bleaching on bonding composite to enamel can be reduced or eliminated by using either ethanol- or acetone-based bonding agent. Clinical Significances: Immediate bonding following bleaching procedure can be done using ethanol- or acetone-based bonding agent without compromising bond strength.

  20. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials.

    Science.gov (United States)

    Qi, Xuejun; Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite's chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface.

  1. Evaluation of characteristics on titanium surface treatment for absorption of functional groups

    Institute of Scientific and Technical Information of China (English)

    JIN Guang-chun; PARK Rl-song; PARK Hyeoung-ho; SEO Jae-min; LEE Sook-jeong; LEE Min-ho

    2010-01-01

    Background In order to bind or fix bioactive materials directly to the surface of a Ti implant, the prior binding process of functional groups (FGs, -COOH and -OH) to the implant surface is necessary. Conventional binding processes are so high-cost and complex, so it is essential to find a simple and effective procedure for Ti-FG binding.Methods Various electrolyte compositions and electrochemical processing were adopted in this study to develop a relatively simple and effective Ti-FG binding process. The ability of Ti-FG binding and calcium (Ca)/phosphorous (P)absorption and corrosion resistance were evaluated according to various titanium surface treatment in electrolyte involving -COOH and -OH ion by using X ray photoelectron spectroscopy (XPS), field emission scanning electron microscope (FE-SEM) and potentiodynamic scan method respectively.Results In cases of -COOH, the anodic oxidation process (AN) showed an effective binding ability between -COOH and Ti surface. On the other hand, in cases of -OH, there were no significant differences in the result between the conditions used. In regard to the absorption of Ca and P on Ti surface, there was a minimal amount of Ca absorbed but no P was absorbed. The anodic oxidation series showed homogenous corrosion, whereas the electrolyte immersion (EL)series showed unstable corrosion. Although EL-OH showed a novel corrosion potential, the EL-COOH series showed good corrosion resistance over the anodic potential range.Conclusions The ability of binding between FG and the Ti surface and Ca/P absorption were strongly associated with the surface potential (ξ, potential), which was dependent on the pH of the electrolyte. Accordingly, in order to achieve the effective absorption of various FGs on the Ti surface, it is needed to develop the combination process in addition to the electric affinity, relation with the ξ, potential.

  2. Shear Bond Strength of Resin Bonded to Bleached Enamel Using Different Modified 35% Hydrogen Peroxides

    Directory of Open Access Journals (Sweden)

    Moosavi H

    2015-12-01

    Full Text Available Statement of Problem: Bleaching systems with different concentrations and applications are widely used to improve the visual appearance of the teeth, but one of the complications of these materials is reduction of bond strength for immediately bonding to the bleached enamel. Objectives: The aim of this study was to evaluate the influence of using different modified hydrogen peroxide bleaching agents on the shear bond strength of composite resin bonded to the bleached enamel. Materials and Methods: Forty-eight sound extracted premolar teeth were collected, sectioned 1 mm below the CEJ to detach the root. The proximal surfaces of the teeth were flattened using diamond disks and silicon carbide papers to achieve flat homogeneous enamel surfaces without exposure to the dentin. The teeth were randomly divided into four groups as follows (n = 12: group 1: bleaching with 35% hydrogen peroxide gel; group 2: bleaching with 35% hydrogen peroxide gel contained (casein phosphopeptide-amorphous calcium phosphate (CPP-ACP; group 3: bleaching with 35% hydrogen peroxide gel combined with fluoride; and group 4: bleaching with 35% hydrogen peroxide applying one week before resin restoration placement. Composite resin, Clearfil AP-X (Kuraray, Tokyo, Japan, was bonded on each tooth in the mould (4 mm diameter × 3 mm height using Clearfil SE Bond (Kuraray, Tokyo, Japan. After 24 hours of storage and 1000 cycles of thermocycling, the shear bond strength of the specimens at a cross-head speed of 0.5 mm/min was measured in MPa. Data were analyzed using ANOVA and Tukey’s post-hoc test. Results: The minimum and maximum mean shear bond strength values were observed in groups 2 (15.82 ± 4.41 and 4 (21.00 ± 3.90, respectively. Multiple comparisons of groups revealed no significant differences among the groups except between group 4 and all the other groups. The most common type of failure was adhesive. Conclusions: Using modified bleaching agents decreased the bond

  3. 用电生的Fe(Ⅱ)-EDTA络合物在Fe(Ⅲ)-EDTA-ClCH2COOH-NaOAc缓冲溶液中精密库仑滴定金%Precise Coulometric Titration of Gold with Electrogenerated Fe(Ⅱ)-EDTA Complex in Fe(Ⅲ)-EDTA-ClCH2COOH-NaOAc Buffer Medium

    Institute of Scientific and Technical Information of China (English)

    董守安; 吴长蓉

    2003-01-01

    A method of precise coulometric titration of Au(Ⅲ)was studied with electrogenerating Fe(Ⅱ)-EDTA as titrant in Fe(Ⅲ)-EDTA-ClCH2COOH-NaOAc buffer solution.For the determination of gold in the range of 5.2 to 17.0mg ,the relative average errors and RSD of the results were≤0.03%(n=5),using potentiometric end point detection.The proposed method has been applied to the precise analysis of gold content in pure gold,gold alloys and jewelry with good selectivity.The theoretical basis for electrogeneration Fe(Ⅱ)-EDTA complex as a coulometric titrant was also discussed and a useful conclusion was obtained.%提出了在Fe(Ⅲ)-EDTA-ClCH2COOH-NaOAc缓冲溶液中利用电生Fe(Ⅱ)-ED-TA络合物精密库仑滴定Au的方法.采用电位法检测终点,测定范围在5.2~17.0mg Au时,相对平均误差和标准偏差≤0.03%.方法可用于纯金、金合金和首饰等材料中Au含量的精密分析,选择性很好.讨论了电生Fe(Ⅱ)-EDTA络合物作库仑滴定剂的理论基础,获得了有益的结论.

  4. Comparison of shear bond strength of orthodontic brackets bonded using two different hydrophilic primers: An in vitro study

    Directory of Open Access Journals (Sweden)

    M Kumaraswamy Anand

    2014-01-01

    Full Text Available Context: Salivary control and maintenance of a dry operating field is a prime requisite of orthodontic bonding. Moisture insensitive primer (MIP with a clinical significant bond strength values have a better edge over the conventional hydrophobic bonding systems. Aim: The aim of this study is to investigate the effectiveness of two hydrophilic primers with respect to conventional hydrophobic primer by comparing their shear bond strength (SBS and adhesive-failure locations after contamination with saliva and saliva substitute. Materials and Methods: A total of 150 extracted human premolars were randomly divided into five group s ; Group A (Transbond MIP/saliva substitute, Group B (Opal Primo/saliva substitute, Group C (Transbond MIP/natural saliva, Group D (Opal Primo/natural saliva, control group - Group E (Transbond XT/dry, adhesive-Transbond XT used for all five groups and bonded using stainless steel brackets. Shear forces were applied to the samples with a universal testing machine. SBSs was measured in megapascals. The mode of bond failure was determined using the adhesive remnant index (ARI. Results: The mean SBS produced by Transbond MIP was higher than Opal Primo, which was statistically significant according to one-way analysis of variance. Both the tested groups showed lesser bond strength values than Transbond XT (the control. ARI scores revealed that there was no statistically significant difference in the site of bond failure between study groups. ARI scores were found to be lower for study groups suggesting adhesive failure, compared to higher ARI scores for the control group suggesting cohesive failure. Conclusion: Transbond XT adhesive with Transbond MIP or Opal Primo have clinically acceptable bond strength in wet fields. Opal Primo is a viable option to use as a hydrophilic primer clinically.

  5. Limitations in Bonding to Dentin and Experimental Strategies to Prevent Bond Degradation

    OpenAIRE

    Liu, Y.; Tjäderhane, L.; Breschi, L; A. Mazzoni; Li, N; J. Mao; Pashley, D.H.; Tay, F.R.

    2011-01-01

    The limited durability of resin-dentin bonds severely compromises the lifetime of tooth-colored restorations. Bond degradation occurs via hydrolysis of suboptimally polymerized hydrophilic resin components and degradation of water-rich, resin-sparse collagen matrices by matrix metalloproteinases (MMPs) and cysteine cathepsins. This review examined data generated over the past three years on five experimental strategies developed by different research groups for extending the longevity of resi...

  6. Molecular model with quantum mechanical bonding information.

    Science.gov (United States)

    Bohórquez, Hugo J; Boyd, Russell J; Matta, Chérif F

    2011-11-17

    The molecular structure can be defined quantum mechanically thanks to the theory of atoms in molecules. Here, we report a new molecular model that reflects quantum mechanical properties of the chemical bonds. This graphical representation of molecules is based on the topology of the electron density at the critical points. The eigenvalues of the Hessian are used for depicting the critical points three-dimensionally. The bond path linking two atoms has a thickness that is proportional to the electron density at the bond critical point. The nuclei are represented according to the experimentally determined atomic radii. The resulting molecular structures are similar to the traditional ball and stick ones, with the difference that in this model each object included in the plot provides topological information about the atoms and bonding interactions. As a result, the character and intensity of any given interatomic interaction can be identified by visual inspection, including the noncovalent ones. Because similar bonding interactions have similar plots, this tool permits the visualization of chemical bond transferability, revealing the presence of functional groups in large molecules.

  7. The Trouble With Bonds

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    @@ In early June,global financial markets gyrated downwards in the wake of central banks'tough language on inflation.At one point bond prices reflected expectations of four rate hikes by the US Federal Reserve (Fed) in the next 12 months.As a result,the dollar firmed,oil prices stabilized,and yield curves flattened around the world.If all these inflation-fighting measures are real,the situation bodes well for bonds.But,I think otherwise.

  8. Anodic bonded graphene

    Science.gov (United States)

    Balan, Adrian; Kumar, Rakesh; Boukhicha, Mohamed; Beyssac, Olivier; Bouillard, Jean-Claude; Taverna, Dario; Sacks, William; Marangolo, Massimiliano; Lacaze, Emanuelle; Gohler, Roger; Escoffier, Walter; Poumirol, Jean-Marie; Shukla, Abhay

    2010-09-01

    We show how to prepare graphene samples on a glass substrate with the anodic bonding method. In this method, a graphite precursor in flake form is bonded to a glass substrate with the help of an electrostatic field and then cleaved off to leave few layer graphene on the substrate. Now that several methods are available for producing graphene, the relevance of our method is in its simplicity and practicality for producing graphene samples of about 100 µm lateral dimensions. This method is also extensible to other layered materials. We discuss some detailed aspects of the fabrication and results from Raman spectroscopy, local probe microscopy and transport measurements on these samples.

  9. Anodic bonded graphene

    Energy Technology Data Exchange (ETDEWEB)

    Balan, Adrian; Kumar, Rakesh; Boukhicha, Mohamed; Beyssac, Olivier; Bouillard, Jean-Claude; Taverna, Dario; Sacks, William; Shukla, Abhay [Universite Pierre et Marie Curie-Paris 6, CNRS-UMR7590, Institut de Mineralogie et de Physique des Milieux Condenses, 140 rue de Lourmel, Paris, F-75015 France (France); Marangolo, Massimiliano; Lacaze, Emanuelle; Gohler, Roger [Universite Pierre et Marie Curie-Paris 6, CNRS-UMR7588, Institut des Nanosciences de Paris, 140 rue de Lourmel, Paris, F-75015 France (France); Escoffier, Walter; Poumirol, Jean-Marie, E-mail: abhay.shukla@upmc.f [Laboratoire National des Champs Magnetiques Intenses, INSA UPS CNRS, UPR 3228, Universite de Toulouse, 143 avenue de Rangueil, 31400 Toulouse (France)

    2010-09-22

    We show how to prepare graphene samples on a glass substrate with the anodic bonding method. In this method, a graphite precursor in flake form is bonded to a glass substrate with the help of an electrostatic field and then cleaved off to leave few layer graphene on the substrate. Now that several methods are available for producing graphene, the relevance of our method is in its simplicity and practicality for producing graphene samples of about 100 {mu}m lateral dimensions. This method is also extensible to other layered materials. We discuss some detailed aspects of the fabrication and results from Raman spectroscopy, local probe microscopy and transport measurements on these samples.

  10. Hydrogen bonded supramolecular materials

    CERN Document Server

    Li, Zhan-Ting

    2015-01-01

    This book is an up-to-date text covering topics in utilizing hydrogen bonding for constructing functional architectures and supramolecular materials. The first chapter addresses the control of photo-induced electron and energy transfer. The second chapter summarizes the formation of nano-porous materials. The following two chapters introduce self-assembled gels, many of which exhibit unique functions. Other chapters cover the advances in supramolecular liquid crystals and the versatility of hydrogen bonding in tuning/improving the properties and performance of materials. This book is designed

  11. Cooperativity in beryllium bonds.

    Science.gov (United States)

    Alkorta, Ibon; Elguero, José; Yáñez, Manuel; Mó, Otilia

    2014-03-07

    A theoretical study of the beryllium bonded clusters of the (iminomethyl)beryllium hydride and (iminomethyl)beryllium fluoride [HC(BeX)=NH, X = H, F] molecules has been carried out at the B3LYP/6-311++G(3df,2p) level of theory. Linear and cyclic clusters have been characterized up to the decamer. The geometric, energetic, electronic and NMR properties of the clusters clearly indicate positive cooperativity. The evolution of the molecular properties, as the size of the cluster increases, is similar to those reported in polymers held together by hydrogen bonds.

  12. Shear bond strength of metallic brackets: influence of saliva contamination

    Directory of Open Access Journals (Sweden)

    Luciana Borges Retamoso

    2009-06-01

    Full Text Available OBJECTIVE: To evaluate the influence of saliva contamination on shear bond strength and the bond failure pattern of 3 adhesive systems (Transbond XT, AdheSE and Xeno III on orthodontic metallic brackets bonded to human enamel. MATERIAL AND METHODS: Seventy-two permanent human molars were cut longitudinally in a mesiodistal direction, producing seventy-two specimens randomly divided into six groups. Each system was tested under 2 different enamel conditions: no contamination and contaminated with saliva. In T, A and X groups, the adhesive systems were applied to the enamel surface in accordance with manufacturer's instructions. In TS, AS and XS groups, saliva was applied to enamel surface followed by adhesive system application. The samples were stored in distilled water at 37ºC for 24 h, and then tested for shear bond strength in a universal testing machine (Emic, DL 2000 running at a crosshead speed of 1 mm/min. After bond failure, the enamel surfaces were observed under an optical microscope at 40x magnification. RESULTS: The control and contaminated groups showed no significant difference in shear bond strength for the same adhesive system. However, shear bond strength of T group (17.03±4.91 was significantly higher than that of AS (8.58±1.73 and XS (10.39±4.06 groups (p<0.05. Regarding the bond failure pattern, TS group had significantly higher scores of no adhesive remaining on the tooth in the bonding area than other groups considering the adhesive remnant index (ARI used to evaluate the amount of adhesive left on the enamel. CONCLUSIONS: Saliva contamination showed little influence on the 24-h shear bond strength of orthodontic brackets.

  13. Hydrogen bond and halogen bond inside the carbon nanotube

    Science.gov (United States)

    Wang, Weizhou; Wang, Donglai; Zhang, Yu; Ji, Baoming; Tian, Anmin

    2011-02-01

    The hydrogen bond and halogen bond inside the open-ended single-walled carbon nanotubes have been investigated theoretically employing the newly developed density functional M06 with the suitable basis set and the natural bond orbital analysis. Comparing with the hydrogen or halogen bond in the gas phase, we find that the strength of the hydrogen or halogen bond inside the carbon nanotube will become weaker if there is a larger intramolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom donor to the antibonding orbital of the X-H or X-Hal bond involved in the formation of the hydrogen or halogen bond and will become stronger if there is a larger intermolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom acceptor to the antibonding orbital of the X-H or X-Hal bond. According to the analysis of the molecular electrostatic potential of the carbon nanotube, the driving force for the electron-density transfer is found to be the negative electric field formed in the carbon nanotube inner phase. Our results also show that the X-H bond involved in the formation of the hydrogen bond and the X-Hal bond involved in the formation of the halogen bond are all elongated when encapsulating the hydrogen bond and halogen bond within the carbon nanotube, so the carbon nanotube confinement may change the blue-shifting hydrogen bond and the blue-shifting halogen bond into the red-shifting hydrogen bond and the red-shifting halogen bond. The possibility to replace the all electron nanotube-confined calculation by the simple polarizable continuum model is also evaluated.

  14. Adsorption structure and bonding of trimesic acid on Cu(100)

    Science.gov (United States)

    Kanninen, L.; Jokinen, N.; Ali-Löytty, H.; Jussila, P.; Lahtonen, K.; Hirsimäki, M.; Valden, M.; Kuzmin, M.; Pärna, R.; Nõmmiste, E.

    2011-12-01

    Combining scanning tunneling microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy using synchrotron radiation, we have studied the adsorption and growth of trimesic acid (TMA, 1,3,5-benzenetricarboxylic acid, C6H3(COOH)3) on Cu(100) in a wide range of coverages (from submonolayer to multilayer ones) at room temperature and after subsequent annealing. A series of coverage-dependent TMA structures, transitions between these structures, and their properties are characterized, demonstrating the interplay between the bonding, orientation, and deprotonation reaction of adsorbed species. In particular, it is shown that the degree of deprotonation in TMA overlayers depends on the amount of deposited molecules non-monotonously, and that such behavior is well consistent with the formation mechanism proposed for the TMA/Cu(100) system. The results provide a good platform for further understanding of non-covalent interactions and self-assembly phenomena underlying the growth of supramolecular nanoassemblies of aromatic carboxylic (benzenecarboxylic) acids on metallic substrates.

  15. Effect of self-etching primer/adhesive and conventional bonding on the shear bond strength in metallic and ceramic brackets

    Science.gov (United States)

    Kimyai, Soodabeh; Hydari, Mahboubeh; Shahrbaf, Shirin; Mirzakouchaki-Boroujeni, Parvin

    2012-01-01

    Introduction: Bracket debonding from the tooth surface is a common problem in fixed orthodontics. The aims of the present study were to assess the bond strength and failure sites in two ways of bonding technique, with metallic and ceramic brackets. Material and Methods: One hundred premolars were assigned to 4 groups of 25 each: Group A, metallic brackets/ conventional procedure; Group B, metallic brackets/Transbond XT; Group C, ceramic brackets/conventional procedure; and Group D, ceramic brackets/Transbond XT. Transbond XT composite paste was used for bracket bonding and cured by conventional light-cure device. Specimens were subjected to thermocycling. One week after bonding shearing force was applied to the bracket-tooth interface. Bonding failure site optically examined using a stereomicroscope under 10 × magnifications and scoring was done using the adhesive remnant index (ARI). Data were subjected to analysis of One-way variance, Tukey post hoc, Chi-square and Spearman’s tests. Results: Mean bond strength (in MPa) were: group A=9.2, group B=8.5, group C=6.2 and group D=5.7. Bond strength differences between groups A and B, and between C and D were not significant, (pceramic ones and the selfetching primer produce fewer bonds than the conventional method (clinically acceptable). A positive correlation found between changes in shearing bond strength and ARI. Key words: Acid etching, adhesive remnant index, orthodontic brackets, self-etching primer, shearing bond strength. PMID:21743430

  16. Shear bond strength of the Tenure Solution dentin bonding system.

    Science.gov (United States)

    Barkmeier, W W; Cooley, R L

    1989-10-01

    A liquid solution of an oxalate bonding system containing NTG-GMA and PMDM has become commercially available. The bond strength of this oxalate adhesive (Tenure Solution) to dentin was determined by bonding composite resin cylinders to extracted teeth. The bond strengths obtained in this study are compared to the bond strengths obtained in earlier studies with the first and second generation oxalate adhesives whose components were supplied as powders and required mixing. The oxalate solutions developed significantly higher bond strengths than the original powder type systems.

  17. Micro-tensile bond strength of adhesive systems applied on occlusal primary enamel.

    Science.gov (United States)

    Ramires-Romito, Ana Cláudia; Reis, Alessandra; Loguercio, Alessandro Dourado; de Góes, Mario Fernando; Grande, Rosa Helena Miranda

    2004-01-01

    The aim of this study was to evaluate the micro-tensile bond strength of adhesive systems (OptiBond Solo, Kerr; Prime & Bond NT, Dentsply) on occlusal surface of primary molars. The adhesives were tested under manufacturers' specifications and after contamination of the bonding site with saliva. Hourglass cylindrical-shaped samples were obtained and subjected to a tensile force. No significant difference was observed among the groups. OptiBond Solo and Prime & Bond NT showed similar values of bond strengths when applied on occlusal enamel of primary molar under either saliva contamination or not.

  18. Amide-directed photoredox-catalysed C-C bond formation at unactivated sp3 C-H bonds

    Science.gov (United States)

    Chu, John C. K.; Rovis, Tomislav

    2016-11-01

    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 enable access to molecules that would otherwise be inaccessible and the development of more efficient syntheses of complex molecules. Here 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 amide-directed selective C-C bond formation at unactivated sp3 C-H bonds in molecules that contain many such bonds that are seemingly indistinguishable. Selectivity arises through a relayed photoredox-catalysed oxidation of a nitrogen-hydrogen bond. We anticipate that our findings will serve as a starting point for functionalization at inert C-H bonds through a strategy involving hydrogen-atom transfer.

  19. Bonding in cementitious composites

    Energy Technology Data Exchange (ETDEWEB)

    Mindess, S. (British Columbia Univ., Vancouver, BC (Canada)) Shah, S.P. (Northwestern Univ., Evanston, IL (USA))

    1988-01-01

    These proceedings discuss the papers presented at the symposium on the subject of high performance cement composites. Some of the topics discussed were; calcium hydroxides treated ceramics microspheres and mechanical properties of high temperature light weight cements; microstructure and chemical variations of class F fly ash; microstructure and bond strength of cement and crack propagation as detected by laser holography and acoustic emission.

  20. Photochemical tissue bonding

    Science.gov (United States)

    Redmond, Robert W.; Kochevar, Irene E.

    2012-01-10

    Photochemical tissue bonding methods include the application of a photosensitizer to a tissue and/or tissue graft, followed by irradiation with electromagnetic energy to produce a tissue seal. The methods are useful for tissue adhesion, such as in wound closure, tissue grafting, skin grafting, musculoskeletal tissue repair, ligament or tendon repair and corneal repair.

  1. Thermal Bond System.

    Science.gov (United States)

    1995-10-31

    a twill weave, a crowfoot weave, a satin weave (FIG. 2), and a leno weave. Descriptions of the various weave types can be found in " Composite ...together to define a fabric mesh having first and second opposing woven surfaces. An adhesive bond that is flowable prior to drying is used to wet and

  2. Bonding, Achievement, and Activities: School Bonding, Academic Achievement, and Participation in Extracurricular Activities

    Science.gov (United States)

    Howard, Anissa K.; Ziomek-Daigle, Jolie

    2009-01-01

    Utilizing a single-group interrupted time series design (Creswell, 2003), this pilot study examined the relationship between academic achievement, school bonding, and the extracurricular activity participation of "uninvolved" students (n=11) who participated in a voluntary support group at a suburban high school in the southeast. Results…

  3. Resilient Parenting: Overcoming Poor Parental Bonding

    Science.gov (United States)

    Travis, Wendy J.; Combs-Orme, Terri

    2007-01-01

    This study identified groups of mothers with varying patterns of adaptive functioning and bonds with their own parents. These patterns were related to mothers' parenting of their own children to understand how some mothers avoid repeating the cycle of poor parenting. Data from 210 new mothers were analyzed before hospital discharge about bonding…

  4. 酸处理MWNTs对PBO/环氧界面性能的影响%Influence of MWNTs-COOH on Interface Property of PBO Fiber/Epoxy Composites

    Institute of Scientific and Technical Information of China (English)

    李霞; 黄玉东; 曹海琳; 刘丽; 宋元军

    2008-01-01

    多壁碳纳米管经过强氧化性酸的处理后,经XPS表征结果得出表面含有羧基的碳纳米管(MWNTs-COOH).MWNTs-COOH经过超声处理后放入4,6-二氨基间苯二酚和对苯二甲酸的多聚磷酸体系中,原位聚合得到MWNTs-COOH/聚对苯撑苯并双噁唑(PBO)复合材料,经液晶纺丝得到MWNTs-COOH/PBO纤维.用纤维界面分析仪测试MWNTs-COOH的加入对PBO纤维/环氧树脂界面剪切强度的影响.通过SEM和AFM对纤维的表面形貌进行观察,可看出MWNTs-COOH的加入改善了PBO与环氧树脂的界面强度.

  5. Effect of dentin surface roughness on the shear bond strength of resin bonded restorations

    Science.gov (United States)

    Koodaryan, Roodabeh; Poursoltan, Sajjad

    2016-01-01

    PURPOSE This study aimed to investigate whether dentin surface preparation with diamond rotary instruments of different grit sizes affects the shear bond strength of resin-bonded restorations. MATERIALS AND METHODS The buccal enamel of 60 maxillary central incisors was removed with a low speed diamond saw and wet ground with silicon carbide papers. The polished surfaces of the teeth were prepared with four groups of rotary diamond burs with super-coarse (SC), coarse (C), medium (M), and fine (F) grit sizes. Following surface preparation, 60 restorations were casted with nickel-chromium alloy and bonded with Panavia cement. To assess the shear bond strength, the samples were mounted on a universal testing machine and an axial load was applied along the cement-restoration interface at the crosshead speed of 0.5 mm/min. The acquired data was analyzed with one way ANOVA and Tukey post hoc test (α=.05). RESULTS The mean ± SD shear bond strengths (in MPa) of the study groups were 17.75 ± 1.41 for SC, 13.82 ± 1.13 for C, 10.40 ± 1.45 for M, and 7.13 ± 1.18 for F. Statistical analysis revealed the significant difference among the study groups such that the value for group SC was significantly higher than that for group F (P<.001). CONCLUSION Dentin surface roughness created by diamond burs of different grit sizes considerably influences the shear bond strength of resin bonded restorations. PMID:27350858

  6. On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

    Energy Technology Data Exchange (ETDEWEB)

    Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in [Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore (India); Periyasamy, Ganga [Department of Chemistry, Central College Campus, Bangalore University, Bangalore (India)

    2015-06-28

    In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.

  7. Effects of functional groups and soluble matrices in fish otolith on calcium carbonate mineralization

    Energy Technology Data Exchange (ETDEWEB)

    Ren Dongni; Li Zhuo; Gao Yonghua; Feng Qingling, E-mail: biomater@mail.tsinghua.edu.c [State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China)

    2010-10-01

    Calcium carbonate mineralization is significantly influenced by organic matrices in vivo. The effect mainly relies on functional groups in proteins. In order to study the influence of functional groups on calcium carbonate mineralization, -OH, -NH{sub 2} and -COOH groups were grafted onto single crystal silicon chips, and such modified chips were used as substrates in in vitro mineralization experiments. An x-ray photoelectron spectroscopy (XPS) test was conducted to examine the grafting efficiency, and the three groups were successfully grafted. Calcium carbonate mineralization on a modified silicon substrate was examined by a scanning electron microscope (SEM) and x-ray diffraction (XRD), and the results showed that the effects of -OH, -NH{sub 2} and -COOH groups were quite different. Furthermore, a water-soluble protein matrix (WSM) and an acid-soluble protein matrix (ASM) extracted from fish otolith were adsorbed onto the -COOH-modified silicon substrate, and the effects of the protein matrices on calcium carbonate mineralization were studied. The results showed that both WSM and ASM of lapillus could mediate aragonite crystallization, but the size and morphology of the formed crystals were different. The WSM and ASM of asteriscus adsorbed on the silicon substrate had little effect on calcium carbonate mineralization; almost all the crystals were calcite, while both asteriscus WSM and ASM in solution could mediate vaterite crystals, and the morphologies of vaterite crystal aggregates were different.

  8. EFFECTS OF POTASSIUM NITRATE ON SHEAR BOND STRENGTH OF BRACKETS

    OpenAIRE

    Carrillo Barreto, Diana; Duarte Gómez, Diana; González Acuña, María E.; Madero Gómez, Sandra M.; Morales García, Harold; Delgado, Linda P.; Ordóñez Monak, Ivonne

    2014-01-01

    Introduction: During 2010 the degree research “Effects of potassium nitrate on shear bond strength of brackets” was carried out at Universidad Cooperativa de Colombia in Bogota. Objective: To determine whether the use of desensitizing with potassium nitrate affects the bond bracket strength to enamel. Materials and Methods: Forty-five human premolar teeth were randomly allocated in three groups (n = 15 each). Group 1: control (not treated), Group 2: desensitizer treated and after 24-hour brac...

  9. Bonding Ni-Cr alloy to tooth structure with adhesive resin cements.

    Science.gov (United States)

    Penugonda, B; Scherer, W; Cooper, H; Kokoletsos, N; Koifman, V

    1992-01-01

    This study was to determine the shear bond strengths of Ni-Cr alloy to Ni-Cr alloy (Group I), Ni-Cr alloy to enamel (Group II), and Ni-Cr alloy to dentin (Group III) using Imperva Dual, DC Metabond, All-Bond, Geristore, and Panavia. All bonded specimens were thermocycled 2000 x (5 degrees C-55 degrees C) after 24 hours and subjected to shear bond testing on a Universal Instron Testing Machine. In all groups of the study, Imperva Dual and CB Metabond had significantly (p bond values than Panavia.

  10. Trading in Treasury Bond Futures Contracts and Bonds in Australia

    OpenAIRE

    Belinda Cheung

    2014-01-01

    Treasury bond futures are a key financial product in Australia, with turnover in Treasury bond futures contracts significantly larger than turnover in the market for Commonwealth Government securities (CGS). Treasury bond futures contracts provide a wide variety of market participants with the ability to hedge against, or gain exposure to, interest rate risk. This article discusses some of the features of the Treasury bond futures contract, and how the contract is used to facilitate hedging a...

  11. Predictions of Glass Transition Temperature for Hydrogen Bonding Biomaterials

    NARCIS (Netherlands)

    Sman, van der R.G.M.

    2013-01-01

    We show that the glass transition of a multitude of mixtures containing hydrogen bonding materials correlates strongly with the effective number of hydroxyl groups per molecule, which are available for intermolecular hydrogen bonding. This correlation is in compliance with the topological constraint

  12. Indirect bonding technique in orthodontics

    Directory of Open Access Journals (Sweden)

    Kübra Yıldırım

    2016-08-01

    Full Text Available ‘Direct Bonding Technique’ which allows the fixed orthodontic appliances to be directly bonded to teeth without using bands decreased the clinic time for bracket bonding and increased esthetics and oral hygiene during orthodontic treatment. However, mistakes in bracket positioning were observed due to decreased direct visual sight and access to posterior teeth. ‘Indirect Bonding Technique’ was developed for eliminating these problems. Initially, decreased bond strength, higher bond failure rate, periodontal tissue irritation, compromised oral hygiene and increased laboratory time were the main disadvantages of this technique when compared to direct bonding. The newly developed materials and modified techniques help to eliminate these negative consequences. Today, the brackets bonded with indirect technique have similar bond strength with brackets bonded directly. Moreover, indirect and direct bonding techniques have similar effects on periodontal tissues. However, indirect bonding technique requires more attention and precision in laboratory and clinical stage, and has higher cost. Orthodontist's preference between these two bonding techniques may differ according to time spent in laboratory and clinic, cost, patient comfort and personal opinion.

  13. The Evaluation of a Resin-modified Glass Ionome Cement for Bonding Orthodontic Brackets

    Institute of Scientific and Technical Information of China (English)

    LI Fujun; PENG Youjian; PENG Bin

    2009-01-01

    To evaluate the shear bond strength(SBS)and bond failure interface after the debonding of orthodontic brackets with a resin-modified glass ionomer cement(RMGIC)under six bonding conditions,140 premolar teeth were randomly divided into seven groups.The brackets of all groups,except for control group,were bonded using a RMGIC.The teeth were debonded using a universal testing machine.The shear bond strength,adhesive remnant index(ARI)and enamel fracture were examined for each debonding.A significant difference existed in SBS under wet and dry condi-tions in two groups of Fuji Ortho LC.Different degree of enamel fracture was seen in groups of Fuji Ortho LC(dry/37%phosphoric acid treated)after debonding.Bond failed predominantly at the enamel-adhesive interface,except for phosphoric acid treated groups.The RMGIC achieve a clinically effective adhesion in orthodontics under different bonding conditions.

  14. Shear Bond Strengths of Different Adhesive Systems to Biodentine

    Directory of Open Access Journals (Sweden)

    Mesut Enes Odabaş

    2013-01-01

    Full Text Available The aim of this study was to measure the shear bond strength of different adhesive systems to Biodentine with different time intervals. Eighty specimens of Biodentine were prepared and divided into 8 groups. After 12 minutes, 40 samples were randomly selected and divided into 4 groups of 10 each: group 1: (etch-and-rinse adhesive system Prime & Bond NT; group 2: (2-step self-etch adhesive system Clearfil SE Bond; group 3: (1-step self-etch adhesive systems Clearfil S3 Bond; group 4: control (no adhesive. After the application of adhesive systems, composite resin was applied over Biodentine. This procedure was repeated 24 hours after mixing additional 40 samples, respectively. Shear bond strengths were measured using a universal testing machine, and the data were subjected to 1-way analysis of variance and Scheffé post hoc test. No significant differences were found between all of the adhesive groups at the same time intervals (12 minutes and 24 hours (. Among the two time intervals, the lowest value was obtained for group 1 (etch-and-rinse adhesive at a 12-minute period, and the highest was obtained for group 2 (two-step self-etch adhesive at a 24-hour period. The placement of composite resin used with self-etch adhesive systems over Biodentine showed better shear bond strength.

  15. Shear bond strengths of different adhesive systems to biodentine.

    Science.gov (United States)

    Odabaş, Mesut Enes; Bani, Mehmet; Tirali, Resmiye Ebru

    2013-01-01

    The aim of this study was to measure the shear bond strength of different adhesive systems to Biodentine with different time intervals. Eighty specimens of Biodentine were prepared and divided into 8 groups. After 12 minutes, 40 samples were randomly selected and divided into 4 groups of 10 each: group 1: (etch-and-rinse adhesive system) Prime & Bond NT; group 2: (2-step self-etch adhesive system) Clearfil SE Bond; group 3: (1-step self-etch adhesive systems) Clearfil S(3) Bond; group 4: control (no adhesive). After the application of adhesive systems, composite resin was applied over Biodentine. This procedure was repeated 24 hours after mixing additional 40 samples, respectively. Shear bond strengths were measured using a universal testing machine, and the data were subjected to 1-way analysis of variance and Scheffé post hoc test. No significant differences were found between all of the adhesive groups at the same time intervals (12 minutes and 24 hours) (P > .05). Among the two time intervals, the lowest value was obtained for group 1 (etch-and-rinse adhesive) at a 12-minute period, and the highest was obtained for group 2 (two-step self-etch adhesive) at a 24-hour period. The placement of composite resin used with self-etch adhesive systems over Biodentine showed better shear bond strength.

  16. Shear Bond Strengths of Different Adhesive Systems to Biodentine

    Science.gov (United States)

    Odabaş, Mesut Enes; Bani, Mehmet; Tirali, Resmiye Ebru

    2013-01-01

    The aim of this study was to measure the shear bond strength of different adhesive systems to Biodentine with different time intervals. Eighty specimens of Biodentine were prepared and divided into 8 groups. After 12 minutes, 40 samples were randomly selected and divided into 4 groups of 10 each: group 1: (etch-and-rinse adhesive system) Prime & Bond NT; group 2: (2-step self-etch adhesive system) Clearfil SE Bond; group 3: (1-step self-etch adhesive systems) Clearfil S3 Bond; group 4: control (no adhesive). After the application of adhesive systems, composite resin was applied over Biodentine. This procedure was repeated 24 hours after mixing additional 40 samples, respectively. Shear bond strengths were measured using a universal testing machine, and the data were subjected to 1-way analysis of variance and Scheffé post hoc test. No significant differences were found between all of the adhesive groups at the same time intervals (12 minutes and 24 hours) (P > .05). Among the two time intervals, the lowest value was obtained for group 1 (etch-and-rinse adhesive) at a 12-minute period, and the highest was obtained for group 2 (two-step self-etch adhesive) at a 24-hour period. The placement of composite resin used with self-etch adhesive systems over Biodentine showed better shear bond strength. PMID:24222742

  17. Routes to Hydrogen Bonding Chain-End Functionalized Polymers.

    Science.gov (United States)

    Bertrand, Arthur; Lortie, Frédéric; Bernard, Julien

    2012-12-21

    The contribution of supramolecular chemistry to polymer science opens new perspectives for the design of polymer materials exhibiting valuable properties and easier processability due to the dynamic nature of non-covalent interactions. Hydrogen bonding polymers can be used as supramolecular units for yielding larger assemblies that possess attractive features, arising from the combination of polymer properties and the responsiveness of hydrogen bonds. The post-polymerization modification of reactive end-groups is the most common procedure for generating such polymers. Examples of polymerizations mediated by hydrogen bonding-functionalized precursors have also recently been reported. This contribution reviews the current synthetic routes toward hydrogen bonding sticker chain-end functionalized polymers.

  18. Symmetry in bonding and spectra an introduction

    CERN Document Server

    Douglas, Bodie E

    1985-01-01

    Many courses dealing with the material in this text are called ""Applications of Group Theory."" Emphasizing the central role and primary importance of symmetry in the applications, Symmetry in Bonding and Spectra enables students to handle applications, particularly applications to chemical bonding and spectroscopy. It contains the essential background in vectors and matrices for the applications, along with concise reviews of simple molecular orbital theory, ligand field theory, and treatments of molecular shapes, as well as some quantum mechanics. Solved examples in the text illustra

  19. Biocompatible "click" wafer bonding for microfluidic devices.

    Science.gov (United States)

    Saharil, Farizah; Carlborg, Carl Fredrik; Haraldsson, Tommy; van der Wijngaart, Wouter

    2012-09-07

    We introduce a novel dry wafer bonding concept designed for permanent attachment of micromolded polymer structures to surface functionalized silicon substrates. The method, designed for simultaneous fabrication of many lab-on-chip devices, utilizes a chemically reactive polymer microfluidic structure, which rapidly bonds to a functionalized substrate via"click" chemistry reactions. The microfluidic structure consists of an off-stoichiometry thiol-ene (OSTE) polymer with a very high density of surface bound thiol groups and the substrate is a silicon wafer that has been functionalized with common bio-linker molecules. We demonstrate here void free, and low temperature (silane functionalized silicon wafer.

  20. Wafer bonding using Cu-Sn intermetallic bonding layers

    NARCIS (Netherlands)

    Flötgen, C.; Pawlak, M.; Pabo, E.; Wiel, H.J. van de; Hayes, G.R.; Dragoi, V.

    2014-01-01

    Wafer-level Cu-Sn intermetallic bonding is an interesting process for advanced applications in the area of MEMS and 3D interconnects. The existence of two intermetallic phases for Cu-Sn system makes the wafer bonding process challenging. The impact of process parameters on final bonding layer

  1. The bond length and bond energy of gaseous CrW.

    Science.gov (United States)

    Matthew, Daniel J; Oh, Sang Hoon; Sevy, Andrew; Morse, Michael D

    2016-06-07

    Supersonically cooled CrW was studied using resonant two-photon ionization spectroscopy. The vibronically resolved spectrum was recorded over the region 21 100 to 23 400 cm(-1), showing a very large number of bands. Seventeen of these bands, across three different isotopologues, were rotationally resolved and analyzed. All were found to arise from the ground (1)Σ(+) state of the molecule and to terminate on states with Ω' = 0. The average r0 bond length across the three isotopic forms was determined to be 1.8814(4) Å. A predissociation threshold was observed in this dense manifold of vibronic states at 23 127(10) cm(-1), indicating a bond dissociation energy of D0(CrW) = 2.867(1) eV. Using the multiple bonding radius determined for atomic Cr in previous work, the multiple bonding radius for tungsten was calculated to be 1.037 Å. Comparisons are made between CrW and the previously investigated group 6 diatomic metals, Cr2, CrMo, and Mo2, and to previous computational studies of this molecule. It is also found that the accurately known bond dissociation energies of group 5/6 metal diatomics Cr2, V2, CrW, NbCr, VNb, Mo2, and Nb2 display a qualitative linear dependence on the sum of the d-orbital radial expectation values, r; this relationship allows the bond dissociation energies of other molecules of this type to be estimated.

  2. Development and validation of an automated liquid-liquid extraction GC/MS method for the determination of THC, 11-OH-THC, and free THC-carboxylic acid (THC-COOH) from blood serum.

    Science.gov (United States)

    Purschke, Kirsten; Heinl, Sonja; Lerch, Oliver; Erdmann, Freidoon; Veit, Florian

    2016-06-01

    The analysis of Δ(9)-tetrahydrocannabinol (THC) and its metabolites 11-hydroxy-Δ(9)-tetrahydrocannabinol (11-OH-THC), and 11-nor-9-carboxy-Δ(9)-tetrahydrocannabinol (THC-COOH) from blood serum is a routine task in forensic toxicology laboratories. For examination of consumption habits, the concentration of the phase I metabolite THC-COOH is used. Recommendations for interpretation of analysis values in medical-psychological assessments (regranting of driver's licenses, Germany) include threshold values for the free, unconjugated THC-COOH. Using a fully automated two-step liquid-liquid extraction, THC, 11-OH-THC, and free, unconjugated THC-COOH were extracted from blood serum, silylated with N-methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA), and analyzed by GC/MS. The automation was carried out by an x-y-z sample robot equipped with modules for shaking, centrifugation, and solvent evaporation. This method was based on a previously developed manual sample preparation method. Validation guidelines of the Society of Toxicological and Forensic Chemistry (GTFCh) were fulfilled for both methods, at which the focus of this article is the automated one. Limits of detection and quantification for THC were 0.3 and 0.6 μg/L, for 11-OH-THC were 0.1 and 0.8 μg/L, and for THC-COOH were 0.3 and 1.1 μg/L, when extracting only 0.5 mL of blood serum. Therefore, the required limit of quantification for THC of 1 μg/L in driving under the influence of cannabis cases in Germany (and other countries) can be reached and the method can be employed in that context. Real and external control samples were analyzed, and a round robin test was passed successfully. To date, the method is employed in the Institute of Legal Medicine in Giessen, Germany, in daily routine. Automation helps in avoiding errors during sample preparation and reduces the workload of the laboratory personnel. Due to its flexibility, the analysis system can be employed for other liquid-liquid extractions as

  3. Role of bonding agents in the repair of composite resin restorations.

    Science.gov (United States)

    Staxrud, Frode; Dahl, Jon E

    2011-08-01

    Six commonly used composite resin materials and recommended bonding systems were tested to assess shear bond strength at the interface between aged and new composites with and without bonding. Test specimens were aged in water for 60 d before new composite was placed. Shear bond strength was assessed after 22 ± 2 h (Test 1) and after additional ageing by thermocycling (5-55°C/5,000 cycles) (Test 2). After an additional 180 d in water, the aged specimens were randomly divided into three groups to blind the test with respect to the aged composite. New composites were placed on aged specimens (two groups with and one without bonding agent) and thermocycled (Test 3). After 24 h (Test 1), the mean shear bond strength of the test specimens was 21-26 MPa when bonding agents were used, as opposed to 10-15 MPa without bonding agents. After thermocycling (Test 2), the mean shear bond strength was 16-23 MPa with a bonding agent and 17 MPa without a bonding agent. After 180 d in water and subsequent thermocycling (Test 3), the mean shear bond strength was 9-13 MPa with bonding agent and 2-3 MPa when no bonding agent was used. The results of this study therefore indicate that the use of bonding agents significantly improves the quality of composite repair.

  4. China-Russia Bond

    Institute of Scientific and Technical Information of China (English)

    Ji Zhiye; Ma Zongshi

    2007-01-01

    @@ Thanks to China's successful launching of the Year of Russia, 2006 will surely go down as a milestone in the history of the China-Russia bond. Furthermore, a still-warmer climate will continue to prevail in 2007 when Moscow, in its turn, hosts the Year of China, trying to outshine its next-door neighbor in this regard, as Russian President Vladimir Putin promised in the exchange of new year greetings with his Chinese counterpart, President Hu Jintao.

  5. Bonding of acrylic denture teeth to resin denture bases.

    Science.gov (United States)

    Geerts, G A V M; Stuhlinger, M E

    2012-07-01

    Anterior teeth debonding from dentures is a common problem. This study tested the bond strength of denture teeth to two types of denture resin, with and without grooving the ridge-lap surface. Bond strength and fracture type of three different groups were compared: 1. Teeth bonded to heat-cured polymethyl methacrylate (PMMA); 2. Teeth bonded to pour-type PMMA; 3. Grooved teeth bonded to pour-type PMMA. Specimens were manufactured following ISO standard 22112. Force values at failure were analysed using one-way analysis of variance, using the mixed procedure with confidence interval of 95%. Types of failure were identified as adhesive, cohesive or combination. In descending order, mean failure forces were 418.55N (Group One), 367.55N (Group Two) and 290.05N (Group Three). There was no significant difference between the means of groups 1 and 2 (p = 0.0627). Group Three differed from both other groups (p denture teeth (83% and 72% respectively); group Three showed predominantly cohesive fractures within the denture PMMA (75%). Without ridge-lap modification, the bond strengths of denture teeth to pour-type and heat-cured denture resin were similar. Failures were predominantly of cohesive nature within the teeth themselves. Grooving the ridge-lap reduced fracture resistance and led to breakages predominantly in denture PMMA.

  6. Coulombic Models in Chemical Bonding.

    Science.gov (United States)

    Sacks, Lawrence J.

    1986-01-01

    Compares the coulumbic point charge model for hydrogen chloride with the valence bond model. It is not possible to assign either a nonpolar or ionic canonical form of the valence bond model, while the covalent-ionic bond distribution does conform to the point charge model. (JM)

  7. Optimal Investment in Structured Bonds

    DEFF Research Database (Denmark)

    Jessen, Pernille; Jørgensen, Peter Løchte

    The paper examines the role of structured bonds in the optimal portfolio of a small retail investor. We consider the typical structured bond essentially repacking an exotic option and a zero coupon bond, i.e. an investment with portfolio insurance. The optimal portfolio is found when the investment...

  8. Mittal bonded tongue thrusting appliance

    Directory of Open Access Journals (Sweden)

    Rekha Mittal

    2014-01-01

    Full Text Available These days majority of orthodontist includes bonded molar attachment in their inventory to eliminate the discomfort of molar separation during initial appointment and band spaces left at the end of treatment. This article describes a innovative and economical method of attachment of bonded tongue crib if required during the initial or later stages of treatment along with bonded molar tubes.

  9. Evaluation of zirconia bonding to veneering porcelain

    Directory of Open Access Journals (Sweden)

    Aneta Mijoska

    2014-10-01

    Full Text Available Zirconium dioxide as core ceramic material for dental crowns and bridges, possess high strength, chemical stability and superior aesthetics after veneering. Veneering ceramic is considered to be the weakest part of all-ceramic restorations. The adhesion between the core and veneering porcelain is based on the manner in which the connection occurs in metal-ceramic structures. Standard procedures for connecting zirconia to hard dental tissues and veneering materials do not achieve the required strength of bonding. The aim of the paper is to investigate different surface treatments of the zirconium dioxide ceramic core and find the best, for achieving highest adhesive bonding values to veneering porcelain. The study was primarily designed to investigate the bonding strength of the veneering porcelain to zirconia with in vitro Macro shear bond strength test. The specimens with different surface treatment of the zirconia were divided in five groups of twelve according to the treatment of zirconium surface and results showed highest bonding values for specimens treated with Rocatec system.

  10. Reduced peptide bond pseudopeptide analogues of neurotensin.

    Science.gov (United States)

    Doulut, S; Rodriguez, M; Lugrin, D; Vecchini, F; Kitabgi, P; Aumelas, A; Martinez, J

    1992-01-01

    Pseudopeptide analogues of the C-terminal hexapeptide of neurotensin (H-Arg-Arg-Pro-Tyr-Ile-Leu-OH) were obtained by replacing each peptide bond by the reduced peptide bond CH2NH. The resulting analogues were then examined for their ability to inhibit binding of labeled neurotensin to new-born mouse brain membranes and for stimulation of guinea pig ileum contraction. Replacement of the Ile12-Leu13, Tyr11-Ile12, Pro10-Tyr11 and Lys9-Pro10 peptide bonds resulted in about 2000-, 3400-, 200- and 3400-fold losses, respectively, in binding affinity and 400-, 750-, 250- and 300-fold losses, respectively, in biological activity. Replacement of both Arg8 and Arg9 by lysine led to an analogue exhibiting the same pharmacological profile as the C-terminal hexapeptide of neurotensin. Interestingly, replacement of the Lys8-Lys9 peptide bond by the CH2NH bond produced an analogue exhibiting the same affinity for neurotensin receptors, but 10 times more potent in stimulating guinea pig ileum contraction. N-terminal protected analogues (by the Boc group) showed decreased potency as compared with their amino-free corresponding compounds.

  11. Electronic structure and bonding in crystalline peroxides

    Science.gov (United States)

    Königstein, Markus; Sokol, Alexei A.; Catlow, C. Richard A.

    1999-08-01

    Hartree-Fock and density-functional PW91 theories as realized in the CRYSTAL95 code have been applied to investigate the structural and electronic properties of Ba, Sr, and Ca peroxide materials with the calcium carbide crystal structure, results for which are compared with those for the corresponding oxides. Special attention is paid to the stabilization of the peroxide molecular ion O2-2 in the ionic environment provided by the lattice, and to chemical bonding effects. In order to describe the covalent bonding within the O2-2 ion and the polarization of the O- ion in the crystal electrostatic field, it is essential to include an account of the effects of electron correlation. The PW91 density functional has allowed us to reproduce the crystallographic parameters within a 3% error. The chemical bonding within the peroxide molecular ion has a complex nature with a balance between the weak covalent bond of σz type and the strong electrostatic repulsion of the closed-shell electron groups occupying O 2s and O 2px and 2py states. Compression of the peroxide ion in the ionic crystals gives rise to an excessive overlap of the O 2s closed shells of the two O- ions of a peroxide molecular ion O2-2, which in turn determines the antibonding character of the interaction and chemical bonding in the O2-2 molecular ion.

  12. Evaluation of enamel damages following orthodontic bracket debonding in fluorosed teeth bonded with adhesion promoter.

    Science.gov (United States)

    Baherimoghadam, Tahreh; Akbarian, Sahar; Rasouli, Reza; Naseri, Navid

    2016-01-01

    To evaluate shear bond strength (SBS) of the orthodontic brackets bonded to fluorosed and nonfluorosed teeth using Light Bond with and without adhesion promoters and compare their enamel damages following debonding. In this study, 30 fluorosed (Thylstrup and Fejerskov Index = 4-5) and 30 nonfluorosed teeth were randomly distributed between two subgroups according to the bonding materials: Group 1, fluorosed teeth bonded with Light Bond; Group 2, fluorosed teeth bonded with adhesion promoters and Light Bond; Group 3, nonfluorosed teeth bonded with Light Bond; Group 4, nonfluorosed bonded with adhesion promoters and Light Bond. After bonding, the SBS of the brackets was tested with a universal testing machine. Stereomicroscopic evaluation was performed by unbiased stereology in all teeth to determine the amount of adhesive remnants and the number and length of enamel cracks before bonding and after debonding. The data were analyzed using two-way analysis of variance, Kruskal-Wallis, Wilcoxon Signed Rank, and Mann-Whitney test. While fluorosis reduced the SBS of orthodontic bracket (P = 0.017), Enhance Locus Ceruleus LC significantly increased the SBS of the orthodontic bracket in fluorosed and nonfluorosed teeth (P = 0.039). Significant increasing in the number and length of enamel crack after debonding was found in all four groups. There were no significant differences in the length of enamel crack increased after debonding among four groups (P = 0.768) while increasing in the number of enamel cracks after debonding was significantly different among the four groups (P = 0.023). Teeth in Group 2 showed the highest enamel damages among four groups following debonding. Adhesion promoters could improve the bond strength of orthodontic brackets, but conservative debonding methods for decreasing enamel damages would be necessary.

  13. Evaluation of enamel damages following orthodontic bracket debonding in fluorosed teeth bonded with adhesion promoter

    Science.gov (United States)

    Baherimoghadam, Tahreh; Akbarian, Sahar; Rasouli, Reza; Naseri, Navid

    2016-01-01

    Objective: To evaluate shear bond strength (SBS) of the orthodontic brackets bonded to fluorosed and nonfluorosed teeth using Light Bond with and without adhesion promoters and compare their enamel damages following debonding. Materials and Methods: In this study, 30 fluorosed (Thylstrup and Fejerskov Index = 4–5) and 30 nonfluorosed teeth were randomly distributed between two subgroups according to the bonding materials: Group 1, fluorosed teeth bonded with Light Bond; Group 2, fluorosed teeth bonded with adhesion promoters and Light Bond; Group 3, nonfluorosed teeth bonded with Light Bond; Group 4, nonfluorosed bonded with adhesion promoters and Light Bond. After bonding, the SBS of the brackets was tested with a universal testing machine. Stereomicroscopic evaluation was performed by unbiased stereology in all teeth to determine the amount of adhesive remnants and the number and length of enamel cracks before bonding and after debonding. The data were analyzed using two-way analysis of variance, Kruskal–Wallis, Wilcoxon Signed Rank, and Mann–Whitney test. Results: While fluorosis reduced the SBS of orthodontic bracket (P = 0.017), Enhance Locus Ceruleus LC significantly increased the SBS of the orthodontic bracket in fluorosed and nonfluorosed teeth (P = 0.039). Significant increasing in the number and length of enamel crack after debonding was found in all four groups. There were no significant differences in the length of enamel crack increased after debonding among four groups (P = 0.768) while increasing in the number of enamel cracks after debonding was significantly different among the four groups (P = 0.023). Teeth in Group 2 showed the highest enamel damages among four groups following debonding. Conclusion: Adhesion promoters could improve the bond strength of orthodontic brackets, but conservative debonding methods for decreasing enamel damages would be necessary. PMID:27095895

  14. Transition-Metal-Catalyzed C-H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds.

    Science.gov (United States)

    Hummel, Joshua R; Boerth, Jeffrey A; Ellman, Jonathan A

    2016-12-12

    The transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds has emerged as a particularly efficient and powerful approach for the construction of an incredibly diverse array of heteroatom-substituted products. Readily available and stable inputs are typically employed, and reactions often proceed with very high functional group compatibility and without the production of waste byproducts. Additionally, many transition-metal-catalyzed C-H bond additions to polarized π bonds occur within cascade reaction sequences to provide rapid access to a diverse array of different heterocyclic as well as carbocyclic products. This review highlights the diversity of transformations that have been achieved, catalysts that have been used, and types of products that have been prepared through the transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds.

  15. [The adhesive properties of two bonding systems to tetracycline stained dentin].

    Science.gov (United States)

    Liu, H L; Liang, K N; Cheng, L; Li, J Y; He, L B

    2016-01-01

    To investigate and compare the bonding properties of Single Bond 2 and SE Bond to tetracycline stained dentin in vitro. Ten extracted tetracycline stained human teeth and ten extracted normal human teeth were collected and the occlusal dentin surfaces of all extracted teeth were exposed. The tetracycline stained teeth and normal teeth were divided into two groups, respectively and randomly, based on the adhesives applied. Total-etch adhesive(Single Bond 2) and self-etch adhesive(SE Bond) were used. After application of the adhesives to the dentin surfaces, composite crowns were built up. After 24 h water storage, the teeth were sectioned longitudinally into sticks(0.9 mm×0.9 mm bonding area) for micro tensile testing or micro Raman spectroscopy detection. Bonding strength(μTBS) and resin conversion rate were analyzed using one-way ANOVA. The tetracycline Single Bond 2 group presented lower bonding strength[(16.17 ± 3.16) MPa] than the tetracycline SE Bond group[(25.82 ± 2.62) MPa], and also demonstrated lower bonding strength than the normal Single Bond 2 group[(29.13 ± 2.44) MPa] and the normal SE Bond group[(24.29±2.83) MPa] (P0.05). The resin conversion rate of tetracycline Single Bond 2 group[(55±6)%] was significantly lower than the tetracycline SE Bond group[(66±3)% ](P0.05). The bonding strength of total-etch adhesive system to the tetracycline stained dentin was significantly lower than that to the normal dentin.

  16. The chemical bond in inorganic chemistry the bond valence model

    CERN Document Server

    Brown, I David

    2016-01-01

    The bond valence model is a version of the ionic model in which the chemical constraints are expressed in terms of localized chemical bonds formed by the valence charge of the atoms. Theorems derived from the properties of the electrostatic flux predict the rules obeyed by both ionic and covalent bonds. They make quantitative predictions of coordination number, crystal structure, bond lengths and bond angles. Bond stability depends on the matching of the bonding strengths of the atoms, while the conflicting requirements of chemistry and space lead to the structural instabilities responsible for the unusual physical properties displayed by some materials. The model has applications in many fields ranging from mineralogy to molecular biology.

  17. How universal are hydrogen bond correlations? A density functional study of intramolecular hydrogen bonding in low-energy conformers of α-amino acids

    Science.gov (United States)

    Ramaniah, Lavanya M.; Kamal, C.; Kshirsagar, Rohidas J.; Chakrabarti, Aparna; Banerjee, Arup

    2013-10-01

    Hydrogen bonding is one of the most important and ubiquitous interactions present in Nature. Several studies have attempted to characterise and understand the nature of this very basic interaction. These include both experimental and theoretical investigations of different types of chemical compounds, as well as systems subjected to high pressure. The O-H..O bond is of course the best studied hydrogen bond, and most studies have concentrated on intermolecular hydrogen bonding in solids and liquids. In this paper, we analyse and characterise normal hydrogen bonding of the general type, D-H...A, in intramolecular hydrogen bonding interactions. Using a first-principles density functional theory approach, we investigate low energy conformers of the twenty α-amino acids. Within these conformers, several different types of intramolecular hydrogen bonds are identified. The hydrogen bond within a given conformer occurs between two molecular groups, either both within the backbone itself, or one in the backbone and one in the side chain. In a few conformers, more than one (type of) hydrogen bond is seen to occur. Interestingly, the strength of the hydrogen bonds in the amino acids spans quite a large range, from weak to strong. The signature of hydrogen bonding in these molecules, as reflected in their theoretical vibrational spectra, is analysed. With the new first-principles data from 51 hydrogen bonds, various parameters relating to the hydrogen bond, such as hydrogen bond length, hydrogen bond angle, bond length and vibrational frequencies are studied. Interestingly, the correlation between these parameters in these bonds is found to be in consonance with those obtained in earlier experimental studies of normal hydrogen bonds on vastly different systems. Our study provides some of the most detailed first-principles support, and the first involving vibrational frequencies, for the universality of hydrogen bond correlations in materials.

  18. Effect of Adhesive Type on the Shear Bond Strength of Metal Brackets to Two Ceramic Substrates

    Directory of Open Access Journals (Sweden)

    Mohammad Sadegh Ahmad Akhoundi

    2014-04-01

    Full Text Available Increased number of adult patients requesting orthodontic treatment result in bonding bracket to ceramic restorations more than before. The aim of this study was to evaluate and compare the shear bond strength of orthodontic brackets bonded to two types of ceramic bases with conventional orthodontic bonding resin and a new nano-filled composite resin.Twenty four feldespathic porcelain and 24 lithium disilicate ceramic disks were fabricated. All of the samples were conditioned by sandblasting, hydrofluoric acid and silane. Maxillary incisor metal brackets were bonded to half of the disks in each group by conventional orthodontic bonding resin and the other half bonded with a nano-filled composite. The samples then were thermocycled for 2000 cycle between 5-55° C. Shear bond strength was measured and the mode of failure was examined. Randomly selected samples were also evaluated by SEM.The lowest bond strength value was found infeldespathic ceramic bonded by nano-filled composite (p<0.05. There was not any statistically significant difference between other groups regarding bond strength. The mode of failure in the all groups except group 1 was cohesive and porcelain damages were detected.Since less damages to feldspathic porcelain was observed when the nano-filled composite was used to bond brackets, the use of nano-filled composite resins can be suggested for bonding brackets to feldspathic porcelain restorations.

  19. Shear bond strength of precoated orthodontic brackets: an in vivo study

    Directory of Open Access Journals (Sweden)

    Ali H Hassan

    2010-06-01

    Full Text Available Ali H HassanDepartment of Preventive Dental Sciences, Faculty of Dentistry, King Abdulaziz University, Jeddah, Saudi ArabiaObjective: To evaluate the shear bond strength of precoated orthodontic brackets bonded with self-etching primer relative to that of noncoated conventionally-bonded brackets at two different time intervals.Methods: Twenty-one subjects were selected for randomized split-mouth bonding of two types of brackets to the maxillary arch. Half of the teeth had precoated brackets bonded using selfetching adhesive, and the other half had regular brackets bonded using Transbond XT adhesive. Nitinol wires were tied to the upper arch and were left until the time of debonding. The patients were randomly divided into two groups: one debonded after one hour and the other debonded two weeks after the initial wire placement. The shear bond strength was directly recorded from the patients’ mouths using an in vivo debonding device.Results: There were no significant differences in shear bond strength between the precoated and conventional groups or within each group at different time intervals. There were significant differences between anterior and posterior teeth in both the precoated and conventional groups. Conclusion: Pre-coated brackets bonded with self-etching adhesive have the same bonding strength as the conventionally bonded brackets.Keywords: shear bond, bonding, orthodontics, precoated, brackets, self-etching adhesive

  20. Forced twin-chair conformation in 7-benzoyl- and 7-phenylacetyl-r-2,c-4,t-6,t-8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonanes with 1,3-diaxial phenyl groups in the piperidine ring: single- and double-layered supramolecular sheets built from C-H...O and C-H...pi(arene) hydrogen bonds.

    Science.gov (United States)

    Sakthivel, Chinniah; Jeyaraman, Ramasubbu

    2010-08-01

    The crystal structures of 7-benzoyl-r-2,c-4,t-6,t-8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonane, C(38)H(33)NOS, (I), and r-2,c-4,t-6,t-8-tetraphenyl-7-phenylacetyl-3-thia-7-azabicyclo[3.3.1]nonane [systematic name: 2-phenyl-1-(r-2,c-4,t-6,t-8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonan-7-yl)ethanone], C(39)H(35)NOS, (II), both reveal a forced twin-chair conformation with the 1,3-diaxial phenyl groups in the piperidine ring, and flattening at the N-atom end of the piperidine ring of the bicyclic system. In the crystal structure of (I), molecules are linked into sheets by a combination of two weak C-H...O and one C-H...pi(arene) hydrogen bond, while in the crystal structure of (II), the molecules extend into double-layered sheets assisted by three C-H...pi(arene) hydrogen bonds.

  1. Bond strength of composite resin to enamel: assessment of two ethanol wet-bonding techniques.

    Directory of Open Access Journals (Sweden)

    Maryam Khoroushi

    2014-04-01

    Full Text Available Ethanol wet-bonding (EWB technique has been stated to decrease degradation of resin-dentin bond. This study evaluated the effect of two EWB techniques on composite resin-to-enamel bond strength.Silicon carbide papers were used to produce flat enamel surfaces on the buccal faces of forty-five molars. OptiBond FL (OFL adhesive was applied on enamel surfaces in three groups of 15 namely: Enamel surface and OFL (control;Protocol 1 of the EWB technique: absolute ethanol was applied to water-saturated acid-etched enamel surfaces for 1 minute before the application of ethanol-solvated hydrophobic adhesive resin of OFL 3 times;Protocol 2: progressive ethanol replacement; water was gradually removed from the enamel matrix using ascending ethanol concentrations before OFL application. Composite build-ups were made and the specimens were stored for 24 hours at 37°C and 100% relative humidity. Shear bond strength test was performed using a universal testing machine at 1 mm/min crosshead speed. Fracture patterns were evaluated microscopically. Data were analyzed with one-way ANOVA and Fisher's exact test (α=0.05.There were no significant differences in bond strength between the groups (P=0.73. However, regarding failure patterns, the highest cohesive enamel fractures were recorded in groups 2 and 3.In this study, although both methods of EWB did not influence immediate bond strength of composite resin to enamel, the majority of failure patterns occurred cohesively in enamel.

  2. Bond Strength of Composite Resin to Enamel: Assessment of Two Ethanol Wet-Bonding Techniques

    Science.gov (United States)

    Khoroushi, Maryam; Rafizadeh, Mojgan; Samimi, Pouran

    2014-01-01

    Objective Ethanol wet-bonding (EWB) technique has been stated to decrease degradation of resin-dentin bond. This study evaluated the effect of two EWB techniques on composite resin-to-enamel bond strength. Materials and Methods: Silicon carbide papers were used to produce flat enamel surfaces on the buccal faces of forty-five molars. OptiBond FL (OFL) adhesive was applied on enamel surfaces in three groups of 15 namely: Enamel surface and OFL (control);Protocol 1 of the EWB technique: absolute ethanol was applied to water-saturated acid-etched enamel surfaces for 1 minute before the application of ethanol-solvated hydrophobic adhesive resin of OFL 3 times;Protocol 2: progressive ethanol replacement; water was gradually removed from the enamel matrix using ascending ethanol concentrations before OFL application. Composite build-ups were made and the specimens were stored for 24 hours at 37°C and 100% relative humidity. Shear bond strength test was performed using a universal testing machine at 1 mm/min crosshead speed. Fracture patterns were evaluated microscopically. Data were analyzed with one-way ANOVA and Fisher’s exact test (α=0.05). Results: There were no significant differences in bond strength between the groups (P=0.73). However, regarding failure patterns, the highest cohesive enamel fractures were recorded in groups 2 and 3. Conclusion: In this study, although both methods of EWB did not influence immediate bond strength of composite resin to enamel, the majority of failure patterns occurred cohesively in enamel. PMID:24910690

  3. Optimal Investment in Structured Bonds

    DEFF Research Database (Denmark)

    Jessen, Pernille; Jørgensen, Peter Løchte

    The paper examines the role of structured bonds in the optimal portfolio of a small retail investor. We consider the typical structured bond essentially repacking an exotic option and a zero coupon bond, i.e. an investment with portfolio insurance. The optimal portfolio is found when the investment...... opportunities consist of a risky reference fund, a risk-free asset and a structured bond. Key model elements are the trading strategy and utility function of the investor. Our numerical results indicate structured bonds do have basis for consideration in the optimal portfolio. The product holdings...

  4. A New Palladium-Catalyzed Phenyl-Alkene Bond Formation

    Directory of Open Access Journals (Sweden)

    René Roy

    2002-05-01

    Full Text Available A new method of palladium-catalyzed phenyl-alkene bond formation is reported. This reaction involves transfer of all three phenyl groups from triphenylantimony onto alkenes containing allylic protons.

  5. Additional disulfide bonds in insulin

    DEFF Research Database (Denmark)

    Vinther, Tine N; Pettersson, Ingrid; Huus, Kasper

    2015-01-01

    The structure of insulin, a glucose homeostasis-controlling hormone, is highly conserved in all vertebrates and stabilized by three disulfide bonds. Recently, we designed a novel insulin analogue containing a fourth disulfide bond located between positions A10-B4. The N-terminus of insulin's B......-chain is flexible and can adapt multiple conformations. We examined how well disulfide bond predictions algorithms could identify disulfide bonds in this region of insulin. In order to identify stable insulin analogues with additional disulfide bonds, which could be expressed, the Cβ cut-off distance had...... in comparison to analogues with additional disulfide bonds that were more difficult to predict. In contrast, addition of the fourth disulfide bond rendered all analogues resistant to fibrillation under stress conditions and all stable analogues bound to the insulin receptor with picomolar affinities. Thus...

  6. Scientific Opinion on Flavouring Group Evaluation 203, Revision 1 (FGE.203Rev1: α,β-Unsaturated aliphatic aldehydes and precursors from chemical subgroup 1.1.4 of FGE.19 with two or more conjugated double-bonds and with or without additional non-conjugated double-bonds

    Directory of Open Access Journals (Sweden)

    EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF

    2014-04-01

    Full Text Available The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to evaluate the genotoxic potential of flavouring substances from subgroup 1.1.4 of FGE.19 in the Flavouring Group Evaluation 203, Revision 1 (FGE.203Rev1. The Flavour Industry has provided additional genotoxicity studies for one representative substance in FGE.203, namely 2,4-decadienal [FL-no: 05.140]. Based on the available data, on newly submitted studies and on the scientific evidence from the literature, the Panel concluded that the genotoxic potential cannot be ruled out for the flavouring substances in this FGE.

  7. Comparison of shear bond strength of amalgam bonded to primary and permanent dentin.

    Science.gov (United States)

    Mahdi, S; Bahman, S; Arghavan, A B; Fatemeh, M

    2008-06-01

    Amalgam's non-adhesive characteristics necessitate cavity preparations incorporating retentive features, which often require the removal of non-carious tooth structure. Use of adhesives beneath amalgam restorations, would be helpful to overcome this disadvantage. This study was undertaken to compare the mean shear bond strength of amalgam bonded to primary and permanent dentin, to evaluate the efficacy of amalgam adhesives in pediatric dentistry.27 primary and 28 permanent posterior teeth with intact buccal or lingual surfaces were grounded to expose dentin and wet-polished with 400-grit silicone carbide paper. Scotchbond Multi Purpose Plus adhesive system was applied to the dentin surfaces and light cured. Amalgam was condensed onto the treated dentin through a plastic mold.shear bond strength testing was done using an Instron Universal testing machine, at a crosshead speed of 0.5 mm/min.The data were analyzed by independent samples t-test The difference among the two groups was not statistically significant (p>0.05) Bonded amalgam showed the same level of bond strength to primary and permanent dentin; so, application of amalgam bonding agents in pediatric dentistry can be recommended.

  8. Comparison of shear bond strength of amalgam bonded to primary and permanent dentin

    Directory of Open Access Journals (Sweden)

    Mahdi S

    2008-06-01

    Full Text Available Amalgam′s non-adhesive characteristics necessitate cavity preparations incorporating retentive features, which often require the removal of non-carious tooth structure. Use of adhesives beneath amalgam restorations, would be helpful to overcome this disadvantage. This study was undertaken to compare the mean shear bond strength of amalgam bonded to primary and permanent dentin, to evaluate the efficacy of amalgam adhesives in pediatric dentistry.27 primary and 28 permanent posterior teeth with intact buccal or lingual surfaces were grounded to expose dentin and wet-polished with 400-grit silicone carbide paper. Scotchbond Multi Purpose Plus adhesive system was applied to the dentin surfaces and light cured. Amalgam was condensed onto the treated dentin through a plastic mold.shear bond strength testing was done using an Instron Universal testing machine, at a crosshead speed of 0.5 mm/min.The data were analyzed by independent samples t-test The difference among the two groups was not statistically significant (p>0.05 Bonded amalgam showed the same level of bond strength to primary and permanent dentin; so, application of amalgam bonding agents in pediatric dentistry can be recommended.

  9. Cooperative effects between tetrel bond and other σ-hole bond interactions: a comparative investigation

    Science.gov (United States)

    Esrafili, Mehdi D.; Nurazar, Roghaye; Mohammadian-Sabet, Fariba

    2015-12-01

    Covalently bonded atoms of Groups IV-VII tend to have anisotropic charge distributions, the electronic densities being less on the extensions of the bonds (σ-holes) than in the intervening regions. These σ-holes often give rise to positive electrostatic potentials through which the atom can interact attractively and highly directionally with negative sites. In this work, cooperative effects between tetrel bond and halogen/chalcogen/pnicogen bond interactions are studied in multi-component YH3M...NCX...NH3 complexes, where Y = F, CN; M = C, Si and X = Cl, SH and PH2. These effects are analysed in detail in terms of the structural, energetic, charge-transfer and electron density properties of the complexes. The nature of the σ-hole bonds is unveiled by quantum theory of atoms in molecules and natural bond orbital theory. A favourable cooperativity is found with values that range between -0.34 and -1.15 kcal/mol. Many-body decomposition of interaction energies indicate that two-body energy term is the most important source of the attraction, which its contribution accounts for 87%-96% of the total interaction energy.

  10. The effect of concentration ratio and type of functional group on synthesis of CNT-ZnO hybrid nanomaterial by an in situ sol-gel process

    Science.gov (United States)

    Hosseini Largani, Sekineh; Akbarzadeh Pasha, Mohammad

    2016-12-01

    In this research, MWCNT-ZnO hybrid nanomaterials were synthesized by a simple sol-gel process using Zn(CH3COO)2·2H2O and functionalized MWCNT with carboxyl(COOH) and hydroxyl(OH) groups. Three different mass ratios of MWCNT:ZnO = 3:1, 1:1 and 1:3 were examined. The prepared nanomaterials were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and Fourier transform infrared spectroscopy (FTIR). Successful growth of MWCNT-ZnO hybrids for both COOH and OH functional groups and all the three mass ratios were obtained. The ZnO nanoparticles attached on the surfaces of CNTs have rather spherical shapes and hexagonal crystal structure. By increasing the concentration of ZnO, the number and average size of ZnO nanoparticles decorated the body of CNTs in hybrid structures increase. By increasing the ZnO precursor, the distribution of ZnO nanoparticles that appeared on the surface of CNTs becomes more uniform. The SEM observation beside EDX analysis revealed that at the same concentration ratio the amount of ZnO loading on the surface of MWCNT-COOH is more than MWCNT-OH. Moreover, the average size of ZnO nanoparticles attached on the surface of COOH functionalized CNTs is relatively smaller than that of OH functionalized ones.

  11. Adsorption of croconate dyes on TiO2 anatase (101) surface: A periodic DFT study to understand the binding of diketo groups

    Indian Academy of Sciences (India)

    Avinash L Puyad; Ch Ramesh Kumar; K Bhanuprakash

    2012-01-01

    The adsorption of model croconate dyes on the stoichiometric TiO2 anatase (101) surface has been studied by means of periodic density functional calculations to understand the adsorption of the diketo (-COCO-) groups. Past experimental and theoretical results have shown the strong binding ability of the acid group (-COOH) to the TiO2 surface but here the theoretical studies predicts the binding strength of the diketo group to be also significant and comparable with that of the -COOH group. This may cause a competitive binding between the keto groups and the acid groups on the TiO2 surface in the case of croconate dyes and cause a reduction in the efficiency of the DSSC.

  12. Comparative Evaluation of Microshear Bond Strength of 5(th), 6(th) and 7(th) Generation Bonding Agents to Coronal Dentin Versus Dentin at Floor of Pulp Chamber: An In vitro Study.

    Science.gov (United States)

    Deepa, Velagala Lakshmi; Damaraju, Bhargavi; Priyadharsini, Bollu Indira; Subbarao, Vummidisetti V; Raju, K Rama Krishna

    2014-09-01

    Lack of seal and adhesion between the final restoration and tooth structure adversely affects the results of root canal treatment. Lots of adhesive bonding agents are marketed to overcome this deficiency and achieve successful restoration. So the study compares and evaluates the micro shear bond strength of coronal dentin and pulp chamber dentin using three different generation dentin bonding systems and to know clinical efficiency for clinical use. DIFFERENT GENERATION DENTIN BONDING SYSTEMS USED WERE: (1) One bottle total etch system (XP Bond-5(th) generation), (2) Two-step self-etch system (Clearfil SE Bond-6(th) generation) and (3) All-in-one system (G Bond-7(th) generation). Thirty human mandibular molars were collected out of which sixty samples were prepared by sectioning each tooth into coronal dentin and pulpal floor dentin. They were divided into two major groups. Group I: 30 Coronal dentin samples. Group II:30 Pulpal floor dentin samples. Both the groups were further subdivided depending on the bonding agent used. Subgroup Ia:XP Bond, Subgroup Ib:Clearfil SE Bond, Subgroup Ic:G Bond, Subgroup IIa:XP Bond, Subgroup IIb:Clearfil SE Bond, Subgroup IIc:G Bond. Resin composite was bonded to these samples and tested for micro-shear bond strength. The mean bond strengths and standard deviations were calculated and analyzed using one-way ANOVA test and Student's t-test (unpaired) and honestly significant difference post-hoc tests. Coronal dentin showed higher values of micro shear bond strength than the pulpal floor dentin. All-in-one system (G Bond) showed least bond strength values to both the regions coronal dentin and pulpal floor dentin. Factors affecting the shear bond strength are dependent on material (adhesive system), substrate depth and adhesive/depth interaction. Hence composition and substrate treatment should be considered for good adhesive. Chemical composition of adhesive system determines clinical successes.

  13. Hydrogen and Dihydrogen Bonds in the Reactions of Metal Hydrides.

    Science.gov (United States)

    Belkova, Natalia V; Epstein, Lina M; Filippov, Oleg A; Shubina, Elena S

    2016-08-10

    The dihydrogen bond-an interaction between a transition-metal or main-group hydride (M-H) and a protic hydrogen moiety (H-X)-is arguably the most intriguing type of hydrogen bond. It was discovered in the mid-1990s and has been intensively explored since then. Herein, we collate up-to-date experimental and computational studies of the structural, energetic, and spectroscopic parameters and natures of dihydrogen-bonded complexes of the form M-H···H-X, as such species are now known for a wide variety of hydrido compounds. Being a weak interaction, dihydrogen bonding entails the lengthening of the participating bonds as well as their polarization (repolarization) as a result of electron density redistribution. Thus, the formation of a dihydrogen bond allows for the activation of both the MH and XH bonds in one step, facilitating proton transfer and preparing these bonds for further transformations. The implications of dihydrogen bonding in different stoichiometric and catalytic reactions, such as hydrogen exchange, alcoholysis and aminolysis, hydrogen evolution, hydrogenation, and dehydrogenation, are discussed.

  14. Effect of Curing Direction on Microtensile Bond Strength of Fifth and Sixth Generation Dental Adhesives

    Directory of Open Access Journals (Sweden)

    Ali Nadaf

    2012-09-01

    Full Text Available Background and Aims: Composite restorative materials and dental adhesives are usually cured with light sources. The light direction may influence the bond strength of dental adhesives. The aim of this study was to evaluate the effect of light direction on the microtensile bond strength of fifth and sixth generation dental adhesives.Materials and Methods: Prime & Bond NT and Clearfil SE bond were used with different light directions.Sixty human incisor teeth were divided into 4 groups (n=15. In groups A and C, Clearfil SE bond with light curing direction from buccal was used for bonding a composite resin to dentin. In groups B and D, Prime & Bond NT with light curing direction from composite was used. After thermocycling the specimens were subjected to tensile force until debonding occurred and values for microtensile bond strength were recorded. The data were analyzed using two-way ANOVA and Tukey post hoc test.Results: The findings showed that the bond strength of Clearfil SE bond was significantly higher than that of Prime&Bond NT (P<0.001. There was no significant difference between light curing directions (P=0.132.Conclusion: Light curing direction did not have significant effect on the bond strength. Sixth generation adhesives was more successful than fifth generation in terms of bond strength to dentin.

  15. Research progress of III-V laser bonding to Si

    Science.gov (United States)

    Bo, Ren; Yan, Hou; Yanan, Liang

    2016-12-01

    The vigorous development of silicon photonics makes a silicon-based light source essential for optoelectronics' integration. Bonding of III-V/Si hybrid laser has developed rapidly in the last ten years. In the tireless efforts of researchers, we are privileged to see these bonding methods, such as direct bonding, medium adhesive bonding and low temperature eutectic bonding. They have been developed and applied to the research and fabrication of III-V/Si hybrid lasers. Some research groups have made remarkable progress. Tanabe Katsuaki of Tokyo University successfully implemented a silicon-based InAs/GaAs quantum dot laser with direct bonding method in 2012. They have bonded the InAs/GaAs quantum dot laser to the silicon substrate and the silicon ridge waveguide, respectively. The threshold current of the device is as low as 200 A/cm2. Stevan Stanković and Sui Shaoshuai successfully produced a variety of hybrid III-V/Si laser with the method of BCB bonding, respectively. BCB has high light transmittance and it can provide high bonding strength. Researchers of Tokyo University and Peking University have realized III-V/Si hybrid lasers with metal bonding method. We describe the progress in the fabrication of III-V/Si hybrid lasers with bonding methods by various research groups in recent years. The advantages and disadvantages of these methods are presented. We also introduce the progress of the growth of III-V epitaxial layer on silicon substrate, which is also a promising method to realize silicon-based light source. I hope that readers can have a general understanding of this field from this article and we can attract more researchers to focus on the study in this field.

  16. An In vitro Evaluation of the Effect of Four Dentin Bonding System on the Bond Strength between Quartz Fiber Post and Composite Core

    Directory of Open Access Journals (Sweden)

    Shirinzad M.

    2013-09-01

    Full Text Available Statement of Problem: A strong bond of fiber post to resin core, as well as to dentin would critically ensure the durability of restorations in endodontically treated teeth. Purpose: The purpose of this study was to evaluate the effect of etch-and-rinse dentin bonding systems on the bond strength between resin core and fiber post after application of 24% hydrogen peroxide. Materials and Method: 24 fiber posts (RTD; St. Egèven, France were treated with 24% hydrogen peroxide for 10 minutes. They were randomly divided into 4 groups (n=6 based on the bonding agent used: Group P: Prime&Bond, Group O: One Step, Group S: Single Bond and Group E: Excite. Each group was prepared according to the manufacturer’s instructions. For all posts, a flowable composite core (ÆliteFlo; Bisco, USA was built-up over the bonded area. Each specimen was sectioned to produce 2 sticks, 1mm in thickness and underwent microtensile bond strength (µTBS. Data were analyzed using one-way ANOVA at the 0.05 level. The fractured surfaces of all sticks were evaluated by stereomicroscope (× 20. Scanning electron microscopy(SEM assessment of two sticks from each group was performed to evaluate the surface morphology. Results: The means and SDs of µTBS were: Group P: 10.95±1.74; Group S: 10.25±2.39; Group E: 9.52±2.07; and Group O: 9.12±1.34. There was no statistically significant difference in bond strength means between the groups tested (p> 0.05. Conclusion: The results of this study indicated the bonding agents used had no significant influence on the bond strength of fiber post to composite core.

  17. An In vitro Evaluation of the Effect of Four Dentin Bonding System on the Bond Strength between Quartz Fiber Post and Composite Core

    Directory of Open Access Journals (Sweden)

    Shirinzad M.

    2014-03-01

    Full Text Available Statement of Problem: A strong bond of fiber post to resin core, as well as to dentin would critically ensure the durability of restorations in endodontically treated teeth. Purpose: The purpose of this study was to evaluate the effect of etch-and-rinse dentin bonding systems on the bond strength between resin core and fiber post after application of 24% hydrogen peroxide. Materials and Method: Twenty-four fiber posts (RTD; St. Egèven, France were treated with 24% hydrogen peroxide for 10 minutes. They were randomly divided into 4 groups (n=6 based on the bonding agent used: Group P: Prime&Bond, Group O: One Step, Group S: Single Bond and Group E: Excite. Each group was prepared according to the manufacturer’s instructions. For all posts, a flowable composite core (ÆliteFlo, Bisco, USA were built-up over the bonded area. Each specimen was sectioned to produce 2 sticks, 1mm in thickness and underwent microtensile bond strength (µTBS. Data were analyzed using one-way ANOVA at the 0.05 level. The fractured surfaces of all sticks were evaluated by stereomicroscope (× 20. SEM assessment of two sticks from each group was performed to evaluate the surface morphology. Results: The means and SDs of µTBS were: Group P: 10.95±1.74; Group S: 10.25±2.39; Group E: 9.52±2.07; and Group O: 9.12±1.34. There was no statistic means and SDs ally significant difference in bond strength means between the groups used (p> 0.05. Conclusion: The results of this study indicated the bonding agents used had no significant influence on the bond strength of fiber post to composite core.

  18. An In vitro Evaluation of the Effect of Four Dentin Bonding System on the Bond Strength between Quartz Fiber Post and Composite Core.

    Science.gov (United States)

    Shirinzad, M; Ebadi, Sh; Shokripour, M; Darabi, Ma

    2014-03-01

    A strong bond of fiber post to resin core, as well as to dentin would critically ensure the durability of restorations in endodontically treated teeth. The purpose of this study was to evaluate the effect of etch-and-rinse dentin bonding systems on the bond strength between resin core and fiber post after application of 24% hydrogen peroxide.  24 fiber posts (RTD; St. Egèven, France) were treated with 24% hydrogen peroxide for 10 minutes. They were randomly divided into 4 groups (n=6) based on the bonding agent used: Group P: Prime&Bond, Group O: One Step, Group S: Single Bond and Group E: Excite. Each group was prepared according to the manufacturer's instructions. For all posts, a flowable composite core (ÆliteFlo; Bisco, USA) was built-up over the bonded area. Each specimen was sectioned to produce 2 sticks, 1mm in thickness and underwent microtensile bond strength (µTBS). Data were analyzed using one-way ANOVA at the 0.05 level. The fractured surfaces of all sticks were evaluated by stereomicroscope (× 20). Scanning electron microscopy(SEM) assessment of two sticks from each group was performed to evaluate the surface morphology. The means and SDs of µTBS were: Group P: 10.95±1.74; Group S: 10.25±2.39; Group E: 9.52±2.07; and Group O: 9.12±1.34. There was no statistically significant difference in bond strength means between the groups tested (p> 0.05).   The results of this study indicated the bonding agents used had no significant influence on the bond strength of fiber post to composite core.

  19. Comparison of Bond in Roll-bonded and Adhesively Bonded Aluminums

    Science.gov (United States)

    Schwensfeir, R. J., Jr.; Trenkler, G.; Delagi, R. G.; Forster, J. A.

    1985-01-01

    Lap-shear and peel test measurements of bond strength have been carried out as part of an investigation of roll bonding of 2024 and 7075 aluminum alloys. Shear strengths of the bonded material in the F temper are in the range of 14 to 16 ksi. Corresponding peel strengths are 120 to 130 lb/inch. These values, which are three to five times those reported in the literature for adhesively bonded 2024 and 7075, are a result of the true metallurgical bond achieved. The effects of heat-treating the bonded material are described and the improvements in bond strength discussed relative to the shear strength of the parent material. The significance of the findings for aerospace applications is discussed.

  20. Limitations in bonding to dentin and experimental strategies to prevent bond degradation.

    Science.gov (United States)

    Liu, Y; Tjäderhane, L; Breschi, L; Mazzoni, A; Li, N; Mao, J; Pashley, D H; Tay, F R

    2011-08-01

    The limited durability of resin-dentin bonds severely compromises the lifetime of tooth-colored restorations. Bond degradation occurs via hydrolysis of suboptimally polymerized hydrophilic resin components and degradation of water-rich, resin-sparse collagen matrices by matrix metalloproteinases (MMPs) and cysteine cathepsins. This review examined data generated over the past three years on five experimental strategies developed by different research groups for extending the longevity of resin-dentin bonds. They include: (1) increasing the degree of conversion and esterase resistance of hydrophilic adhesives; (2) the use of broad-spectrum inhibitors of collagenolytic enzymes, including novel inhibitor functional groups grafted to methacrylate resins monomers to produce anti-MMP adhesives; (3) the use of cross-linking agents for silencing the activities of MMP and cathepsins that irreversibly alter the 3-D structures of their catalytic/allosteric domains; (4) ethanol wet-bonding with hydrophobic resins to completely replace water from the extrafibrillar and intrafibrillar collagen compartments and immobilize the collagenolytic enzymes; and (5) biomimetic remineralization of the water-filled collagen matrix using analogs of matrix proteins to progressively replace water with intrafibrillar and extrafibrillar apatites to exclude exogenous collagenolytic enzymes and fossilize endogenous collagenolytic enzymes. A combination of several of these strategies should result in overcoming the critical barriers to progress currently encountered in dentin bonding.

  1. Bonding durability between acrylic resin adhesives and titanium with surface preparations.

    Science.gov (United States)

    Yanagida, Hiroaki; Minesaki, Yoshito; Matsumura, Kousuke; Tanoue, Naomi; Muraguchi, Koichi; Minami, Hiroyuki

    2017-01-31

    The purpose of the present study was to evaluate the efficacy of pretreatment on the bonding durability between titanium casting and two acrylic adhesives. Cast titanium disk specimens treated with four polymer-metal bonding systems as follow: 1) air-abraded with 50-70 μm alumina, 2) 1)+Alloy Primer, 3) 1)+M.L. Primer and 4) tribochemical silica/silane coating system (Rocatec System). The specimens were bonded with M bond or Super-bond C&B adhesive. The shear bond strengths were determined before and after thermocycling (20,000 cycles). The surface characteristics after polishing, and for the 1) and 4) preparations were determined. The bond strengths for all combinations significantly decreased after thermocycling. The combination of Super-bond C&B adhesive and 2) led to significantly higher bond strength than the other preparations after thermocycling. The maximum height of the profile parameters for the polishing group was lower than other preparations.

  2. 27 CFR 28.66 - Strengthening bonds.

    Science.gov (United States)

    2010-04-01

    ... bonds. In all cases where the penal sum of any bond becomes insufficient, the principal shall either give a strengthening bond with the same surety to attain a sufficient penal sum, or give a new bond to... of any bond to less than its full penal sum. Strengthening bonds shall show the current date...

  3. Two-photon laser confocal microscopy of micropermeability of resin-dentin bonds made with water or ethanol wet bonding.

    Science.gov (United States)

    Sauro, Salvatore; Watson, Timothy F; Mannocci, Francesco; Miyake, Katsuya; Huffman, Bradford P; Tay, Franklin R; Pashley, David H

    2009-07-01

    This study evaluated the micropermeability of six etch-and-rinse adhesives bonded to dentin. There were two principal groups: wet bonding with water or wet bonding with absolute ethyl alcohol. After bonding and the creation of composite build-ups, the pulp chambers were filled with 0.1% lucifer yellow. The contents of the pulp chamber were kept under 20 cm H(2)O pressure to simulate pulpal pressure for 3 h. The specimens were vertically sectioned into multiple 0.5-mm thick slabs that were polished and then examined using a two-photon confocal laser scanning microscope (TPCLSM). The results showed that specimens bonded with adhesives using the water wet-bonding condition all showed tracer taken up uniformly by the hybrid layer. This uptake of fluorescent tracer into the hybrid layer was quantified by computer software. The most hydrophobic experimental resins showed the highest fluorescent tracer uptake (ca. 1800 +/- 160 arbitrary fluorescent units/std. surface area). The most hydrophilic experimental resins showed the lowest tracer uptake into water-saturated hybrid layers. When ethanol wet-bonding was used, significantly less fluorescent tracer was seen in hybrid layers. The most hydrophilic experimental resins and Single Bond Plus showed little micropermeability. Clearly, ethanol wet-bonding seals dentin significantly better than water-wet dentin regardless of the adhesive in etch-and-rinse systems.

  4. Comparative evaluation of the shear bond strength of metal brackets bonded to porcelain using different porcelain surface treatments

    Directory of Open Access Journals (Sweden)

    Eslami Amirabadi GH

    2011-02-01

    Full Text Available "nBackground and Aims: The aim of this in vitro study was to compare shear bond strength of metal brackets bonded to dental porcelain on the basis of presence or absence of silane, type of acid [hydrofluoric acid (HF or phosphoric acid (H3PO4] and roughness of porcelain surface (glazed or deglazed within mouth-like environment."nMaterials and Methods: Eighty glazed ceramic disks were randomly divided into 8 groups of 10 disks: group 1 [HF+silane], group 2 [deglazed+HF+silane], group 3 [HF], group 4 [deglazed+HF], group 5 [H3PO4+silane], group 6 [deglazed+H3PO4+silane], group 7 [H3PO4], group 8 [deglazed+H3PO4]. Then the brackets were bonded and thermocycled. After that, shear bond strength test was done using the Zwick device and the type of bond failure was determined under stereomicroscope at 4X magnification. 3-way ANOVA and Kruskal-Wallis were used for statistical analyses."nResults: The shear bond strength for the test groups were as follows: group (1:13.05±7.7 MPa , group (2:25.16±10.66 MPa, group (3:6.7±5.86 MPa, group (4:15.39±8.97 MPa, group (5:12.76±7.91 MPa, group (6:13.57±7.85 MPa, group (7:0.54±0.67 MPa, group (8: 9.34±6.52 MPa. The type of bond failure in all groups was adhesive failure except for group 2. No significant difference in the interaction between (glazed or deglazed, (presence or absence of silane, and type of acid was found (P>0.05."nConclusion: Under the conditions of this study, the best clinical method was the use of 37% phosphoric acid and silane that resulted in the optimal clinical strength and adhesive bond failure.

  5. pH-Regulated Reversible Transition Between Polyion Complexes (PIC) and Hydrogen-Bonding Complexes (HBC) with Tunable Aggregation-Induced Emission.

    Science.gov (United States)

    Tian, Sidan; Liu, Guhuan; Wang, Xiaorui; Wu, Tao; Yang, Jinxian; Ye, Xiaodong; Zhang, Guoying; Hu, Jinming; Liu, Shiyong

    2016-02-17

    The mimicking of biological supramolecular interactions and their mutual transitions to fabricate intelligent artificial systems has been of increasing interest. Herein, we report the fabrication of supramolecular micellar nanoparticles consisting of quaternized poly(ethylene oxide)-b-poly(2-dimethylaminoethyl methacrylate) (PEO-b-PQDMA) and tetrakis(4-carboxylmethoxyphenyl)ethene (TPE-4COOH), which was capable of reversible transition between polyion complexes (PIC) and hydrogen bonding complexes (HBC) with tunable aggregation-induced emission (AIE) mediated by solution pH. At pH 8, TPE-4COOH chromophores can be directly dissolved in aqueous milieu without evident fluorescence emission. However, upon mixing with PEO-b-PQDMA, polyion complexes were formed by taking advantage of electrostatic interaction between carboxylate anions and quaternary ammonium cations and the most compact PIC micelles were achieved at the isoelectric point (i.e., [QDMA(+)]/[COO(-)] = 1), as confirmed by dynamic light scattering (DLS) measurement. Simultaneously, fluorescence spectroscopy revealed an evident emission turn-on and the maximum fluorescence intensity was observed near the isoelectric point due to the restriction of intramolecular rotation of TPE moieties within the PIC cores. The kinetic study supported a micelle fusion/fission mechanism on the formation of PIC micelles at varying charge ratios, exhibiting a quick time constant (τ1) relating to the formation of quasi-equilibrium micelles and a slow time constant (τ2) corresponding to the formation of final equilibrium micelles. Upon deceasing the pH of PIC micelles from 8 to 2 at the [QDMA(+)]/[COO(-)] molar ratio of 1, TPE-4COOH chromophores became gradually protonated and hydrophobic. The size of micellar nanoparticles underwent a remarkable decrease, whereas the fluorescence intensity exhibited a further increase by approximately 7.35-fold, presumably because of the formation of HBC micelles comprising cationic PQDMA

  6. The comparison between carboxyl, amido and hydroxy group in influencing electrorheological performance

    Science.gov (United States)

    Li, Huo; Li, Jun-Ran; Liao, Fu-Hui

    2011-03-01

    Three kinds of electrorheological (ER) materials with carboxyl, amido and hydroxyl group, respectively, were synthesized by a simple adsorption method. The powder of silicon dioxide as a substrate of the materials, as well as terephthalic acid [ p-C6H4(COOH)2, abbr.: phen-COOH], p-phenylenediamine [ p-C6H4(NH2)2, abbr.: phen-NH2] and hydroquinone [ p-C6H4(OH)2, abbr.: phen-OH] were chosen as starting materials. The ER properties of suspensions of the materials in silicon oil were studied. The suspension of the material adsorbing phen-COOH reveals the highest ER activity, the relative shear stress of the suspension (25 wt%), τr(=τE/τ0, τE and τ0 are the shear stresses at electric field strengths of E=4.2 and 0 kV/mm, respectively), reaches 220 under a DC electric field at a shear rate of 14.5 s-1. The shear stress of the suspension of the material adsorbing phen-NH2 is the largest at an high electric field strength. The ER activity of the material adsorbing phen-OH is the lowest among the three materials. The molecule structure is an importance factor in influencing ER performance of the materials for similar compounds with different polar function groups. The relationship between the ER activity and dielectric property of the materials was discussed.

  7. 1,3-Diamido-calix[4]arene conjugates of amino acids: recognition of -COOH side chain present in amino acids, peptides, and proteins by experimental and computational studies.

    Science.gov (United States)

    Acharya, Amitabha; Ramanujam, Balaji; Chinta, Jugun Prakash; Rao, Chebrolu P

    2011-01-01

    Lower rim 1,3-diamido conjugates of calix[4]arene have been synthesized and characterized, and the structures of some of these have been established by single crystal XRD. The amido-calix conjugates possessing a terminal -COOH moiety have been shown to exhibit recognition toward guest molecules possessing -COOH moiety, viz., Asp, Glu, and reduced and oxidized glutathione (GSH, GSSG), by switch-on fluorescence in aqueous acetonitrile and methanol solutions when compared to the control molecules via forming a 1:1 complex. The complex formed has been shown by mass spectrometry, and the structural features of the complexes were derived on the basis of DFT computations. The association constants observed for the recognition of Asp/Glu by Phe-calix conjugate, viz., 532/676 M(-1), are higher than that reported for the recognition of Val, Leu, Phe, His, and Trp (16-63 M(-1)) by a water-soluble calixarene (Arena, G., et al. Tetrahedron Lett. 1999, 40, 1597). For this recognition, there should be a free -COOH moiety from the guest molecule. AFM, SEM, and DLS data exhibited spherical particles with a hundred-fold reduction in the size of the complexes when compared to the particles of the precursors. These spherical particles have been computationally modeled to possess hexameric species reminiscent of the hexameric micellar structures shown for a Ag(+) complex of a calix[6]arene reported in the literature (Houmadi, S., et al. Langmuir 2007, 23, 4849). Both AFM and TEM studies demonstrated the formation of nanospheres in the case of GSH-capped Ag nanoparticles in interaction with the amido-calix conjugate that possesses terminal -COOH moiety. The AFM studies demonstrated in this paper have been very well applied to albumin proteins to differentiate the aggregational behavior and nanostructural features exhibited by the complexes of proteins from those of the uncomplexed ones. To our knowledge, this is the first report wherein a amido-calix[4]arene conjugate and its amino acid

  8. Microleakage under orthodontic brackets bonded with different adhesive systems.

    Science.gov (United States)

    Alkis, Huseyin; Turkkahraman, Hakan; Adanir, Necdet

    2015-01-01

    This in vitro study aimed to compare the microleakage of orthodontic brackets between enamel-adhesive and adhesive-bracket interfaces at the occlusal and gingival margins bonded with different adhesive systems. A total of 144 human maxillary premolar teeth extracted for orthodontic reasons was randomly divided into four groups. Each group was then further divided into three sub-groups. Three total-etching bonding systems (Transbond XT, Greengloo and Kurasper F), three one-step self-etching bonding systems (Transbond Plus SEP, Bond Force and Clearfil S3), three two-step self-etching bonding systems (Clearfil SE Bond, Clearfil Protectbond and Clearfil Liner Bond), and three self-adhesive resin cements (Maxcem Elite, Relyx U 100 and Clearfil SA Cement) were used to bond the brackets to the teeth. After bonding, all teeth were sealed with nail varnish and stained with 0.5% basic fuchsine for 24 h. All samples were sectioned and examined under a stereomicroscope to score for microleakage at the adhesive-enamel and adhesive-bracket interfaces from both occlusal and gingival margins. Statistical analyses were performed with Kruskal-Wallis and Wilcoxon signed-rank tests. The results indicate no statistically significant differences between the microleakage scores of the adhesives; microleakage was detected in all groups. Comparison of the average values of the microleakage scores in the enamel-adhesive and adhesive-bracket interfaces indicated statistically significant differences (P adhesive interface than at the bracket-adhesive interface. All of the brackets exhibited some amount of microleakage. This result means that microleakage does not depend on the type of adhesive used.

  9. Bond strength of adhesive resin cement with different adhesive systems

    Science.gov (United States)

    Lorenzoni e Silva, Fabrizio; Pamato, Saulo; Kuga, Milton-Carlos; Só, Marcus-Vinicius-Reis

    2017-01-01

    Background To assess the immediate bond strength of a dual-cure adhesive resin cement to the hybridized dentin with different bonding systems. Material and Methods Fifty-six healthy human molars were randomly divided into 7 groups (n=8). After 3 longitudinal sections, the central cuts were included in PVC matrix and were submitted to dentin hybridization according to the groups: G1 - etch & rinse system with 3-step (Apder™ Scotchbond™ Multi-Purpose, 3M ESPE), G2 - etch & rinse system with 3-step (Optibond™ FL, Kerr), G3 - etch & rinse system with 3-step (All-Bond 3®, Bisco), G4 - etch & rinse simplified system (Adper™ Single Bond 2, 3M ESPE), G5 - self-etching system with one step (Bond Force, Tokuyama), G6 - universal system in moist dentin (Single Bond Universal, 3M ESPE), G7 - universal system in dry dentin (Single Bond Universal, 3M ESPE). Then all groups received the cementing of a self-adhesive resin cement cylinder (Duo-link, Bisco) made from a polypropylene matrix. In the evaluation of bond strength, the samples were subjected to the microshear test and evaluated according to the fracture pattern by optical microscopy. Results The Kruskal-Wallis test suggests a statistically significant difference between groups (p=0,039), and Tukey for multiple comparisons, indicating a statistically significant difference between G3 and G4 (p<0.05). It was verified high prevalence of adhesive failures, followed by mixed failure and cohesive in dentin. Conclusions The technique and the system used to dentin hybridization are able to affect the immediate bond strength of resin cement dual adhesive. Key words:Adhesion, adhesive resin cement, adhesive systems, microshear. PMID:28149471

  10. Microshear bond strength between restorative composites and resin cements

    Directory of Open Access Journals (Sweden)

    Rubens Nazareno GARCIA

    2008-08-01

    Full Text Available Introduction and objective: The techniques of adhesive cementationhave been widely used in dental restoration. The purpose of this studywas to evaluate the microshear bond strength between restorativecomposites and resin cements. Material and methods: Twenty composites blocks were prepared in order to obtain a flat surface, using 600-grid sandpaper. The samples were randomly divided in four groups(n=15 according to the experimental groups: [1] Z250 block + Single Bond + cylinder of RelyX ARC; [2] Z250 block + Single Bond + cylinder of Panavia F; [3] Clearfil AP-X block + Clearfil SE Bond adhesive + cylinder of RelyX ARC; [4] Clearfil AP-X block + Clearfil SE Bond adhesive + cylinder of Panavia F. The adhesive systems and the resin cements were applied according to the experimental groups, using a Tygon matrix.The samples were stored in distilled water at 37±2ºC for 24 hours.Microshear bond strengths were determined using an apparatus attached to an Instron universal testing machine at a crosshead speed of 0.5 mm/minute. Results: The results obtained in MPa (SD were statistically analyzed (ANOVA and Tukey test, p<0.05, and showed the following results: [1] 39.76 (5.34; [2] 45.01 (8.53; [3] 46.39 (9.22; [4]45.78 (9.06.There was no statistically significant difference between groups [1] and [2]; and between groups [3] and [4]. However, there was statistically significant difference between groups [1] and [3]. Conclusion:When Clearfil AP-X block was used with Clearfil SE Bond adhesive or RelyX resin cement, the microshear bond strength values were higher.The results suggest that in the union of the resin cements to the restorative composites, hydrophobic adhesives are necessary.

  11. A simplified indirect bonding technique

    Directory of Open Access Journals (Sweden)

    Radha Katiyar

    2014-01-01

    Full Text Available With the advent of lingual orthodontics, indirect bonding technique has become an integral part of practice. It involves placement of brackets initially on the models and then their transfer to teeth with the help of transfer trays. Problems encountered with current indirect bonding techniques used are (1 the possibility of adhesive flash remaining around the base of the brackets which requires removal (2 longer time required for the adhesive to gain enough bond strength for secure tray removal. The new simplified indirect bonding technique presented here overcomes both these problems.

  12. Photoinduced hydrogen-bonding dynamics.

    Science.gov (United States)

    Chu, Tian-Shu; Xu, Jinmei

    2016-09-01

    Hydrogen bonding dynamics has received extensive research attention in recent years due to the significant advances in femtolaser spectroscopy experiments and quantum chemistry calculations. Usually, photoexcitation would cause changes in the hydrogen bonding formed through the interaction between hydrogen donor and acceptor molecules on their ground electronic states, and such transient strengthening or weakening of hydrogen bonding could be crucial for the photophysical transformations and the subsequent photochemical reactions that occurred on a time scale from tens of femtosecond to a few nanoseconds. In this article, we review the combined experimental and theoretical studies focusing on the ultrafast electronic and vibrational hydrogen bonding dynamics. Through these studies, new mechanisms and proposals and common rules have been put forward to advance our understanding of the hydrogen bondings dynamics in a variety of important photoinduced phenomena like photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer processes, chemosensor fluorescence sensing, rearrangements of the hydrogen-bond network including forming and breaking hydrogen bond in water. Graphical Abstract We review the recent advances on exploring the photoinduced hydrogen bonding dynamics in solutions through a joint approach of laser spectroscopy and theoretical calculation. The reviewed studies have put forward a new mechanism, new proposal, and new rule for a variety of photoinduced phenomena such as photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer, chemosensor fluorescence sensing, and rearrangements of the hydrogen-bond network in water.

  13. Wafer bonding applications and technology

    CERN Document Server

    Gösele, Ulrich

    2004-01-01

    During the past decade direct wafer bonding has developed into a mature materials integration technology. This book presents state-of-the-art reviews of the most important applications of wafer bonding written by experts from industry and academia. The topics include bonding-based fabrication methods of silicon-on-insulator, photonic crystals, VCSELs, SiGe-based FETs, MEMS together with hybrid integration and laser lift-off. The non-specialist will learn about the basics of wafer bonding and its various application areas, while the researcher in the field will find up-to-date information about this fast-moving area, including relevant patent information.

  14. Bond Growth under Temperature Gradient.

    Directory of Open Access Journals (Sweden)

    P.K. Satyawali

    1999-12-01

    Full Text Available Grain and bond growth for dry snow are determined by the distribution of temperature andtemperature gradient in the snow matrix. From the standpoint of particle approach and based oncubic packing structure, a bond growth model has been developed for TG metamorphism. The paper.highlights the importance of bond formation and its effect on snow viscosity and finally on the rateof settlement. This is very important for developing a numerical snow pack model if microstructureis considered to be a basic parameter. A few experiments have been carried out to validate bond formation under temperature gradient.

  15. Covalent bonding from alchemical linear response density functional theory

    CERN Document Server

    Chang, K Y Samuel; Ramakrishnan, Raghunathan; von Lilienfeld, O Anatole

    2015-01-01

    We assess the predictive accuracy of linear response based estimates of changes in covalent bonding due to linear alchemical interpolations among molecules. We have investigated single bonds to hydrogen, as well as single, double, and triple bonds between main-group elements, occurring in small iso-electronic molecular spaces with atomic elements drawn from rows 2-3 in the $p$-block of the periodic table. Numerical evidence suggests that first order estimates of bonding potentials can achieve chemical accuracy if the alchemical interpolation connects molecules containing late elements in the periodic table (3$^{rd}$ and 4$^{th}$ row) and identical number of atoms and molecular geometries. For these interpolations, changes in bonding potential are near-linear in the coupling parameter, resulting in accurate Hellmann-Feynman predictions. Second order estimates for such interpolations yield worse predictions. The predictions become substantially worse if initial and final molecules differ not only in composition...

  16. Construct Polyoxometalate Frameworks through Covalent Bonds.

    Science.gov (United States)

    Chen, Hong; Zhao, Huishuang; Yu, Zheng-Bao; Wang, Lei; Sun, Licheng; Sun, Junliang

    2015-09-08

    An emerging strategy for exploring the application of polyoxometalates (POMs) is to assemble POM clusters into open-framework materials, especially inorganic-organic hybrid three-dimensional (3D) open-framework materials, via the introduction of different organic linkers between the POM clusters. This strategy has yielded a few 3D crystalline POMs of which a typical class is the group of polyoxometalate metal-organic frameworks (POMMOFs). However, for reported POMMOFs, only coordination bonds are involved between the linkers and POM clusters, and it has not yet produced any covalently bonded polyoxometalate frameworks. Here, the concept of "covalently bonded POMs (CPOMs)" is developed. By using vanadoborates as an example, we showed that the 3D CPOMs can be obtained by a condensation reaction through the oxolation mechanism of polymer chemistry. In particular, suitable single crystals were harvested and characterized by single-crystal X-ray diffraction. This work forges a link among polymer science, POM chemistry, and open-framework materials by demonstrating that it is possible to use covalent bonds according to polymer chemistry principles to construct crystalline 3D open-framework POM materials.

  17. Reactive Bonding Film for Bonding Carbon Foam Through Metal Extrusion

    CERN Document Server

    Chertok, Maxwell; Irving, Michael; Neher, Christian; Tripathi, Mani; Wang, Ruby; Zheng, Gayle

    2016-01-01

    Future tracking detectors, such as those under development for the High Luminosity LHC, will require mechanical structures employing novel materials to reduce mass while providing excellent strength, thermal conductivity, and radiation tolerance. Adhesion methods for such materials are under study at present. This paper demonstrates the use of reactive bonding film as an adhesion method for bonding carbon foam.

  18. Digital Control of Bonding Force for Gold Wire Bonding Machine

    Directory of Open Access Journals (Sweden)

    Xiaochu Wang

    2013-01-01

    Full Text Available In order to digitally control the bonding force of a wire bonder precisely, this paper uses a DC solenoid as a force source, and by controlling the solenoid’s current, which causes the electromagnetic force, we can control the bonding force that capillary applies. The bonding force control system in this paper is composed of PC (Personal Computer and hypogyny MCU (Micro Controller Unit, which communicate using a RS485 interface. The digital value of a given bonding force is given by the PC to the MCU. By comparing the sampling current of the solenoid, and through PID regulation, D/A converter of the digital potentiometer and the solenoid driver circuit, the half-closed loop control system of bonding force is accomplished. Tuning of the PID parameters is accomplished with fuzzy adaptive control theory and simulated by Matlab simulink. The control system is tested by comparing the desired bonding force and the force actually applied and examming the relationship between bonding quality and bonding force.

  19. Molecularly Tuning the Radicaloid N-H···O═C Hydrogen Bond.

    Science.gov (United States)

    Lu, Norman; Chung, Wei-Cheng; Ley, Rebecca M; Lin, Kwan-Yu; Francisco, Joseph S; Negishi, Ei-Ichi

    2016-03-01

    Substituent effects on the open shell N-H···O═C hydrogen-bond has never been reported. This study examines how 12 functional groups composed of electron donating groups (EDG), halogen atoms and electron withdrawing groups (EWG) affect the N-H···O═C hydrogen-bond properties in a six-membered cyclic model system of O═C(Y)-CH═C(X)N-H. It is found that group effects on this open shell H-bonding system are significant and have predictive trends when X = H and Y is varied. When Y is an EDG, the N-H···O═C hydrogen-bond is strengthened; and when Y is an EWG, the bond is weakened; whereas the variation in electronic properties of X group do not exhibit a significant impact upon the hydrogen bond strength. The structural impact of the stronger N-H···O═C hydrogen-bond are (1) shorter H and O distance, r(H···O) and (2) a longer N-H bond length, r(NH). The stronger N-H···O═C hydrogen-bond also acts to pull the H and O in toward one another which has an effect on the bond angles. Our findings show that there is a linear relationship between hydrogen-bond angle and N-H···O═C hydrogen-bond energy in this unusual H-bonding system. In addition, there is a linear correlation of the r(H···O) and the hydrogen bond energy. A short r(H···O) distance corresponds to a large hydrogen bond energy when Y is varied. The observed trends and findings have been validated using three different methods (UB3LYP, M06-2X, and UMP2) with two different basis sets.

  20. Redshift or adduct stabilization -- a computational study of hydrogen bonding in adducts of protonated carboxylic acids

    DEFF Research Database (Denmark)

    Olesen, Solveig Gaarn; Hammerum, Steen

    2009-01-01

    changes and the redshift favor the Z OH group, matching the results of NBO and AIM calculations. This reflects that the thermochemistry of adduct formation is not a good measure of the hydrogen bond strength in charged adducts, and that the ionic interactions in the E and Z adducts of protonated......It is generally expected that the hydrogen bond strength in a D-H-A adduct is predicted by the difference between the proton affinities of D and A, measured by the adduct stabilization, and demonstrated by the IR redshift of the D-H bond stretching vibrational frequency. These criteria do...... not always yield consistent predictions, as illustrated by the hydrogen bonds formed by the E and Z OH groups of protonated carboxylic acids. The delta-PA and the stabilization of a series of hydrogen bonded adducts indicate that the E OH group forms the stronger hydrogen bonds, whereas the bond length...

  1. 29 CFR 2580.412-19 - Term of the bond, discovery period, other bond clauses.

    Science.gov (United States)

    2010-07-01

    ... SECURITY ACT OF 1974 TEMPORARY BONDING RULES General Bond Rules § 2580.412-19 Term of the bond, discovery... 29 Labor 9 2010-07-01 2010-07-01 false Term of the bond, discovery period, other bond clauses... new bond must be obtained each year. There is nothing in the Act that prohibits a bond for a...

  2. Bonding resin thixotropy and viscosity influence on dentine bond strength.

    Science.gov (United States)

    Niem, Thomas; Schmidt, Alexander; Wöstmann, Bernd

    2016-08-01

    To investigate the influence of bonding resin thixotropy and viscosity on dentine tubule penetration, blister formation and consequently on dentine bond strength as a function of air-blowing pressure (air-bp) intensity. Two HEMA-free, acetone-based, one-bottle self-etch adhesives with similar composition except disparate silica filler contents and different bonding resin viscosities were investigated. The high-filler-containing adhesive (G-Bond) featured a lower viscous bonding resin with inherent thixotropic resin (TR) properties compared to the low-filler-containing adhesive (iBond) exhibiting a higher viscous bonding resin with non-thixotropic resin (NTR) properties. Shear bond strength tests for each adhesive with low (1.5bar; 0.15MPa; n=16) and high (3.0bar; 0.30MPa; n=16) air-bp application were performed after specimen storage in distilled water (24h; 37.0±1.0°C). Results were analysed using a Student's t-test to identify statistically significant differences (padhesive specimens were morphologically characterised by SEM. Statistically significant bond strength differences were obtained for the thixotropic resin adhesive (high-pressure: 24.6MPa, low-pressure: 9.6MPa). While high air-bp specimens provided SEM images revealing resin-plugged dentine tubules, resin tags and only marginally blister structures, low air-bp left copious droplets and open dentine tubules. In contrast, the non-thixotropic resin adhesive showed no significant bond strength differences (high-pressure: 9.3MPa, low-pressure: 7.6MPa). A pressure-dependent distinct influence of bonding resin thixotropy and viscosity on dentine bond strength has been demonstrated. Stronger adhesion with high air-bp application is explained by improved resin fluidity and facilitated resin penetration into dentine tubules. Filler particles used in adhesive systems may induce thixotropic effects in bonding resin layers, accounting for improved free-flowing resin properties. In combination with high air

  3. Influence of glass particle size of resin cements on bonding to glass ceramic: SEM and bond strength evaluation.

    Science.gov (United States)

    Valentini, Fernanda; Moraes, Rafael R; Pereira-Cenci, Tatiana; Boscato, Noéli

    2014-05-01

    This study investigated the effect of the filler particle size (micron or submicron) of experimental resin cements on the microtensile bond strength to a glass-ceramic pretreated with hydrofluoric acid (HFA) etching or alumina airborne-particle abrasion (AA). Cements were obtained from a Bis-GMA/TEGDMA mixture filled with 60 mass% micron-sized (1 ± 0.2 µm) or submicron-sized (180 ± 30 µm) Ba-Si-Al glass particles. Ceramic blocks (PM9; VITA) were treated with 10% HFA for 60 s or AA for 15 s. Silane and adhesive were applied. Ceramic blocks were bonded to resin composite blocks (Z250; 3M ESPE) using one of the cements. Bonded specimens were sectioned into beams (n = 20/group) and subjected to microtensile bond strength tests. Data were analyzed using ANOVA and Student-Newman-Keuls' tests (5%). Failure modes were classified under magnification. Morphologies of the treated ceramic surfaces and bonded interfaces were evaluated by scanning electron microscopy. The HFA-submicron group had lower bond strengths than the other groups. All AA-submicron specimens debonded prematurely. Mixed failures were predominant for HFA groups, whereas interfacial failures predominated for AA groups. SEM revealed a honeycomb-like aspect in the HFA-treated ceramic, whereas the AA-treated groups showed an irregular retentive pattern. Continuity of cement infiltration along the bonded interface was more uniform for HFA-treated compared to AA-treated specimens. Cracks toward the bulk of the ceramic were observed in AA-treated specimens. Particle size significantly influenced the ceramic bond strength, whereas surface treatment had a minor effect.

  4. Evaluation of shear bond strength of composite resin bonded to alloy treated with sandblasting and electrolytic etching.

    Science.gov (United States)

    Goswami, M M; Gupta, S H; Sandhu, H S

    2014-03-01

    Conservation of natural tooth structure precipitated the emergence of resin-retained fixed partial dentures. The weakest link in this modality is the bond between resin cement and alloy of the retainer. Various alloy surface treatment have been recommended to improve alloy-resin bond. This in vitro study was carried out to observe changes in the Nickel-Chromium alloy (Wiron 99, Bego) surface following sandblasting or electrolytic etching treatment by scanning electron microscope (SEM) and to evaluate the shear bond strength of a resin luting cement bonded to the surface treated alloy. 80 alloy blocks were cast and divided into four groups of 20 each. In groups-A & B, the test surfaces were treated by sandblasting with 50 and 250 μm sized aluminium oxide particles respectively. In groups-C & D, the test surfaces were first treated by sandblasting with 50 and 250 μm sized aluminium oxide particles respectively followed by electrolytic etching. Test surfaces were observed under SEM at 1,000× magnification. Two alloy blocks of each group were luted together by a resin luting cement (Rely X, 3M) and their shear bond strength was tested. The mean shear bond strength in MPa of groups-A to D were 6.44 (±0.74), 8.18 (±0.51), 14.45 (±0.59) and 17.43 (±1.20) respectively. Group-D showed bond strength that is more than clinically acceptable bond strength. It is rec