Synthesis of nitriles via palladium-catalyzed water shuffling from amides to acetonitrile.

PubMed

Zhang, Wandi; Haskins, Christopher W; Yang, Yang; Dai, Mingji

2014-12-07

Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.

Chemiluminescent reaction of oxygen atoms with some nitrile compounds

NASA Astrophysics Data System (ADS)

Upadhyaya, Hari P.; Pavanaja, Ubaradka B.; Sapre, Avinash V.; Rama Rao, Kuchimanchi V. S.; Mittal, Jai P.

1994-09-01

In a discharge-flow experiment, chemiluminescent reactions of oxygen atoms (O( 3P)) with organic nitriles (RCN) are studied. For unsaturated nitriles RCN (R: CH 2=CH; CH 2=C(CH 3); CH 2=CH(CH 2)) the observed emission is attributed to CN * (B→X) and NO * (γ:A→X and β: B→X, bands). For saturated and phenyl nitriles (R: CH 3; C 2H 5; C 6H 5) emission is only observed from CN * (B 2Σ +). A suitable reaction mechanism for the observed emission is proposed.

Correlating Nitrile IR Frequencies to Local Electrostatics Quantifies Noncovalent Interactions of Peptides and Proteins.

PubMed

Deb, Pranab; Haldar, Tapas; Kashid, Somnath M; Banerjee, Subhrashis; Chakrabarty, Suman; Bagchi, Sayan

2016-05-05

Noncovalent interactions, in particular the hydrogen bonds and nonspecific long-range electrostatic interactions are fundamental to biomolecular functions. A molecular understanding of the local electrostatic environment, consistently for both specific (hydrogen-bonding) and nonspecific electrostatic (local polarity) interactions, is essential for a detailed understanding of these processes. Vibrational Stark Effect (VSE) has proven to be an extremely useful method to measure the local electric field using infrared spectroscopy of carbonyl and nitrile based probes. The nitrile chemical group would be an ideal choice because of its absorption in an infrared spectral window transparent to biomolecules, ease of site-specific incorporation into proteins, and common occurrence as a substituent in various drug molecules. However, the inability of VSE to describe the dependence of IR frequency on electric field for hydrogen-bonded nitriles to date has severely limited nitrile's utility to probe the noncovalent interactions. In this work, using infrared spectroscopy and atomistic molecular dynamics simulations, we have reported for the first time a linear correlation between nitrile frequencies and electric fields in a wide range of hydrogen-bonding environments that may bridge the existing gap between VSE and H-bonding interactions. We have demonstrated the robustness of this field-frequency correlation for both aromatic nitriles and sulfur-based nitriles in a wide range of molecules of varying size and compactness, including small molecules in complex solvation environments, an amino acid, disordered peptides, and structured proteins. This correlation, when coupled to VSE, can be used to quantify noncovalent interactions, specific or nonspecific, in a consistent manner.

Degradation of blending vulcanized natural rubber and nitril rubber (NR/NBR) by dimethyl ether through variation of elastomer ratio

NASA Astrophysics Data System (ADS)

Saputra, A. H.; Juneva, S.; Sari, T. I.; Cifriadi, A.

2018-04-01

Dimethyl ether can cause degradation of the rubber material seal in some applications. In order to use of natural rubber in industry, research about a blending of natural rubber (NR) and nitrile rubber (NBR) to produce rubber to meet the standard seal material application were conducted. This study will observe the degradation mechanisms that occur in the blending natural rubber and nitrile rubber (NR/NBR) by dimethyl ether. Nitrile rubber types used in this study is medium quality nitrile rubber with 33% of acrylonitrile content (NBR33). The observed parameters are percent change in mass, mechanical properties and surface morphology. This study is limited to see the effect of variation vulcanized blending ratio (NR/NBR33) against to swelling. The increase of nitrile rubber (NBR33) ratio of blending rubber vulcanized can reduce the tensile strength and elongation. The best elastomer variation was obtained after comparing with the standard feasibility material of seal is rubber vulcanized blending (NR/NBR33) with ratio 40:60 NR: NBR.

A comparative study of warheads for design of cysteine protease inhibitors.

PubMed

Silva, Daniel G; Ribeiro, Jean F R; De Vita, Daniela; Cianni, Lorenzo; Franco, Caio Haddad; Freitas-Junior, Lucio H; Moraes, Carolina Borsoi; Rocha, Josmar R; Burtoloso, Antonio C B; Kenny, Peter W; Leitão, Andrei; Montanari, Carlos A

2017-11-15

The effects on potency of cruzain inhibition of replacing a nitrile group with alternative warheads were explored. The oxime was almost an order of magnitude more potent than the corresponding nitrile and has the potential to provide access to the prime side of the catalytic site. Dipeptide aldehydes and azadipeptide nitriles were found to be two orders of magnitude more potent cruzain inhibitors than the corresponding dipeptide nitriles although potency differences were modulated by substitution at P1 and P3. Replacement of the α methylene of a dipeptide aldehyde with cyclopropane led to a loss of potency of almost three orders of magnitude. The vinyl esters and amides that were characterized as reversible inhibitors were less potent than the corresponding nitrile by between one and two orders of magnitude. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Infrared Spectrum of Matrix Isolated Aminoacetonitrile: A Precursor to the Amino Acid Glycine

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Bauschlicher, Charles W., Jr.; Sandford, Scott A.

2003-01-01

We present infrared (IR) spectral data from matrix isolation experiments and density functional theory calculations on the pre-biologically interesting molecule aminoacetonitrile, a precursor to glycine. We find that this nitrile has an unusually weak nitrile (C=N) stretch in the infrared, in contrast to expectations based on measurements and models of other nitriles under astrophysical conditions. The absence of an observable nitrile absorption feature in the infrared will make the IR search for this molecule considerably more difficult, and will raise estimates of upper limits on nitriles in interstellar and outer Solar System ices. This is also of relevance to assessing the formation routes of the amino acid glycine, since aminoacetonitrile is the putative precursor to glycine via the Strecker synthesis, the mechanism postulated to have produced the amino acids in meteorites.

Changes in chemical permeation of disposable latex, nitrile, and vinyl gloves exposed to simulated movement.

PubMed

Phalen, Robert N; Le, Thi; Wong, Weng Kee

2014-01-01

Glove movement can affect chemical permeation of organic compounds through polymer glove products. However, conflicting reports make it difficult to compare the effects of movement on chemical permeation through commonly available glove types. The aim of this study was to evaluate the effect of movement on chemical permeation of an organic solvent through disposable latex, nitrile, and vinyl gloves. Simulated whole-glove permeation testing was conducted using ethyl alcohol and a previously designed permeation test system. With exposure to movement, a significant decrease (p ≤ 0.001) in breakthrough time (BT) was observed for the latex (-23%) and nitrile gloves (-31%). With exposure to movement, only the nitrile glove exhibited a significant increase (p ≤ 0.001) in steady-state permeation rate (+47%) and cumulative permeation at 30 min (+111%). Even though the nitrile glove provided optimum chemical resistance against ethyl alcohol, it was most affected by movement. With exposure to movement, the latex glove was an equivalent option for overall worker protection, because it was less affected by movement and the permeation rate was lower than that of the nitrile glove. In contrast, the vinyl glove was the least affected by movement, but did not provide adequate chemical resistance to ethyl alcohol in comparison with the nitrile and latex gloves. Glove selection should take movement and polymer type into account. Some glove polymer types are less affected by movement, most notably the latex glove in this test. With nitrile gloves, at least a factor of three should be used when attempting to assign a protection factor when repetitive hand motions are anticipated. Ultimately, the latex gloves outperformed nitrile and vinyl in these tests, which evaluated the effect of movement on chemical permeation. Future research should aim to resolve some of the observed discrepancies in test results with latex and vinyl gloves.

Changes in Chemical Permeation of Disposable Latex, Nitrile and Vinyl Gloves Exposed to Simulated Movement

PubMed Central

Phalen, Robert N.; Le, Thi; Wong, Weng Kee

2014-01-01

Glove movement can affect chemical permeation of organic compounds through polymer glove products. However, conflicting reports make it difficult to compare the effects of movement on chemical permeation through commonly available glove types. This study was aimed to evaluate the effect of movement on chemical permeation of an organic solvent through disposable latex, nitrile, and vinyl gloves. Simulated whole-glove permeation testing was conducted using ethyl alcohol and a previously designed permeation test system. With exposure to movement, a significant decrease (p ≤ 0.001) in breakthrough time was observed for the latex (-23%) and nitrile gloves (-31%). With exposure to movement, only the nitrile glove exhibited a significant increase (p ≤ 0.001) in steady-state permeation rate (+47%) and cumulative permeation at 30 min (+111%). Even though the nitrile glove provided optimum chemical resistance against ethyl alcohol, it was most affected by movement. With exposure to movement, the latex glove was an equivalent option for overall worker protection, because it was less affected by movement and the permeation rate was lower than that of the nitrile glove. In contrast, the vinyl glove was the least affected by movement, but did not provide adequate chemical resistance to ethyl alcohol in comparison with the nitrile and latex gloves. In conclusion, glove selection should take movement and polymer type into account. Some glove polymer types are less affected by movement, most notably the latex glove in this test. With nitrile gloves, at least a factor of three should be used when attempting to assign a protection factor when repetitive hand motions are anticipated. Ultimately, the latex gloves outperformed nitrile and vinyl in these tests, which evaluated the effect of movement on chemical permeation. Future research should aim to resolve some of the observed discrepancies in test results with latex and vinyl gloves. PMID:24689368

Replacement Packing for 37MM Antitank Gun Recoil

DTIC Science & Technology

2008-04-01

Parts Per Hundred Rubber (PPHR) NBR -07-GRS-01 Paracril AJ Nitrile Rubber 100.00 Zinc Oxide 5.00 Stearic Acid 1.00 AC) 617 Polyethylene 2.00 (DQ...3 Figure 4. Nitrile rubber compound being produced on rolling mill. ..............................................5 Figure 5. The two...9 List of Tables Table 1. Composition and properties of Nitrile rubber ...................................................................4

Unexpected Catalytic Reactions of Silyl-protected Enoldiazoacetates With Nitrile Oxides That Form 5- Arylaminofuran-2(3H)-one-4-carboxylates

PubMed Central

Xu, Xinfang; Shabashov, Dmitry; Zavalij, Peter Y.; Doyle, Michael P.

2012-01-01

Silyl-protected enoldiazoacetates undergo dirhodium(II) catalyzed reactions with nitrile oxides to form acid-labile ketenimines via dipolar cycloaddition of nitrile oxides to a donor/acceptor cyclopropene and Lossen rearrangement of the dipolar adduct; acid catalysis converts the ketenimine to the furan product. PMID:22272728

Measurement of the membrane dipole electric field in DMPC vesicles using vibrational shifts of p-cyanophenylalanine and molecular dynamics simulations.

PubMed

Shrestha, Rebika; Cardenas, Alfredo E; Elber, Ron; Webb, Lauren J

2015-02-19

The magnitude of the membrane dipole field was measured using vibrational Stark effect (VSE) shifts of nitrile oscillators placed on the unnatural amino acid p-cyanophenylalanine (p-CN-Phe) added to a peptide sequence at four unique positions. These peptides, which were based on a repeating alanine-leucine motif, intercalated into small unilamellar DMPC vesicles which formed an α-helix as confirmed by circular dichroic (CD) spectroscopy. Molecular dynamics simulations of the membrane-intercalated helix containing two of the nitrile probes, one near the headgroup region of the lipid (αLAX(25)) and one buried in the interior of the bilayer (αLAX(16)), were used to examine the structure of the nitrile with respect to the membrane normal, the assumed direction of the dipole field, by quantifying both a small tilt of the helix in the bilayer and conformational rotation of the p-CN-Phe side chain at steady state. Vibrational absorption energies of the nitrile oscillator at each position showed a systematic blue shift as the nitrile was stepped toward the membrane interior; for several different concentrations of peptide, the absorption energy of the nitrile located in the middle of the bilayer was ∼3 cm(-1) greater than that of the nitrile closest to the surface of the membrane. Taken together, the measured VSE shifts and nitrile orientations within the membrane resulted in an absolute magnitude of 8-11 MV/cm for the dipole field, at the high end of the range of possible values that have been accumulated from a variety of indirect measurements. Implications for this are discussed.

Measurement of the Membrane Dipole Electric Field in DMPC Vesicles Using Vibrational Shifts of p-Cyanophenylalanine and Molecular Dynamics Simulations

PubMed Central

Shrestha, Rebika; Cardenas, Alfredo E.; Elber, Ron; Webb, Lauren J.

2015-01-01

The magnitude of the membrane dipole field was measured using vibrational Stark effect (VSE) shifts of nitrile oscillators placed on the unnatural amino acid p-cyanophenylalanine (p-CN-Phe) added to a peptide sequence at four unique positions. These peptides, which were based on a repeating alanine-leucine motif, intercalated into small unilamellar DMPC vesicles which formed an α-helix as confirmed by circular dichroic (CD) spectroscopy. Molecular dynamics simulations of the membrane-intercalated helix containing two of the nitrile probes, one near the head-group region of the lipid (αLAX(25)) and one buried in the interior of the bilayer (αLAX(16)), were used to examine the structure of the nitrile with respect to the membrane normal, the assumed direction the dipole field, by quantifying both a small tilt of the helix in the bilayer and conformational rotation of the p-CN-Phe side chain at steady-state. Vibrational absorption energies of the nitrile oscillator at each position showed a systematic blue shift as the nitrile was stepped towards the membrane interior; for several different concentrations of peptide, the absorption energy of the nitrile located in the middle of the bilayer was ~3 cm−1 greater than that of the nitrile closest to the surface of the membrane. Taken together, the measured VSE shifts and nitrile orientations within the membrane resulted in a value of 8 – 11 MV/cm for the dipole field, at the high end of the range of possible values that have been accumulated from a variety of indirect measurements. Implications for this are discussed. PMID:25602635

Kinetic effects of sulfur oxidation on catalytic nitrile hydration: nitrile hydratase insights from bioinspired ruthenium(II) complexes.

PubMed

Kumar, Davinder; Nguyen, Tho N; Grapperhaus, Craig A

2014-12-01

Kinetic investigations inspired by the metalloenzyme nitrile hydratase were performed on a series of ruthenium(II) complexes to determine the effect of sulfur oxidation on catalytic nitrile hydration. The rate of benzonitrile hydration was quantified as a function of catalyst, nitrile, and water concentrations. Precatalysts L(n)RuPPh3 (n = 1-3; L(1) = 4,7-bis(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(2) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(3) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-sulfenato-propyl)-1-thia-4,7-diazacyclononane) were activated by substitution of triphenylphosphine with substrate in hot dimethylformamide solution. Rate measurements are consistent with a dynamic equilibrium between inactive aqua (L(n)Ru-OH2) and active nitrile (L(n)Ru-NCR) derivatives with K = 21 ± 1, 9 ± 0.9, and 23 ± 3 for L(1) to L(3), respectively. Subsequent hydration of the L(n)Ru-NCR intermediate yields the amide product with measured hydration rate constants (k's) of 0.37 ± 0.01, 0.82 ± 0.07, and 1.59 ± 0.12 M(-1) h(-1) for L(1) to L(3), respectively. Temperature dependent studies reveal that sulfur oxidation lowers the enthalpic barrier by 27 kJ/mol, but increases the entropic barrier by 65 J/(mol K). Density functional theory (DFT) calculations (B3LYP/LanL2DZ (Ru); 6-31G(d) (all other atoms)) support a nitrile bound catalytic cycle with lowering of the reaction barrier as a consequence of sulfur oxidation through enhanced nitrile binding and attack of the water nucleophile through a highly organized transition state.

Unexpected catalytic reactions of silyl-protected enol diazoacetates with nitrile oxides that form 5-arylaminofuran-2(3H)-one-4-carboxylates.

PubMed

Xu, Xinfang; Shabashov, Dmitry; Zavalij, Peter Y; Doyle, Michael P

2012-02-03

Silyl-protected enol diazoacetates undergo dirhodium(II)-catalyzed reactions with nitrile oxides to form acid-labile ketenimines via dipolar cycloaddition of nitrile oxides to a donor/acceptor cyclopropene and Lossen rearrangement of the dipolar adduct; acid catalysis converts the ketenimine to the furan product. © 2012 American Chemical Society

Synthesis of Quinolines through Three-Component Cascade Annulation of Aryl Diazonium Salts, Nitriles, and Alkynes.

PubMed

Wang, Hao; Xu, Qian; Shen, Sheng; Yu, Shouyun

2017-01-06

An efficient and rapid synthesis of multiply substituted quinolines is described. This method is enabled by a three-component cascade annulation of readily available aryl diazonium salts, nitriles, and alkynes. This reaction is catalyst- and additive-free. Various aryl diazonium salts, nitriles, and alkynes can participate in this transformation, and the yields are up to 83%.

Optical and Thermal Stability of Oligofluorene/Rubber Luminescent Blend.

PubMed

Barbosa, Camila G; Faez, Roselena; Péres, Laura O

2016-09-01

This paper proposes to obtain homogeneous and stable blends of oligo(9,9-dioctylfluorene)-co-phenylene (OF), a conjugated oligomer with strong tendency of formation of excimers in the solid state, and nitrile rubber (NBR). This rubber protection reduces the formation of polymer excimers in the films. The fluorene oligomer was synthesized via Suzuki reaction and incorporated in the nitrile rubber. The films were formed by spin coating and casting techniques on the proportions of 1, 5, 10, 20 and 50 % (w/w) of OF in the nitrile rubber (NBR). The structural, optical and thermal properties of the films were evaluated with infrared, UV-Vis, fluorescence and thermogravimetry, respectively. The nitrile rubber proved to be essential for the preparation of homogeneous and stable films, since it was not possible to obtain films with only fluorene using the above-mentioned techniques. Furthermore, luminescent properties of OF are unchanged and the excimers formation in the solid state decrease suggesting the efficiency of nitrile rubber as the matrix for making films.

Measuring Electric Fields in Biological Matter Using the Vibrational Stark Effect of Nitrile Probes

NASA Astrophysics Data System (ADS)

Slocum, Joshua D.; Webb, Lauren J.

2018-04-01

Measurement of the electrostatic interactions that give rise to biological functions has been a longstanding challenge in biophysics. Advances in spectroscopic techniques over the past two decades have allowed for the direct measurement of electric fields in a wide variety of biological molecules and systems via the vibrational Stark effect (VSE). The frequency of the nitrile stretching oscillation has received much attention as an electric field reporter because of its sensitivity to electric fields and its occurrence in a relatively transparent region of the infrared spectrum. Despite these advantages and its wide use as a VSE probe, the nitrile stretching frequency is sensitive to hydrogen bonding in a way that complicates the straightforward relationship between measured frequency and environmental electric field. Here we highlight recent applications of nitrile VSE probes with an emphasis on experiments that have helped shape our understanding of the determinants of nitrile frequencies in both hydrogen bonding and nonhydrogen bonding environments.

Trimerization of aromatic nitriles

NASA Technical Reports Server (NTRS)

Hsu, L. C. (Inventor)

1977-01-01

Triazine compounds and cross-linked polymer compositions were made by heating aromatic nitriles to a temperature in the range of about 100 C to about 700 C, in the presence of a catalyst or mixture of catalysts. Aromatic nitrile-modified (terminated and/or appended) imide, benzimidazole, imidazopyrrolone, quinoxaline, and other condensation type prepolymers or their precopolymers were made which were trimerized with or without a filler by the aforementioned catalytic trimerization process.

Improved Synthesis of 5-Substituted 1H-Tetrazoles via the [3+2] Cycloaddition of Nitriles and Sodium Azide Catalyzed by Silica Sulfuric Acid

PubMed Central

Du, Zhenting; Si, Changmei; Li, Youqiang; Wang, Yin; Lu, Jing

2012-01-01

A silica supported sulfuric acid catalyzed [3+2] cycloaddition of nitriles and sodium azide to form 5-substituted 1H-tetrazoles is described. The protocol can provide a series of 5-substituted 1H-tetrazoles using silica sulfuric acid from nitriles and sodium azide in DMF in 72%–95% yield. PMID:22606004

Multifaceted adsorption of α-cyano-4-hydroxycinnamic acid on silver colloidal and island surfaces

NASA Astrophysics Data System (ADS)

Jung, Dawoon; Jeon, Kooknam; Yeo, Juhyun; Hussain, Shafqat; Pang, Yoonsoo

2017-12-01

The surface adsorption of organic nitrile compounds on the silver colloidal and island surfaces has been studied using surface-enhanced Raman scattering (SERS). α-Cyano-4-hydroxycinnamic acid (CHCA) with nitrile and carboxyl groups shows various surface adsorption on the silver surfaces. In acidic conditions, the surface adsorption of CHCA via the nitrile group with a more or less tilted geometry to the surface was found. When the solution pH increases, the carboxylate and nitrile groups of deprotonated CHCA participate in the surface adsorption, whereas the molecular plane of CHCA becomes more parallel to the surface. The ν(Ctbnd N) band in SERS of CHCA is the indicator of the surface adsorption geometry. The strongly red-shifted and broadened ν(Ctbnd N) band in SERS represents the surface adsorption via π-electrons of the Ctbnd N bond (side-on geometry; π-coordination). Nitriles adsorbed on the surface via the nonbonding electron pair of the nitrogen atom (end-on geometry; σ-coordination) often cause the blue-shifts and small band broadening in ν(Ctbnd N) in SERS. The surface adsorption geometry of organic nitriles based on many previous experimental results was further confirmed by the surface adsorption of CHCA on the silver island surfaces and dinitrile compounds on the silver colloidal surfaces.

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

Lebrilla, C.B.; Drewello, T.; Schwarz, H.

The gas-phase reactions of the transition-metal ions Fe/sup +/ and Co/sup +/ with linear C(4)-C(12) nitriles are reported. In spite of an overall similar reactivity pattern, a more detailed analysis, based on the study of labeled nitriles, reveals distinct differences with regard to the mechanisms of elimination of alkenes and alkanes. For both metal ions, hydrogen and alkenes are generated from linear C(4)-C(12) nitriles, and the intermediates are formed via oxidative addition to terminal and internal C-H bonds. For the RCN/Fe/sup +/ system insertion in an internal C-H bond commences at position C(8) of the nitrile; for the analogous RCN/Co/supmore » +/ system, the oxidative addition to an internal C-H bond starts at position C(7) of the nitrile. Similarly, alkane formation is different for the two transition-metal ions. For RCN/Fe/sup +/ the generation of alkanes is observed for nitriles having at least eight carbon atoms; in contrast, the elimination of alkanes from RCN/Co/sup +/ is already observed for C(6) nitriles. Alkane elimination seems to follow the conventional mechanism (i.e., oxidative addition to a C-C bond, ..beta..-hydrogen transfer, and reductive elimination) for the RCN/Co/sup +/ system, whereas for the RCN/Fe/sup +/ complex there is an additional mechanism. This mechanism corresponds to the loss of H/sub 2/ from an internal position of the alkyl chain followed by the elimination of an alkene. Some possible origins of the different behavior of Fe/sup +/ vs. Co/sup +/ are discussed.« less

Electron localization of anions probed by nitrile vibrations

DOE PAGES

Mani, Tomoyasu; Grills, David C.; Newton, Marshall D.; ...

2015-08-02

Localization and delocalization of electrons is a key concept in chemistry, and is one of the important factors determining the efficiency of electron transport through organic conjugated molecules, which have potential to act as “molecular wires”. This, in turn, substantially influences the efficiencies of organic solar cells and other molecular electronic devices. It is also necessary to understand the electronic energy landscape and the dynamics of electrons through molecular chain that govern their transport capabilities in one-dimensional conjugated chains so that we can better define the design principles of conjugated molecules for their applications. We show that nitrile ν(C≡N) vibrationsmore » respond to the degree of electron localization in nitrile-substituted organic anions by utilizing time-resolved infrared (TRIR) detection combined with pulse radiolysis. Measurements of a series of aryl nitrile anions allow us to construct a semi-empirical calibration curve between the changes in the ν(C≡N) IR shifts and the changes in the electronic charges from the neutral to the anion states in the nitriles; more electron localization in the nitrile anion results in larger IR shifts. Furthermore, the IR linewidth in anions can report a structural change accompanying changes in the electronic density distribution. Probing the shift of the nitrile ν(C≡N) IR vibrational bands enables us to determine how the electron is localized in anions of nitrile-functionalized oligofluorenes, considered as organic mixed-valence compounds. We estimate the diabatic electron transfer distance, electronic coupling strengths, and energy barriers in these organic mixed-valence compounds. The analysis reveals a dynamic picture, showing that the electron is moving back and forth within the oligomers with a small activation energy of ≤ k BT, likely controlled by the movement of dihedral angles between monomer units. Thus, implications for the electron transport capability in "molecular wires" are discussed.« less

NITRILE ELASTOMER-NYLON LAMINATES INCLUDING BARRIER FILMS.

DTIC Science & Technology

ADHESIVES, *NYLON, *NITRILE RUBBER , LAMINATES, LAMINATES, FILMS, TEXTILES, RUBBER COATINGS, BUTADIENES, ACRYLONITRILE POLYMERS, BONDING, ADHESION... DEGRADATION , MOISTUREPROOFING, PHENOLIC PLASTICS, HALOGENATED HYDROCARBONS, ISOCYANATES, CURING AGENTS, ELASTOMERS.

The Effect of Switch-Loading Fuels on Fuel-Wetted Elastomers

DTIC Science & Technology

2007-01-10

material and age of the material”. In summing up past experience, the bulletin stated that “the common denominator is expected to be nitrile rubber ...The expert also noted that “most, if not all manufacturers, responded by eliminating nitrile rubber seals and replacing them with fluorocarbon...materials identified as from the Acrylonitrile- 4 Viton is a name trademarked by DuPont Performance Elastomers L.L.C. Butadiene family (nitrile, NBR

Tetra­kis(aceto­nitrile)copper(I) hydrogen oxalate–oxalic acid–aceto­nitrile (1/0.5/0.5)

PubMed Central

Royappa, A. Timothy; Stepherson, Jacob R.; Vu, Oliver D.; Royappa, Andrew D.; Stern, Charlotte L.; Müller, Peter

2013-01-01

In the title compound, [Cu(CH3CN)4](C2HO4)·0.5C2H2O4·0.5CH3CN, the CuI ion is coordinated by the N atoms of four aceto­nitrile ligands in a slightly distorted tetra­hedral environment. The oxalic acid mol­ecule lies across an inversion center. The aceto­nitrile solvent mol­ecule is disordered across an inversion center and was refined with half occupancy. In the crystal, the hydrogen oxalate anions and oxalic acid mol­ecules are linked via O—H⋯O hydrogen bonds, forming chains along [010]. PMID:24098175

Vacuum Ultraviolet Photoabsorption Spectra of Nitrile Ices for their Identification on Pluto

NASA Astrophysics Data System (ADS)

Sivaraman, B.; Pavithraa, S.; Lo, J.-I.; Raja Sekhar, B. N.; Hill, H.; Cheng, B.-M.; Mason, N. J.

2016-07-01

Icy bodies, such as Pluto, are known to harbor simple and complex molecules. The recent New Horizons flyby of Pluto has revealed a complex surface composed of bright and dark ice surfaces, indicating a rich chemistry based on nitrogen (N2), methane (CH4), and carbon monoxide (CO). Nitrile (CN) containing molecules such as acetonitrile (CH3CN), propionitrile (CH3CH2CN), butyronitrile (CH3CH2CH2CN), and isobutyronitrile ((CH3)2CHCN) are some of the nitrile molecules that are known to be synthesized by radiative processing of such simple ices. Through the provision of a spectral atlas for such compounds we propose that such nitriles may be identified from the ALICE payload on board New Horizons.

Nitriles as directionally tolerant hydrogen bond acceptors: IR-UV ion depletion spectroscopy of benzenepropanenitrile and its hydrate clusters

NASA Astrophysics Data System (ADS)

Robertson, Patrick A.; Lobo, Isabella A.; Wilson, David J. D.; Robertson, Evan G.

2016-09-01

Benzenepropanenitrile (BPN) and its hydrate clusters are studied by R2PI and IR-UV ion-depletion spectroscopy in the CH/OH stretch regions, aided by theoretical calculations. A single water molecule binds to the terminal nitrile 'lone-pair' of the anti-BPN host, but there is also evidence for a side-type structure with OH donating to the nitrile π-electrons. In the gauche-BPN cluster, water is located at an intermediate angle that facilitates O⋯HC(ortho) interaction. A wide range of attachment angles is possible, as the intrinsic preference for linear hydrogen bonding is mediated by additional CH⋯O interactions that depend on molecular geometry near the nitrile group.

NSP-Dependent Simple Nitrile Formation Dominates upon Breakdown of Major Aliphatic Glucosinolates in Roots, Seeds, and Seedlings of Arabidopsis thaliana Columbia-0.

PubMed

Wittstock, Ute; Meier, Kathrin; Dörr, Friederike; Ravindran, Beena M

2016-01-01

One of the best-studied plant defense systems, the glucosinolate-myrosinase system of the Brassicales, is composed of thioglucosides known as glucosinolates and their hydrolytic enzymes, the myrosinases. Tissue disruption brings these components together, and bioactive products are formed as a consequence of myrosinase-catalyzed glucosinolate hydrolysis. Among these products, isothiocyanates have attracted most interest as chemical plant defenses against herbivores and pathogens and health-promoting compounds in the human diet. Previous research has identified specifier proteins whose presence results in the formation of alternative product types, e.g., nitriles, at the expense of isothiocyanates. The biological roles of specifier proteins and alternative breakdown products are poorly understood. Here, we assessed glucosinolate breakdown product profiles obtained upon maceration of roots, seedlings and seeds of Arabidopsis thaliana Columbia-0. We identified simple nitriles as the predominant breakdown products of the major endogenous aliphatic glucosinolates in root, seed, and seedling homogenates. In agreement with this finding, genes encoding nitrile-specifier proteins (NSPs) are expressed in roots, seeds, and seedlings. Analysis of glucosinolate breakdown in mutants with T-DNA insertions in any of the five NSP genes demonstrated, that simple nitrile formation upon tissue disruption depended almost entirely on NSP2 in seeds and mainly on NSP1 in seedlings. In roots, about 70-80% of the nitrile-forming activity was due to NSP1 and NSP3 . Thus, glucosinolate breakdown product profiles are organ-specifically regulated in A. thaliana Col-0, and high proportions of simple nitriles are formed in some parts of the plant. This should be considered in future studies on biological roles of the glucosinolate-myrosinase system.

NSP-Dependent Simple Nitrile Formation Dominates upon Breakdown of Major Aliphatic Glucosinolates in Roots, Seeds, and Seedlings of Arabidopsis thaliana Columbia-0

PubMed Central

Wittstock, Ute; Meier, Kathrin; Dörr, Friederike; Ravindran, Beena M.

2016-01-01

One of the best-studied plant defense systems, the glucosinolate-myrosinase system of the Brassicales, is composed of thioglucosides known as glucosinolates and their hydrolytic enzymes, the myrosinases. Tissue disruption brings these components together, and bioactive products are formed as a consequence of myrosinase-catalyzed glucosinolate hydrolysis. Among these products, isothiocyanates have attracted most interest as chemical plant defenses against herbivores and pathogens and health-promoting compounds in the human diet. Previous research has identified specifier proteins whose presence results in the formation of alternative product types, e.g., nitriles, at the expense of isothiocyanates. The biological roles of specifier proteins and alternative breakdown products are poorly understood. Here, we assessed glucosinolate breakdown product profiles obtained upon maceration of roots, seedlings and seeds of Arabidopsis thaliana Columbia-0. We identified simple nitriles as the predominant breakdown products of the major endogenous aliphatic glucosinolates in root, seed, and seedling homogenates. In agreement with this finding, genes encoding nitrile-specifier proteins (NSPs) are expressed in roots, seeds, and seedlings. Analysis of glucosinolate breakdown in mutants with T-DNA insertions in any of the five NSP genes demonstrated, that simple nitrile formation upon tissue disruption depended almost entirely on NSP2 in seeds and mainly on NSP1 in seedlings. In roots, about 70–80% of the nitrile-forming activity was due to NSP1 and NSP3. Thus, glucosinolate breakdown product profiles are organ-specifically regulated in A. thaliana Col-0, and high proportions of simple nitriles are formed in some parts of the plant. This should be considered in future studies on biological roles of the glucosinolate-myrosinase system. PMID:27990154

Controllable cyanation of carbon-hydrogen bonds by zeolite crystals over manganese oxide catalyst

PubMed Central

Wang, Liang; Wang, Guoxiong; Zhang, Jian; Bian, Chaoqun; Meng, Xiangju; Xiao, Feng-Shou

2017-01-01

The synthesis of organic nitriles without using toxic cyanides is in great demand but challenging to make. Here we report an environmentally benign and cost-efficient synthesis of nitriles from the direct oxidative cyanation of primary carbon-hydrogen bonds with easily available molecular oxygen and urea. The key to this success is to design and synthesize manganese oxide catalysts fixed inside zeolite crystals, forming a manganese oxide catalyst with zeolite sheath (MnOx@S-1), which exhibits high selectivity for producing nitriles by efficiently facilitating the oxidative cyanation reaction and hindering the side hydration reaction. The work delineates a sustainable strategy for synthesizing nitriles while avoiding conventional toxic cyanide, which might open a new avenue for selective transformation of carbon-hydrogen bonds. PMID:28504259

Aging-Resistant Functionalized LDH⁻SAS/Nitrile-Butadiene Rubber Composites: Preparation and Study of Aging Kinetics/Anti-Aging Mechanism.

PubMed

Li, Tianxiang; Shi, Zhengren; He, Xianru; Jiang, Ping; Lu, Xiaobin; Zhang, Rui; Wang, Xin

2018-05-18

With the aim of improving the anti-aging properties of nitrile-butadiene rubber (NBR), a functional organic filler, namely LDH⁻SAS, prepared by intercalating 4-amino-benzenesulfonic acid monosodium salt (SAS) into layered double hydroxides (LDHs) through anion exchange, was added to nitrile-butadiene rubber (NBR), giving the NBR/LDH⁻SAS composites. Successful preparation of LDH⁻SAS was confirmed by XRD, TGA and FTIR. LDH⁻SAS was well dispersed in the NBR matrix, owing to its strong interaction with the nitrile group of NBR. The obtained NBR/LDH⁻SAS composites exhibited excellent thermo-oxidative aging resistance as shown by TGA-DSC. Further investigation by ATR-FTIR indicated that SAS can capture the radical groups, even during the aging process, which largely accounts for the improved aging resistance.

Development of tough, moisture resistant laminating resins

NASA Technical Reports Server (NTRS)

Brand, R. A.; Harrison, E. S.

1982-01-01

Tough, moisture resistant laminating resins for employment with graphite fibers were developed. The new laminating resins exhibited cost, handleability and processing characteristics equivalent to 394K (250 F) curing epoxies. The laminating resins were based on bisphenol A dicyanate and monofunctional cyanates with hydrophobic substituents. These resins sorb only small quantities of moisture at equilibrium (0.5% or less) with minimal glass transition temperature depression and represent an improvement over epoxies which sorb around 2% moisture at equilibrium. Toughening was accomplished by the precipitation of small diameter particles of butadiene nitrile rubber throughout the resin matrix. The rubber domains act as microcrack termini and energy dissipation sites, allowing increased stress accommodation prior to catastrophic failure. A unique blend of amine terminated butadiene nitrile elastomer (MW 2,000) and a high nitrile content butadiene nitrile rubber yielded the desired resin morphology.

Aging-Resistant Functionalized LDH–SAS/Nitrile-Butadiene Rubber Composites: Preparation and Study of Aging Kinetics/Anti-Aging Mechanism

PubMed Central

Li, Tianxiang; Shi, Zhengren; He, Xianru; Jiang, Ping; Lu, Xiaobin; Zhang, Rui

2018-01-01

With the aim of improving the anti-aging properties of nitrile-butadiene rubber (NBR), a functional organic filler, namely LDH–SAS, prepared by intercalating 4-amino-benzenesulfonic acid monosodium salt (SAS) into layered double hydroxides (LDHs) through anion exchange, was added to nitrile-butadiene rubber (NBR), giving the NBR/LDH–SAS composites. Successful preparation of LDH–SAS was confirmed by XRD, TGA and FTIR. LDH–SAS was well dispersed in the NBR matrix, owing to its strong interaction with the nitrile group of NBR. The obtained NBR/LDH–SAS composites exhibited excellent thermo-oxidative aging resistance as shown by TGA-DSC. Further investigation by ATR-FTIR indicated that SAS can capture the radical groups, even during the aging process, which largely accounts for the improved aging resistance. PMID:29783656

VACUUM ULTRAVIOLET PHOTOABSORPTION SPECTRA OF NITRILE ICES FOR THEIR IDENTIFICATION ON PLUTO

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

Sivaraman, B.; Pavithraa, S.; Lo, J.-I.

Icy bodies, such as Pluto, are known to harbor simple and complex molecules. The recent New Horizons flyby of Pluto has revealed a complex surface composed of bright and dark ice surfaces, indicating a rich chemistry based on nitrogen (N{sub 2}), methane (CH{sub 4}), and carbon monoxide (CO). Nitrile (CN) containing molecules such as acetonitrile (CH{sub 3}CN), propionitrile (CH{sub 3}CH{sub 2}CN), butyronitrile (CH{sub 3}CH{sub 2}CH{sub 2}CN), and isobutyronitrile ((CH{sub 3}){sub 2}CHCN) are some of the nitrile molecules that are known to be synthesized by radiative processing of such simple ices. Through the provision of a spectral atlas for such compoundsmore » we propose that such nitriles may be identified from the ALICE payload on board New Horizons .« less

Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles.

PubMed

Lambert, Kyle M; Bobbitt, James M; Eldirany, Sherif A; Kissane, Liam E; Sheridan, Rose K; Stempel, Zachary D; Sternberg, Francis H; Bailey, William F

2016-04-04

Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98% isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Biotransformation of β-keto nitriles to chiral (S)-β-amino acids using nitrilase and ω-transaminase.

PubMed

Mathew, Sam; Nadarajan, Saravanan Prabhu; Sundaramoorthy, Uthayasuriya; Jeon, Hyunwoo; Chung, Taeowan; Yun, Hyungdon

2017-04-01

To enzymatically synthesize enantiomerically pure β-amino acids from β-keto nitriles using nitrilase and ω-transaminase. An enzyme cascade system was designed where in β-keto nitriles are initially hydrolyzed to β-keto acids using nitrilase from Bradyrhizobium japonicum and subsequently β-keto acids were converted to β-amino acids using ω-transaminases. Five different ω-transaminases were tested for this cascade reaction, To enhance the yields of β-amino acids, the concentrations of nitrilase and amino donor were optimized. Using this enzymatic reaction, enantiomerically pure (S)-β-amino acids (ee > 99%) were generated. As nitrilase is the bottleneck in this reaction, molecular docking analysis was carried out to depict the poor affinity of nitrilase towards β-keto acids. A novel enzymatic route to generate enantiomerically pure aromatic (S)-β-amino acids from β-keto nitriles is demonstrated for the first time.

40 CFR Table 5 to Subpart U of... - Known Organic HAP Emitted From the Production of Elastomer Products

Code of Federal Regulations, 2014 CFR

2014-07-01

... products] Organic HAP/Chemical name (CAS No.) Elastomer product/subcategory BR EPI EPR HYP NEO NBL NBR PBR.... NEO = Neoprene. NBL = Nitrile Butadiene Latex. NBR = Nitrile Butadiene Rubber. PBR/SBRS...

40 CFR Table 5 to Subpart U of... - Known Organic HAP Emitted From the Production of Elastomer Products

Code of Federal Regulations, 2012 CFR

2012-07-01

... products] Organic HAP/Chemical name (CAS No.) Elastomer product/subcategory BR EPI EPR HYP NEO NBL NBR PBR.... NEO = Neoprene. NBL = Nitrile Butadiene Latex. NBR = Nitrile Butadiene Rubber. PBR/SBRS...

40 CFR Table 5 to Subpart U of... - Known Organic HAP Emitted From the Production of Elastomer Products

Code of Federal Regulations, 2011 CFR

2011-07-01

... products] Organic HAP/Chemical name (CAS No.) Elastomer product/subcategory BR EPI EPR HYP NEO NBL NBR PBR.... NEO = Neoprene. NBL = Nitrile Butadiene Latex. NBR = Nitrile Butadiene Rubber. PBR/SBRS...

40 CFR Table 5 to Subpart U of... - Known Organic HAP Emitted From the Production of Elastomer Products

Code of Federal Regulations, 2013 CFR

2013-07-01

... products] Organic HAP/Chemical name (CAS No.) Elastomer product/subcategory BR EPI EPR HYP NEO NBL NBR PBR.... NEO = Neoprene. NBL = Nitrile Butadiene Latex. NBR = Nitrile Butadiene Rubber. PBR/SBRS...

Investigation of surface halide modification of nitrile butadiene rubber

NASA Astrophysics Data System (ADS)

Sukhareva, K. V.; Mikhailov, I. A.; Andriasyan, Yu O.; Mastalygina, E. E.; Popov, A. A.

2017-12-01

The investigation is devoted to the novel technology of surface halide modification of rubber samples based on nitrile butadiene rubber (NBR). 1,1,2-trifluoro-1,2,2-trichlorethane was used as halide modifier. The developed technology is characterized by production stages reduction to one by means of treating the rubber compound with a halide modifier. The surface halide modification of compounds based on nitrile butadiene rubber (NBR) was determined to result in increase of resistance to thermal oxidation and aggressive media. The conducted research revealed the influence of modification time on chemical resistance and physical-mechanical properties of rubbers under investigation.

Test and Evaluation for Chemical Resistance of Gloves Worn for Protection against Exposure to H-70 Hydrazine.

DTIC Science & Technology

1980-07-01

Edmont-Wilson 37-165 NBR .056 (22) 10 J Edmont-Wilson 26-665 Rubber .046 (18) 10 K Edmont-Wilson 36-755 Rubber .102 (40) 10 L Surety 10-112L Nitrile...4367 Dickenson & Company Charleston SC 29405 Coshocton OH 43812 International Playtex Company Surety Rubber Company Industrial Gloves Division P.O. Box...B Pioneer A-10 Nitrile .025 (10) 9 C Pioneer A-15 Nitrile .038 (15) 9 D Norton NSN 8415-00-753-6551 Butyl rubber .076 (30) M E Norton NSN 8415-01-025

Ferric Hydrogensulfate [Fe(HSO4)3] As a Reusable Heterogeneous Catalyst for the Synthesis of 5-Substituted-1H-Tetrazoles and Amides

PubMed Central

Eshghi, Hossein; Seyedi, Seyed Mohammad; Zarei, Elaheh Rahimi

2011-01-01

Ferric hydrogensulfate catalyzed the synthesis of 5-substituted 1H-tetrazoles via [2 + 3] cycloaddition of nitriles and sodium azide. This method has the advantages of high yields, simple methodology, and easy workup. The catalyst can be recovered by simple filtration and reused delivering good yields. Also, ferric hydrogensulfate catalyzed the hydrolysis of nitriles to primary amides under aqueous conditions. Various aliphatic and aromatic nitriles converted to the corresponding amides in good yields without any contamination with carboxylic acids. PMID:24052817

Reactions of nitriles in ices relevant to Titan, comets, and the interstellar medium: formation of cyanate ion, ketenimines, and isonitriles

NASA Astrophysics Data System (ADS)

Hudson, R. L.; Moore, M. H.

2004-12-01

Motivated by detections of nitriles in Titan's atmosphere, cometary comae, and the interstellar medium, we report laboratory investigations of the low-temperature chemistry of acetonitrile, propionitrile, acrylonitrile, cyanoacetylene, and cyanogen (CH 3CN, CH 3CH 2CN, CH 2CHCN, HCCCN, and NCCN, respectively). A few experiments were also done on isobutyronitrile and trimethylacetonitrile ((CH 3) 2CHCN and (CH 3) 3CCN, respectively). Trends were sought, and found, in the photo- and radiation chemical products of these molecules at 12-25 K. In the absence of water, all of these molecules isomerized to isonitriles, and CH 3CN, CH 3CH 2CN, and (CH 3) 2CHCN also formed ketenimines. In the presence of H 2O, no isonitriles were detected but rather the cyanate ion (OCN -) was seen in all cases. Although isonitriles, ketenimines, and OCN - were the main focus of our work, we also describe cases of hydrogen loss, to make smaller nitriles, and hydrogen addition (reduction), to make larger nitriles. HCN formation also was seen in most experiments. The results are presented in terms of nitrile ice chemistry on Titan, in cometary ice, and in the interstellar medium. Possible connections to prebiotic chemistry are briefly discussed.

Formation and nitrile hydrogenation performance of Ru nanoparticles on a K-doped Al2O3 surface.

PubMed

Muratsugu, Satoshi; Kityakarn, Sutasinee; Wang, Fei; Ishiguro, Nozomu; Kamachi, Takashi; Yoshizawa, Kazunari; Sekizawa, Oki; Uruga, Tomoya; Tada, Mizuki

2015-10-14

Decarbonylation-promoted Ru nanoparticle formation from Ru3(CO)12 on a basic K-doped Al2O3 surface was investigated by in situ FT-IR and in situ XAFS. Supported Ru3(CO)12 clusters on K-doped Al2O3 were converted stepwise to Ru nanoparticles, which catalyzed the selective hydrogenation of nitriles to the corresponding primary amines via initial decarbonylation, the nucleation of the Ru cluster core, and the growth of metallic Ru nanoparticles on the surface. As a result, small Ru nanoparticles, with an average diameter of less than 2 nm, were formed on the support and acted as efficient catalysts for nitrile hydrogenation at 343 K under hydrogen at atmospheric pressure. The structure and catalytic performance of Ru catalysts depended strongly on the type of oxide support, and the K-doped Al2O3 support acted as a good oxide for the selective nitrile hydrogenation without basic additives like ammonia. The activation of nitriles on the modelled Ru catalyst was also investigated by DFT calculations, and the adsorption structure of a nitrene-like intermediate, which was favourable for high primary amine selectivity, was the most stable structure on Ru compared with other intermediate structures.

Vibrational Stark effect spectroscopy reveals complementary electrostatic fields created by protein-protein binding at the interface of Ras and Ral.

PubMed

Walker, David M; Hayes, Ellen C; Webb, Lauren J

2013-08-07

Electrostatic fields at the interface of the GTPase H-Ras (Ras) docked with the Ras binding domain of the protein Ral guanine nucleoside dissociation stimulator (Ral) were measured with vibrational Stark effect (VSE) spectroscopy. Nine residues on the surface of Ras that participate in the protein-protein interface were systematically mutated to cysteine and subsequently converted to cyanocysteine in order to introduce a nitrile VSE probe into the protein-protein interface. The absorption energy of the nitrile was measured both on the surface of Ras in its monomeric state, then after incubation with the Ras binding domain of Ral to form the docked complex. Boltzmann-weighted structural snapshots of the nitrile-labeled Ras protein were generated both in monomeric and docked configurations from molecular dynamics simulations using enhanced sampling of the cyanocysteine side chain's χ2 dihedral angle. These snapshots were used to determine that on average, most of the nitrile probes were aligned along the Ras surface, parallel to the Ras-Ral interface. The average solvent-accessible surface areas (SASA) of the cyanocysteine side chain were found to be <60 Å(2) for all measured residues, and was not significantly different whether the nitrile was on the surface of the Ras monomer or immersed in the docked complex. Changes in the absorption energy of the nitrile probe at nine positions along the Ras-Ral interface were compared to results of a previous study examining this interface with Ral-based probes, and found a pattern of low electrostatic field in the core of the interface surrounded by a ring of high electrostatic field around the perimeter of the interface. These data are used to rationalize several puzzling features of the Ras-Ral interface.

Characterization of a nitrilase and a nitrile hydratase from Pseudomonas sp. strain UW4 that converts indole-3-acetonitrile to indole-3-acetic acid.

PubMed

Duca, Daiana; Rose, David R; Glick, Bernard R

2014-08-01

Indole-3-acetic acid (IAA) is a fundamental phytohormone with the ability to control many aspects of plant growth and development. Pseudomonas sp. strain UW4 is a rhizospheric plant growth-promoting bacterium that produces and secretes IAA. While several putative IAA biosynthetic genes have been reported in this bacterium, the pathways leading to the production of IAA in strain UW4 are unclear. Here, the presence of the indole-3-acetamide (IAM) and indole-3-acetaldoxime/indole-3-acetonitrile (IAOx/IAN) pathways of IAA biosynthesis is described, and the specific role of two of the enzymes (nitrilase and nitrile hydratase) that mediate these pathways is assessed. The genes encoding these two enzymes were expressed in Escherichia coli, and the enzymes were isolated and characterized. Substrate-feeding assays indicate that the nitrilase produces both IAM and IAA from the IAN substrate, while the nitrile hydratase only produces IAM. The two nitrile-hydrolyzing enzymes have very different temperature and pH optimums. Nitrilase prefers a temperature of 50°C and a pH of 6, while nitrile hydratase prefers 4°C and a pH of 7.5. Based on multiple sequence alignments and motif analyses, physicochemical properties and enzyme assays, it is concluded that the UW4 nitrilase has an aromatic substrate specificity. The nitrile hydratase is identified as an iron-type metalloenzyme that does not require the help of a P47K activator protein to be active. These data are interpreted in terms of a preliminary model for the biosynthesis of IAA in this bacterium.

Impact of thermal processing on sulforaphane yield from broccoli ( Brassica oleracea L. ssp. italica).

PubMed

Wang, Grace C; Farnham, Mark; Jeffery, Elizabeth H

2012-07-11

In broccoli, sulforaphane forms when the glucosinolate glucoraphanin is hydrolyzed by the endogenous plant thiohydrolase myrosinase. A myrosinase cofactor directs hydrolysis away from the formation of bioactive sulforaphane and toward an inactive product, sulforaphane nitrile. The cofactor is more heat sensitive than myrosinase, presenting an opportunity to preferentially direct hydrolysis toward sulforaphane formation through regulation of thermal processing. Four broccoli cultivars were microwave heated, boiled, or steamed for various lengths of time. Production of nitrile during hydrolysis of unheated broccoli varied among cultivars from 91 to 52% of hydrolysis products (Pinnacle > Marathon > Patriot > Brigadier). Boiling and microwave heating caused an initial loss of nitrile, with a concomitant increase in sulforaphane, followed by loss of sulforaphane, all within 1 min. In contrast, steaming enhanced sulforaphane yield between 1.0 and 3.0 min in all but Brigadier. These data are proof of concept that steaming for 1.0-3.0 min provides less nitrile and more sulforaphane yield from a broccoli meal.

Isolation, identification, and culture optimization of a novel glycinonitrile-hydrolyzing fungus-Fusarium oxysporum H3.

PubMed

Gong, Jin-Song; Lu, Zhen-Ming; Shi, Jing-Song; Dou, Wen-Fang; Xu, Hong-Yu; Zhou, Zhe-Min; Xu, Zheng-Hong

2011-10-01

Microbial transformation of glycinonitrile into glycine by nitrile hydrolase is of considerable interest to green chemistry. A novel fungus with high nitrile hydrolase was newly isolated from soil samples and identified as Fusarium oxysporum H3 through 18S ribosomal DNA, 28S ribosomal DNA, and the internal transcribed spacer sequence analysis, together with morphology characteristics. After primary optimization of culture conditions including pH, temperature, carbon/nitrogen sources, inducers, and metal ions, the enzyme activity was greatly increased from 326 to 4,313 U/L. The preferred carbon/nitrogen sources, inducer, and metal ions were glucose and yeast extract, caprolactam, and Cu(2+), Mn(2+), and Fe(2+), respectively. The maximum enzyme formation was obtained when F. oxysporum H3 was cultivated at 30 °C for 54 h with the initial pH of 7.2. There is scanty report about the optimization of nitrile hydrolase production from nitrile-converting fungus.

Optimization of triazine nitriles as rhodesain inhibitors: structure-activity relationships, bioisosteric imidazopyridine nitriles, and X-ray crystal structure analysis with human cathepsin L.

PubMed

Ehmke, Veronika; Winkler, Edwin; Banner, David W; Haap, Wolfgang; Schweizer, W Bernd; Rottmann, Matthias; Kaiser, Marcel; Freymond, Céline; Schirmeister, Tanja; Diederich, François

2013-06-01

The cysteine protease rhodesain of Trypanosoma brucei parasites causing African sleeping sickness has emerged as a target for the development of new drug candidates. Based on a triazine nitrile moiety as electrophilic headgroup, optimization studies on the substituents for the S1, S2, and S3 pockets of the enzyme were performed using structure-based design and resulted in inhibitors with inhibition constants in the single-digit nanomolar range. Comprehensive structure-activity relationships clarified the binding preferences of the individual pockets of the active site. The S1 pocket tolerates various substituents with a preference for flexible and basic side chains. Variation of the S2 substituent led to high-affinity ligands with inhibition constants down to 2 nM for compounds bearing cyclohexyl substituents. Systematic investigations on the S3 pocket revealed its potential to achieve high activities with aromatic vectors that undergo stacking interactions with the planar peptide backbone forming part of the pocket. X-ray crystal structure analysis with the structurally related enzyme human cathepsin L confirmed the binding mode of the triazine ligand series as proposed by molecular modeling. Sub-micromolar inhibition of the proliferation of cultured parasites was achieved for ligands decorated with the best substituents identified through the optimization cycles. In cell-based assays, the introduction of a basic side chain on the inhibitors resulted in a 35-fold increase in antitrypanosomal activity. Finally, bioisosteric imidazopyridine nitriles were studied in order to prevent off-target effects with unselective nucleophiles by decreasing the inherent electrophilicity of the triazine nitrile headgroup. Using this ligand, the stabilization by intramolecular hydrogen bonding of the thioimidate intermediate, formed upon attack of the catalytic cysteine residue, compensates for the lower reactivity of the headgroup. The imidazopyridine nitrile ligand showed excellent stability toward the thiol nucleophile glutathione in a quantitative in vitro assay and fourfold lower cytotoxicity than the parent triazine nitrile. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural Characteristics and Swelling Mechanism of Two Commercial Nitrile-Butadiene Elastomers in Various Fluids

DTIC Science & Technology

2012-01-06

polyacrylonitrile, -(CH2=CH- C ≡ N )- n and polybutadiene, -(CH2-CH=CH-CH2)- n . The characteristics of a given elastomer are therefore expected to depend on the...presence of the nitrile (cyano) - C ≡ N group which is known to yield a sharp peak at 2235 cm-1 in IR spectra. The presence of the line due to C = C double bond...70 and N0741-75 obtained using KBr pellet method are shown in Fig. 2. In the IR spectra of both elastomers, the nitrile (- C ≡ N ) band at 2235 cm-1 is

Ruthenium-catalyzed aerobic oxidative decarboxylation of amino acids: a green, zero-waste route to biobased nitriles.

PubMed

Claes, Laurens; Verduyckt, Jasper; Stassen, Ivo; Lagrain, Bert; De Vos, Dirk E

2015-04-18

Oxidative decarboxylation of amino acids into nitriles was performed using molecular oxygen as terminal oxidant and a heterogeneous ruthenium hydroxide-based catalyst. A range of amino acids was oxidized in very good yield, using water as the solvent.

Bio-inspired nitrile hydration by peptidic ligands based on L-cysteine, L-methionine or L-penicillamine and pyridine-2,6-dicarboxylic acid.

PubMed

Byrne, Cillian; Houlihan, Kate M; Devi, Prarthana; Jensen, Paul; Rutledge, Peter J

2014-12-12

Nitrile hydratase (NHase, EC 4.2.1.84) is a metalloenzyme which catalyses the conversion of nitriles to amides. The high efficiency and broad substrate range of NHase have led to the successful application of this enzyme as a biocatalyst in the industrial syntheses of acrylamide and nicotinamide and in the bioremediation of nitrile waste. Crystal structures of both cobalt(III)- and iron(III)-dependent NHases reveal an unusual metal binding motif made up from six sequential amino acids and comprising two amide nitrogens from the peptide backbone and three cysteine-derived sulfur ligands, each at a different oxidation state (thiolate, sulfenate and sulfinate). Based on the active site geometry revealed by these crystal structures, we have designed a series of small-molecule ligands which integrate essential features of the NHase metal binding motif into a readily accessible peptide environment. We report the synthesis of ligands based on a pyridine-2,6-dicarboxylic acid scaffold and L-cysteine, L-S-methylcysteine, L-methionine or L-penicillamine. These ligands have been combined with cobalt(III) and iron(III) and tested as catalysts for biomimetic nitrile hydration. The highest levels of activity are observed with the L-penicillamine ligand which, in combination with cobalt(III), converts acetonitrile to acetamide at 1.25 turnovers and benzonitrile to benzamide at 1.20 turnovers.

40 CFR 721.555 - Alkyl amino nitriles (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... (c). A full face shield is required if splashing or spraying occurs. (ii) Hazard communication... to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96-1674 and P-96-1675) are subject to reporting under this section for the significant new uses described...

40 CFR 63.494 - Back-end process provisions-residual organic HAP and emission limitations.

Code of Federal Regulations, 2011 CFR

2011-07-01

... producing butyl rubber, epichlorohydrin elastomer, neoprene, and nitrile butadiene rubber shall not exceed... processes at affected sources producing butyl rubber, epichlorohydrin elastomer, neoprene, and nitrile... submitted in accordance with § 63.499(f)(1). (i) For butyl rubber, the organic HAP emission limitation shall...

A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides

EPA Science Inventory

One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this...

Ruthenium hydroxide supported on magnetic nanoparticles: a benign aqueous protocol for hydration of nitriles

EPA Science Inventory

Amides are an important class of compounds in the chemical and pharmaceutical industry1,2. Conventionally, amides have been synthesized by the hydration of nitriles, catalyzed by strong acids3 and bases4. Many by-products such as carboxylic acids are produced due to hydrolysis of...

Crystal structure of 2-azido-1 H -imidazole-4,5-dicarbonitrile

DOE PAGES

Windler, G. Kenneth; Scott, Brian L.; Tomson, Neil C.; ...

2015-08-06

We report that in the title compound, C 5HN 7, the nitrile and azido substituents are close to being coplanar with the central ring. Molecules in the crystal are linked via an N—H...N hydrogen bond to a nitrile acceptor, forming a chain extending along the c-axis direction.

Nitrilase enzymes and their role in plant–microbe interactions

PubMed Central

Howden, Andrew J. M.; Preston, Gail M.

2009-01-01

Summary Nitrilase enzymes (nitrilases) catalyse the hydrolysis of nitrile compounds to the corresponding carboxylic acid and ammonia, and have a wide range of industrial and biotechnological applications, including the synthesis of industrially important carboxylic acids and bioremediation of cyanide and toxic nitriles. Nitrilases are produced by a wide range of organisms, including plants, bacteria and fungi, but despite their biotechnological importance, the role of these enzymes in living organisms is relatively underexplored. Current research suggests that nitrilases play important roles in a range of biological processes. In the context of plant–microbe interactions they may have roles in hormone synthesis, nutrient assimilation and detoxification of exogenous and endogenous nitriles. Nitrilases are produced by both plant pathogenic and plant growth‐promoting microorganisms, and their activities may have a significant impact on the outcome of plant–microbe interactions. In this paper we review current knowledge of the role of nitriles and nitrilases in plants and plant‐associated microorganisms, and discuss how greater understanding of the natural functions of nitrilases could be applied to benefit both industry and agriculture. PMID:21255276

Infrared Spectra and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

NASA Technical Reports Server (NTRS)

Anderson, Carrie; Ferrante, Robert F.; Moore, W. James; Hudson, Reggie; Moore, Marla H.

2011-01-01

Spectra and optical constants of nitrile ices known or suspected to be in Titan?s atmosphere have been determined from 2.0 to 333.3 microns (approx.5000 to 30/cm). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan?s winter pole. Ices studied were: HCN, hydrogen cyanide; C2N2, cyanogen; CH3CN, acetonitrile; C2H5CN, propionitrile; and HC3N, cyanoacetylene. Optical constants were calculated, using Kramers-Kronig analysis, for each nitrile ice?s spectrum measured at a variety of temperatures, in both the amorphous- and crystalline phases. Spectra were also measured for many of the nitriles after quenching at the annealing temperature and compared with those of annealed ices. For each of these molecules we also measured the real component, n, of the refractive index for amorphous and crystalline phases at 670 nm. Several examples of the information contained in these new data sets and their usefulness in modeling Titan?s observed features will be presented (e.g., the broad emission feature at 160/cm; Anderson and Samuelson, 2011).

Nitrile imines and nitrile ylides: rearrangements of benzonitrile N-methylimine and benzonitrile dimethylmethylide to azabutadienes, carbodiimides, and ketenimines. Chemical activation in thermolysis of azirenes, tetrazoles, oxazolones, isoxazolones, and oxadiazolones.

PubMed

Bégué, Didier; Dargelos, Alain; Berstermann, Hans M; Netsch, Klaus P; Bednarek, Pawel; Wentrup, Curt

2014-02-07

Flash vacuum thermolysis (FVT) of 1-methyl-5-phenyltetrazole (5b), 2-methyl-5-phenyltetrazole (1b), and 3-methyl-5-phenyl-1,3,4-oxadiazol-2(3H)-one (3b) affords the nitrile imine (2b), which rearranges in part to N-methyl-N'-phenylcarbodiimide (7b). Another part of 2b undergoes a 1,4-H shift to the diazabutadiene (13). 13 undergoes two chemically activated decompositions, to benzonitrile and CH2═NH and to styrene and N2. FVT of 2,2-dimethyl-4-phenyl-oxazol-5(2H)-one (16) at 400 °C yields 3-methyl-1-phenyl-2-azabutadiene (18) in high yield. In contrast, FVT of 3,3-dimethyl-2-phenyl-1-azirene (21) at 600 °C or 4,4-dimethyl-3-phenyl-isoxazolone (20) at 600 °C affords only a low yield of azabutadiene (18) due to chemically activated decomposition of 18 to styrene and acetonitrile. There are two reaction paths from azirene (21): one (path a) leading to nitrile ylide (17) and the major products styrene and acetonitrile and the other (path b) leading to the vinylnitrene (22) and ketenimine (23). The nitrile ylide PhC(-)═N(+)═C(CH3)2 (17) is implicated as the immediate precursor of azabutadiene (18). FVT of either 3-phenylisoxazol-5(4H)one (25) or 2-phenylazirene (26) at 600 °C affords N-phenylketenimine (28). The nitrile ylide PhC(-)═N(+)═CH2 (30) is postulated as a reversibly formed intermediate. N-Phenylketenimine (28) undergoes chemically activated free radical rearrangement to benzyl cyanide. The mechanistic interpretations are supported by calculations of the energies of key intermediates and transition states.

Nitriles at Silica Interfaces Resemble Supported Lipid Bilayers.

PubMed

Berne, Bruce J; Fourkas, John T; Walker, Robert A; Weeks, John D

2016-09-20

Nitriles are important solvents not just for bulk reactions but also for interfacial processes such as separations, heterogeneous catalysis, and electrochemistry. Although nitriles have a polar end and a lipophilic end, the cyano group is not hydrophilic enough for these substances to be thought of as prototypical amphiphiles. This picture is now changing, as research is revealing that at a silica surface nitriles can organize into structures that, in many ways, resemble lipid bilayers. This unexpected organization may be a key component of unique interfacial behavior of nitriles that make them the solvents of choice for so many applications. The first hints of this lipid-bilayer-like (LBL) organization of nitriles at silica interfaces came from optical Kerr effect (OKE) experiments on liquid acetonitrile confined in the pores of sol-gel glasses. The orientational dynamics revealed by OKE spectroscopy suggested that the confined liquid is composed of a relatively immobile sublayer of molecules that accept hydrogen bonds from the surface silanol groups and an interdigitated, antiparallel layer that is capable of exchanging into the centers of the pores. This picture of acetonitrile has been borne out by molecular dynamics simulations and vibrational sum-frequency generation (VSFG) experiments. Remarkably, these simulations further indicate that the LBL organization is repeated with increasing disorder at least 20 Å into the liquid from a flat silica surface. Simulations and VSFG and OKE experiments indicate that extending the alkyl chain to an ethyl group leads to the formation of even more tightly packed LBL organization featuring entangled alkyl tails. When the alkyl portion of the molecule is a bulky t-butyl group, packing constraints prevent well-ordered LBL organization of the liquid. In each case, the surface-induced organization of the liquid is reflected in its interfacial dynamics. Acetonitrile/water mixtures are favored solvent systems for separations technologies such as hydrophilic interaction chromatography. Simulations had suggested that although a monolayer of water partitions to the silica surface in such mixtures, acetonitrile tends to associate with this monolayer. VSFG experiments reveal that, even at high water mole fractions, patches of well-ordered acetonitrile bilayers remain at the silica surface. Due to its ability to donate and accept hydrogen bonds, methanol also partitions to a silica surface in acetonitrile/methanol mixtures and can serve to take the place of acetonitrile in the sublayer closest to the surface. These studies reveal that liquid nitriles can exhibit an unexpected wealth of new organizational and dynamic behaviors at silica surfaces, and presumably at the surfaces of other chemically important materials as well. This behavior cannot be predicted from the bulk organization of these liquids. Our new understanding of the interfacial behavior of these liquids will have important implications for optimizing a wide range of chemical processes in nitrile solvents.

Synthesis of benzimidazoles by potassium tert-butoxide-promoted intermolecular cyclization reaction of 2-iodoanilines with nitriles.

PubMed

Xiang, Shi-Kai; Tan, Wen; Zhang, Dong-Xue; Tian, Xian-Li; Feng, Chun; Wang, Bi-Qin; Zhao, Ke-Qing; Hu, Ping; Yang, Hua

2013-11-14

The synthesis of benzimidazoles by intermolecular cyclization reaction of 2-iodoanilines with nitriles has been developed. These reactions proceeded without the aid of any transition metals or ligands and just using KOBu(t) as the base. A variety of substituted benzimidazole derivatives can be synthesized by the approach.

Electric Fields at the Active Site of an Enzyme: Direct Comparison of Experiment with Theory

NASA Astrophysics Data System (ADS)

Suydam, Ian T.; Snow, Christopher D.; Pande, Vijay S.; Boxer, Steven G.

2006-07-01

The electric fields produced in folded proteins influence nearly every aspect of protein function. We present a vibrational spectroscopy technique that measures changes in electric field at a specific site of a protein as shifts in frequency (Stark shifts) of a calibrated nitrile vibration. A nitrile-containing inhibitor is used to deliver a unique probe vibration to the active site of human aldose reductase, and the response of the nitrile stretch frequency is measured for a series of mutations in the enzyme active site. These shifts yield quantitative information on electric fields that can be directly compared with electrostatics calculations. We show that extensive molecular dynamics simulations and ensemble averaging are required to reproduce the observed changes in field.

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

Schoendorff, George E.; De Jong, Wibe A.; Gordon, Mark S.

The formation of uranyl dicationic complexes containing water and nitrile (acetonitrile, propionitrile, and benzonitrile) ligands, [UO2(H2O)n(RCN)m]2+, has been studied using density functional theory (DFT) with a relativistic effective core potential (RECP) to account for scalar relativistic effects on uranium. It is shown that nitrile addition is favored over the addition of water ligands. Decomposition of these complexes to [UO2OH(H2O)n(RCN)m]+ by the loss of either H3O+ or (RCN+H)+ is also examined. It is found that this reaction occurs when the coordination sphere of uranyl is unsaturated. Additionally, this reaction is influenced by the size of the nitrile ligand with reactions involvingmore » acetonitrile being the most prevalent.« less

Selectivity switch for nitrogen functionalization of styrene on Au(1 1 1)

NASA Astrophysics Data System (ADS)

Deng, Xingyi; Friend, Cynthia M.

2008-03-01

Functionalization of styrene to form N-containing hydrocarbons, e.g. 2-phenylaziridine, benzonitrile, and benzyl nitrile, is achieved by reaction with adsorbed NH a and N a on Au(1 1 1). Electron-induced decomposition of condensed NH 3 was used to produce NH a, N a and H a on Au(1 1 1) at 110 K. The selectivity of the reactions is strongly dependent on the relative concentrations of the surface species. The addition of NH to styrene results in the production of 2-phenylaziridine, whereas adsorbed N and H atoms lead to the formation of nitriles benzonitrile and benzyl nitrile and, respectively, ethylbenzene. This work clearly establishes the utility of Au for promoting functionalization of olefins with nitrogen.

A DFT study of the mechanism and the regioselectivity of [3 + 2] cycloaddition reactions of nitrile oxides with α,β-acetylenic aldehyde

NASA Astrophysics Data System (ADS)

Sobhi, Chafia; Nacereddine, Abdelmalek Khorief; Nasri, Lilia; Lechtar, Zohra; Djerourou, Abdelhafid

2016-11-01

A DFT study of the (32CA) reaction of a series of some nitrile oxides with electron-deficient alkyne (3-phenylpropionlaldehyde) in gas phase and in toluene has been carried out using B3LYP functional with 6-31G(d) basis set. Two reactive channels 4- and 5-associated with the two regioisomeric modes have been located and characterised. These 32CA reactions are characterised by a low asynchronous one-step mechanism with a low-polar character. Analysis of the DFT reactivity indices indicates that the nucleophilic centre of the different nitrile oxides accounts for the 4-regioselectivity. Our calculations are in a good agreement with the experimental findings.

A randomized control hands-on defibrillation study-Barrier use evaluation.

PubMed

Wampler, David; Kharod, Chetan; Bolleter, Scotty; Burkett, Alison; Gabehart, Caitlin; Manifold, Craig

2016-06-01

Chest compressions and defibrillation are the only therapies proven to increase survival in cardiac arrest. Historically, rescuers must remove hands to shock, thereby interrupting chest compressions. This hands-off time results in a zero blood flow state. Pauses have been associated with poorer neurological recovery. This was a blinded randomized control cadaver study evaluating the detection of defibrillation during manual chest compressions. An active defibrillator was connected to the cadaver in the sternum-apex configuration. The sham defibrillator was not connected to the cadaver. Subjects performed chest compressions using 6 barrier types: barehand, single and double layer nitrile gloves, firefighter gloves, neoprene pad, and a manual chest compression/decompression device. Randomized defibrillations (10 per barrier type) were delivered at 30 joules (J) for bare hand and 360J for all other barriers. After each shock, the subject indicated degree of sensation on a VAS scale. Ten subjects participated. All subjects detected 30j shocks during barehand compressions, with only 1 undetected real shock. All barriers combined totaled 500 shocks delivered. Five (1%) active shocks were detected, 1(0.2%) single layer of Nitrile, 3(0.6%) with double layer nitrile, and 1(0.2%) with the neoprene barrier. One sham shock was reported with the single layer nitrile glove. No shocks were detected with fire gloves or compression decompression device. All shocks detected barely perceptible (0.25(±0.05)cm on 10cm VAS scale). Nitrile gloves and neoprene pad prevent (99%) responder's detection of defibrillation of a cadaver. Fire gloves and compression decompression device prevented detection. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Base induced chemical conversion of 3-carbamoyl-2-isoxazolines.

PubMed

Nishiwaki, Nagatoshi; Maki, Asaka; Ariga, Masahiro

2009-01-01

3-Carbamoyl-2-isoxazolines, prepared by cycloaddition of functionalized nitrile oxide, serve as masked 3-unsubstituted isoxazolines to afford 2-isoxazoline-3-carboxylic acid, beta-cyanoalcohol, alpha,beta-unsaturated nitrile, and alpha,beta-unsaturated amide upon heating in the alkaline solution. The present reaction is also applicable to synthesis of 3,4-difunctionalized isoxazoles and beta-hydroxy-gamma-lactone.

Nitrile functionalized disiloxanes with dissolved LiTFSI as lithium ion electrolytes with high thermal and electrochemical stability

NASA Astrophysics Data System (ADS)

Pohl, Benjamin; Hiller, Martin M.; Seidel, Sarah M.; Grünebaum, Mariano; Wiemhöfer, Hans-Dieter

2015-01-01

Liquid disiloxanes functionalized with terminal nitrile groups are introduced as alternative non-volatile solvents for lithium-ion battery electrolytes in combination with LiTFSI as lithium salt. Two series of disiloxanes were investigated differing with respect to the attachment of the nitrile containing side group to silicon, i.e. via a Si-C or a Si-O bond. Total conductivities up to 1 mS cm-1 at 30 °C were measured by impedance spectroscopy. Electrochemical characterization was done on half cells using LiFePO4 cathodes by cyclic voltammetry and constant current cycling. Attractive issues and advantages of the investigated LiTFSI containing disiloxanes in comparison to current electrolyte solvents are: a) In spite of the presence of LiTFSI, the aluminum pitting corrosion is suppressed, b) the electrochemical stability window is extended on the cathode side up to 5.6 V vs. Li/Li+, for a LiTFSI concentration of 0.7 mol kg-1, c) the reported nitrile functionalized disiloxanes show excellent thermal stability with a boiling point up to 106 °C (0.1 mbar), a rather low glass transition temperature of -107 °C, while no melting/crystallization was observed.

A first principle study of graphene functionalized with hydroxyl, nitrile, or methyl groups

NASA Astrophysics Data System (ADS)

Barhoumi, M.; Rocca, D.; Said, M.; Lebègue, S.

2017-01-01

By means of ab initio calculations, we study the functionalization of graphene by different chemical groups such as hydroxyl, nitrile, or methyl. Two extreme cases of functionalization are considered: a single group on a supercell of graphene and a sheet of graphene fully functionalized. Once the equilibrium geometry is obtained by density functional theory, we found that the systems are metallic when a single group is attached to the sheet of graphene. With the exception of the nitrile functionalized boat configuration, a large bandgap is obtained at full coverage. Specifically, by using the GW approximation, our calculated bandgaps are direct and range between 5.0 and 5.5 eV for different configurations of hydroxyl functionalized graphene. An indirect GW bandgap of 6.50 eV was found in nitrile functionalized graphene while the methyl group functionalization leads to a direct bandgap with a value of 4.50 eV. Since in the two limiting cases of minimal and full coverage, the electronic structure changes drastically from a metal to a wide bandgap semiconductor, a series of intermediate states might be expected by tuning the amount of functionalization with these different groups.

Laccase-catalyzed α-arylation of benzoylacetonitrile with substituted hydroquinones

DOE PAGES

Cannatelli, Mark D.; Ragauskas, Arthur J.

2014-09-03

This article investigates a green method for α-arylation of a primary nitrile. Compounds possessing a benzylic nitrile have shown to exhibit biological activity. Laccases (benzenediol:oxygen oxidoreductase EC 1.10.3.2) were used as the catalysts to perform the cross-coupling reaction between benzoylacetonitrile and substituted hydroquinones. The corresponding 2-substituted 3-oxo-3-phenylpropanenitriles where synthesized in moderate to excellent yields in pH 7.0 buffered water under mild conditions. The substituent on the hydroquinone had a significant impact on product yields and regioselectivity of reaction. The use of laccases, which require O 2 as their only co-substrate and produce H 2O as their only by-product, to performmore » this transformation is an environmentally benign method for α-arylation of primary nitriles.« less

Glove permeation by semiconductor processing mixtures containing glycol-ether derivatives.

PubMed

Zellers, E T; Ke, H Q; Smigiel, D; Sulewski, R; Patrash, S J; Han, M W; Zhang, G Z

1992-02-01

Results of permeation tests of several glove materials challenged with semiconductor processing formulations containing glycolether derivatives are described. Commercial glove samples of nitrile rubber (Edmont), natural rubber (Edmont and Baxter), butyl rubber (North), PVC Baxter), a natural rubber/neoprene/nitrile blend (Pioneer), and a natural rubber/neoprene blend (Playtex) were tested according to the ASTM F739-85 permeation test method (open-loop configuration). The liquid formulations examined included a positive photoresist thinner containing 2-ethoxyethyl acetate (2-EEA), n-butyl acetate, and xylene; a positive photoresist containing 2-EEA, n-butyl acetate, xylene, polymer resins, and photoactive compounds; a negative photoresist containing 2-methoxyethanol (2-ME), xylene, and cyclized poly(isoprene); and pure 2-methoxyethyl acetate (2-MEA), which is the solvent used in a commercial electron-beam resist. With the exception of the negative photoresist, butyl rubber provided the highest level of protection against the solvent mixtures tested, with no breakthrough observed after 4 hr of continuous exposure at 25 degrees C. Nitrile rubber provided the highest level of protection against the negative photoresist and reasonably good protection against initial exposure to the other solvent mixtures. Gloves consisting of natural rubber or natural rubber blends provided less protection against the mixtures than either nitrile or butyl rubber. For most of the glove samples, permeation of the glycol-ether derivatives contained in the mixtures was faster than that predicted from the permeation of the pure solvents. Increasing the exposure temperature from 25 to 37 degrees C did not significantly affect the performance of the butyl rubber glove. For the other gloves, however, exposures at 37 degrees C resulted in decreases in breakthrough times of 25-75% and increases in steady-state permeation rates of 80-457% relative to values obtained at 25 degrees C. Repeated exposure of nitrile rubber samples resulted in shorter breakthrough times for all mixture components. In fact, exposure for as little as one-half of the nominal breakthrough time followed by air drying overnight resulted in measurable quantities of one or more of the component solvents at the inner surface of the gloves at the beginning of the next exposure. This effect was not observed with the butyl rubber samples. With the exception of the negative photoresist, heating previously exposed nitrile rubber samples at 70 degrees C for 20 hr prior to retesting reduced or eliminated the effects of residual solvents, permitting reuse of the gloves. The use of thin PVC or natural rubber gloves adjacent to the nitrile gloves provided moderate increases in permeation resistance.(ABSTRACT TRUNCATED AT 400 WORDS)

A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: aqueous hydration of nitriles to amides.

PubMed

Baig, R B Nasir; Varma, Rajender S

2012-06-25

One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involves the in situ generation of magnetic silica (Fe(3)O(4)@SiO(2)) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this catalyst which proceeds exclusively in aqueous medium under neutral conditions.

Titan's Stratospheric Condensibles at High Northern Latitudes During Northern Winter

NASA Technical Reports Server (NTRS)

Anderson, Carrie; Samuelson, R.; Achterberg, R.

2012-01-01

The Infrared Interferometer Spectrometer (IRIS) instrument on board Voyager 1 caught the first glimpse of an unidentified particulate feature in Titan's stratosphere that spectrally peaks at 221 per centimeter. Until recently, this feature that we have termed 'the haystack,' has been seen persistently at high northern latitudes with the Composite Infrared Spectrometer (CIRS) instrument onboard Cassini, The strength of the haystack emission feature diminishes rapidly with season, becoming drastically reduced at high northern latitudes, as Titan transitions from northern winter into spring, In contrast to IRIS whose shortest wavenumber was 200 per centimeter, CIRS extends down to 10 per centimeter, thus revealing an entirely unexplored spectral region in which nitrile ices have numerous broad lattice vibration features, Unlike the haystack, which is only found at high northern latitudes during northern winter/early northern spring, this geometrically thin nitrile cloud pervades Titan's lower stratosphere, spectrally peaking at 160 per centimeter, and is almost global in extent spanning latitudes 85 N to 600 S, The inference of nitrile ices are consistent with the highly restricted altitude ranges over which these features are observed, and appear to be dominated by a mixture of HCN and HC3N, The narrow range in altitude over which the nitrile ices extend is unlike the haystack, whose vertical distribution is significantly broader, spanning roughly 70 kilometers in altitude in Titan's lower stratosphere, The nitrile clouds that CIRS observes are located in a dynamically stable region of Titan's atmosphere, whereas CH4 clouds, which ordinarily form in the troposphere, form in a more dynamically unstable region, where convective cloud systems tend to occur. In the unusual situation where Titan's tropopause cools significantly from the HASI 70.5K temperature minimum, CH4 should condense in Titan's lower stratosphere, just like the aforementioned nitrile clouds, although in significantly larger abundances. We will present the spectral and vertical distribution of Titan's stratospheric particulates during northern winter on Titan. The drastically changing abundance of the haystack over a small latitude range will be highlighted, specifically comparing the IRIS and CIRS epochs, Finally, we will discuss the situation in which CH4 condenses in Titan's lower stratosphere, forming an unexpected quasi steady-state stratospheric Ice cloud.

Optimizing electrostatic field calculations with the Adaptive Poisson-Boltzmann Solver to predict electric fields at protein-protein interfaces II: explicit near-probe and hydrogen-bonding water molecules.

PubMed

Ritchie, Andrew W; Webb, Lauren J

2014-07-17

We have examined the effects of including explicit, near-probe solvent molecules in a continuum electrostatics strategy using the linear Poisson-Boltzmann equation with the Adaptive Poisson-Boltzmann Solver (APBS) to calculate electric fields at the midpoint of a nitrile bond both at the surface of a monomeric protein and when docked at a protein-protein interface. Results were compared to experimental vibrational absorption energy measurements of the nitrile oscillator. We examined three methods for selecting explicit water molecules: (1) all water molecules within 5 Å of the nitrile nitrogen; (2) the water molecule closest to the nitrile nitrogen; and (3) any single water molecule hydrogen-bonding to the nitrile. The correlation between absolute field strengths with experimental absorption energies were calculated and it was observed that method 1 was only an improvement for the monomer calculations, while methods 2 and 3 were not significantly different from the purely implicit solvent calculations for all protein systems examined. Upon taking the difference in calculated electrostatic fields and comparing to the difference in absorption frequencies, we typically observed an increase in experimental correlation for all methods, with method 1 showing the largest gain, likely due to the improved absolute monomer correlations using that method. These results suggest that, unlike with quantum mechanical methods, when calculating absolute fields using entirely classical models, implicit solvent is typically sufficient and additional work to identify hydrogen-bonding or nearest waters does not significantly impact the results. Although we observed that a sphere of solvent near the field of interest improved results for relative field calculations, it should not be consider a panacea for all situations.

Hydrogen-bonding interactions between a nitrile-based functional ionic liquid and DMSO

NASA Astrophysics Data System (ADS)

Zheng, Yan-Zhen; Zhou, Yu; Deng, Geng; Yu, Zhi-Wu

2016-11-01

Task-specific ionic liquids (TSILs) have been introduced by incorporating additional functional groups in the cation or anion to impart specific properties or reactivates. In this work, the hydrogen-bonding interactions between a nitrile-functional TSIL 1-propylnitrile-3-methylimidazolium tetrafluoroborate ([PCNMIM][BF4]) and dimethyl sulphoxide (DMSO) were investigated in detail by attenuated total reflection infrared spectroscopy (ATR-IR), combined with hydrogen nuclear magnetic resonance (1H NMR) and density functional theory calculations (DFT). It was found that, first, introducing a nitrile group into the alkyl chain does not change the main interaction site in the cation. It is still the C2 hydrogen. So the v(C2-H) is more sensitive to the environmental change and can be used as an indicator of the environments change of IL. Second, the wavenumber shift changes of v(C2-H) have two turning points (xDMSO ≈ 0.6 and 0.9), dividing the dilution process into three stages. Combined with the calculation results, the dilution process is identified as: From larger ion clusters to smaller ion clusters (xDMSO < 0.6), then to ion pairs (0.6 0.9). Introducing a nitrile group into the alkyl chain does not influence the dilution process of IL dissolving in DMSO. Third, the Ctbnd N in [PCNMIM][BF4] can work as an electron donor in forming hydrogen-bonds with the methyl group of [PCNMIM]+ and DMSO, but its strength is weaker than that formed by the imidazolium ring C-Hs. The dual roles of the cation to work as both electron acceptor and donor expand the wide applications of this nitrile-functional ionic liquid.

Carboxylic Acids as Indicators of Parent Body Conditions

NASA Technical Reports Server (NTRS)

Lerner N. R.; Chang, Sherwood (Technical Monitor)

1995-01-01

Alpha-hydroxy and alpha-amino carboxylic acids found on the Murchison meteorite are deuterium enriched. It is postulated that they arose from a common interstellar scurce: the reaction of carbonyl compounds in an aqueous mixture containing HCN and NH3. Carbonyl compounds react with HCN to form alpha-hydroxy nitriles, RR'CO + HCN right and left arrow RR'C(OH)CN. If ammonia is also present, the alpha-hydroxy nitriles will exist in equilibrium with the alpha-amino nitriles, RR'C(OH)CN + NH3 right and left arrow - RRCNH2CN + H2O. Both nitrites are hydrolyzed by water to form carboxylic acids: RR'C(OH)CN + H2O yields RR'C(OH)CO2H and RR'C(NH2)CN + H2O yields RR'C(NH2)CO2H.

Palladium-Catalyzed, Copper(I)-Mediated Coupling of Boronic Acids and Benzylthiocyanate. A Cyanide-Free Cyanation of Boronic Acids

PubMed Central

Zhang, Zhihui; Liebeskind, Lanny S.

2008-01-01

A new method for the synthesis of nitriles is described. As a complement to the classic cyanation of aryl halides using cyanide sources and a transition metal catalyst, the palladium-catalyzed cross-coupling of thiocyanates with boronic acids in the presence of copper(I) thiophene-2-carboxylate (CuTC) affords nitriles in good to excellent yields. PMID:16956219

Nanoparticle-supported and magnetically recoverable ruthenium hydroxide catalyst: efficient hydration of nitriles to amides in aqueous medium.

PubMed

Polshettiwar, Vivek; Varma, Rajender S

2009-01-01

Magnetic attraction not filtration: A magnetic nanoparticle-supported ruthenium hydroxide catalyst (see figure) was readily prepared from inexpensive starting materials and shown to catalyze the hydration of nitriles with excellent yield in a benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity, and the inherent stability of the catalyst system are additional sustainable attributes of this protocol.

Mining of Microbial Genomes for the Novel Sources of Nitrilases.

PubMed

Sharma, Nikhil; Thakur, Neerja; Raj, Tilak; Savitri; Bhalla, Tek Chand

2017-01-01

Next-generation DNA sequencing (NGS) has made it feasible to sequence large number of microbial genomes and advancements in computational biology have opened enormous opportunities to mine genome sequence data for novel genes and enzymes or their sources. In the present communication in silico mining of microbial genomes has been carried out to find novel sources of nitrilases. The sequences selected were analyzed for homology and considered for designing motifs. The manually designed motifs based on amino acid sequences of nitrilases were used to screen 2000 microbial genomes (translated to proteomes). This resulted in identification of one hundred thirty-eight putative/hypothetical sequences which could potentially code for nitrilase activity. In vitro validation of nine predicted sources of nitrilases was done for nitrile/cyanide hydrolyzing activity. Out of nine predicted nitrilases, Gluconacetobacter diazotrophicus , Sphingopyxis alaskensis , Saccharomonospora viridis , and Shimwellia blattae were specific for aliphatic nitriles, whereas nitrilases from Geodermatophilus obscurus , Nocardiopsis dassonvillei , Runella slithyformis , and Streptomyces albus possessed activity for aromatic nitriles. Flavobacterium indicum was specific towards potassium cyanide (KCN) which revealed the presence of nitrilase homolog, that is, cyanide dihydratase with no activity for either aliphatic, aromatic, or aryl nitriles. The present study reports the novel sources of nitrilases and cyanide dihydratase which were not reported hitherto by in silico or in vitro studies.

4-[(1-Benzyl-1H-1,2,3-triazol-4-yl)meth-oxy]benzene-1,2-dicarbo-nitrile: crystal structure, Hirshfeld surface analysis and energy-minimization calculations.

PubMed

Shamsudin, Norzianah; Tan, Ai Ling; Young, David J; Jotani, Mukesh M; Otero-de-la-Roza, A; Tiekink, Edward R T

2016-04-01

In the solid state, the title compound, C18H13N5O, adopts a conformation whereby the phenyl ring and meth-oxy-benzene-1,2-dicarbo-nitrile residue (r.m.s. deviation of the 12 non-H atoms = 0.041 Å) lie to opposite sides of the central triazolyl ring, forming dihedral angles of 79.30 (13) and 64.59 (10)°, respectively; the dihedral angle between the outer rings is 14.88 (9)°. This conformation is nearly 7 kcal mol(-1) higher in energy than the energy-minimized structure which has a syn disposition of the outer rings, enabling intra-molecular π-π inter-actions. In the crystal, methyl-ene-C-H⋯N(triazol-yl) and carbo-nitrile-N⋯π(benzene) inter-actions lead to supra-molecular chains along the a axis. Supra-molecular layers in the ab plane arise as the chains are connected by benzene-C-H⋯N(carbo-nitrile) inter-actions; layers stack with no directional inter-actions between them. The specified inter-molecular contacts along with other, weaker contributions to the supra-molecular stabilization are analysed in a Hirshfeld surface analysis.

Melamine-Schiff base/manganese complex with denritic structure: An efficient catalyst for oxidation of alcohols and one-pot synthesis of nitriles.

PubMed

Kazemnejadi, Milad; Nikookar, Mahsa; Mohammadi, Mohammad; Shakeri, Alireza; Esmaeilpour, Mohsen

2018-05-18

Efficient and selective oxidation of alcohol to the corresponding carbonyl and/or nitrile was carried out by a new water-soluble melamine-based dendritic Mn(III) complex (Melamine-Mn (III)-Schiff base complex) in the presence of 2,4,6-trichloro-1,3,5-triazine (TCT) and O 2 at room temperature. Also, the oxidation of amine to the corresponding nitrile with high selectivity and conversion was performed at room temperature using the current method and high amounts of turnover frequencies (TOFs) were obtained for reactions. This system was also applicable for direct preparation of oxime through oxidation of alcohol. The catalyst was characterized by Fourier-transform infrared (FTIR), ultraviolet-visible (UV-Vis), thermogravimetric analysis (TGA), energy-dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS), CHN and inductively coupled plasma (ICP) analyses. Also, oxidation/reduction behavior of the catalyst was studied by cyclic voltammetry (CV). Moreover, chemoselectivity of the catalyst was discussed with various combinations. The water-soluble catalyst could be recycled from the reaction mixture and reused for several times with a very low losing in efficiency. The recovered catalyst was also investigated with various analyses. Finally, gram scale preparation of nitrile was evaluated by present method. Copyright © 2018 Elsevier Inc. All rights reserved.

Elastomers for Service as Seals for Engine Lubricants and Hydraulic Fluids

DTIC Science & Technology

1976-02-01

mm NBR PNF psi - fluorocarbon rubber - hour per degrees Fahrenheit - inch-pound per cubic inch - minute per degrees Fahrenheit - milliliter...millimeter - nitrile-butadiene rubber - polyffluoroalkoxy)phosphazene - pounds per square inch t I (1 MAT-75-78 <V ■ >«..*, njf:~-. I...I I I I I I r i. L I I 1 ! «WJBDXNB PA« BUNUfOT FIIMID BACKGROUND Nitrile-butadiene robber ( NBR ) O-nngs have had an accept

Development and Implementation of the National Test Facility (NaTeF) for Fuels and Propulsion

DTIC Science & Technology

2013-10-01

permanent indentation. This equipment is used in the Materials Laboratory to determine hardness in polymers, elastomers, and rubbers , characteristics...impacted by exposure to synthetic fuels was the nitrile rubber , one of the materials selected for this research. Further research found a relationship...Similarly, as the molecular weight decreased, the volume swell increased. Therefore, it is indicated that the greatest swell in nitrile rubber will be

Multicomponent Approach to the Synthesis of Oxidized Amides through Nitrile Hydrozirconation

PubMed Central

Wan, Shuangyi; Green, Michael E.; Park, Jung-Hyun; Floreancig, Paul E.

2008-01-01

“Oxidized” amides, as represented by acyl aminals and acyl hemiaminals, are integral subunits of several natural products that exhibit useful biological activity. In this manuscript a multicomponent approach to these groups from acylimine intermediates is demonstrated. The acylimines are accessed through a sequence of nitrile hydrozirconation and acylation, making this highly versatile amide synthesis useful for a range of range of applications in target- and diversity-oriented synthesis. PMID:18020344

CAM-7/LTO Cells for Lithium-Ion Batteries with Rapid Charging Capability at Low Temperature

DTIC Science & Technology

2012-04-06

TIAX’s high energy, high power CAM-7 cathode material, high rate capability lithium titanate (LTO) anode material, and a nitrile-cosolvent...employing TIAX’s high energy, high power CAM-7 cathode material, high rate capability lithium titanate (LTO) anode material, and a nitrile- cosolvent...electrolyte formulation. CAM-7 provides the highest energy content and rate capability of any market- ready cathode material. Commercially available

Improved Schmidt Conversion of Aldehydes to Nitriles Using Azidotrimethylsilane in 1,1,1,3,3,3-Hexafluoro-2-propanol.

PubMed

Motiwala, Hashim F; Yin, Qin; Aubé, Jeffrey

2015-12-29

The Schmidt reaction of aromatic aldehydes using a substoichiometric amount (40 mol %) of triflic acid is described. Low catalyst loading was enabled by a strong hydrogen-bond-donating solvent hexafluoro-2-propanol (HFIP). This improved protocol tolerates a broad scope of aldehydes with diverse functional groups and the corresponding nitriles were obtained in good to high yields without the need for aqueous work up.

Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Colizza, Kevin; Mahoney, Keira E.; Yevdokimov, Alexander V.; Smith, James L.; Oxley, Jimmie C.

2016-11-01

Efforts to analyze trace levels of cyclic peroxides by liquid chromatography/mass spectrometry gave evidence that acetonitrile suppressed ion formation. Further investigations extended this discovery to ketones, linear peroxides, esters, and possibly many other types of compounds, including triazole and menadione. Direct ionization suppression caused by acetonitrile was observed for multiple adduct types in both electrospray ionization and atmospheric pressure chemical ionization. The addition of only 2% acetonitrile significantly decreased the sensitivity of analyte response. Efforts to identify the mechanism were made using various nitriles. The ion suppression was reduced by substitution of an acetonitrile hydrogen with an electron-withdrawing group, but was exacerbated by electron-donating or steric groups adjacent to the nitrile. Although current theory does not explain this phenomenon, we propose that polar interactions between the various functionalities and the nitrile may be forming neutral aggregates that manifest as ionization suppression.

The prospect of life on Jupiter.

NASA Technical Reports Server (NTRS)

Ponnamperuma, C.; Molton, P.

1973-01-01

We have simulated electrical discharges in the Jovian atmosphere, using anhydrous methane-ammonia mixtures, and shown the formation of simple aliphatic nitriles, amino-nitriles, and their oligomers. Including hydrogen sulfide in the gas mixture, it appears that sulfur-containing amino-nitriles are not formed, since the hydrolysate of the products did not contain the corresponding amino-acids. There is a strong analogy between these reactions and the classical spark reactions simulating the primitive earth's atmosphere. We are attempting a closer simulation of Jupiter's atmosphere by using appropriate temperature and pressure conditions. It seems that prebiotic synthesis on Jupiter may have reached an advanced state. As an alternative approach we have tested the survival ability of common terrestrial microorganisms in aqueous media at 102 atmospheres pressure and at 20 C in a simulated Jovian atmosphere. E. coli, S. marcescens, A. aerogenes, and B. subtilis will all tolerate 24 hr under these conditions with little death.

Studies on nitrile rubber degradation in zinc bromide completion fluid and its prevention by surface fluorination

NASA Astrophysics Data System (ADS)

Vega-Cantu, Yadira Itzel

Poly(acrylonitrile-co-butadiene) or nitrile-butadiene rubber (NBR) is frequently used as an O-ring material in the oil extraction industry due to its excellent chemical properties and resistance to oil. However, degradation of NBR gaskets is known to occur during the well completion and oil extraction process where packers are exposed to completion fluids such as ZnBr2 brine. Under these conditions NBR exhibits accelerated chemical degradation resulting in embrittlement and cracking. Samples of NBR, poly(acrylonitrile) (PAN) and poly(butadiene) (PB) have been exposed to ZnBr2 based completion fluid, and analyzed by ATR and diffuse reflectance IR. Analysis shows the ZnBr2 based completion fluid promotes hydrolysis of the nitrile group to form amides and carboxylic groups. Analysis also shows that carbon-carbon double bonds in NBR are unaffected after short exposure to zinc bromide based completion fluid, but are quickly hydrolyzed in acidic bromide mixtures. Although fluoropolymers have excellent chemical resistance, their strength is less than nitrile rubber and replacing the usual gasket materials with fluoroelastomers is expensive. However, a fluoropolymer surface on a nitrile elastomer can provide the needed chemical resistance while retaining their strength. In this study, we have shown that this can be achieved by direct fluorination, a rather easy and inexpensive process. Samples of NBR O-rings have been fluorinated by exposure to F2 and F2/HF mixtures at various temperatures. Fluorination with F 2 produces the desired fluoropolymer layer; however, fluorination by F2/HF mixtures gave a smoother fluorinated layer at lower temperatures and shorter times. Fluorinated samples were exposed to ZnBr2 drilling fluid and solvents. Elemental analysis shows that the fluorinated layer eliminates ZnBr2 diffusion into the NBR polymeric matrix. It was also found that surface fluorination significantly retards the loss of mechanical properties such as elasticity, tensile strength, toughness and compression set of nitrile rubber when exposed to zinc bromide fluid. This surface fluorination can be applied to extend the useful life of O-rings and packers in the field during oil extraction. The extended life can save millions of dollars by limiting the downtime of the well.

Analysis of a Compressible Fluid Soft Recoil (CFSR) Concept Applied to a 155 MM Howitzer

DTIC Science & Technology

1979-03-01

Nitrile or Buna-N ( NBR ) rubber with ’ backup rings of nylotron. HITRILE NVLOTRON Piston seals An unresolved problem is that the coefficient of...fluid at atmospheric pressure Poisson’s ratio for Nitrile rubber dynamic coefficient of friction for rubber mass of recoiling parts weight of...Greene, tweed 5 Co. Palmetto catalog.) 43 [i^ - 0.50 = coefficient of friction (An approximate figure for rubber supplied by RIA Rubber

Dramatic inversion of charge polarity in diketopyrrolopyrrole-based organic field-effect transistors via a simple nitrile group substitution.

PubMed

Yun, Hui-Jun; Kang, Seok-Ju; Xu, Yong; Kim, Seul Ong; Kim, Yun-Hi; Noh, Yong-Young; Kwon, Soon-Ki

2014-11-19

A record-breaking high electron mobility of 7.0 cm(2) V(-1) s(-1) for n-channel polymer OFETs is reported. By the incorporation of only one nitrile group as an electron-withdrawing function in the vinyl linkage of the DPP-based copolymer, a dramatic inversion of majority charge-carriers from holes to electrons is achieved. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic trimerization of aromatic nitriles for synthesis of polyimide matrix resins

NASA Technical Reports Server (NTRS)

Hsu, L. C.

1974-01-01

Aromatic nitriles may be trimerized at moderate temperature and pressure with p-toluenesulfonic acid as catalyst. Studies were conducted to establish the effect of the reaction temperature, pressure, time, and catalyst concentration on yield of the trimerized product. Trimerization studies were also conducted to establish the effect of substituting electron donating or withdrawing groups on benzonitrile. Preliminary results of using the catalytic trimerization approach to prepare s-triazine cross-linked polyimide/graphite fiber composites are presented.

Performance Analysis of Exam Gloves Used for Aseptic Rodent Surgery

PubMed Central

LeMoine, Dana M; Bergdall, Valerie K; Freed, Carrie

2015-01-01

Aseptic technique includes the use of sterile surgical gloves for survival surgeries in rodents to minimize the incidence of infections. Exam gloves are much less expensive than are surgical gloves and may represent a cost-effective, readily available option for use in rodent surgery. This study examined the effectiveness of surface disinfection of exam gloves with 70% isopropyl alcohol or a solution of hydrogen peroxide and peracetic acid (HP–PA) in reducing bacterial contamination. Performance levels for asepsis were met when gloves were negative for bacterial contamination after surface disinfection and sham ‘exertion’ activity. According to these criteria, 94% of HP–PA-disinfected gloves passed, compared with 47% of alcohol-disinfected gloves. In addition, the effect of autoclaving on the integrity of exam gloves was examined, given that autoclaving is another readily available option for aseptic preparation. Performance criteria for glove integrity after autoclaving consisted of: the ability to don the gloves followed by successful simulation of wound closure and completion of stretch tests without tearing or observable defects. Using this criteria, 98% of autoclaved nitrile exam gloves and 76% of autoclaved latex exam gloves met performance expectations compared with the performance of standard surgical gloves (88% nitrile, 100% latex). The results of this study support the use of HP–PA-disinfected latex and nitrile exam gloves or autoclaved nitrile exam gloves as viable cost-effective alternatives to sterile surgical gloves for rodent surgeries. PMID:26045458

Performance analysis of exam gloves used for aseptic rodent surgery.

PubMed

LeMoine, Dana M; Bergdall, Valerie K; Freed, Carrie

2015-05-01

Aseptic technique includes the use of sterile surgical gloves for survival surgeries in rodents to minimize the incidence of infections. Exam gloves are much less expensive than are surgical gloves and may represent a cost-effective, readily available option for use in rodent surgery. This study examined the effectiveness of surface disinfection of exam gloves with 70% isopropyl alcohol or a solution of hydrogen peroxide and peracetic acid (HP-PA) in reducing bacterial contamination. Performance levels for asepsis were met when gloves were negative for bacterial contamination after surface disinfection and sham 'exertion' activity. According to these criteria, 94% of HP-PA-disinfected gloves passed, compared with 47% of alcohol-disinfected gloves. In addition, the effect of autoclaving on the integrity of exam gloves was examined, given that autoclaving is another readily available option for aseptic preparation. Performance criteria for glove integrity after autoclaving consisted of: the ability to don the gloves followed by successful simulation of wound closure and completion of stretch tests without tearing or observable defects. Using this criteria, 98% of autoclaved nitrile exam gloves and 76% of autoclaved latex exam gloves met performance expectations compared with the performance of standard surgical gloves (88% nitrile, 100% latex). The results of this study support the use of HP-PA-disinfected latex and nitrile exam gloves or autoclaved nitrile exam gloves as viable cost-effective alternatives to sterile surgical gloves for rodent surgeries.

4-[(1-Benzyl-1H-1,2,3-triazol-4-yl)meth­oxy]benzene-1,2-dicarbo­nitrile: crystal structure, Hirshfeld surface analysis and energy-minimization calculations

PubMed Central

Shamsudin, Norzianah; Tan, Ai Ling; Young, David J.; Jotani, Mukesh M.; Otero-de-la-Roza, A.; Tiekink, Edward R. T.

2016-01-01

In the solid state, the title compound, C18H13N5O, adopts a conformation whereby the phenyl ring and meth­oxy–benzene-1,2-dicarbo­nitrile residue (r.m.s. deviation of the 12 non-H atoms = 0.041 Å) lie to opposite sides of the central triazolyl ring, forming dihedral angles of 79.30 (13) and 64.59 (10)°, respectively; the dihedral angle between the outer rings is 14.88 (9)°. This conformation is nearly 7 kcal mol−1 higher in energy than the energy-minimized structure which has a syn disposition of the outer rings, enabling intra­molecular π–π inter­actions. In the crystal, methyl­ene-C—H⋯N(triazol­yl) and carbo­nitrile-N⋯π(benzene) inter­actions lead to supra­molecular chains along the a axis. Supra­molecular layers in the ab plane arise as the chains are connected by benzene-C—H⋯N(carbo­nitrile) inter­actions; layers stack with no directional inter­actions between them. The specified inter­molecular contacts along with other, weaker contributions to the supra­molecular stabilization are analysed in a Hirshfeld surface analysis. PMID:27375890

Isoxazolodihydropyridinones: 1,3-dipolar cycloaddition of nitrile oxides onto 2,4-dioxopiperidines

PubMed Central

Coffman, Keith C.; Hartley, Timothy P.; Dallas, Jerry L.; Kurth, Mark J.

2012-01-01

Practical and efficient methods have been developed for the diversity-oriented synthesis of isoxazolodihydropyridinones via the 1,3-dipolar cycloaddition of nitrile oxides onto 2,4-dioxopiperidines. A select few of these isoxazolodihydropyridinones were further elaborated with triazoles by copper catalyzed azide-alkyne cycloaddition reactions. A total of 70 compounds and intermediates were synthesized and analyzed for drug likeness. Sixty-four of these novel compounds were submitted to the NIH Molecular Libraries Small Molecule Repository for high-throughput biological screening. PMID:22352295

Oxonitriles: a grignard addition-acylation route to enamides.

PubMed

Fleming, Fraser F; Wei, Guoqing; Zhang, Zhiyu; Steward, Omar W

2006-10-12

[reaction: see text] Sequential addition of three different Grignard reagents and pivaloyl chloride to 3-oxo-1-cyclohexene-1-carbonitrile installs four new bonds to generate a diverse array of cyclic enamides. Remarkably, formation of the C-magnesiated nitrile intermediate is followed by preferential acylation by pivaloyl chloride rather than consumption by an in situ Grignard reagent. Rapid N-acylation of the C-magnesiated nitrile generates an acyl ketenimine that reacts readily with Grignard reagents or a trialkylzincate, effectively assembling highly substituted, cyclic enamides.

Oxonitriles: A Grignard Addition-Acylation Route to Enamides

PubMed Central

Wei, Guoqing; Zhang, Zhiyu; Steward, Omar W.

2008-01-01

Sequential addition of three different Grignard reagents and pivaloyl chloride to 3-oxo-1-cyclohexene-1-carbonitrile installs four new bonds to generate a diverse array of cyclic enamides. Remarkably, formation of the C-magnesiated nitrile intermediate is followed by preferential acylation by pivaloyl chloride rather than consumption by in situ Grignard reagent. Rapid N-acylation of the C-magnesiated nitrile generates an acyl ketenimine that reacts readily with Grignard reagents, or a trialkyl zincate, effectively assembling highly substituted, cyclic enamides. PMID:17020332

Nitrile crosslinked polyphenyl-quinoxaline/graphite fiber composites

NASA Technical Reports Server (NTRS)

Alston, W. B.

1976-01-01

Studies were performed to reduce the 600 F thermoplasticity of polyphenylquinoxaline (PPQ) matrix resins by introducing crosslinking by the reaction of terminal nitrile groups. Seven solvents and solvent mixtures were studied as the crosslinking catalysts and used to fabricate crosslinked PPQ/HMS graphite fiber composites. The room temperature and 600 F composite mechanical properties after short time and prolonged 600 F air exposure and the 600 F composite weight loss were determined and compared to those properties of high molecular weight, linear PPQ/HMS graphite fiber composites.

Virtually Instantaneous, Room-temperature [11C]-Cyanation Using Biaryl Phosphine Pd(0) Complexes

PubMed Central

Lee, Hong Geun; Milner, Phillip J.; Placzek, Michael S.; Buchwald, Stephen L.; Hooker, Jacob M.

2015-01-01

A new radiosynthetic protocol for the preparation of [11C]aryl nitriles has been developed. This process is based on the direct reaction of in situ prepared L•Pd(Ar)X complexes (L=biaryl phosphine) with [11C]HCN. The strategy is operationally simple, exhibits a remarkably wide substrate scope with short reaction times, and demonstrates superior reactivity compared to previously reported systems. With this procedure, a variety of [11C]nitrile-containing pharmaceuticals were prepared with high radiochemical efficiency. PMID:25565277

An experimental and theoretical study of reaction mechanisms between nitriles and hydroxylamine.

PubMed

Vörös, Attila; Mucsi, Zoltán; Baán, Zoltán; Timári, Géza; Hermecz, István; Mizsey, Péter; Finta, Zoltán

2014-10-28

The industrially relevant reaction between nitriles and hydroxylamine yielding amidoximes was studied in different molecular solvents and in ionic liquids. In industry, this procedure is carried out on the ton scale in alcohol solutions and the above transformation produces a significant amount of unexpected amide by-product, depending on the nature of the nitrile, which can cause further analytical and purification issues. Although there were earlier attempts to propose mechanisms for this transformation, the real reaction pathway is still under discussion. A new detailed reaction mechanistic explanation, based on theoretical and experimental proof, is given to augment the former mechanisms, which allowed us to find a more efficient, side-product free procedure. Interpreting the theoretical results obtained, it was shown that the application of specific imidazolium, phosphonium and quaternary ammonium based ionic liquids could decrease simultaneously the reaction time while eliminating the amide side-product, leading to the targeted product selectively. This robust and economic procedure now affords a fast, selective amide free synthesis of amidoximes.

Condensation Reactions and Formation of Amides, Esters, and Nitriles Under Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Rushdi, Ahmed I.; Simoneit, Bernd R. T.

2004-06-01

Hydrothermal pyrolysis experiments were performed to assess condensation (dehydration) reactions to amide, ester, and nitrile functionalities from lipid precursors. Beside product formation, organic compound alteration and stability were also evaluated. Mixtures of nonadecanoic acid, hexadecanedioic acid, or hexadecanamide with water, ammonium bicarbonate, and oxalic acid were heated at 300°C for 72 h. In addition, mixtures of ammonium bicarbonate and oxalic acid solutions were used to test the abiotic formation of organic nitrogen compounds at the same temperature. The resulting products were condensation compounds such as amides, nitriles, and minor quantities of N-methylalkyl amides, alkanols, and esters. Mixtures of alkyl amide in water or oxalic acid yielded mainly hydrolysis and dehydration products, and with ammonium bicarbonate and oxalic acid the yield of condensation products was enhanced. The synthesis experiments with oxalic acid and ammonium bicarbonate solutions yielded homologous series of alkyl amides, alkyl amines, alkanes, and alkanoic acids, all with no carbon number predominances. These organic nitrogen compounds are stable and survive under the elevated temperatures of hydrothermal fluids.

Crosslinked polyarylene ether nitrile film as flexible dielectric materials with ultrahigh thermal stability.

PubMed

Yang, Ruiqi; Wei, Renbo; Li, Kui; Tong, Lifen; Jia, Kun; Liu, Xiaobo

2016-11-09

Dielectric film with ultrahigh thermal stability based on crosslinked polyarylene ether nitrile is prepared and characterized. The film is obtained by solution-casting of polyarylene ether nitrile terminated phthalonitrile (PEN-Ph) combined with post self-crosslinking at high temperature. The film shows a 5% decomposition temperature over 520 °C and a glass transition temperature (T g ) around 386 °C. Stable dielectric constant and low dielectric loss are observed for this film in the frequency range of 100-200 kHz and in the temperature range of 25-300 °C. The temperature coefficient of dielectric constant is less than 0.001 °C -1 even at 400 °C. By cycling heating and cooling up to ten times or heating at 300 °C for 12 h, the film shows good reversibility and robustness of the dielectric properties. This crosslinked PEN film will be a potential candidate as high performance film capacitor electronic devices materials used at high temperature.

Snapshot of the equilibrium dynamics of a drug bound to HIV-1 reverse transcriptase

NASA Astrophysics Data System (ADS)

Kuroda, Daniel G.; Bauman, Joseph D.; Challa, J. Reddy; Patel, Disha; Troxler, Thomas; Das, Kalyan; Arnold, Eddy; Hochstrasser, Robin M.

2013-03-01

The anti-AIDS drug rilpivirine undergoes conformational changes to bind HIV-1 reverse transcriptase (RT), which is an essential enzyme for the replication of HIV. These changes allow it to retain potency against mutations that otherwise would render the enzyme resistant. Here we report that water molecules play an essential role in this binding process. Femtosecond experiments and theory expose the molecular level dynamics of rilpivirine bound to HIV-1 RT. Two nitrile substituents, one on each arm of the drug, are used as vibrational probes of the structural dynamics within the binding pocket. Two-dimensional vibrational echo spectroscopy reveals that one nitrile group is unexpectedly hydrogen-bonded to a mobile water molecule, not identified in previous X-ray structures. Ultrafast nitrile-water dynamics are confirmed by simulations. A higher (1.51 Å) resolution X-ray structure also reveals a water-drug interaction network. Maintenance of a crucial anchoring hydrogen bond may help retain the potency of rilpivirine against pocket mutations despite the structural variations they cause.

Triton - Stratospheric molecules and organic sediments

NASA Technical Reports Server (NTRS)

Thompson, W. Reid; Singh, Sushil K.; Khare, B. N.; Sagan, Carl

1989-01-01

Continuous-flow plasma discharge techniques show production rates of hydrocarbons and nitriles in N2 + CH4 atmospheres appropriate to the stratosphere of Titan, and indicate that a simple eddy diffusion model together with the observed electron flux quantitatively matches the Voyager IRIS observations for all the hydrocarbons, except for the simplest ones. Charged particle chemistry is very important in Triton's stratosphere. In the more CH4-rich case of Titan, many hydrocarbons and nitriles are produced in high yield. If N2 is present, the CH4 fraction is low, but hydrocarbons and nitriles are produced in fair yield, abundances of HCN and C2H2 in Triton's stratosphere exceed 10 to the 19th molecules/sq cm per sec, and NCCN, C3H4, and other species are predicted to be present. These molecules may be detected by IRIS if the stratosphere is as warm as expected. Both organic haze and condensed gases will provide a substantial UV and visible opacity in Triton's atmosphere.

Blue phosphorescent nitrile containing C^C* cyclometalated NHC platinum(II) complexes.

PubMed

Tronnier, Alexander; Metz, Stefan; Wagenblast, Gerhard; Muenster, Ingo; Strassner, Thomas

2014-02-28

Since C^C* cyclometalated Pt(II) complexes with N-heterocyclic carbene (NHC) ligands have been identified as potential emitter materials in organic light-emitting devices (OLEDs), very promising results regarding quantum yields, colour and stability have been presented. Herein, we report on four nitrile substituted complexes with a chelating NHC ligand (1-(4-cyanophenyl)-3-isopropyl-1H-benzo[d]imidazole or 4-(tert-butyl)-1-(4-cyanophenyl)-3-methyl-1H-imidazole) and a bidentate monoanionic auxiliary ligand (acetylacetone or dimesitoylmethane). The complexes have been fully characterized including extensive 2D NMR studies (COSY, HSQC, HMBC, NOESY, (195)Pt NMR), three of them also by solid-state structures. Photophysical measurements in amorphous PMMA films and pure emitter films at room temperature reveal the impact of the mesityl groups in the auxiliary ligand, which led to a significant increase of the quantum yield, while the decay lifetimes decreased. The electron withdrawing nitrile groups shift the emission towards blue colour coordinates.

Crosslinked polyarylene ether nitrile film as flexible dielectric materials with ultrahigh thermal stability

NASA Astrophysics Data System (ADS)

Yang, Ruiqi; Wei, Renbo; Li, Kui; Tong, Lifen; Jia, Kun; Liu, Xiaobo

2016-11-01

Dielectric film with ultrahigh thermal stability based on crosslinked polyarylene ether nitrile is prepared and characterized. The film is obtained by solution-casting of polyarylene ether nitrile terminated phthalonitrile (PEN-Ph) combined with post self-crosslinking at high temperature. The film shows a 5% decomposition temperature over 520 °C and a glass transition temperature (Tg) around 386 °C. Stable dielectric constant and low dielectric loss are observed for this film in the frequency range of 100-200 kHz and in the temperature range of 25-300 °C. The temperature coefficient of dielectric constant is less than 0.001 °C-1 even at 400 °C. By cycling heating and cooling up to ten times or heating at 300 °C for 12 h, the film shows good reversibility and robustness of the dielectric properties. This crosslinked PEN film will be a potential candidate as high performance film capacitor electronic devices materials used at high temperature.

Electron solvation and localization at interfaces

NASA Astrophysics Data System (ADS)

Harris, Charles B.; Szymanski, Paul; Garrett-Roe, Sean; Miller, Andre D.; Gaffney, Kelly J.; Liu, Simon H.; Bezel, Ilya

2003-12-01

Two-photon photoemission of thiolate/Ag(111), nitrile/Ag(111), and alcohol/Ag(111) interfaces elucidates electron solvation and localization in two dimensions. For low coverages of thiolates on Ag(111), the occupied (HOMO) and unoccupied (LUMO) electronic states of the sulfer-silver bond are localized due to the lattice gas structure of the adsorbate. As the coverage saturates and the adsorbate-adsorbate nearest neighbor distance decreases, the HOMO and LUMO delocalize across many adsorbate molecules. Alcohol- and nitrile-covered Ag(111) surfaces solvate excess image potential state (IPS) electrons. In the case of alcohol-covered surfaces, this solvation is due to a shift in the local workfunction of the surface. For two-monolayer coverages of nitriles/Ag(111), localization accompanies solvation of the IPS. The size of the localized electron can be estimated by Fourier transformation of the wavefunction from momentum- to position-space. The IPS electron localizes to 15 +/- 4 angstroms full-width at half maximum in the plane of the surface, i.e., to a single lattice site.

Methodology for in situ protection of aldehydes and ketones using trimethylsilyl trifluoromethanesulfonate and phosphines: selective alkylation and reduction of ketones, esters, amides, and nitriles.

PubMed

Yahata, Kenzo; Minami, Masaki; Yoshikawa, Yuki; Watanabe, Kei; Fujioka, Hiromichi

2013-01-01

A methodology for selective transformations of ketones, esters, Weinreb amides, and nitriles in the presence of aldehydes has been developed. The use of a combination of PPh(3)-trimethylsilyl trifluoromethanesulfonate (TMSOTf) promotes selective transformation of aldehydes to their corresponding, temporarily protected, O,P-acetal type phosphonium salts. Because, hydrolytic work-up following ensuing reactions of other carbonyl moieties in the substrates liberates the aldehyde moiety, a sequence involving aldehyde protection, transformation of other carbonyl groups, and deprotection can be accomplished in a one-pot manner. Furthermore, the use of PEt(3) instead of PPh(3) enables ketones to be converted in situ to their corresponding O,P-ketal type phosphonium salts and, consequently, selective transformations of esters, Weinreb amides, and nitriles in the presence of ketones can be performed. This methodology is applicable to various dicarbonyl compounds, including substrates that possess heteroaromatic skeletons and hydroxyl protecting groups.

Site-Specific Measurement of Water Dynamics in the Substrate Pocket of Ketosteroid Isomerase Using Time-Resolved Vibrational Spectroscopy

PubMed Central

Jha, Santosh Kumar; Ji, Minbiao; Gaffney, Kelly J.; Boxer, Steven G.

2012-01-01

Little is known about the reorganization capacity of water molecules at the active sites of enzymes and how this couples to the catalytic reaction. Here, we study the dynamics of water molecules at the active site of a highly proficient enzyme, Δ5-3-ketosteroid isomerase (KSI), during a light-activated mimic of its catalytic cycle. Photo-excitation of a nitrile containing photo-acid, coumarin183 (C183), mimics the change in charge density that occurs at the active site of KSI during the first step of the catalytic reaction. The nitrile of C183 is exposed to water when bound to the KSI active site, and we used time-resolved vibrational spectroscopy as a site-specific probe to study the solvation dynamics of water molecules in the vicinity of the nitrile. We observed that water molecules at the active site of KSI are highly rigid, during the light-activated catalytic cycle, compared to the solvation dynamics observed in bulk water. Based upon this result we hypothesize that rigid water dipoles at the active site might help in the maintenance of the pre-organized electrostatic environment required for efficient catalysis. The results also demonstrate the utility of nitrile probes in measuring the dynamics of local (H-bonded) water molecules in contrast to the commonly used fluorescence methods which measure the average behavior of primary and subsequent spheres of solvation. PMID:22931297

A novel strategy for acetonitrile wastewater treatment by using a recombinant bacterium with biofilm-forming and nitrile-degrading capability.

PubMed

Li, Chunyan; Yue, Zhenlei; Feng, Fengzhao; Xi, Chuanwu; Zang, Hailian; An, Xuejiao; Liu, Keran

2016-10-01

There is a great need for efficient acetonitrile removal technology in wastewater treatment to reduce the discharge of this pollutant in untreated wastewater. In this study, a nitrilase gene (nit) isolated from a nitrile-degrading bacterium (Rhodococcus rhodochrous BX2) was cloned and transformed into a biofilm-forming bacterium (Bacillus subtilis N4) that expressed the recombinant protein upon isopropylthio-β-galactoside (IPTG) induction. The recombinant bacterium (B. subtilis N4-pHT01-nit) formed strong biofilms and had nitrile-degrading capability. Further testing demonstrated that biofilms formed by B. subtilis N4-pHT01-nit were highly resistant to loading shock from acetonitrile and almost completely degraded the initial concentration of acetonitrile (800 mg L(-1)) within 24 h in a moving bed biofilm reactor (MBBR) after operation for 35 d. The bacterial composition of the biofilm, identified by high-throughput sequencing, in a reactor in which the B. subtilis N4-pHT01-nit bacterium was introduced indicated that the engineered bacterium was successfully immobilized in the reactor and became dominant genus. This work demonstrates that an engineered bacterium with nitrile-degrading and biofilm-forming capacity can improve the degradation of contaminants in wastewater. This approach offers a novel strategy for enhancing the biological oxidation of toxic pollutants in wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature

PubMed Central

Kim, Jinho; Stahl, Shannon S.

2013-01-01

An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4′-tBu2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction. PMID:24015373

Mechanistic Insight Facilitates Discovery of a Mild and Efficient Copper-Catalyzed Dehydration of Primary Amides to Nitriles Using Hydrosilanes.

PubMed

Liu, Richard Y; Bae, Minwoo; Buchwald, Stephen L

2018-02-07

Metal-catalyzed silylative dehydration of primary amides is an economical approach to the synthesis of nitriles. We report a copper-hydride(CuH)-catalyzed process that avoids a typically challenging 1,2-siloxane elimination step, thereby dramatically increasing the rate of the overall transformation relative to alternative metal-catalyzed systems. This new reaction proceeds at ambient temperature, tolerates a variety of metal-, acid-, or base-sensitive functional groups, and can be performed using a simple ligand, inexpensive siloxanes, and low catalyst loading.

Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature.

PubMed

Kim, Jinho; Stahl, Shannon S

2013-07-05

An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4'- t Bu 2 bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N -oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction.

Isolation and reconstitution of cytochrome P450ox and in vitro reconstitution of the entire biosynthetic pathway of the cyanogenic glucoside dhurrin from sorghum.

PubMed Central

Kahn, R A; Bak, S; Svendsen, I; Halkier, B A; Møller, B L

1997-01-01

A cytochrome P450, designated P450ox, that catalyzes the conversion of (Z)-p-hydroxyphenylacetaldoxime (oxime) to p-hydroxymandelonitrile in the biosynthesis of the cyanogenic glucoside beta-D-glucopyranosyloxy-(S)-p-hydroxymandelonitrile (dhurrin), has been isolated from microsomes prepared from etiolated seedlings of sorghum (Sorghum bicolor L. Moench). P450ox was solubilized using nonionic detergents, and isolated by ion-exchange chromatography, Triton X-114 phase partitioning, and dye-column chromatography. P450ox has an apparent molecular mass of 55 kD, its N-terminal amino acid sequence is -ATTATPQLLGGSVP, and it contains the internal sequence MDRLVADLDRAAA. Reconstitution of P450ox with NADPH-P450 oxidoreductase in micelles of L-alpha-dilauroyl phosphatidylcholine identified P450ox as a multifunctional P450 catalyzing dehydration of (Z)-oxime to p-hydroxyphenylaceto-nitrile (nitrile) and C-hydroxylation of p-hydroxyphenylacetonitrile to nitrile. P450ox is extremely labile compared with the P450s previously isolated from sorghum. When P450ox is reconstituted in the presence of a soluble uridine diphosphate glucose glucosyltransferase, oxime is converted to dhurrin. In vitro reconstitution of the entire dhurrin biosynthetic pathway from tyrosine was accomplished by the insertion of CYP79 (tyrosine N-hydroxylase), P450ox, and NADPH-P450 oxidoreductase in lipid micelles in the presence of uridine diphosphate glucose glucosyltransferase. The catalysis of the conversion of Tyr into nitrile by two multifunctional P450s explains why all intermediates in this pathway except (Z)-oxime are channeled. PMID:9414567

INFRARED AND ULTRAVIOLET SPECTRA OF METHANE DILUTED IN SOLID NITROGEN AND IRRADIATED WITH ELECTRONS DURING DEPOSITION AT VARIOUS TEMPERATURES

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

Chin, Chih-Hao; Chen, Sian-Cong; Liu, Meng-Chen

We recorded the infrared and ultraviolet absorption spectra of CH{sub 4}:N{sub 2} matrix samples that underwent electron bombardment during deposition in the temperature range of 10–44 K. In contrast to a previous experiment on the IR spectroscopy of electron-bombarded icy samples, methyl and azide radicals became the main products upon electron bombardment during deposition; furthermore, reduced production of nitrile species was observed for deposition at 10 and 20 K. On the other hand, for deposition above 33 K, the observed bands of the radical species (such as methyl and azide) decreased, and bands of large nitriles appeared. This observation maymore » suggest that radical species easily diffuse and recombine to form more complex molecules in solid nitrogen at higher temperatures. Further measurements of similar samples at 10–33 K in the UV region revealed the intense band of azide radicals at 272.5 nm and weak, broad, overlapping features of methyl and azide radicals in the 225–197 nm region. For deposition at 44 K, only a broad feature centered at 219.4 nm was observed, and the possible carriers of nitrile species were proposed based on the corresponding IR spectrum and theoretical predictions of excitation energy. This band is similar to the observed absorption feature of Pluto’s surface recorded by the Hubble telescope in terms of both band position and bandwidth. Our findings therefore further support the suggestion that complex nitrile species may exist on the surface of Pluto.« less

Catalytic trimerization of aromatic nitriles and triaryl-s-triazine ring cross-linked high temperature resistant polymers and copolymers made thereby

NASA Technical Reports Server (NTRS)

Hsu, L. C. (Inventor)

1979-01-01

Triazine compounds and cross-linked polymer compositions are made by heating aromatic nitriles to a temperature in the range of from about 100 C to about 700 C, and preferably in the range of from about 200 C to about 350 C, in the presence of a catalyst or mixture of catalysts selected from one or more of the following groups: (1) organic sulfonic and sulfinic acids, (2) organic phosphonic and phosphinic acids, and (3)metallic acetylacetonates, at a pressure in the range of from about atmospheric pressure to about 10,000 psi and preferably in the range of from about 200 psi to about 750 psi. Aromatic nitrile-modified (terminated and/or appended) imide, benzimidazole, imidazopyrrolone, quinoxaline, and other condensation type prepolymers or their precopolymers are made which are trimerized with or without a filler by the aforementioned catalytic trimerization process into triaryl-s-triazine ring containing or cross-linked polymeric or copolymeric products useful in applications requiring high thermal-oxidative stability and high performance structural properties at elevated temperatures.

Towards understanding the mechanisms and the kinetics of nanoparticle penetration through protective gloves

NASA Astrophysics Data System (ADS)

Vinches, L.; Peyrot, C.; Lemarchand, L.; Boutrigue, N.; Zemzem, M.; Wilkinson, K. J.; Hallé, S.; Tufenkji, N.

2015-05-01

Parallel to the increased use of engineered nanoparticles (ENP) in the formulation of commercial products or in medicine, numerous health & safety agencies have recommended the application of the precautionary principle to handle ENP; namely, the recommendation to use protective gloves against chemicals. However, recent studies reveal the penetration of titanium dioxide nanoparticles through nitrile rubber protective gloves in conditions simulating occupational use. This project is designed to understand the links between the penetration of gold nanoparticles (nAu) through nitrile rubber protective gloves and the mechanical and physical behaviour of the elastomer material subjected to conditions simulating occupational use (i.e., mechanical deformations (MD) and sweat). Preliminary analyses show that nAu suspensions penetrate selected glove materials after exposure to prolonged (3 hours) dynamic deformations. Significant morphological changes are observed on the outer surface of the glove sample; namely, the number and the surface of the micropores on the surface increase. Moreover, nitrile rubber protective gloves are also shown to be sensitive to the action of nAu suspension and to the action of the saline solution used to simulate sweat (swelling).

Crosslinked polyarylene ether nitrile film as flexible dielectric materials with ultrahigh thermal stability

PubMed Central

Yang, Ruiqi; Wei, Renbo; Li, Kui; Tong, Lifen; Jia, Kun; Liu, Xiaobo

2016-01-01

Dielectric film with ultrahigh thermal stability based on crosslinked polyarylene ether nitrile is prepared and characterized. The film is obtained by solution-casting of polyarylene ether nitrile terminated phthalonitrile (PEN-Ph) combined with post self-crosslinking at high temperature. The film shows a 5% decomposition temperature over 520 °C and a glass transition temperature (Tg) around 386 °C. Stable dielectric constant and low dielectric loss are observed for this film in the frequency range of 100–200 kHz and in the temperature range of 25–300 °C. The temperature coefficient of dielectric constant is less than 0.001 °C−1 even at 400 °C. By cycling heating and cooling up to ten times or heating at 300 °C for 12 h, the film shows good reversibility and robustness of the dielectric properties. This crosslinked PEN film will be a potential candidate as high performance film capacitor electronic devices materials used at high temperature. PMID:27827436

Nitrile functionalized halloysite nanotubes/poly(arylene ether nitrile) nanocomposites: Interface control, characterization, and improved properties

NASA Astrophysics Data System (ADS)

Wan, Xinyi; Zhan, Yingqing; Zeng, Guangyong; He, Yi

2017-01-01

To develop high-performance halloysite nanotube (HNT)-based nanocomposites, the two key issues need to be considered: precise interface control and the dispersal of HNTs. This study presents an efficient way to functionalize halloysite nanotubes with 3-aminophenoxy-phthalonitrile, followed by compounding with poly(arylene ether nitrile) (PEN), to prepare functional nanocomposite films. The surface functionalization of HNTs was characterized and confirmed by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Compared with neat PEN, the tensile strength and modulus of the resulting PEN nanocomposites with 3 wt% functionalized HNTs were found to increase by 25.7% and 20.7%, respectively. The good dispersion and high capacitance of the dielectric layer resulted in PEN/HNTs nancomposites with enhanced dielectric permittivity and relatively low dielectric loss. Moreover, the addition of functional HNTs greatly improved the thermal stability of PEN, which could be further enhanced through the chemical cross-linking reaction between the functional HNTs and the PEN matrix. This work provides a new path toward obtaining advanced polymer-based nanocomposites with functional properties.

New strategy and easy fabrication of solid-state supercapacitor based on polypyrrole and nitrile rubber.

PubMed

Lee, Sangyool; Lee, Youngkwan; Cho, Mi-Suk; Nam, Jae-Do

2008-09-01

Solid state redox supercapacitors were fabricated using a solid polymer electrolyte, nitrile butadiene rubber (NBR)-KCI and chemically deposited polypyrrole (PPy) as the conducting polymer electrodes on both surfaces of a NBR film. The optimal conditions for the preparation of the PPy/NBR electrode were confirmed as functions of the uptake of pyrrole monomer into the NBR matrix as well as the immersion time in an oxidant solution. The morphology of the PPy-NBR-KCI capacitor was observed using scanning electron microscopy. The performance of the capacitors was characterized using a galvanostatic charge-discharge technique.

Analysis of Liquid Propellant Exposed to Elastomeric Materials

DTIC Science & Technology

1989-12-01

Rubber LP-l NBR -2 B. Nitrile Rubber LP-2 N-BR-8 LP-3 NBR -9 LP-4 1203-F60-R2, RADIAN LP-5 VT-380 ( NBR /PVC), RADIAN LP-6 BJLT MI-40, UNIROYAL LP-7 OZO-HA...0221 (70% NBR /30% PVC), UNIROYAL C. Carboxylated Nitrile Rubber LP-8 XNBR-2 LP-9 XN BR-3 LP-10 XNBR-6 D. Polychioroprene Rubber LP-11 CR-i LP-12 CR-2...compatibility of liquid propellants is also determined by the degradation of the propellant by decomposition, by the solution of ballistically undesirable

Serendipitous preparation of fac-(aceto-nitrile-κN)tri-chlorido-[(1,2,5,6-η)-cyclo-octa-1,5-diene]iridium(III).

PubMed

Morris, David M; Merola, Joseph S

2015-04-01

A reaction between [(COD)IrCl]2 (COD is cyclo-octa-1,5-diene), HCl and indene failed to provide the hoped for chlorido-indenyliridium dimer, but instead produced the title compound, [IrCl3(CH3CN)(C8H12)], which is an octa-hedral complex of iridium(III) with a chelating cyclo-octa-1,5-diene ligand, three chloride ligands in a fac arrangement, and one aceto-nitrile ligand. Attempts to devise a rational synthesis for the title compound were unsuccessful.

Conserved electrostatic fields at the Ras-effector interface measured through vibrational Stark effect spectroscopy explain the difference in tilt angle in the Ras binding domains of Raf and RalGDS.

PubMed

Walker, David M; Wang, Ruifei; Webb, Lauren J

2014-10-07

Vibrational Stark effect (VSE) spectroscopy was used to measure the electrostatic fields present at the interface of the human guanosine triphosphatase (GTPase) Ras docked with the Ras binding domain (RBD) of the protein kinase Raf. Nine amino acids located on the surface of Raf were selected for labeling with a nitrile vibrational probe. Eight of the probe locations were situated along the interface of Ras and Raf, and one probe was 2 nm away on the opposite side of Raf. Vibrational frequencies of the nine Raf nitrile probes were compared both in the monomeric, solvated protein and when docked with wild-type (WT) Ras to construct a comprehensive VSE map of the Ras-Raf interface. Molecular dynamics (MD) simulations employing an umbrella sampling strategy were used to generate a Boltzmann-weighted ensemble of nitrile positions in both the monomeric and docked complexes to determine the effect that docking has on probe location and orientation and to aid in the interpretation of VSE results. These results were compared to an identical study that was previously conducted on nine nitrile probes on the RBD of Ral guanidine dissociation stimulator (RalGDS) to make comparisons between the docked complexes formed when either of the two effectors bind to WT Ras. This comparison finds that there are three regions of conserved electrostatic fields that are formed upon docking of WT Ras with both downstream effectors. Conservation of this pattern in the docked complex then results in different binding orientations observed in otherwise structurally similar proteins. This work supports an electrostatic cause of the known binding tilt angle between the Ras-Raf and Ras-RalGDS complexes.

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

Mani, Tomoyasu; Grills, David C.

Delocalization of charges is one of the factors controlling charge transport in conjugated molecules. It is considered to play an important role in the performance of a wide range of molecular technologies, including organic solar cells and organic electronics. Dimerization reactions are well-suited as a model to investigate intermolecular spatial delocalization of charges. And while dimerization reactions of radical cations are well investigated, studies on radical anions are still scarce. Upon dimerization of radical anions with neutral counterparts, an electron is considered to delocalize over the two molecules. By using time-resolved infrared (TRIR) detection coupled with pulse radiolysis, we showmore » that radical anions of 4-n-hexyl-4'-cyanobiphenyl (6CB) undergo such dimerization reactions, with an electron equally delocalized over the two molecules. We have recently demonstrated that nitrile ν(C≡N) vibrations respond to the degree of electron localization of nitrile-substituted anions: we can quantify the changes in the electronic charges from the neutral to the anion states in the nitriles by monitoring the ν(C≡N) IR shifts. In the first part of this article, we show that the sensitivity of the ν(C≡N) IR shifts does not depend on solvent polarity. In the second part, we describe how probing the shifts of the nitrile IR vibrational band unambiguously confirms the formation of dimer radical anions, with K dim = 3 × 10 4 M –1. IR findings are corroborated by electronic absorption spectroscopy and electronic structure calculations. We find that the presence of a hexyl chain and the formation of π–π interactions are both crucial for dimerization of radical anions of 6CB with neutral 6CB. Our study provides clear evidence of spatial delocalization of electrons over two molecular fragments.« less

Probing Intermolecular Electron Delocalization in Dimer Radical Anions by Vibrational Spectroscopy

DOE PAGES

Mani, Tomoyasu; Grills, David C.

2017-07-05

Delocalization of charges is one of the factors controlling charge transport in conjugated molecules. It is considered to play an important role in the performance of a wide range of molecular technologies, including organic solar cells and organic electronics. Dimerization reactions are well-suited as a model to investigate intermolecular spatial delocalization of charges. And while dimerization reactions of radical cations are well investigated, studies on radical anions are still scarce. Upon dimerization of radical anions with neutral counterparts, an electron is considered to delocalize over the two molecules. By using time-resolved infrared (TRIR) detection coupled with pulse radiolysis, we showmore » that radical anions of 4-n-hexyl-4'-cyanobiphenyl (6CB) undergo such dimerization reactions, with an electron equally delocalized over the two molecules. We have recently demonstrated that nitrile ν(C≡N) vibrations respond to the degree of electron localization of nitrile-substituted anions: we can quantify the changes in the electronic charges from the neutral to the anion states in the nitriles by monitoring the ν(C≡N) IR shifts. In the first part of this article, we show that the sensitivity of the ν(C≡N) IR shifts does not depend on solvent polarity. In the second part, we describe how probing the shifts of the nitrile IR vibrational band unambiguously confirms the formation of dimer radical anions, with K dim = 3 × 10 4 M –1. IR findings are corroborated by electronic absorption spectroscopy and electronic structure calculations. We find that the presence of a hexyl chain and the formation of π–π interactions are both crucial for dimerization of radical anions of 6CB with neutral 6CB. Our study provides clear evidence of spatial delocalization of electrons over two molecular fragments.« less

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

Javahery, G.; Petrie, S.; Wang, J.

Results are reported for the reactions of the fullerene ions C[sub 60[center dot]+], C[sub 70[center dot]+], C[sub 60][sup 2+], C[sub 70][sup 2+], and C[sub 60[center dot]3+] with the nitriles HCN, CH[sub 3]CN, CH[sub 2]CHCN, CH[sub 3]CH[sub 2]CN, CH[sub 2]CHCH[sub 2]CN, CH[sub 3]CH[sub 2]CH[sub 2]CN, (CH[sub 3])[sub 2]CHCN, C[sub 2]N[sub 2], and CH[sub 2](CN)[sub 2]. The reactions were studied using a selected-ion flow tube (SIFT) at 294 [+-] 2 K and a helium buffer gas pressure of 0.35 [+-] 0.01 Torr and exhibited a wide range of chemical behavior. For the monocations C[sub 60][sup [center dot]+] and C[sub 70][sup [center dot]+],more » no detectable reaction occurred with any of the nitriles. For the dications C[sub 60][sup 2+], and C[sub 70][sup 2+], the only primary or secondary product channel evident in all instances was addition: tertiary association was seen to be considerably less efficient than the primary and secondary reactions, and the formation of a quadruple adduct C[sub 60](RCN)[sub 4][sup 2+] was only detected in the reaction with butyronitrile, CH[sub 3]CH[sub 2]CH[sub 2]CN. The observed primary rate coefficients show a very clear dependence upon the molecular complexity of the nitrile: association proceeds more efficiently for nitriles with a higher number of hydrogen atoms. This observation is explained in terms of a model which relates the number of C-H bonds - or, alternatively, the number of internal rotational modes - in the collision complex to the lifetime and probability of stabilization of this complex. 42 refs., 5 figs., 3 tabs.« less

New Complexity-Building Reactions of Alpha-Keto Esters

NASA Astrophysics Data System (ADS)

Bartlett, Samuel L.

I. Introduction: Importance of Asymmetric Catalysis and the Reactivity Patterns of alpha-Keto Esters. II. Synthesis of Complex Tertiary Glycolates by Enantioconvergent Arylation of Stereochemically Labile alpha-Keto Esters. Enantioconvergent arylation reactions of boronic acids and racemic ?-stereogenic alpha-keto esters have been developed. The reactions are catalyzed by a chiral (diene)Rh(I) complex and provide a wide array of beta-stereogenic tertiary aryl glycolate derivatives with high levels of diastereo- and enantioselectivity. Racemization studies employing a series of sterically differentiated tertiary amines suggest that the steric nature of the amine base additive exerts a significant influence on the rate of substrate racemization. III. Palladium-Catalyzed beta-Arylation of alpha-Keto Esters . A catalyst system derived from commercially available Pd2(dba) 3 and PtBu3 has been applied to the coupling of alpha-keto ester enolates and aryl bromides. The reaction provides access to an array of beta-stereogenic alpha-keto ester derivatives. When the air stable ligand precursor PtBu 3˙HBF4 is employed, the reaction can be carried out without use of a glovebox. The derived products are of broad interest given the prevalence of the alpha-keto acid substructure in biologically important molecules. IV. Catalytic Enantioselective [3+2] Cycloaddition of alpha-Keto Ester Enolates and Nitrile Oxides. An enantioselective [3+2] cycloaddition reaction between nitrile oxides and transiently generated enolates of alpha-keto esters has been developed. The catalyst system was found to be compatible with in situ nitrile oxide generation conditions. A versatile array of nitrile oxides and alpha-keto esters could participate in the cycloaddition, providing novel 5-hydroxy-2-isoxazolines in high chemical yield with high levels of diastereo- and enantioselectivity. Notably, the optimal reaction conditions circumvented concurrent reaction via O-imidoylation and hetero-[3+2] pathways.

Survey of dermal protection in Washington State collision repair industry.

PubMed

Ceballos, Diana M; Fent, Kenneth W; Whittaker, Stephen G; Gaines, Linda G T; Thomasen, Jennifer M; Flack, Sheila L; Nylander-French, Leena A; Yost, Michael G; Reeb-Whitaker, Carolyn K

2011-09-01

Substantial exposure to isocyanates may occur during spray painting in autobody shops, yet information is lacking on the efficacy of the protective clothing used during spray painting. We investigated the personal and workplace factors associated with painters' dermal protection use during a large-scale exposure assessment study. Survey data indicated that 69% of painters always used gloves, with latex gloves (47%) and nitrile gloves (34%) used most frequently. Among latex glove users, 53% used thin latex (0.05-0.13 mm), 6% used medium latex (0.15-0.20 mm), and 12% used thick latex (> 0.20 mm). Among nitrile glove users, 27% used thin nitrile and 45% used medium nitrile. Sixty-three percent of painters always used coveralls, 44% preferring one particular brand. Although overspray presents an opportunity for dermal exposure to the neck and face, only 19% of painters protected these areas with personal protective equipment. Painters who always used coveralls were more likely to use gloves (odds ratio = 7.9, p = 0.061). Painters who reported ever having smoked cigarettes used gloves (p = 0.05) and coveralls (p = 0.04) more frequently. Painters who sprayed more than 34 clear coat jobs per month used coveralls most frequently (p = 0.038). Exact logistic regressions along with random sample calculations indicated that the survey results were independent of the shops. Because of the small sample size in this study, future research is warranted to corroborate these results. Studying the effectiveness of gloves and coveralls against polyurethane paints and understanding the underlying motivators and preferences for painters and business owners is needed for the development of best practices for the selection and use of dermal protection.

Highly selective separation of carbon dioxide from nitrogen and methane by nitrile/glycol-difunctionalized ionic liquids in supported ionic liquid membranes (SILMs).

PubMed

Hojniak, Sandra D; Silverwood, Ian P; Khan, Asim Laeeq; Vankelecom, Ivo F J; Dehaen, Wim; Kazarian, Sergei G; Binnemans, Koen

2014-07-03

Novel difunctionalized ionic liquids (ILs) containing a triethylene glycol monomethyl ether chain and a nitrile group on a pyrrolidinium or imidazolium cation have been synthesized and incorporated into supported ionic liquid membranes (SILMs). These ILs exhibit ca. 2.3 times higher CO2/N2 and CO2/CH4 gas separation selectivities than analogous ILs functionalized only with a glycol chain. Although the glycol moiety ensures room temperature liquidity of the pyrrolidinium and imidazolium ILs, the two classes of ILs benefit from the presence of a nitrile group in different ways. The difunctionalized pyrrolidinium ILs exhibit an increase in CO2 permeance, whereas the permeances of the contaminant gases rise negligibly, resulting in high gas separation selectivities. In the imidazolium ILs, the presence of a nitrile group does not always increase the CO2 permeance nor does it increase the CO2 solubility, as showed in situ by the ATR-FTIR spectroscopic method. High selectivity of these ILs is caused by the considerably reduced permeances of N2 and CH4, most likely due to the ability of the -CN group to reject the nonpolar contaminant gases. Apart from the CO2 solubility, IL-CO2 interactions and IL swelling were studied with the in situ ATR-FTIR spectroscopy. Different strengths of the IL-CO2 interactions were found to be the major difference between the two classes of ILs. The difunctionalized ILs interacted stronger with CO2 than the glycol-functionalized ILs, as manifested in the smaller bandwidths of the bending mode band of CO2 for the latter.

Carbohydrates as efficient catalysts for the hydration of α-amino nitriles.

PubMed

Chitale, Sampada; Derasp, Joshua S; Hussain, Bashir; Tanveer, Kashif; Beauchemin, André M

2016-11-01

Directed hydration of α-amino nitriles was achieved under mild conditions using simple carbohydrates as catalysts exploiting temporary intramolecularity. A broadly applicable procedure using both formaldehyde and NaOH as catalysts efficiently hydrated a variety of primary and secondary susbtrates, and allowed the hydration of enantiopure substrates to proceed without racemization. This work also provides a rare comparison of the catalytic activity of carbohydrates, and shows that the simple aldehydes at the basis of chemical evolution are efficient organocatalysts mimicking the function of hydratase enzymes. Optimal catalytic efficiency was observed with destabilized aldehydes, and with difficult substrates only simple carbohydrates such as formaldehyde and glycolaldehyde proved reliable.

Synthesis of δ- and α-Carbolines via Nickel-Catalyzed [2 + 2 + 2] Cycloaddition of Functionalized Alkyne-Nitriles with Alkynes.

PubMed

Wang, Gaonan; You, Xu; Gan, Yi; Liu, Yuanhong

2017-01-06

A new method for the synthesis of δ- and α-carbolines through Ni-catalyzed [2 + 2 + 2] cycloaddition of ynamide-nitriles or alkyne-cyanamides with alkynes has been developed. The catalytic system of NiCl 2 (DME)/dppp/Zn with a low-cost Ni(II)-precursor was first utilized in Ni-catalyzed [2 + 2 + 2] cycloaddition reactions, and the in situ generated Lewis acid may play an important role for the successful transformation. Not only internal alkynes but also terminal alkynes undergo the desired cycloaddition reactions efficiently to furnish the carboline derivatives with wide diversity and functional group tolerance.

Enantioselective construction of quaternary stereogenic carbons by the Lewis base catalyzed additions of silyl ketene imines to aldehydes.

PubMed

Denmark, Scott E; Wilson, Tyler W; Burk, Matthew T; Heemstra, John R

2007-12-05

Silyl ketene imines derived from a variety of alpha-branched nitriles have been developed as highly useful reagents for the construction of quaternary stereogenic centers via the aldol addition reaction. In the presence of SiCl4 and the catalytic action of chiral phosphoramide (R,R)-5, silyl ketene imines undergo extremely rapid and high yielding addition to a wide variety of aromatic aldehydes with excellent diastereo- and enantioselectivity. Of particular note is the high yields and selectivities obtained from electron-rich, electron-poor, and hindered aldehydes. The nitrile function serves as a useful precursor for further synthetic manipulation.

5-(Methylthio)tetrazoles as Versatile Synthons in the Stereoselective Synthesis of Polycyclic Pyrazolines via Photoinduced Intramolecular Nitrile Imine–Alkene 1,3-Dipolar Cycloaddition

PubMed Central

Pla, Daniel; Tan, Derek S.; Gin, David Y.

2014-01-01

A key thioether substituent in readily accessible 2-alkyl-5-(methylthio)tetrazoles enables facile photoinduced denitrogenation and intramolecular nitrile imine 1,3-dipolar cycloaddition to afford a wide range of polycyclic pyrazoline products with excellent diastereoselectivity. The methylthio group red-shifts the UV absorbance of the tetrazole, obviating the requirement in all previous substrate systems for at least one aryl substituent, and can subsequently be converted into a variety of other functionalities. This synthetic platform has been applied to the concise total syntheses of the alkaloid natural products (±)-newbouldine and withasomnine. PMID:25114776

Expeditious microwave-assisted synthesis of 5-alkoxyoxazoles from α-triflyloxy esters and nitriles.

PubMed

Jouanno, Laurie-Anne; Sabot, Cyrille; Renard, Pierre-Yves

2012-10-05

A rapid and general access to diversely substituted 5-alkoxyoxazoles 2 (i.e., R(1), R(2) = alkyl, phenyl) from easily accessible α-triflyloxy/hydroxy esters 1 and nitriles with good yields (41-76%) is reported. The versatility of the cyclization is shown for a range of substrates with high selectivity toward triflates over mesylates and proved to be compatible with sensitive functional groups. As an illustration of this transformation, the first synthesis of the recently isolated hydroxypyridine methyl multijuguinate 4 was achieved in four steps through a hetero Diels-Alder reaction of the 5-alkoxyoxazole and acrylic acid, followed by a protodecarboxylation reaction.

NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions.

PubMed

Adam, Rosa; Alberico, Elisabetta; Baumann, Wolfgang; Drexler, Hans-Joachim; Jackstell, Ralf; Junge, Henrik; Beller, Matthias

2016-03-24

A series of seven novel N(Im)N(H)P-type pincer imidazolylphosphine ruthenium complexes has been synthesized and fully characterized. The use of hydrogenation of benzonitrile as a benchmark test identified [RuHCl(CO)(N(Im)N(H) P(tBu))] as the most active catalyst. With its stable Ru-BH4 analogue, in which chloride is replaced by BH4, a broad range of (hetero)aromatic and aliphatic nitriles, including industrially interesting adiponitrile, has been hydrogenated under mild and base-free conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adhesion of nitrile rubber to UV-assisted surface chemical modified PET fabric, part II: Interfacial characterization of MDI grafted PET

NASA Astrophysics Data System (ADS)

Razavizadeh, Mahmoud; Jamshidi, Masoud

2016-08-01

Fiber to rubber adhesion is an important subject in rubber industry. It is well known that surface treatment (i.e. physical, mechanical and chemical) is an effective method to improve interfacial bonding of fibers and/or fabrics to rubbers. UV irradiation is an effective method which has been used to increase fabric-rubber interfacial interactions. In this research UV assisted chemical modification of PET fabrics was used to increase PET to nitrile rubber (NBR) adhesion. Nitrile rubber is a perfect selection as fuel and oil resistant rubber. However it has weak bonding to PET fabric. For this purpose PET fabric was carboxylated under UV irradiation and then methylenediphenyl diisocyanate (MDI) was grafted on carboxylated PET. The chemical composition of the fabric before and after surface treatment was investigated by X-ray photoelectron spectroscopy (XPS). The sectional morphology of the experimental PET fibers and the interface between rubber compound and PET fabric was studied using scanning electron microscope (SEM). The morphology and structure of the product were analyzed by an energy dispersive X-ray spectrometer (EDX). FTIR-ATR and H NMR analysis were used to assess surface modifications on the PET irradiated fabrics.

μ-Hexa-thio-metadiphosphato-bis-[(1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane-κ(6) O)rubidium] aceto-nitrile disolvate.

PubMed

Gjikaj, Mimoza; Pook, Niels-Patrick; Qarri, Flora

2013-12-01

The asymmetric unit of the title compound, [Rb2(P2S6)(C12H24O6)2]·2CH3CN, contains one half of an [Rb(18-crown-6)2]2[P2S6] unit and one aceto-nitrile solvent mol-ecule. The [Rb(18-crown-6)]2[P2S6] unit is completed by inversion symmetry. Its Rb(+) ion is situated near the centre of the macrocyclic cavity, but is displaced by 0.8972 (1) Å from the O atoms of the crown in the direction of the [P2S6](2-) moiety. The overall coordination number of the cation is eight, defined by the six crown ether O atoms and by two terminal S atoms of the [P2S6](2-) anion. The hexa-thio-metadiphosphate anion is built up from two tetra-hedral PS4 units joined together by a common edge. The crystal structure is characterized by alternating layers of [Rb(18-crown-6)]2[P2S6] and aceto-nitrile solvent mol-ecules stacked along [010].

A new class of renewable thermoplastics with extraordinary performance from nanostructured lignin-elastomers

DOE PAGES

Chen, Jihua D.; Keum, Jong Kahk; Naskar, Amit K.; ...

2016-03-22

In this study, a new class of thermoplastic elastomers has been created by introducing nanoscale-dispersed lignin (a biomass-derived phenolic oligomer) into nitrile rubber. Temperature-induced controlled miscibility between the lignin and the rubber during high shear melt-phase synthesis allows tuning the material s morphology and performance. The sustainable product has unprecedented yield stress (15–45 MPa), strain hardens at large deformation, and has outstanding recyclability. The multiphase polymers developed from an equal-mass mixture of a melt-stable lignin fraction and nitrile rubber with optimal acrylonitrile content, using the method described here, show 5–100 nm lignin lamellae with a high-modulus rubbery interphase. Molded ormore » printed elastomeric products prepared from the lignin-nitrile material offer an additional revenue stream to pulping mills and biorefineries. Research was sponsored by the Technology Innovation Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U.S. Department of Energy. TEM (J.C. and C.D.T.) and SAXS (J.K.K.) experiments were conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.« less

Caterpillar-induced plant volatiles attract conspecific adults in nature

PubMed Central

El-Sayed, Ashraf M.; Knight, Alan L.; Byers, John A.; Judd, Gary J. R.; Suckling, David M.

2016-01-01

Plants release volatiles in response to caterpillar feeding that attract natural enemies of the herbivores, a tri-trophic interaction which has been considered an indirect plant defence against herbivores. The caterpillar-induced plant volatiles have been reported to repel or attract conspecific adult herbivores. To date however, no volatile signals that either repel or attract conspecific adults under field conditions have been chemically identified. Apple seedlings uniquely released seven compounds including acetic acid, acetic anhydride, benzyl alcohol, benzyl nitrile, indole, 2-phenylethanol, and (E)-nerolidol only when infested by larvae of the light brown apple moth, Epiphyas postvittana. In field tests in New Zealand, a blend of two of these, benzyl nitrile and acetic acid, attracted a large number of conspecific male and female adult moths. In North America, male and female adults of the tortricid, oblique-banded leafroller, Choristoneura rosaceana, were most attracted to a blend of 2-phenylethanol and acetic acid. Both sexes of the eye-spotted bud moth, Spilonota ocellana, were highly attracted to a blend of benzyl nitrile and acetic acid. This study provides the first identification of caterpillar-induced plant volatiles that attract conspecific adult herbivores under natural conditions, challenging the expectation of herbivore avoidance of these induced volatiles. PMID:27892474

Treponemycin, a nitrile antibiotic active against Treponema hyodysenteriae.

PubMed

Singh, S K; Gurusiddaiah, S; Whalen, J W

1985-02-01

Two strains of Streptomyces sp. (isolates 275 and 124) were isolated from soil samples collected from the fields around Lewiston, Idaho. Based on their cellular morphology and physiology, the two isolates were identified as Streptomyces albovinaceous. Both isolates produced an antibiotic when grown in liquid culture medium containing homogenized oats. The antibiotic (treponemycin) was isolated from the culture broth by solvent extraction and purified by silica gel column and preparative thin-layer chromatographies. Treponemycin is a crystalline light-yellow compound with an mp of 93 to 95 degrees C, levorotatory, and soluble in most organic solvents. It is sparingly soluble in water but insoluble in petroleum ether. On the basis of elemental analysis and mass spectral data, the molecular formula of the antibiotic was deduced to be C28H43O6N. The infrared spectrum of the antibiotic indicated the presence of unsaturation, nitrile, lactone, or ester or all three functions, and carbonyl functions in the molecule. A sharp infrared absorption band for nitrile at 2,220 cm-1 and the presence of an unsaturated group indicated that the nitrile function may be attached to an unsaturated carbon atom. The presence of dienenitrile functions was further supported by the UV absorption spectrum of the antibiotic, which gave a UVmax at 257 nm. The proton magnetic resonance spectrum of the antibiotic did not give any peak which could be exchanged with deuterated water, which is an indication of the absence of carboxylic and hydroxyl functions in the molecule. All of the functional groupings indicated by the infrared and UV spectra of the molecule were further confirmed by the 13C-magnetic resonance spectrum of the compound. A brief hydrogenation of the antibiotic yielded a biologically active tetrahydro derivative, whereas extended hydrogenation produced an inactive primary amine. Mild alkaline hydrolysis and subsequent esterification of the antibiotic with diazomethane produced an inactive dimethyl ester. Apparently both the nitrile and the lactone functions are essential for the treponomycin molecule to show antimicrobial activity. The antibiotic showed inhibitory activity against several species of bacteria, especially Treponema hyodysenteriae, the causative agent of swine dysentery. In view of the oral 50% lethal dose of 400 mg/g and its low MIC against four stains of T.hyodysenteriae, the antibiotic may have value as a swine dysentery therapeutic.

Treponemycin, a nitrile antibiotic active against Treponema hyodysenteriae.

PubMed Central

Singh, S K; Gurusiddaiah, S; Whalen, J W

1985-01-01

Two strains of Streptomyces sp. (isolates 275 and 124) were isolated from soil samples collected from the fields around Lewiston, Idaho. Based on their cellular morphology and physiology, the two isolates were identified as Streptomyces albovinaceous. Both isolates produced an antibiotic when grown in liquid culture medium containing homogenized oats. The antibiotic (treponemycin) was isolated from the culture broth by solvent extraction and purified by silica gel column and preparative thin-layer chromatographies. Treponemycin is a crystalline light-yellow compound with an mp of 93 to 95 degrees C, levorotatory, and soluble in most organic solvents. It is sparingly soluble in water but insoluble in petroleum ether. On the basis of elemental analysis and mass spectral data, the molecular formula of the antibiotic was deduced to be C28H43O6N. The infrared spectrum of the antibiotic indicated the presence of unsaturation, nitrile, lactone, or ester or all three functions, and carbonyl functions in the molecule. A sharp infrared absorption band for nitrile at 2,220 cm-1 and the presence of an unsaturated group indicated that the nitrile function may be attached to an unsaturated carbon atom. The presence of dienenitrile functions was further supported by the UV absorption spectrum of the antibiotic, which gave a UVmax at 257 nm. The proton magnetic resonance spectrum of the antibiotic did not give any peak which could be exchanged with deuterated water, which is an indication of the absence of carboxylic and hydroxyl functions in the molecule. All of the functional groupings indicated by the infrared and UV spectra of the molecule were further confirmed by the 13C-magnetic resonance spectrum of the compound. A brief hydrogenation of the antibiotic yielded a biologically active tetrahydro derivative, whereas extended hydrogenation produced an inactive primary amine. Mild alkaline hydrolysis and subsequent esterification of the antibiotic with diazomethane produced an inactive dimethyl ester. Apparently both the nitrile and the lactone functions are essential for the treponomycin molecule to show antimicrobial activity. The antibiotic showed inhibitory activity against several species of bacteria, especially Treponema hyodysenteriae, the causative agent of swine dysentery. In view of the oral 50% lethal dose of 400 mg/g and its low MIC against four stains of T.hyodysenteriae, the antibiotic may have value as a swine dysentery therapeutic. Images PMID:3838636

40 CFR 442.2 - General definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... pesticides, hazardous waste, organic chemicals including: alcohols, aldehydes, formaldehydes, phenols...: ketones, nitriles, organo-metallic compounds containing chromium, cadmium, mercury, copper, zinc; and...

40 CFR 442.2 - General definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... pesticides, hazardous waste, organic chemicals including: alcohols, aldehydes, formaldehydes, phenols...: ketones, nitriles, organo-metallic compounds containing chromium, cadmium, mercury, copper, zinc; and...

40 CFR 442.2 - General definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... pesticides, hazardous waste, organic chemicals including: alcohols, aldehydes, formaldehydes, phenols...: ketones, nitriles, organo-metallic compounds containing chromium, cadmium, mercury, copper, zinc; and...

Stereo-, Regio-, and Chemoselective [3 + 2]-Cycloaddition of (2E,4E)-Ethyl 5-(Phenylsulfonyl)penta-2,4-dienoate with Various Azomethine Ylides, Nitrones, and Nitrile Oxides: Synthesis of Pyrrolidine, Isoxazolidine, and Isoxazoline Derivatives and a Computational Study.

PubMed

Sankar, Ulaganathan; Surya Kumar, Ch Venkata; Subramanian, V; Balasubramanian, K K; Mahalakshimi, S

2016-03-18

One-pot chemo-, regio-, and stereoselective synthesis of series of heterocyclic and spiroheterocyclic compounds was accomplished through mono- and bis[3 + 2]-cycloaddition reactions of (2E,4E)-ethyl 5-(phenylsulfonyl)penta-2,4-dienoate as a dipolarophile with azomethine ylides, nitrones, and nitrile oxides in good yields. The structures of the products were established by spectroscopic techniques as well as by single-crystal XRD study, and DFT calculations were performed to further understand the mechanism of this [3 + 2]-cycloaddition reaction.

Polybenzoxazole-filled nitrile butadiene rubber compositions

NASA Technical Reports Server (NTRS)

Gajiwala, Himansu M. (Inventor); Guillot, David G. (Inventor)

2008-01-01

An insulation composition that comprises at least one nitrile butadiene rubber (NBR) having an acrylonitrile content that ranges from approximately 26% by weight to approximately 35% by weight and polybenzoxazole (PBO) fibers. The NBR may be a copolymer of acrylonitrile and butadiene and may be present in the insulation composition in a range of from approximately 45% by weight to approximately 56% by weight of a total weight of the insulation composition. The PBO fibers may be present in a range of from approximately 3% by weight to approximately 10% by weight of a total weight of the insulation composition. A rocket motor including the insulation composition and a method of insulating a rocket motor are also disclosed.

Nitrilases in nitrile biocatalysis: recent progress and forthcoming research

PubMed Central

2012-01-01

Over the past decades, nitrilases have drawn considerable attention because of their application in nitrile degradation as prominent biocatalysts. Nitrilases are derived from bacteria, filamentous fungi, yeasts, and plants. In-depth investigations on their natural sources function mechanisms, enzyme structure, screening pathways, and biocatalytic properties have been conducted. Moreover, the immobilization, purification, gene cloning and modifications of nitrilase have been dwelt upon. Some nitrilases are used commercially as biofactories for carboxylic acids production, waste treatment, and surface modification. This critical review summarizes the current status of nitrilase research, and discusses a number of challenges and significant attempts in its further development. Nitrilase is a significant and promising biocatalyst for catalytic applications. PMID:23106943

Studies of bio-mimetic medium of ionic and non-ionic micelles by a simple charge transfer fluorescence probe N,N-dimethylaminonapthyl-(acrylo)-nitrile

NASA Astrophysics Data System (ADS)

Samanta, Anuva; Paul, Bijan Kumar; Guchhait, N.

2011-05-01

In this report we have studied micellization process of anionic, cationic and non-ionic surfactants using N,N-dimethylaminonapthyl-(acrylo)-nitrile (DMANAN) as an external fluorescence probe. Micropolarity, microviscosity, critical micellar concentration of these micelles based on steady state absorption and fluorescence and time resolved emission spectroscopy of the probe DMANAN show that the molecule resides in the micelle-water interface for ionic micelles and in the core for the non-ionic micelle. The effect of variation of pH of the micellar solution as well as fluorescence quenching measurements of DMANAN provide further support for the location of the probe in the micelles.

High-Temperature Syntheses of New, Thermally-Stable Chemical Compounds.

DTIC Science & Technology

SYNTHESIS(CHEMISTRY), HEAT RESISTANT PLASTICS, NITRILES, FLUORINE COMPOUNDS, COMPLEX COMPOUNDS, NITROGEN, SULFIDES, ORGANOMETALLIC COMPOUNDS, ORGANOBORANES, BORIDES, SPINEL, CARBIDES, NITRIDES, SILICIDES .

40 CFR 442.2 - General definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., organic chemicals including: alcohols, aldehydes, formaldehydes, phenols, peroxides, organic salts, amines..., glycerines, and organic polymers; refractory organic compounds including: ketones, nitriles, organo-metallic...

In situ electrochemical SFG/DFG study of CN- and nitrile adsorption at Au from 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ionic liquid([BMP][TFSA]) containing 4-{2-[1-(2-cyanoethyl)-1,2,3,4-tetrahydroquinolin-6-yl]diazenyl} benzonitrile (CTDB) and K[Au(CN)₂].

PubMed

Bozzini, Benedetto; Busson, Bertrand; Gayral, Audrey; Humbert, Christophe; Mele, Claudio; Six, Catherine; Tadjeddine, Abderrahmane

2012-06-25

In this paper we report an in situ electrochemical Sum-/Difference Frequency Generation (SFG/DFG) spectroscopy investigation of the adsorption of nitrile and CN⁻ from the ionic liquid 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ([BMP][TFSA]) containing 4-{2-[1-(2-cyanoethyl)-1,2,3,4-tetrahydroquinolin-6-yl]-diazenyl}benzonitrile (CTDB) at Au electrodes in the absence and in the presence of the Au-electrodeposition process from K[Au(CN)₂]. The adsorption of nitrile and its coadsorption with CN⁻ resulting either from the cathodic decomposition of the dye or from ligand release from the Au(I) cyanocomplex yield potential-dependent single or double SFG bands in the range 2,125-2,140 cm⁻¹, exhibiting Stark tuning values of ca. 3 and 1 cm⁻¹ V⁻¹ in the absence and presence of electrodeposition, respectively. The low Stark tuning found during electrodeposition correlates with the cathodic inhibiting effect of CTDB, giving rise to its levelling properties. The essential insensitivity of the other DFG parameters to the electrodeposition process is due to the growth of smooth Au.

Antibiotic-functionalized graphite nanofibers and applications of cyanoglycosides in graphite nanofiber functionalization

NASA Astrophysics Data System (ADS)

Rotella, Madeline

The synthesis of functionalized graphite nanofibers (GNFs) with antibiotics and cyclic boronate esters is described. By first oxidizing the GNFs, surface oxides are introduced to the fiber that serve as sites for the attachment of larger molecules such as aminoglycoside antibiotics and carbohydrates. On the one hand, the aminoglycoside antibiotic tobramycin can be attached to the surface of a GNF via the carboxyl groups. This tobramycin-labeled GNF was prepared, characterized for its antibiotic content by X-ray photoelectron spectroscopy (XPS), and studied for its retention of antibacterial activity against the common bacterium Pseudomonas aeruginosa. On the other hand, Boc-protected amine precursors which may serve as key intermediates in the preparation of a reversible GNF label were prepared starting from two similar carbohydrate substrates, tri-O-acetyl-D-galactal and tri-O-acetyl-D-glucal. A nitrile group was added to the C1 of the substrate via Ferrier addition with trimethylsilyl cyanide followed by reduction of the C2-C3 double bond and finally a deacylation to yield stereoisomeric diol nitriles. The diol nitriles in both series were converted to analogous protected Boc amines. Products were characterized by 1H and 13C NMR spectroscopy, mass spectrometry and X-ray crystallography.

μ-Hexa­thio­metadiphosphato-bis­[(1,4,7,10,13,16-hexa­oxa­cyclo­octa­decane-κ6 O)rubidium] aceto­nitrile disolvate

PubMed Central

Gjikaj, Mimoza; Pook, Niels-Patrick; Qarri, Flora

2013-01-01

The asymmetric unit of the title compound, [Rb2(P2S6)(C12H24O6)2]·2CH3CN, contains one half of an [Rb(18-crown-6)2]2[P2S6] unit and one aceto­nitrile solvent mol­ecule. The [Rb(18-crown-6)]2[P2S6] unit is completed by inversion symmetry. Its Rb+ ion is situated near the centre of the macrocyclic cavity, but is displaced by 0.8972 (1) Å from the O atoms of the crown in the direction of the [P2S6]2− moiety. The overall coordination number of the cation is eight, defined by the six crown ether O atoms and by two terminal S atoms of the [P2S6]2− anion. The hexa­thio­metadiphosphate anion is built up from two tetra­hedral PS4 units joined together by a common edge. The crystal structure is characterized by alternating layers of [Rb(18-crown-6)]2[P2S6] and aceto­nitrile solvent mol­ecules stacked along [010]. PMID:24860286

Retrievals of abundances of hydrocarbon and nitrile species in Titan’s upper atmosphere

NASA Astrophysics Data System (ADS)

Yung, Yuk; Fan, Siteng; Shemansky, D. E.; Li, Cheng; Gao, Peter

2017-10-01

We develop an innovative retrieval method for Titan occultation measurements by the Cassini UVIS experiment. The T35 occultation is analyzed to illustrate the methodology. A significant number of occultations observed using the UVIS spectrographs show loss of pointing control required for correction of the spectral vectors. Consequently, only three stellar occultations have been analyzed to date. We use the Markov Chain Monte-Carlo (MCMC) method to retrieve the abundances or upper limits of thirteen hydrocarbon and nitrile species (N2, CH4, C2H2, C2H4, C2H6, HCN, C4H2, C6N2, C6H6, tholin, HC3N, C2N2, NH3) along with the pointing error using the Cassini/UVIS simulator. These numbers are derived for the fast T35 occultation, which has never been analyzed because of large pointing errors. Uncertainty in the retrievals is determined using an intrinsic fitting probability distribution function. The Caltech/JPL photochemical and kinetics model, KINETICS, is used to calculate the atmospheric aforementioned species. Comparisons between model and observations reveal gaps in our current understanding of the chemical kinetics of hydrocarbons and nitrile species, especially for C6H6.

Expanding the utility of 4-cyano-L-phenylalanine as a vibrational reporter of protein environments.

PubMed

Bazewicz, Christopher G; Lipkin, Jacob S; Smith, Emily E; Liskov, Melanie T; Brewer, Scott H

2012-09-06

The ability to genetically incorporate amino acids modified with spectroscopic reporters site-specifically into proteins with high efficiency and fidelity has greatly enhanced the ability to probe local protein structure and dynamics. Here, we have synthesized the unnatural amino acid (UAA), 4-cyano-L-phenylalanine (pCNPhe), containing the nitrile vibrational reporter and three isotopomers ((15)N, (13)C, (13)C(15)N) of this UAA to enhance the ability of pCNPhe to study local protein environments. Each pCNPhe isotopic variant was genetically incorporated in an efficient, site-specific manner into superfolder green fluorescent protein (sfGFP) in response to an amber codon with high fidelity utilizing an engineered, orthogonal aminoacyl-tRNA synthetase. The isotopomers of 4-cyano-L-phenylalanine permitted the nitrile symmetric stretch vibration of these UAAs to be unambiguously assigned utilizing the magnitude and direction of the isotopic shift of this vibration. The sensitivity of the nitrile symmetric stretching frequency of each isotopic variant to the local environment was measured by individually incorporating the probes into two distinct local environments of sfGFP. The UAAs were also utilized in concert to probe multiple local environments in sfGFP simultaneously to increase the utility of 4-cyano-L-phenylalanine.

Chemical investigation of Titan and Triton tholins

NASA Technical Reports Server (NTRS)

Mcdonald, Gene D.; Thompson, W. R.; Heinrich, Michael; Khare, Bishun N.; Sagan, Carl

1994-01-01

We report chromatographic and spectroscopic analyses of both Titan and Triton tholins, organic solids made from the plasma irradiation of 0.9:0.1 and 0.999:0.001 N2/CH4 gas mixtures, respectively. The lower CH4 mixing ratio leads to a nitrogen-richer tholin (N/C greater than 1), probably including nitrogen heterocyclic compounds. Unlike Titan tholin, bulk Triton tholin is poor in nitriles. From high-pressure liquid chromatography, ultraviolet and infrared spectroscopy, and molecular weight estimation by gel filtration chromatography, we conclude that (1) several H2O-soluble fractions, each with distinct UV and IR spectral signatures, are present, (2) these fractions are not identical in the two tholins, (3) the H2O-soluble fractions of Titan tholins do not contain significant amounts of nitriles, despite the major role of nitriles in bulk Titan tholin, and (4) the H2O-soluble fractions of both tholins are mainly molcules containing about 10 to 50 (C + N) atoms. We report yields of amino acids upon hydrolysis of Titan and Triton tholins. Titan tholin is largely insoluble in the putative hydrocarbon lakes or oceans on Titan, but can yield the H2O-soluble species investigated here upon contact with transient (e.g., impact-generated) liquid water.

Nitrile versus isonitrile adsorption at interstellar grains surfaces. I. Hydroxylated surfaces

NASA Astrophysics Data System (ADS)

Bertin, M.; Doronin, M.; Fillion, J.-H.; Michaut, X.; Philippe, L.; Lattelais, M.; Markovits, A.; Pauzat, F.; Ellinger, Y.; Guillemin, J.-C.

2017-02-01

Context. Almost 20% of the 200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Among these 37 molecules, 30 are nitrile R-CN compounds, the remaining seven belonging to the isonitrile R-NC family. How these species behave in presence of the grain surfaces is still an open question. Aims: In this contribution we investigate whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of different nature and morphologies. Methods: The question was addressed by means of a concerted experimental and theoretical study of the adsorption energies of CH3CN and CH3NC on the surface water ice and silica. The experimental determination of the molecule - surface interaction energies was carried out using temperature programmed desorption (TPD) under an ultra-high vacuum (UHV) between 70 and 160 K. Theoretically, the question was addressed using first principle periodic density functional theory (DFT) to represent the organized solid support. Results: The most stable isomer (CH3CN) interacts more efficiently with the solid support than the higher energy isomer (CH3NC) for water ice and silica. Comparing with the HCN and HNC pair of isomers, the simulations show an opposite behaviour, in which isonitrile HNC are more strongly adsorbed than nitrile HCN provided that hydrogen bonds are compatible with the nature of the model surface. Conclusions: The present study confirms that the strength of the molecule surface interaction between isomers is not related to their intrinsic stability but instead to their respective ability to generate different types of hydrogen bonds. Coupling TPD to first principle simulations is a powerful method for investigating the possible role of interstellar surfaces in the release of organic species from grains, depending on the environment.

Integrity of Disposable Nitrile Exam Gloves Exposed to Simulated Movement

PubMed Central

Phalen, Robert N.; Wong, Weng Kee

2011-01-01

Every year, millions of health care, first responder, and industry workers are exposed to chemical and biological hazards. Disposable nitrile gloves are a common choice as both a chemical and physical barrier to these hazards, especially as an alternative to natural latex gloves. However, glove selection is complicated by the availability of several types or formulations of nitrile gloves, such as low-modulus, medical-grade, low-filler, and cleanroom products. This study evaluated the influence of simulated movement on the physical integrity (i.e., holes) of different nitrile exam glove brands and types. Thirty glove products were evaluated out-of-box and after exposure to simulated whole-glove movement for 2 hr. In lieu of the traditional 1-L water-leak test, a modified water-leak test, standardized to detect a 0.15 ± 0.05 mm hole in different regions of the glove, was developed. A specialized air inflation method simulated bidirectional stretching and whole-glove movement. A worst-case scenario with maximum stretching was evaluated. On average, movement did not have a significant effect on glove integrity (chi-square; p=0.068). The average effect was less than 1% between no movement (1.5%) and movement (2.1%) exposures. However, there was significant variability in glove integrity between different glove types (p ≤ 0.05). Cleanroom gloves, on average, had the highest percentage of leaks, and 50% failed the water-leak test. Low-modulus and medical-grade gloves had the lowest percentages of leaks, and no products failed the water-leak test. Variability in polymer formulation was suspected to account for the observed discrepancies, as well as the inability of the traditional 1-L water-leak test to detect holes in finger/thumb regions. Unexpectedly, greater than 80% of the glove defects were observed in the finger and thumb regions. It is recommended that existing water-leak tests be re-evaluated and standardized to account for product variability. PMID:21476169

Permeation of gasoline, diesel, bioethanol (E85), and biodiesel (B20) fuels through six glove materials.

PubMed

Chin, Jo-Yu; Batterman, Stuart A

2010-07-01

Biofuels and conventional fuels differ in terms of their evaporation rates, permeation rates, and exhaust emissions, which can alter exposures of workers, especially those in the fuel refining and distribution industries. This study investigated the permeation of biofuels (bioethanol 85%, biodiesel 20%) and conventional petroleum fuels (gasoline and diesel) through gloves used in occupational settings (neoprene, nitrile, and Viton) and laboratories (latex, nitrile, and vinyl), as well as a standard reference material (neoprene sheet). Permeation rates and breakthrough times were measured using the American Society for Testing and Materials F739-99 protocol, and fuel and permeant compositions were measured by gas chromatography/mass spectrometry. In addition, we estimated exposures for three occupational scenarios and recommend chemical protective clothing suitable for use with motor fuels. Permeation rates and breakthrough times depended on the fuel-glove combination. Gasoline had the highest permeation rate among the four fuels. Bioethanol (85%) had breakthrough times that were two to three times longer than gasoline through neoprene, nitrile Sol-Vex, and the standard reference materials. Breakthrough times for biodiesel (20%) were slightly shorter than for diesel for the latex, vinyl, nitrile examination, and the standard neoprene materials. The composition of permeants differed from neat fuels, e.g., permeants were significantly enriched in the lighter aromatics including benzene. Viton was the best choice among the tested materials for the four fuels tested. Among the scenarios, fuel truck drivers had the highest uptake via inhalation based on the personal measurements available in the literature, and gasoline station attendants had highest uptake via dermal exposure if gloves were not worn. Appropriate selection and use of gloves can protect workers from dermal exposures; however, current recommendations from the National Institute for Occupational Safety and Health should be revised to account for contemporary fuel formulations that routinely contain ethanol.

The comparative metabolism of 2,6-dichlorothiobenzamide (prefix) and 2,6-dichlorobenzonitrile in the dog and rat

PubMed Central

Griffiths, M. H.; Moss, J. A.; Rose, J. A.; Hathway, D. E.

1966-01-01

1. A single oral dose of either [14C]Prefix or 2,6-dichlorobenzo[14C]nitrile to rats is almost entirely eliminated in 4 days: 84·8–100·5% of 14C from [14C]Prefix is excreted, 67·3–79·7% in the urine, and 85·8–97·2% of 14C from 2,6-dichlorobenzo-[14C]nitrile is excreted, 72·3–80·7% in the urine. Only 0·37±0·03% of the dose of [14C]Prefix and 0·25±0·03% of the dose of 2,6-dichlorobenzo[14C]nitrile are present in the carcass plus viscera after removal of the gut. Rats do not show sex differences in the pattern of elimination of the respective metabolites of the two herbicides. The rates of elimination of 14C from the two compounds in the 24hr. and 48hr. urines are not significantly different (P >0·05) from one another. 2. After oral administration to dogs, 85·9–106·1% of 14C from [14C]Prefix is excreted, 66·6–80·9% in the urine, and 86·8–92·5% of 14C from 2,6-dichlorobenzo[14C]nitrile is excreted, 60·0–70·1% in the urine. Dogs do not show sex differences in the pattern of eliminating the metabolites of either Prefix or 2,6-dichlorobenzonitrile. 3. Dogs and rats do not show species differences in the patterns of elimination of the two herbicides. 4. Prefix and 2,6-dichlorobenzonitrile are completely metabolized; unchanged Prefix and 2,6-dichlorobenzonitrile are absent from the urine and faeces, and from the carcasses when elimination is complete. In the hydrolysed urine of rats dosed with either [14C]Prefix or 2,6-dichlorobenzo[14C]nitrile, 2,6-dichloro-3-hydroxybenzonitrile accounts for approx. 42% of the 14C, a further 10–11% is accounted for by 2,6-dichlorobenzamide, 2,6-dichlorobenzoic acid, 2,6-dichloro-3- and -4-hydroxybenzoic acid and 2,6-dichloro-4-hydroxybenzonitrile collectively, and 25–30% by six polar constituents, of which two are sulphur-containing amino acids. 5. In the unhydrolysed urines of rats dosed with either [14C]Prefix or 2,6-dichlorobenzo[14C]nitrile, there are present free 2,6-dichloro-3- and -4-hydroxybenzonitrile, their glucuronide conjugates, ester glucuronides of the principal aromatic acids that are present in the hydrolysed urines, and two sulphur-containing metabolites analogous to mercapturic acids or premercapturic acids. 6. Prefix is thus extensively transformed into 2,6-dichlorobenzonitrile: R·CS·NH2→R·CN+H2S, where R=C6H3Cl2. However, the competitive reaction: R·CS·NH2+H2O→R·CO·NH2+H2S takes place to a very limited extent. PMID:5911525

Optimization of mechanical performance of oxidative nano-particle electrode nitrile butadiene rubber conducting polymer actuator.

PubMed

Kim, Baek-Chul; Park, S J; Cho, M S; Lee, Y; Nam, J D; Choi, H R; Koo, J C

2009-12-01

Present work delivers a systematical evaluation of actuation efficiency of a nano-particle electrode conducting polymer actuator fabricated based on Nitrile Butadiene Rubber (NBR). Attempts are made for maximizing mechanical functionality of the nano-particle electrode conducting polymer actuator that can be driven in the air. As the conducting polymer polypyrrole of the actuator is to be fabricated through a chemical oxidation polymerization process that may impose certain limitations on both electrical and mechanical functionality of the actuator, a coordinated study for optimization process of the actuator is necessary for maximizing its performance. In this article actuation behaviors of the nano-particle electrode polypyrrole conducting polymer is studied and an optimization process for the mechanical performance maximization is performed.

Energy Storage of Polyarylene Ether Nitriles at High Temperature

NASA Astrophysics Data System (ADS)

Tang, Xiaohe; You, Yong; Mao, Hua; Li, Kui; Wei, Renbo; Liu, Xiaobo

2018-03-01

Polyarylene ether nitrile (PEN) was synthesized and used as film capacitors for energy storage at high temperature. Scanning electron microscopy observation indicated that the films of PEN have pinholes at nanoscales which restricted the energy storage properties of the material. The pinhole shadowing effect through which the energy storage properties of PEN were effectively improved to be 2.3 J/cm3 was observed by using the overlapped film of PEN. The high glass transition temperature (T g) of PEN was as high as 216 °C and PEN film showed stable dielectric constant, breakdown strength and energy storage density before the T g. The PEN films will be a potential candidate as high performance electronic storage materials used at high temperature.

D-π-A Compounds with Tunable Intramolecular Charge Transfer Achieved by Incorporation of Butenolide Nitriles as Acceptor Moieties.

PubMed

Moreno-Yruela, Carlos; Garín, Javier; Orduna, Jesús; Franco, Santiago; Quintero, Estefanía; López Navarrete, Juan T; Diosdado, Beatriz E; Villacampa, Belén; Casado, Juan; Andreu, Raquel

2015-12-18

Chromophores where a polyenic spacer separates a 4H-pyranylidene or benzothiazolylidene donor and three different butenolide nitriles have been synthesized and characterized. The role of 2(5H)-furanones as acceptor units on the polarization and the second-order nonlinear (NLO) properties has been studied. Thus, their incorporation gives rise to moderately polarized structures with NLO responses that compare favorably to those of related compounds featuring more efficient electron-withdrawing moieties. Derivatives of the proaromatic butenolide PhFu show the best nonlinearities. Benzothiazolylidene-containing chromophores present less alternated structures than their pyranylidene analogues, and, unlike most merocyanines, the degree of charge transfer does not decrease on lengthening the π-bridge.

Fire retardant polyisocyanurate foam

NASA Technical Reports Server (NTRS)

Riccitiello, S. R.; Parker, J. A.

1972-01-01

Fire retardant properties of low density polymer foam are increased. Foam has pendant nitrile groups which form thermally-stable heterocyclic structures at temperature below degradation temperature of urethane linkages.

Crystal structure of paddle-wheel sandwich-type [Cu2{(CH3)2CO}{μ-Fe(η5-C5H4C N)2}3](BF4)2·(CH3)2CO

PubMed Central

Strehler, Frank; Korb, Marcus; Lang, Heinrich

2015-01-01

The mol­ecular structure of (acetone-κO)tris­(μ-ferrocene-1,1′-dicarbo­nitrile-κ2 N:N′)dicopper(I) bis­(tetra­fluorido­borate) acetone monosolvate, [Cu2Fe3(C6H4N)6(C3H6O)](BF4)2·C3H6O, consists of two CuI ions bridged by a ferrocene-1,1′-dicarbo­nitrile moiety in a paddle-wheel-architectured sandwich complex with two BF4 − units as counter-ions. One of the latter is equally disordered over two sets of sites. The two CuI ions are complexed in a trigonal–planar manner by three nitrile N-donor atoms. Further inter­actions by the O atom of an acetone mol­ecule to one of the CuI atoms and a weak η2,π-inter­action of two atoms of a cyclo­penta­dienyl ring to the other CuI atom complete a distorted trigonal–pyramidal environment for each of the metal ions. A further acetone mol­ecule is also present as a solvent mol­ecule. The crystal packing is consolidated by several π–π inter­actions. PMID:25878831

Exploring the structural basis of the selective inhibition of monoamine oxidase A by dicarbonitrile aminoheterocycles: role of Asn181 and Ile335 validated by spectroscopic and computational studies.

PubMed

Juárez-Jiménez, Jordi; Mendes, Eduarda; Galdeano, Carles; Martins, Carla; Silva, Daniel B; Marco-Contelles, José; do Carmo Carreiras, Maria; Luque, F Javier; Ramsay, Rona R

2014-02-01

Since cyanide potentiates the inhibitory activity of several monoamine oxidase (MAO) inhibitors, a series of carbonitrile-containing aminoheterocycles was examined to explore the role of nitriles in determining the inhibitory activity against MAO. Dicarbonitrile aminofurans were found to be potent, selective inhibitors against MAO A. The origin of the MAO A selectivity was identified by combining spectroscopic and computational methods. Spectroscopic changes induced in MAO A by mono- and dicarbonitrile inhibitors were different, providing experimental evidence for distinct binding modes to the enzyme. Similar differences were also found between the binding of dicarbonitrile compounds to MAO A and to MAO B. Stabilization of the flavin anionic semiquinone by monocarbonitrile compounds, but destabilization by dicarbonitriles, provided further support to the distinct binding modes of these compounds and their interaction with the flavin ring. Molecular modeling studies supported the role played by the nitrile and amino groups in anchoring the inhibitor to the binding cavity. In particular, the results highlight the role of Asn181 and Ile335 in assisting the interaction of the nitrile-containing aminofuran ring. The network of interactions afforded by the specific attachment of these functional groups provides useful guidelines for the design of selective, reversible MAO A inhibitors. Copyright © 2013 Elsevier B.V. All rights reserved.

A Survey of CH3CN and HC3N in Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Bergner, Jennifer B.; Guzmán, Viviana G.; Öberg, Karin I.; Loomis, Ryan A.; Pegues, Jamila

2018-04-01

The organic content of protoplanetary disks sets the initial compositions of planets and comets, thereby influencing subsequent chemistry that is possible in nascent planetary systems. We present observations of the complex nitrile-bearing species CH3CN and HC3N toward the disks around the T Tauri stars AS 209, IM Lup, LkCa 15, and V4046 Sgr as well as the Herbig Ae stars MWC 480 and HD 163296. HC3N is detected toward all disks except IM Lup, and CH3CN is detected toward V4046 Sgr, MWC 480, and HD 163296. Rotational temperatures derived for disks with multiple detected lines range from 29 to 73 K, indicating emission from the temperate molecular layer of the disk. V4046 Sgr and MWC 480 radial abundance profiles are constrained using a parametric model; the gas-phase CH3CN and HC3N abundances with respect to HCN are a few to tens of percent in the inner 100 au of the disk, signifying a rich nitrile chemistry at planet- and comet-forming disk radii. We find consistent relative abundances of CH3CN, HC3N, and HCN between our disk sample, protostellar envelopes, and solar system comets; this is suggestive of a robust nitrile chemistry with similar outcomes under a wide range of physical conditions.

Mechlorethamine Topical

MedlinePlus

... the treated areas. Wash your hands well with soap and water after applying or touching mechlorethamine gel. ... disposable nitrile gloves and wash hands well with soap and water after removing the gloves. If a ...

Methods of making organic compounds by metathesis

DOEpatents

Abraham, Timothy W.; Kaido, Hiroki; Lee, Choon Woo; Pederson, Richard L.; Schrodi, Yann; Tupy, Michael John

2015-09-01

Described are methods of making organic compounds by metathesis chemistry. The methods of the invention are particularly useful for making industrially-important organic compounds beginning with starting compositions derived from renewable feedstocks, such as natural oils. The methods make use of a cross-metathesis step with an olefin compound to produce functionalized alkene intermediates having a pre-determined double bond position. Once isolated, the functionalized alkene intermediate can be self-metathesized or cross-metathesized (e.g., with a second functionalized alkene) to produce the desired organic compound or a precursor thereto. The method may be used to make bifunctional organic compounds, such as diacids, diesters, dicarboxylate salts, acid/esters, acid/amines, acid/alcohols, acid/aldehydes, acid/ketones, acid/halides, acid/nitriles, ester/amines, ester/alcohols, ester/aldehydes, ester/ketones, ester/halides, ester/nitriles, and the like.

Preparation and Sound Absorption Properties of a Barium Titanate/Nitrile Butadiene Rubber–Polyurethane Foam Composite with Multilayered Structure

PubMed Central

Jiang, Xueliang; Yang, Zhen; Wang, Zhijie; Zhang, Fuqing; You, Feng

2018-01-01

Barium titanate/nitrile butadiene rubber (BT/NBR) and polyurethane (PU) foam were combined to prepare a sound-absorbing material with an alternating multilayered structure. The effects of the cell size of PU foam and the alternating unit number on the sound absorption property of the material were investigated. The results show that the sound absorption efficiency at a low frequency increased when decreasing the cell size of PU foam layer. With the increasing of the alternating unit number, the material shows the sound absorption effect in a wider bandwidth of frequency. The BT/NBR-PU foam composites with alternating multilayered structure have an excellent sound absorption property at low frequency due to the organic combination of airflow resistivity, resonance absorption, and interface dissipation. PMID:29565321

Preparation and Sound Absorption Properties of a Barium Titanate/Nitrile Butadiene Rubber-Polyurethane Foam Composite with Multilayered Structure.

PubMed

Jiang, Xueliang; Yang, Zhen; Wang, Zhijie; Zhang, Fuqing; You, Feng; Yao, Chu

2018-03-22

Barium titanate/nitrile butadiene rubber (BT/NBR) and polyurethane (PU) foam were combined to prepare a sound-absorbing material with an alternating multilayered structure. The effects of the cell size of PU foam and the alternating unit number on the sound absorption property of the material were investigated. The results show that the sound absorption efficiency at a low frequency increased when decreasing the cell size of PU foam layer. With the increasing of the alternating unit number, the material shows the sound absorption effect in a wider bandwidth of frequency. The BT/NBR-PU foam composites with alternating multilayered structure have an excellent sound absorption property at low frequency due to the organic combination of airflow resistivity, resonance absorption, and interface dissipation.

Cyanide Soap? Dissolved material in Titan's Seas

NASA Astrophysics Data System (ADS)

Lorenz, R. D.; Lunine, J. I.; Neish, C. D.

2011-10-01

Although it is evident that Titan's lakes and seas are dominated by ethane, methane, nitrogen, and (in some models) propane, there is divergence on the predicted relative abundance of minor constituents such as nitriles and C-4 alkanes. Nitriles such as hydrogen cyanide and acetonitrile, which have a significant dipole moment, may have a disproportionate influence on the dielectric properties of Titan seas and may act to solvate polar molecules such as water ice. The hypothesis is offered that such salvation may act to enhance the otherwise negligible solubility of water ice bedrock in liquid hydrocarbons. Such enhanced solubility may permit solution erosion as a formation mechanism for the widespread pits and apparently karstic lakes on Titan. Prospects for testing this hypothesis in the laboratory, and with measurements on Titan, will be discussed.

Multiple Mechanisms for the Thermal Decomposition of Metallaisoxazolin-5-ones from Computational Investigations.

PubMed

Zhou, Chen-Chen; Hawthorne, M Frederick; Houk, K N; Jiménez-Osés, Gonzalo

2017-08-18

The thermal decompositions of metallaisoxazolin-5-ones containing Ir, Rh, or Co are investigated using density functional theory. The experimentally observed decarboxylations of these molecules are found to proceed through retro-(3+2)-cycloaddition reactions, generating the experimentally reported η 2 side-bonded nitrile complexes. These intermediates can isomerize in situ to yield a η 1 nitrile complex. A competitive alternative pathway is also found where the decarboxylation happens concertedly with an aryl migration process, producing a η 1 isonitrile complex. Despite their comparable stability, these η 1 bonded species were not detected experimentally. The experimentally detected η 2 side bound species are likely involved in the subsequent C-H activation reactions with hydrocarbon solvents reported for some of these metallaisoxazolin-5-ones.

Herbivore-induced phenylacetonitrile is biosynthesized from de novo-synthesized L-phenylalanine in the giant knotweed, Fallopia sachalinensis.

PubMed

Noge, Koji; Tamogami, Shigeru

2013-06-19

Plants emit a series of characteristic volatile blends when damaged by insect feeding. Phenylacetonitrile is one of the volatiles from the leaves of the giant knotweed, Fallopia sachalinensis, infested by the Japanese beetle, Popillia japonica, or treated with exogenous airborne methyl jasmonate (MeJA). We examined the precursor of the nitrile and its origin in this system. L-Phenylalanine was determined to be a precursor of the nitrile in F. sachalinensis leaves, and the phenylalanine was also induced by beetle feeding and MeJA treatment. We also found that exogenous MeJA enhanced the biosynthesis of several amino acids in F. sachalinensis leaves. Copyright © 2013 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Stable and Inert Cobalt Catalysts for Highly Selective and Practical Hydrogenation of C≡N and C═O Bonds.

PubMed

Chen, Feng; Topf, Christoph; Radnik, Jörg; Kreyenschulte, Carsten; Lund, Henrik; Schneider, Matthias; Surkus, Annette-Enrica; He, Lin; Junge, Kathrin; Beller, Matthias

2016-07-20

Novel heterogeneous cobalt-based catalysts have been prepared by pyrolysis of cobalt complexes with nitrogen ligands on different inorganic supports. The activity and selectivity of the resulting materials in the hydrogenation of nitriles and carbonyl compounds is strongly influenced by the modification of the support and the nitrogen-containing ligand. The optimal catalyst system ([Co(OAc)2/Phen@α-Al2O3]-800 = Cat. E) allows for efficient reduction of both aromatic and aliphatic nitriles including industrially relevant dinitriles to primary amines under mild conditions. The generality and practicability of this system is further demonstrated in the hydrogenation of diverse aliphatic, aromatic, and heterocyclic ketones as well as aldehydes, which are readily reduced to the corresponding alcohols.

Controlled synthesis of silver nanostructures stabilized by fluorescent polyarylene ether nitrile

NASA Astrophysics Data System (ADS)

Jia, Kun; Shou, Hongguo; Wang, Pan; Zhou, Xuefei; Liu, Xiaobo

2016-07-01

In this work, the intrinsically fluorescent polyarylene ether nitrile (PEN) was explored to realize the controlled synthesis of fluorescent silver nanostructures with different morphology for the first time. Specifically, it was found that silver nitrate (AgNO3) can be effectively reduced to silver nanoparticles using PEN as both reducing and surface capping agents in N, N-dimethylformamide (DMF). More interestingly, the morphology of obtained fluorescent silver nanostructures can be tuned from nanospheres to nanorods by simple variation of reaction time at 130 °C using a relative PEN:AgNO3 molar concentration ratio of 1:8. Meanwhile, the obtained Ag nanostructures exhibited both localized surface plasmon resonance (LSPR) band and fluorescent emission around 420 nm, which would find potential applications in biochemical sensing and optical devices fields.

Nitrile/Buna N Material Failure Assessment for an O-Ring used on the Gaseous Hydrogen Flow Control Valve (FCV) of the Space Shuttle Main Engine

NASA Technical Reports Server (NTRS)

Wingard, Doug

2006-01-01

After the rollout of Space Shuttle Discovery in April 2005 in preparation for return-to-flight, there was a failure of the Orbiter (OV-103) helium signature leak test in the gaseous hydrogen (GH2) system. Leakage was attributed to the Flow Control Valve (FCV) in Main Engine 3. The FCV determined to be the source of the leak for OV-103 is designated as LV-58. The nitrile/Buna N rubber O-ring seal was removed from LV-58, and failure analysis indicated radial cracks providing leak paths in one quadrant. Cracks were eventually found in 6 of 9 FCV O-rings among the three Shuttle Orbiters, though none were as severe as those for LV-58, OV-103. Testing by EM10 at MSFC on all 9 FCV O- rings included: laser dimensional, Shore A hardness and properties from a dynamic mechanical analyzer (DMA) and an Instron tensile machine. The following test data was obtained on the cracked quadrant of the LV-58, OV-103 O-ring: (1) the estimated compression set was only 9.5%, compared to none for the rest of the O-ring; (2) Shore A hardness for the O.D. was higher by almost 4 durometer points than for the rest of the O-ring; and (3) DMA data showed that the storage/elastic modulus E was almost 25% lower than for the rest of the O-ring. Of the 8 FCV O-rings tested on an Instron, 4 yielded tensile strengths that were below the MIL spec requirement of 1350 psi-a likely influence of rubber cracking. Comparisons were made between values of modulus determined by DNA (elastic) and Instron (Young s). Each nitrile/Buna N O-ring used in the FCV conforms to the MIL-P-25732C specification. A number of such O-rings taken from shelf storage at MSFC and Kennedy Space Center (KSC) were used to generate a reference curve of DMA glass transition temperature (Tg) vs. shelf storage time ranging from 8 to 26 years. A similar reference curve of TGA onset temperature (of rubber weight loss) vs. shelf storage time was also generated. The DMA and TGA data for the used FCV O-rings were compared to the reference curves. Correlations were also made between the DMA modulus (at 22 C) and Shore A hardness for all 9 of the FCV O-rings used among the three Shuttle Orbiters. The radial cracking in the FCV O-rings was determined to be due to ozone attack, as nitrile/Buna N rubber is susceptible to such attack. Nitrile/Buna N material under MIL-P25732C should be used in a hydraulic fluid environment to help protect it from cracking. However, the FCV O-rings were used in an air only environment. The FCV design has as much as a 9-mil gap that allows the O.D. of the O-ring to be directly exposed to ozone, pressurized air and some elevated temperatures, accelerating the weathering process that leads to O-ring cracking. Space Shuttle flights will likely not continue past 2010. Therefore, Shuttle management decided to continue using the nitrile/Buna N material for the FCVs, but have each O-ring replaced after 3 years to minimize any chances for crack initiation.

15N fractionation in star-forming regions and Solar System objects

NASA Astrophysics Data System (ADS)

Wirström, Eva; Milam, Stefanie; Adande, Gilles; Charnley, Steven B.; Cordiner, Martin A.

2015-08-01

A central issue for understanding the formation and evolution of matter in the early Solar System is the relationship between the chemical composition of star-forming interstellar clouds and that of primitive Solar System materials. The pristine molecular content of comets, interplanetary dust particles and carbonaceous chondrites show significant bulk nitrogen isotopic fractionation relative to the solar value, 14N/15N ~ 440. In addition, high spatial resolution measurements in primitive materials locally show even more extreme enhancements of 14N/15N < 100.The coherent 15N enrichment in comets from different formation zones suggests that these isotopic enhancements are remnants of the interstellar chemistry in the natal molecular cloud core and the outer protosolar nebula. Indeed, early chemical models of gas-phase ion-molecule nitrogen fractionation showed that HCN and HNC (nitriles) can hold significant 15N enrichments in cold dark clouds where CO is depleted onto dust grains. In addition, 15N fractionation in nitriles and amines (NH2, NH3) follow different chemical pathways. More recently we have shown that once the spin-state dependence in rates of reactions with H2 is included in the models, amines can either be enhanced or depleted in 15N, depending on the core’s evolutionary stage. Observed 15N fractionation in amines and nitriles therefore cannot be expected to be the same, instead their ratio is a potential chemical clock.Observations of molecular isotope ratios in dark cores are challenging. Limited published results in general show higher 15N/14N ratios in HCN and HNC than ammonia, but more measurements are necessary to confirm these trends. We will present recent results from our ongoing observing campaign of 14N/15N isotopic ratios in HCN, HNC and NH3 in dense cores and protostars which seem consistent with significant fractionation in nitriles as compared to other molecules in each object. The few 14N/15N ratios observed in N2H+ are similar to those in NH3, contrary to our model results which predict a significant 15N enhancement in N2 and N2H+. Model upgrades which may address this discrepancy will be presented and discussed.

Expansion of ribosomally produced natural products: a nitrile hydratase- and Nif11-related precursor family

PubMed Central

2010-01-01

Background A new family of natural products has been described in which cysteine, serine and threonine from ribosomally-produced peptides are converted to thiazoles, oxazoles and methyloxazoles, respectively. These metabolites and their biosynthetic gene clusters are now referred to as thiazole/oxazole-modified microcins (TOMM). As exemplified by microcin B17 and streptolysin S, TOMM precursors contain an N-terminal leader sequence and C-terminal core peptide. The leader sequence contains binding sites for the posttranslational modifying enzymes which subsequently act upon the core peptide. TOMM peptides are small and highly variable, frequently missed by gene-finders and occasionally situated far from the thiazole/oxazole forming genes. Thus, locating a substrate for a particular TOMM pathway can be a challenging endeavor. Results Examination of candidate TOMM precursors has revealed a subclass with an uncharacteristically long leader sequence closely related to the enzyme nitrile hydratase. Members of this nitrile hydratase leader peptide (NHLP) family lack the metal-binding residues required for catalysis. Instead, NHLP sequences display the classic Gly-Gly cleavage motif and have C-terminal regions rich in heterocyclizable residues. The NHLP family exhibits a correlated species distribution and local clustering with an ABC transport system. This study also provides evidence that a separate family, annotated as Nif11 nitrogen-fixing proteins, can serve as natural product precursors (N11P), but not always of the TOMM variety. Indeed, a number of cyanobacterial genomes show extensive N11P paralogous expansion, such as Nostoc, Prochlorococcus and Cyanothece, which replace the TOMM cluster with lanthionine biosynthetic machinery. Conclusions This study has united numerous TOMM gene clusters with their cognate substrates. These results suggest that two large protein families, the nitrile hydratases and Nif11, have been retailored for secondary metabolism. Precursors for TOMMs and lanthionine-containing peptides derived from larger proteins to which other functions are attributed, may be widespread. The functions of these natural products have yet to be elucidated, but it is probable that some will display valuable industrial or medical activities. PMID:20500830

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

Shearer, J.; Callan, P; Amie, J

Nitrile hydratases (NHases) are non-heme Fe{sup III} or non-corrin Co{sup III} containing metalloenzymes that possess an N{sub 2}S{sub 3} ligand environment with nitrogen donors derived from amidates and sulfur donors derived from cysteinates. A closely related enzyme is thiocyanate hydrolase (SCNase), which possesses a nearly identical active-site coordination environment as CoNHase. These enzymes are redox inactive and perform hydrolytic reactions; SCNase hydrolyzes thiocyanate anions while NHase converts nitriles into amides. Herein an active CoNHase metallopeptide mimic, [Co{sup III}NHase-m1] (NHase-m1 = AcNH-CCDLP-CGVYD-PA-COOH), that contains Co{sup III} in a similar N{sub 2}S{sub 3} coordination environment as CoNHase is reported. [Co{sup III}NHase-m1] wasmore » characterized by electrospray ionization-mass spectrometry (ESI-MS), gel-permeation chromatography (GPC), Co K-edge X-ray absorption spectroscopy (Co-S: 2.21 {angstrom}; Co-N: 1.93 {angstrom}), vibrational, and optical spectroscopies. We find that [Co{sup III}NHase-m1] will perform the catalytic conversion of acrylonitrile into acrylamide with up to 58 turnovers observed after 18 h at 25 C (pH 8.0). FTIR data used in concert with calculated vibrational data (mPWPW91/aug-cc-TZVPP) demonstrates that the active form of [Co{sup III}NHase-m1] has a ligated SO{sub 2} (? = 1091 cm{sup -1}) moiety and a ligated protonated SO(H) (? = 928 cm{sup -1}) moiety; when only one oxygenated cysteinate ligand (i.e., a mono-SO{sub 2} coordination motif) or the bis-SO{sub 2} coordination motif are found within [Co{sup III}NHase-m1] no catalytic activity is observed. Calculations of the thermodynamics of ligand exchange (B3LYP/aug-cc-TZVPP) suggest that the reason for this is that the SO{sub 2}/SO(H) equatorial ligand motif promotes both water dissociation from the Co{sup III}-center and nitrile coordination to the Co{sup III}-center. In contrast, the under- or overoxidized motifs will either strongly favor a five coordinate Co{sup III}-center or strongly favor water binding to the Co{sup III}-center over nitrile binding.« less

Catena-poly[[bis(1H-benzotriazole-kappaN3)cobalt(II)]-di-mu-tricyanomethanido-kappa2N:N'] and catena-poly[[bis(3,5-dimethyl-1H-pyrazole-kappaN2)manganese(II)]-di-mu-tricyanomethanido-kappa2N:N'].

PubMed

Shao, Ze-Huai; Luo, Jun; Cai, Rui-Fang; Zhou, Xi-Geng; Weng, Lin-Hong; Chen, Zhen-Xia

2004-06-01

Two new one-dimensional coordination polymers, viz. the title compounds, [Co[C(CN)(3)](2)(C(6)H(5)N(3))(2)](n), (I), and [Mn[C(CN)(3)](2)(C(5)H(8)N(2))(2)](n), (II), have been synthesized and characterized by X-ray diffraction. Both complexes consist of linear chains with double 1,5-tricyanomethanide bridges between neighbouring divalent metal ions. The Co and Mn atoms are located on centres of inversion. In (I), the coordination environment of the Co(II) atom is that of an elongated octahedron. The Co(II) atom is coordinated in the equatorial plane by four nitrile N atoms of four bridging tricyanomethanide ions, with Co-N distances of 2.106 (2) and 2.110 (2) A, and in the apical positions by two N atoms from the benzotriazole ligands, with a Co-N distance of 2.149 (2) A. The [Co[C(CN)(3)](2)(C(6)H(5)N(3))(2)] units form infinite chains extending along the a axis. These chains are crosslinked via a hydrogen bond between the uncoordinated nitrile N atom of a tricyanomethanide anion and the H atom on the uncoordinated N atom of a benzotriazole ligand from an adjacent chain, thus forming a three-dimensional network structure. In (II), the Mn(II) atom also adopts a slightly distorted octahedral geometry, with four nitrile N atoms of tricyanomethanide ligands [Mn-N = 2.226 (2) and 2.227 (2) A] in equatorial positions and two N atoms of the monodentate 3,5-dimethylpyrazole ligands [Mn-N = 2.231 (2) A] in the axial sites. In (II), one-dimensional polymeric chains extending along the b axis are formed, with tricyanomethanide anions acting as bidentate bridging ligands. A hydrogen bond between the uncoordinated nitrile N atom of the tricyanomethanide ligand and the H atom on the uncoordinated N atom of a 3,5-dimethylpyrazole group from a neighbouring chain links the molecule into a two-dimensional layered structure.

40 CFR 442.2 - General definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., organic chemicals including: alcohols, aldehydes, formaldehydes, phenols, peroxides, organic salts, amines, amides, other nitrogen compounds, other aromatic compounds, aliphatic organic chemicals, glycols, glycerines, and organic polymers; refractory organic compounds including: ketones, nitriles, organo-metallic...

Cellulose nanocrystals reinforced foamed nitrile rubber nanocomposites.

PubMed

Chen, Yukun; Zhang, Yuanbing; Xu, Chuanhui; Cao, Xiaodong

2015-10-05

Research on foamed nitrile rubber (NBR)/cellulose nanocrystals (CNs) nanocomposites is rarely found in the literatures. In this paper, CNs suspension and NBR latex was mixed to prepared the foamed NBR/CNs nanocomposites. We found that the CNs mainly located in the cell walls, effectively reinforcing the foamed NBR. The strong interaction between the CNs and NBR matrix restricted the mobility of NBR chains surrounding the CNs, hence increasing the crosslink density of the NBR matrix. CNs exhibited excellent reinforcement on the foamed NBR: a remarkable increase nearly 76% in the tensile strength of the foamed nanocomposites was achieved with a load of only 15 phr CNs. Enhanced mechanical properties make the foamed NBR/CNs nanocomposites a promising damping material for industrial applications with a potential to reduce the petroleum consumption. Copyright © 2015 Elsevier Ltd. All rights reserved.

Prediction of the lifetime of nitrile-butadiene rubber by FT-IR.

PubMed

Kawashima, Tetsuya; Ogawa, Toshio

2005-12-01

A quantitative measurement method with FT-IR was proposed for a thermal degradation analysis of nitrile-butadiene rubber (NBR). An NBR film was prepared as a model sample on a barium fluoride (BaF2) crystal plate, which was subjected to a heat treatment. The absorbances of various functional groups were measured directly by FT-IR after thermal degradation at high temperatures. By measuring the absorbances, it was possible to readily determine quantitatively each of the functional groups after the degradation of NBR. By assuming that the NBR lifetime was the point at which the absorbance of a carbon-carbon double bond reaches 45% of that prior to thermal treatment, a method for predicting the lifetime of NBR heated below 150 degrees C was proposed, by using an Arrhenius plot of the heating time versus heating temperature.

CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds

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

Yu, Chao; Fu, Jiaju; Muzzio, Michelle

Here we report a solution phase synthesis of 16 nm CuNi nanoparticles (NPs) with the Cu/Ni composition control. These NPs are assembled on graphene (G) and show Cu/Ni composition-dependent catalysis for methanolysis of ammonia borane (AB) and hydrogenation of aromatic nitro (nitrile) compounds to primary amines in methanol at room temperature. Among five different CuNi NPs studied, the G-Cu 36Ni 64 NPs are the best catalyst for both AB methanolysis (TOF = 49.1 mol H2 mol CuNi -1 min -1 and E a = 24.4 kJ/mol) and hydrogenation reactions (conversion yield >97%). In conclusion, the G-CuNi represents a unique noble-metal-freemore » catalyst for hydrogenation reactions in a green environment without using pure hydrogen.« less

An electrically actuated molecular toggle switch

NASA Astrophysics Data System (ADS)

Gerhard, Lukas; Edelmann, Kevin; Homberg, Jan; Valášek, Michal; Bahoosh, Safa G.; Lukas, Maya; Pauly, Fabian; Mayor, Marcel; Wulfhekel, Wulf

2017-03-01

Molecular electronics is considered a promising approach for future nanoelectronic devices. In order that molecular junctions can be used as electrical switches or even memory devices, they need to be actuated between two distinct conductance states in a controlled and reproducible manner by external stimuli. Here we present a tripodal platform with a cantilever arm and a nitrile group at its end that is lifted from the surface. The formation of a coordinative bond between the nitrile nitrogen and the gold tip of a scanning tunnelling microscope can be controlled by both electrical and mechanical means, and leads to a hysteretic switching of the conductance of the junction by more than two orders of magnitude. This toggle switch can be actuated with high reproducibility so that the forces involved in the mechanical deformation of the molecular cantilever can be determined precisely with scanning tunnelling microscopy.

Beckmann rearrangement within the ring C of oleanolic acid lactone: Synthesis, structural study and reaction mechanism analysis

NASA Astrophysics Data System (ADS)

Froelich, Anna; Bednarczyk-Cwynar, Barbara; Zaprutko, Lucjusz; Gzella, Andrzej

2017-05-01

Synthesis, spectral and X-ray analysis of three compounds, i.e. 3β-acetoxy-12-hydroxyimino-18β-oleanan-28,13β-olide (substrate) and 3β-acetoxy-12-nitrile-12,13-seco-15(14 → 13)-abeoolean-14(27)-en-28,13β-olide and 3β-acetoxy-12-oxo-12a-aza-C-homoolean-13(18)-en-28-oic acid (Beckmann rearrangement reaction products) are described. Structural analysis revealed that the oxime group in the ring C in substrate molecule had an E-configuration. The nitrile product with retained lactone group was a result of major transformations within rings C and D of oleanane skeleton. In lactam product free carboxyl group and a double bond in ring D instead of lactone system were formed in Beckmann rearrangement reaction.

CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds

DOE PAGES

Yu, Chao; Fu, Jiaju; Muzzio, Michelle; ...

2017-01-12

Here we report a solution phase synthesis of 16 nm CuNi nanoparticles (NPs) with the Cu/Ni composition control. These NPs are assembled on graphene (G) and show Cu/Ni composition-dependent catalysis for methanolysis of ammonia borane (AB) and hydrogenation of aromatic nitro (nitrile) compounds to primary amines in methanol at room temperature. Among five different CuNi NPs studied, the G-Cu 36Ni 64 NPs are the best catalyst for both AB methanolysis (TOF = 49.1 mol H2 mol CuNi -1 min -1 and E a = 24.4 kJ/mol) and hydrogenation reactions (conversion yield >97%). In conclusion, the G-CuNi represents a unique noble-metal-freemore » catalyst for hydrogenation reactions in a green environment without using pure hydrogen.« less

Crystal structure and electrochemical properties of [Ni(bztmpen)(CH3CN)](BF4)2 {bztmpen is N-benzyl-N,N',N'-tris-[(6-methyl-pyridin-2-yl)meth-yl]ethane-1,2-di-amine}.

PubMed

Chen, Lin; Ren, Gan; Guo, Yakun; Sang, Ge

2017-06-01

The mononuclear nickel title complex (acetonitrile-κ N ){ N -benzyl- N , N ', N '-tris-[(6-methyl-pyridin-2-yl)meth-yl]ethane-1,2-di-amine}-nickel(II) bis-(tetra-fluor-ido-borate), [Ni(C 30 H 35 N 5 )(CH 3 CN)](BF 4 ) 2 , was prepared from the reaction of Ni(BF 4 ) 2 ·6H 2 O with N -benzyl- N , N ', N '-tris-[(6-methyl-pyridin-2-yl)meth-yl]ethane-1,2-di-amine ( bztmpen ) in aceto-nitrile at room temperature. With an open site occupied by the aceto-nitrile mol-ecule, the nickel(II) atom is chelated by five N-atom sites from the ligand and one N atom from the ligand, showing an overall octa-hedral coordination environment. Compared with analogues where the 6-methyl substituent is absent, the bond length around the Ni 2+ cation are evidently longer. Upon reductive dissociation of the acetro-nitrile mol-ecule, the title complex has an open site for a catalytic reaction. The title complex has two redox couples at -1.50 and -1.80 V ( versus F c +/0 ) based on nickel. The F atoms of the two BF 4 - counter-anions are split into two groups and the occupancy ratios refined to 0.611 (18):0.389 (18) and 0.71 (2):0.29 (2).

Identification of key residues modulating the stereoselectivity of nitrile hydratase toward rac-mandelonitrile by semi-rational engineering.

PubMed

Cheng, Zhongyi; Peplowski, Lukasz; Cui, Wenjing; Xia, Yuanyuan; Liu, Zhongmei; Zhang, Jialei; Kobayashi, Michihiko; Zhou, Zhemin

2018-03-01

Optically pure compounds are important in the synthesis of fine chemicals. Using directed evolution of enzymes to obtain biocatalysts that can selectively produce high-value chiral chemicals is often time-, money-, and resource-intensive; traditional semi-rational designs based on structural data and docking experiments are still limited due to the lack of accurate selection of hot-spot residues. In this study, through ligand-protein collision counts based on steered molecular dynamics simulation, we accurately identified four residues related to improving nitrile hydratase stereoselectivity toward rac-mandelonitrile (MAN). All the four selected residues had numerous collisions with rac-MAN. Five mutants significantly shifting stereoselectivity towards (S)-MAN were obtained from site-saturation mutagenesis, one of them, at position βPhe37, exhibiting efficient production of (S)-MAN with 96.8% ee p , was isolated and further analyzed. The increased pulling force observed during SMD simulation was found to be in good coincidence with the formation of hydrogen bonds between (R)-MAN and residue βHis37. (R)-MAN had to break these barriers to enter the active site of nitrile hydratase and S selectivity was thus improved. The results indicated that combining steered molecular dynamics simulation with a traditional semi-rational design significantly reduced the select range of hot-spot residues for the evolution of NHase stereoselectivity, which could serve as an alternative for the modulation of enzyme stereoselectivity. © 2017 Wiley Periodicals, Inc.

Activation of Remote meta-C–H Bonds Assisted by an “End-on” Template

PubMed Central

Leow, Dasheng; Li, Gang; Mei, Tiansheng; Yu, Jin-Quan

2012-01-01

Controlling positional selectivity of C–H activation in molecules possessing multiple inequivalent C–H bonds is one of the most important challenges in developing synthetically useful C–H activation reactions. One widely used approach utilizes σ-chelating directing groups to achieve ortho-selectivity through conformational rigid five- or six-membered cyclic pre-transition states (TS).1–14 We envisioned that an “end-on” chelating template capable of delivering catalysts to previously inaccessible remote meta-C–H bonds via a macrocyclic cyclophane-like pre-TS could overcome the limitations imposed by traditional ortho-directing groups. Herein, we report a class of readily removable nitrile-containing templates that direct the activation of distal meta-C–H bonds (≥ 10 bonds away) of a tethered arene. We attribute this new mode of C–H activation to the weak “end-on” coordination of the linear nitrile group to metal center, as previously observed by Schwarz in the study of remote C–H activation of alkyl nitriles in gas phase.15, 16 The coordination geometry relieves the strain of the cyclophane-like pre-transition state of the meta-C–H activation event. Remarkably, this template overrides electronic and steric biases and ortho-directing effects with two broadly useful classes of arene substrates (toluene derivatives and hydrocinnamic acids), thus constituting a fundamentally new mode of directed C–H activation that is anticipated to be widely adopted. PMID:22739317

40 CFR 721.555 - Alkyl amino nitriles (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... (c). A full face shield is required if splashing or spraying occurs. (ii) Hazard communication program. Requirements as specified in § 721.72 (c)(1) and (c)(2)(iv). The MSDS required by this paragraph...

40 CFR 721.555 - Alkyl amino nitriles (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... (c). A full face shield is required if splashing or spraying occurs. (ii) Hazard communication program. Requirements as specified in § 721.72 (c)(1) and (c)(2)(iv). The MSDS required by this paragraph...

40 CFR 721.555 - Alkyl amino nitriles (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... (c). A full face shield is required if splashing or spraying occurs. (ii) Hazard communication program. Requirements as specified in § 721.72 (c)(1) and (c)(2)(iv). The MSDS required by this paragraph...

40 CFR 721.555 - Alkyl amino nitriles (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... (c). A full face shield is required if splashing or spraying occurs. (ii) Hazard communication program. Requirements as specified in § 721.72 (c)(1) and (c)(2)(iv). The MSDS required by this paragraph...

Synthesis of the BCDE molecular fragment of azadiradione mediated by titanocene(III).

PubMed

Fernández-Mateos, A; Madrazo, S Encinas; Teijón, P Herrero; Clemente, R Rabanedo; González, R Rubio; González, F Sanz

2013-10-04

A practical, short, and diastereoselective synthesis of the azadiradione BCDE fragment from a readily available starting material is described. The key step was the titanocene(III)-promoted tandem cyclization of unsaturated epoxy nitrile.

78 FR 64246 - Commerce in Explosives; List of Explosives Materials

Federal Register 2010, 2011, 2012, 2013, 2014

2013-10-28

... [2,2-dinitropropyl acrylate]. DNPD [dinitropentano nitrile]. Dynamite. E EDDN [ethylene diamine dinitrate]. EDNA [ethylenedinitramine]. Ednatol. EDNP [ethyl 4,4-dinitropentanoate]. EGDN [ethylene glycol.... Nitroglycol [ethylene glycol dinitrate, EGDN]. Nitroguanidine explosives. Nitronium perchlorate propellant...

A Nitrile Hydratase in the Eukaryote Monosiga brevicollis

PubMed Central

Foerstner, Konrad U.; Doerks, Tobias; Muller, Jean; Raes, Jeroen; Bork, Peer

2008-01-01

Bacterial nitrile hydratase (NHases) are important industrial catalysts and waste water remediation tools. In a global computational screening of conventional and metagenomic sequence data for NHases, we detected the two usually separated NHase subunits fused in one protein of the choanoflagellate Monosiga brevicollis, a recently sequenced unicellular model organism from the closest sister group of Metazoa. This is the first time that an NHase is found in eukaryotes and the first time it is observed as a fusion protein. The presence of an intron, subunit fusion and expressed sequence tags covering parts of the gene exclude contamination and suggest a functional gene. Phylogenetic analyses and genomic context imply a probable ancient horizontal gene transfer (HGT) from proteobacteria. The newly discovered NHase might open biotechnological routes due to its unconventional structure, its new type of host and its apparent integration into eukaryotic protein networks. PMID:19096720

Correlation between free-volume parameters and physical properties of polyethylene-nitrile rubber blend

NASA Astrophysics Data System (ADS)

Gomaa, E.; Mostafa, N.; Mohsen, M.; Mohammed, M.

2004-10-01

Positron annihilation lifetime spectroscopy (PALS) was used to study the immiscibility of a polar nitrile rubber (NBR) that had been blended with pure and waste, low- and high-density polyethylene (PE). The effect of the weight percent of the rubber added to the PE was also investigated. It was found that a complicated variation (positive and negative) in both free-volume parameters (τ3 and I 3) from the values of the initial polymers forms an immiscible blend. These results are supported by a significant broadening in the free-volume hole size distributions. This has been interpreted in terms of interfacial spaces created between the boundaries of the two phases. Furthermore, a correlation was established between the free-volume parameters (τ3 and I 3) and the electrical and mechanical properties of the before mentioned polymer blends as a function of the weight percent of waste PE.

N-Allyl-N-Sulfonyl Ynamides as Synthetic Precursors to Amidines and Vinylogous Amidines. An Unexpected N-to-C 1,3-Sulfonyl Shift in Nitrile Synthesis

PubMed Central

DeKorver, Kyle A.; Johnson, Whitney L.; Zhang, Yu; Hsung, Richard P.; Dai, Huifang; Deng, Jun; Lohse, Andrew G.; Zhang, Yan-Shi

2011-01-01

A detailed study of amidine synthesis from N-allyl-N-sulfonyl ynamides is described here. Mechanistically, this is a fascinating reaction consisting of diverging pathways that could lead to deallylation or allyl transfer depending upon the oxidation state of palladium catalysts, the nucleophilicity of amines, and the nature of the ligands. It essentially constitutes a Pd(0)-catalyzed aza-Claisen rearrangement of N-allyl ynamides, which can also be accomplished thermally. An observation of N-to-C 1,3-sulfonyl shift was made when examining these aza-Claisen rearrangements thermally. This represents a useful approach to nitrile synthesis. While attempts to render this 1,3-sulfonyl shift stereoselective failed, we uncovered another set of tandem sigmatropic rearrangements, leading to vinyl imidate formation. Collectively, this work showcases the rich array of chemistry one can discover using these ynamides. PMID:21563776

Laboratory investigation of nitrile ices of Titan's stratospheric clouds

NASA Astrophysics Data System (ADS)

Nna Mvondo, D.; Anderson, C. M.; McLain, J. L.; Samuelson, R. E.

2017-09-01

Titan's mid to lower stratosphere contains complex cloud systems of numerous organic ice particles comprised of both hydrocarbon and nitrile compounds. Most of these stratospheric ice clouds form as a result of vapor condensation formation processes. However, there are additional ice emission features such as dicyanoacetylene (C4N2) and the 220 cm-1 ice emission feature (the "Haystack") that are difficult to explain since there are no observed vapor emission features associated with these ices. In our laboratory, using a high-vacuum chamber coupled to a FTIR spectrometer, we are engaged in a dedicated investigation of Titan's stratospheric ices to interpret and constrain Cassini Composite InfraRed Spectrometer (CIRS) far-IR data. We will present laboratory transmittance spectra obtained for propionitrile (CH3CH2CN), cyanogen (C2N2) and hydrogen cyanide (HCN) ices, as well as various combinations of their mixtures, to better understand the cloud chemistry occurring in Titan's stratosphere.

Synthesis of perfluoroalkylether oxadiazole elastomers

NASA Technical Reports Server (NTRS)

Rosser, R. W.; Korus, R. A.; Shalhoub, I. M.; Kwong, H.

1979-01-01

A method for the simultaneous chain extension and crosslinking of perfluoroalkylethers which yields a thermally stable perfluoroalkylether oxadiazole elastomer crosslinked by trifunctional perfluoroalkylether-1,3,5-triazine is reported. In the preparation, hydroxylamine crystals prepared from hydroxylamine hydrochloride to which sodium butoxide had been added is mixed with perfluoroalkylether dinitrile to obtain the monomer, as the nitrile is converted to amidoxime. Monomers are heated at 140 to 200 C to form poly(perfluoroalkylether oxadiazole) with a 1,2,4-oxadiazole structure by a step-growth polymerization reaction. Simultaneous chain extension and crosslinking are observed to occur when the purified monomer is heated directly and when the remaining nitrile in the monomer is allowed to react with excess ammonia to form the corresponding amidine, which is then heated. Weight loss studies show the thermal stability of the perfluoroalkylether elastomer to be generally better than fluorosilicone or polyester elastomers, especially in air, indicating its potential usefulness for high-performance elastomeric applications.

Regio- and stereoselective synthesis of pregnane-fused isoxazolines by nitril-oxide/alkene 1,3-dipolar cycloaddition and an evaluation of their cell-growth inhibitory effect in vitro

NASA Astrophysics Data System (ADS)

Mótyán, Gergő; Baji, Ádám; Zupkó, István; Frank, Éva

2016-04-01

Efficient syntheses of some pregnane-fused isoxazolines from 16-dehydropregnenolone acetate with different arylnitrile oxides were carried out by 1,3-dipolar cycloadditions. The intermolecular ring-closures occurred in a highly regio- and stereoselective manner permitting the formation of a single 16α,17α-condensed diastereomer in which the O terminus of the nitrile oxide dipole is attached to C-17 of the sterane core. The conversions were found to be affected significantly by the electronic character of the substituents on the aromatic moiety of the 1,3-dipoles. Deacetylation of the primary products resulted in the corresponding 3β-OH analogs. All of the synthesized compounds were subjected to in vitro pharmacological studies for the determination of their antiproliferative effects on four breast cancer cell lines (MCF7, T47D, MDA-MB-231 and MDA-MB-361).

Experimental studies and performance analyses on polyurethane and nitrile rubber rod seals

NASA Astrophysics Data System (ADS)

Mirza, M.; Temiz, V.; Kamburoǧlu, E.

2012-09-01

The aim of this study is to determine the friction and leakage properties of rod seals made of polyethylene and nitrile rubber with different design geometries, under various pressure and lubricating oil viscosity conditions, in order to make assumptions about their general sealing characteristics and their pros and cons under certain working conditions that involve a range of fluid pressures. The test specimens consist of commercial rod seals of various designs and materials and were mounted on a hard chrome coated shaft subject to reciprocating motion. The test rig is capable of measuring friction force by means of strain measurements on a load cell transmitting the linear motion of a screw shaft to the test shaft. The test results of the reciprocating rod seal samples were evaluated according to leakage amount and friction resistance as a function of materials, design geometries and fluid pressures as well as the lubricating oil viscosity.

P[N(i-Bu)CH(2)CH(2)](3)N: nonionic Lewis base for promoting the room-temperature synthesis of α,β-unsaturated esters, fluorides, ketones, and nitriles using Wadsworth-Emmons phosphonates.

PubMed

Chintareddy, Venkat Reddy; Ellern, Arkady; Verkade, John G

2010-11-05

The bicyclic triaminophosphine P(RNCH(2)CH(2))(3)N (R = i-Bu, 1c) serves as an effective promoter for the room-temperature stereoselective synthesis of α,β-unsaturated esters, fluorides, and nitriles from a wide array of aromatic, aliphatic, heterocyclic, and cyclic aldehydes and ketones, using a range of Wadsworth-Emmons (WE) phosphonates. Among the analogues of 1c [R = Me (1a), i-Pr (1b), Bn (1d)], 1a and 1b performed well, although longer reaction times were involved, and 1d led to poorer yields than 1c. Functionalities such as cyano, chloro, bromo, methoxy, amino, ester, and nitro were well tolerated. We were able to isolate and characterize (by X-ray means; see above) the reactive WE intermediate species formed from 2b and 1c.

The Soleil View on Prototypical Organic Nitriles: Selected Vibrational Modes of Ethyl Cyanide, C_2H_5CN, and Spectroscopic Analysis Using AN Automated Spectral Assignment Procedure (asap)

NASA Astrophysics Data System (ADS)

Endres, Christian; Caselli, Paola; Martin-Drumel, Marie-Aline; McCarthy, Michael C.; Pirali, Olivier; Wehres, Nadine; Schlemmer, Stephan; Thorwirth, Sven

2016-06-01

Vibrational spectra of small organic nitriles, propionitrile and n-butyronitrile, have been investigated at high spectral resolution at the French national synchroton facility SOLEIL using Fourier-transform far-infrared spectroscopy (< 700 cm-1). The Automated Spectral Assignment Procedure (ASAP) has been used for line assignement and accurate determination of rotational level energies, in particular, of the ν20=1 and the ν12=1 states of propionitrile. The analysis does not only confirm the applicability of the ASAP in the treatment of (dense) high-resolution infrared spectra but also reveals some of its limitations which will be discussed in some detail. M. A. Martin-Drumel, C. P. Endres, O. Zingsheim, T. Salomon, J. van Wijngaarden, O. Pirali, S. Gruet, F. Lewen, S. Schlemmer, M. C. McCarthy, and S. Thorwirth 2015, J. Mol. Spectrosc. 315, 72

Vibrational Detection of Odorant Functional Groups by Drosophila melanogaster

PubMed Central

Maniati, Klio; Haralambous, Katherine-Joanne

2017-01-01

Abstract A remarkable feature of olfaction, and perhaps the hardest one to explain by shape-based molecular recognition, is the ability to detect the presence of functional groups in odorants, irrespective of molecular context. We previously showed that Drosophila trained to avoid deuterated odorants could respond to a molecule bearing a nitrile group, which shares the vibrational stretch frequency with the CD bond. Here, we reproduce and extend this finding by showing analogous olfactory responses of Drosophila to the chemically vastly different functional groups, thiols and boranes, that nevertheless possess a common vibration at 2600 cm−1. Furthermore, we show that Drosophila do not respond to a cyanohydrin structure that renders nitrile groups invisible to IR spectroscopy. We argue that the response of Drosophila to these odorants which parallels their perception in humans, supports the hypothesis that odor character is encoded in odorant molecular vibrations, not in the specific shape-based activation pattern of receptors. PMID:29094064

Understanding Factors that Influence Protective Glove Use among Automotive Spray Painters

PubMed Central

Ceballos, Diana; Reeb-Whitaker, Carolyn; Glazer, Patricia; Murphy-Robinson, Helen; Yost, Michael

2017-01-01

Dermal contact with isocyanate-based coatings may lead to systemic respiratory sensitization. The most common isocyanates found in sprayed automotive coatings are monomeric and oligomeric 1,6-hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). Most spray painters use thin (4–5 mil) latex gloves that are not effective at preventing dermal exposures when spraying isocyanate paints. Personal interviews with collision repair industry personnel and focus groups with spray painters were held to characterize risk awareness, to examine perceptions and challenges concerning protective glove use and selection, and to generate ideas for protective glove use interventions. The most popular gloves among spray painters were thin (4–5 mil) and thick (14 mil) latex. We found that medium to thick (6–8 mil) nitrile were not always perceived as comfortable and were expected to be more expensive than thin (4–5 mil) latex gloves. Of concern is the users’ difficulty to distinguish between nitrile and latex gloves; latex gloves are now sold in different colors including blue, which has traditionally been associated with nitrile gloves. Even though spray painters were familiar with the health hazards related to working with isocyanate paints; most were not always aware that dermal exposure to isocyanates could contribute to the development of occupational asthma. There is a need for more research to identify dermal materials that are protective against sprayed automotive coatings. Automotive spray painters and their employers need to be educated in the selection and use of protective gloves, specifically on attributes such as glove material, color, and thickness. PMID:24215135

76 FR 64974 - Commerce in Explosives; List of Explosive Materials (2011R-18T)

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-19

... [dinitropentano nitrile]. Dynamite. E EDDN [ethylene diamine dinitrate]. EDNA [ethylenedinitramine]. Ednatol. EDNP [ethyl 4,4-dinitropentanoate]. EGDN [ethylene glycol dinitrate]. Erythritol tetranitrate explosives..., trinitroglycerine]. Nitroglycide. Nitroglycol [ethylene glycol dinitrate, EGDN]. Nitroguanidine explosives...

77 FR 58410 - Commerce in Explosives; List of Explosive Materials (2012R-10T)

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-20

... [dinitropentano nitrile]. Dynamite. E EDDN [ethylene diamine dinitrate]. EDNA [ethylenedinitramine]. Ednatol. EDNP [ethyl 4,4-dinitropentanoate]. EGDN [ethylene glycol dinitrate]. Erythritol tetranitrate explosives..., RNG, nitro, glyceryl trinitrate, trinitroglycerine]. Nitroglycide. Nitroglycol [ethylene glycol...

Experimental study of the formation processes, optical properties, and chemistry of Titan's stratospheric ice clouds as observed by Cassini CIRS

NASA Astrophysics Data System (ADS)

Nna-Mvondo, D.; Anderson, C. M.; Samuelson, R. E.

2017-12-01

Two types of cloud systems have been repeatedly observed in Titan's atmosphere since the Cassini spacecraft entered into orbit around Saturn in 2004: (1) tropospheric convective methane clouds and (2) stratospheric ice clouds. Most of the stratospheric ice clouds observed by Cassini's Composite InfraRed Spectrometer (CIRS) form as a result of vapor condensation processes from a combination of pure and mixed nitriles and hydrocarbons. Examples include the n6 band of crystalline cyanoacetylene (HC3N) at 506 cm-1 (Anderson et al., 2010 and references therein) and the CIRS-discovered co-condensed nitrile ice feature at 160 cm-1 (Anderson and Samuelson, 2011). Other CIRS-observed stratospheric ice emission features, such as the n8 band of dicyanoacetylene (C4N2) at 478 cm-1 and the Haystack emission feature at 220 cm-1, have no associated observed vapor emission features, and could therefore form through more complex chemical processes such as solid-state photochemistry as suggested by Anderson et al. (2016). In the Spectroscopy for Planetary Ices Environments (SPICE) laboratory at NASA GSFC, we are undergoing investigations of Titan's observed stratospheric ices to better understand their chemical compositions, formation mechanisms, and optical properties. We accomplish this using the SPECtroscopy of Titan-Related ice AnaLogs (SPECTRAL) high-vacuum chamber, in which we perform transmission spectroscopy of thin films of pure and mixed ices, from the near- to far-infrared (50 cm-1 to 11700 cm-1), and dose at low temperatures (30 K to 150 K), to study their spectral evolution and optical properties. Here we discuss our laboratory results obtained for various experiments containing pure and mixed nitrile ices (and some combined with benzene). The first significant result reveals that the libration mode of HCN (166 - 169 cm-1) is drastically altered by the surrounding molecules when mixing occurs in a co-condensed phase. For propionitrile ice, we observe peculiar temperature and time-driven ice phase transitions (as compared to other nitrile ices), revealed by significant spectral changes in the mid and far-IR that cease once a stable crystalline phase is achieved. Results from such experimental measurements provide crucial data to deepen our understanding of Titan's stratospheric chemistry.

Total synthesis and stereochemical assignment of the spiroisoxazoline natural product (+)-calafianin.

PubMed

Bardhan, Sujata; Schmitt, Daniel C; Porco, John A

2006-03-02

Synthesis of the spiroisoxazoline natural product (+)-calafianin is reported using asymmetric nucleophilic epoxidation and nitrile oxide cycloaddition as key steps. Synthesis and spectral analysis of all calafianin stereoisomers led to unambiguous assignment of relative and absolute stereochemistry.

Applications of 2D IR spectroscopy to peptides, proteins, and hydrogen-bond dynamics

PubMed Central

Kim, Yung Sam; Hochstrasser, Robin M.

2010-01-01

Following a survey of 2D IR principles this Feature Article describes recent experiments on the hydrogen-bond dynamics of small ions, amide-I modes, nitrile probes, peptides, reverse transcriptase inhibitors, and amyloid fibrils. PMID:19351162

Isocyanide-mediated multicomponent synthesis of C-oximinoamidines.

PubMed

Mercalli, Valentina; Meneghetti, Fiorella; Tron, Gian Cesare

2013-11-15

By capitalizing on the different reactivity of nitrile N-oxides with isocyanides and amine, α-oximinoamidines, a so far elusive class of compounds, have been synthesized in a straightforward way by reacting isocyanides, syn-chlorooximes, and amines in a multicomponent fashion.

75 FR 70291 - Commerce in Explosives; List of Explosive Materials (2010R-27T)

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-17

... [2,2-dinitropropyl acrylate]. DNPD [dinitropentano nitrile]. Dynamite. E EDDN [ethylene diamine dinitrate]. EDNA [ethylenedinitramine]. Ednatol. EDNP [ethyl 4,4-dinitropentanoate]. EGDN [ethylene glycol.... Nitroglycol [ethylene glycol dinitrate, EGDN]. Nitroguanidine explosives. Nitronium perchlorate propellant...

75 FR 1085 - Commerce in Explosives; List of Explosive Materials (2009R-18T)

Federal Register 2010, 2011, 2012, 2013, 2014

2010-01-08

... [2,2-dinitropropyl acrylate]. DNPD [dinitropentano nitrile]. Dynamite. E EDDN [ethylene diamine dinitrate]. EDNA [ethylenedinitramine]. Ednatol. EDNP [ethyl 4,4-dinitropentanoate]. EGDN [ethylene glycol.... Nitroglycol [ethylene glycol dinitrate, EGDN]. Nitroguanidine explosives. Nitronium perchlorate propellant...

IRIS Toxicological Review of Acrylonitrile (External Review Draft)

EPA Science Inventory

[UPDATE] New Schedule for IRIS Acrylonitrile Assessment

Involvement of DPP-IV catalytic residues in enzyme–saxagliptin complex formation

PubMed Central

Metzler, William J.; Yanchunas, Joseph; Weigelt, Carolyn; Kish, Kevin; Klei, Herbert E.; Xie, Dianlin; Zhang, Yaqun; Corbett, Martin; Tamura, James K.; He, Bin; Hamann, Lawrence G.; Kirby, Mark S.; Marcinkeviciene, Jovita

2008-01-01

The inhibition of DPP-IV by saxagliptin has been proposed to occur through formation of a covalent but reversible complex. To evaluate further the mechanism of inhibition, we determined the X-ray crystal structure of the DPP-IV:saxagliptin complex. This structure reveals covalent attachment between S630 and the inhibitor nitrile carbon (C–O distance <1.3 Å). To investigate whether this serine addition is assisted by the catalytic His-Asp dyad, we generated two mutants of DPP-IV, S630A and H740Q, and assayed them for ability to bind inhibitor. DPP-IVH740Q bound saxagliptin with an ∼1000-fold reduction in affinity relative to DPP-IVWT, while DPP-IVS630A showed no evidence for binding inhibitor. An analog of saxagliptin lacking the nitrile group showed unchanged binding properties to the both mutant proteins, highlighting the essential role S630 and H740 play in covalent bond formation between S630 and saxagliptin. Further supporting mechanism-based inhibition by saxagliptin, NMR spectra of enzyme–saxagliptin complexes revealed the presence of three downfield resonances with low fractionation factors characteristic of short and strong hydrogen bonds (SSHB). Comparison of the NMR spectra of various wild-type and mutant DPP-IV:ligand complexes enabled assignment of a resonance at ∼14 ppm to H740. Two additional DPP-IV mutants, Y547F and Y547Q, generated to probe potential stabilization of the enzyme–inhibitor complex by this residue, did not show any differences in inhibitor binding either by ITC or NMR. Together with the previously published enzymatic data, the structural and binding data presented here strongly support a histidine-assisted covalent bond formation between S630 hydroxyl oxygen and the nitrile group of saxagliptin. PMID:18227430

Involvement of DPP-IV Catalytic Residues in Enzyme-Saxagliptin Complex Formation

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

Metzler,W.; Yanchunas, J.; Weigelt, C.

The inhibition of DPP-IV by saxagliptin has been proposed to occur through formation of a covalent but reversible complex. To evaluate further the mechanism of inhibition, we determined the X-ray crystal structure of the DPP-IV:saxagliptin complex. This structure reveals covalent attachment between S630 and the inhibitor nitrile carbon (C-O distance <1.3 Angstroms). To investigate whether this serine addition is assisted by the catalytic His-Asp dyad, we generated two mutants of DPP-IV, S630A and H740Q, and assayed them for ability to bind inhibitor. DPP-IVH740Q bound saxagliptin with an {approx}1000-fold reduction in affinity relative to DPP-IVWT, while DPP-IVS630A showed no evidence formore » binding inhibitor. An analog of saxagliptin lacking the nitrile group showed unchanged binding properties to the both mutant proteins, highlighting the essential role S630 and H740 play in covalent bond formation between S630 and saxagliptin. Further supporting mechanism-based inhibition by saxagliptin, NMR spectra of enzyme-saxagliptin complexes revealed the presence of three downfield resonances with low fractionation factors characteristic of short and strong hydrogen bonds (SSHB). Comparison of the NMR spectra of various wild-type and mutant DPP-IV:ligand complexes enabled assignment of a resonance at {approx}14 ppm to H740. Two additional DPP-IV mutants, Y547F and Y547Q, generated to probe potential stabilization of the enzyme-inhibitor complex by this residue, did not show any differences in inhibitor binding either by ITC or NMR. Together with the previously published enzymatic data, the structural and binding data presented here strongly support a histidine-assisted covalent bond formation between S630 hydroxyl oxygen and the nitrile group of saxagliptin.« less

Isothiocyanates, Nitriles, and Epithionitriles from Glucosinolates Are Affected by Genotype and Developmental Stage in Brassica oleracea Varieties.

PubMed

Hanschen, Franziska S; Schreiner, Monika

2017-01-01

Vegetables of the Brassica oleracea group, such as broccoli, cauliflower, and cabbage, play an important role for glucosinolate consumption in the human diet. Upon maceration of the vegetable tissue, glucosinolates are degraded enzymatically to form volatile isothiocyanates, nitriles, and epithionitriles. However, only the uptake of isothiocyanates is linked to the cancer-preventive effects. Thus, it is of great interest to evaluate especially the isothiocyanate formation. Here, we studied the formation of glucosinolates and their respective hydrolysis products in sprouts and fully developed vegetable heads of different genotypes of the five B. oleracea varieties: broccoli, cauliflower as well as white, red, and savoy cabbages. Further, the effect of ontogeny (developmental stages) during the head development on the formation of glucosinolates and their respective hydrolysis products was evaluated at three different developmental stages (mini, fully developed, and over-mature head). Broccoli and red cabbage were mainly rich in 4-(methylsulfinyl)butyl glucosinolate (glucoraphanin), whereas cauliflower, savoy cabbage and white cabbage contained mainly 2-propenyl (sinigrin) and 3-(methylsulfinyl)propyl glucosinolate (glucoiberin). Upon hydrolysis, epithionitriles or nitriles were often observed to be the main hydrolysis products, with 1-cyano-2,3-epithiopropane being most abundant with up to 5.7 μmol/g fresh weight in white cabbage sprouts. Notably, sprouts often contained more than 10 times more glucosinolates or their hydrolysis products compared to fully developed vegetables. Moreover, during head development, both glucosinolate concentrations as well as hydrolysis product concentrations changed and mini heads contained the highest isothiocyanate concentrations. Thus, from a cancer-preventive point of view, consumption of mini heads of the B. oleracea varieties is recommended.

Nitrile versus isonitrile adsorption at interstellar grain surfaces. II. Carbonaceous aromatic surfaces

NASA Astrophysics Data System (ADS)

Bertin, M.; Doronin, M.; Michaut, X.; Philippe, L.; Markovits, A.; Fillion, J.-H.; Pauzat, F.; Ellinger, Y.; Guillemin, J.-C.

2017-12-01

Context. Almost 20% of the 200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Of these 37 molecules, 30 are nitrile R-CN compounds, the remaining 7 belonging to the isonitrile R-NC family. How these species behave in their interactions with the grain surfaces is still an open question. Aims: In a previous work, we have investigated whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of various nature and morphologies. This study is a follow up of this work, where we focus on the adsorption on carbonaceous aromatic surfaces. Methods: The question is addressed by means of a concerted experimental and theoretical approach of the adsorption energies of CH3CN and CH3NC on the surface of graphite (with and without surface defects). The experimental determination of the molecule and surface interaction energies is carried out using temperature-programmed desorption in an ultra-high vacuum between 70 and 160 K. Theoretically, the question is addressed using first-principle periodic density functional theory to represent the organised solid support. Results: The adsorption energy of each compound is found to be very sensitive to the structural defects of the aromatic carbonaceous surface: these defects, expected to be present in a large numbers and great diversity on a realistic surface, significantly increase the average adsorption energies to more than 50% as compared to adsorption on perfect graphene planes. The most stable isomer (CH3CN) interacts more efficiently with the carbonaceous solid support than the higher energy isomer (CH3NC), however.

Isothiocyanates, Nitriles, and Epithionitriles from Glucosinolates Are Affected by Genotype and Developmental Stage in Brassica oleracea Varieties

PubMed Central

Hanschen, Franziska S.; Schreiner, Monika

2017-01-01

Vegetables of the Brassica oleracea group, such as broccoli, cauliflower, and cabbage, play an important role for glucosinolate consumption in the human diet. Upon maceration of the vegetable tissue, glucosinolates are degraded enzymatically to form volatile isothiocyanates, nitriles, and epithionitriles. However, only the uptake of isothiocyanates is linked to the cancer-preventive effects. Thus, it is of great interest to evaluate especially the isothiocyanate formation. Here, we studied the formation of glucosinolates and their respective hydrolysis products in sprouts and fully developed vegetable heads of different genotypes of the five B. oleracea varieties: broccoli, cauliflower as well as white, red, and savoy cabbages. Further, the effect of ontogeny (developmental stages) during the head development on the formation of glucosinolates and their respective hydrolysis products was evaluated at three different developmental stages (mini, fully developed, and over-mature head). Broccoli and red cabbage were mainly rich in 4-(methylsulfinyl)butyl glucosinolate (glucoraphanin), whereas cauliflower, savoy cabbage and white cabbage contained mainly 2-propenyl (sinigrin) and 3-(methylsulfinyl)propyl glucosinolate (glucoiberin). Upon hydrolysis, epithionitriles or nitriles were often observed to be the main hydrolysis products, with 1-cyano-2,3-epithiopropane being most abundant with up to 5.7 μmol/g fresh weight in white cabbage sprouts. Notably, sprouts often contained more than 10 times more glucosinolates or their hydrolysis products compared to fully developed vegetables. Moreover, during head development, both glucosinolate concentrations as well as hydrolysis product concentrations changed and mini heads contained the highest isothiocyanate concentrations. Thus, from a cancer-preventive point of view, consumption of mini heads of the B. oleracea varieties is recommended. PMID:28690627

Spectra, Index of Refraction, and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

NASA Astrophysics Data System (ADS)

Moore, Marla; Hudson, Reggie; Ferrante, Robert; Moore, William

Spectra and optical constants of nitrile ices known or suspected to be in Titan's atmosphere are presented from 2.5 to 200 microns (4000 to 50 cm-1 ). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan's winter pole. Ices studied include: HCN, hydrogen cyanide; C2 N2 , cyanogen; CH3 CN, acetonitrile; C2 H5 CN, propionitrile; and HC3 N, cyanoacetylene. For each of these molecules we report new measurements of the index of refraction, n, determined in both the amorphous-and crystalline-phase at 670 nm. Spectra were measured and optical constants were calculated for each nitrile at a variety of temperatures including 20, 35, 50, 75, 95, and 110 K, in the amorphous-and crystalline-phase. This laboratory effort uses a dedicated FTIR spectrometer to record transmission spectra of thin-film ice samples. Laser interference is used to measure film thickness during condensation onto a transparent cold window attached to the tail section of a closed-cycle helium cryo-stat. Optical constants, real (n) and imaginary (k) refractive indices, are determined using Kramers-Kronig (K-K) analysis. Our calculation reproduces the complete spectrum, including all interference effects. Index of refraction measurements are made in a separate dedicated FTIR spectrometer where interference deposit fringes are measured using two 670 nm lasers at different angles to the ice substrate. A survey of these new measurements will be presented along with a discussion of their validation, errors, and application to Titan data. We acknowledge Mark Loeffler who recently joined in our refractive index measurements. The authors also acknowledge support from the Cassini Data Analysis Program. RLH and MHM acknowledge additional funding from NASA's PGG and Outer Planets Programs, and the Goddard Center for Astrobiology.

Monstrous Ice Cloud System in Titan's Present South Polar Stratosphere

NASA Astrophysics Data System (ADS)

Anderson, Carrie; Samuelson, Robert; McLain, Jason; Achterberg, Richard; Flasar, F. Michael; Milam, Stefanie

2015-11-01

During southern autumn when sunlight was still available, Cassini's Imaging Science Subsystem discovered a cloud around 300 km near Titan's south pole (West, R. A. et al., AAS/DPS Abstracts, 45, #305.03, 2013); the cloud was later determined by Cassini's Visible and InfraRed Mapping Spectrometer to contain HCN ice (de Kok et al., Nature, 514, pp 65-67, 2014). This cloud has proven to be only the tip of an extensive ice cloud system contained in Titan's south polar stratosphere, as seen through the night-vision goggles of Cassini's Composite InfraRed Spectrometer (CIRS). As the sun sets and the gloom of southern winter approaches, evidence is beginning to accumulate from CIRS far-IR spectra that a massive system of nitrile ice clouds is developing in Titan's south polar stratosphere. Even during the depths of northern winter, nothing like the strength of this southern system was evident in corresponding north polar regions.From the long slant paths that are available from limb-viewing CIRS far-IR spectra, we have the first definitive detection of the ν6 band of cyanoacetylene (HC3N) ice in Titan’s south polar stratosphere. In addition, we also see a strong blend of nitrile ice lattice vibration features around 160 cm-1. From these data we are able to derive ice abundances. The most prominent (and still chemically unidentified) ice emission feature, the Haystack, (at 220 cm-1) is also observed. We establish the vertical distributions of the ice cloud systems associated with both the 160 cm-1 feature and the Haystack. The ultimate aim is to refine the physical and possibly the chemical relationships between the two. Transmittance thin film spectra of nitrile ice mixtures obtained in our Spectroscopy for Planetary ICes Environments (SPICE) laboratory are used to support these analyses.

Mass and Charge Transport in Electronically Conductive Polymers

DTIC Science & Technology

1990-08-02

This method is based on coating an electrode surface with an insulating nitrile butadiene rubber ( NBR ). The electrolyte for polymerization (LiCIO4...in acetonitrile) etches channels through the NBR ; pyrrole is then polymerized in these channels. After polymerization the NBR is extracted away with

Impact of thermal processing on sulforaphane yield from broccoli (Brassica oleracea L. var. italica)

USDA-ARS?s Scientific Manuscript database

In broccoli, sulforaphane forms when the glucosinolate glucoraphanin is hydrolyzed by the endogenous plant thiohydrolase myrosinase. A myrosinase cofactor directs hydrolysis away from formation of bioactive sulforaphane and toward an inactive product, sulforaphane nitrile. The cofactor is more hea...

21 CFR 177.1480 - Nitrile rubber modified acrylonitrile-methyl acrylate copolymers.

Code of Federal Regulations, 2014 CFR

2014-04-01

... content is in the range 16.5-19 percent as determined by Kjeldahl analysis. (ii) Intrinsic viscosity in... pass through a U.S. standard sieve No. 6 and that will be held on a U.S. standard sieve No. 10: (i...

Investigation on thermal oxidative aging of nitrile rubber (NBR) O-rings under compression stress

NASA Astrophysics Data System (ADS)

Liu, X. R.; Zhang, W. F.; Lou, W. T.; Huang, Y. X.; Dai, W.

2017-11-01

The degradation behaviors of nitrile rubber O-rings exposure to air under compression were investigated at three elevated temperatures. The physical and mechanical properties of the aging samples before and after exposure at selected time were studied by measuring weight loss, tensile strength and elongation at break. The Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and fracture morphology were used to reveal the microstructural changes of the aging samples. The results indicate that the weight decreased with exposure time and temperature. Based on the results of the crosslinking density, the crosslinking predominates during the most of aging process. The significant changes in tensile strength and elongation at break also indicate the severe degradation in air. The fracture morphology results show that the fracture surface after 64 days of exposure to air turns rough and present defects. The ATR-FTIR results demonstrate that the hydroxyl groups were formed for the samples aged in air.

Dermal in vitro penetration of methiocarb, paclobutrazol, and pirimicarb: effect of nonylphenolethoxylate and protective gloves.

PubMed Central

Nielsen, J B; Andersen, H R

2001-01-01

Dermal exposure has become the major route of human occupational exposure to pesticides. Detergents are used as part of formulated pesticide products and are known to change the barrier properties of human skin in vitro. However, studies on the influence of detergents as well as protective glove materials on dermal penetration of pesticides are scarce. In an experiment using in vitro static diffusion cells mounted with human skin, we evaluated the effect of nonylphenol-ethoxylate on dermal penetration of three extensively used pesticides--methiocarb, paclobutrazol, and pirimicarb--and the protection against dermal penetration offered by protective gloves made of latex or nitrile. There was a general tendency, though not statistically significant for all pesticides, for nonylphenolethoxylate to decrease the percutaneous penetration of the three pesticides. The nitrile generally offered better protection against percutaneous penetration of pesticides than did latex, but the degree of protection decreased over time and depended on the pesticides used. PMID:11266321

(Meth­oxy­methyl­idene)di­methyl­aza­nium tetra­phenyl­borate aceto­nitrile monosolvate

PubMed Central

Tiritiris, Ioannis; Saur, Stefan; Kantlehner, Willi

2014-01-01

In the cation of the title salt, C4H10NO+·C24H20B−·C2H3N, the C—N bond lengths are 1.2864 (16), 1.4651 (17) and 1.4686 (16) Å, indicating double- and single-bond character, respectively. The C—O bond length of 1.2978 (15) Å shows double-bond character, pointing towards charge delocalization within the NCO plane of the iminium ion. C—H⋯π inter­actions are present between the methine H atom and two of the phenyl rings of the tetra­phenyl­borate ion. The latter forms an aromatic pocket in which the cation is embedded. The iminium ion is further connected through a C—H⋯N hydrogen bond to the aceto­nitrile mol­ecule. This leads to the formation of a two-dimensional supramolecular pattern along the bc plane. PMID:24765028

Performance characteristics of rubber seed oil biodiesel

NASA Astrophysics Data System (ADS)

Liu, P.; Qin, M.; Wu, J.; Chen, B. S.

2018-01-01

The lubricity, ignition quality, oxidative stability, low temperature flow property and elastomeric compatibility of rubber seed oil biodiesel(RSM) were evaluated and compared with conventional petro-diesel. The results indicated that RSM and its blends with petro-diesel possessed outstanding lubricity manifested by sharp decrease in wear scar diameters in the high-frequency reciprocating rig(HFRR) testing. They also provided acceptable flammability and cold flow property,although the cetane numbers (CN) and cold filter plugging points(CFPP) of biodiesel blends slightly decreased with increasing contents of petro-diesel. However, RSM proved to be very susceptible to oxidation at elevated temperatures during prolonged oxidation durations, characterized by increased peroxide values, viscosity, acid values and isooctane insolubles. The oxidation stability of RSM could be significantly improved by antioxidants such as BD100, a phenol antioxidant produced by Ciba corporation. Furthermore, RSM provided poor compatibility with some elastomeric rubbers such as polyacrylate, nitrile-butadiene and chloroprene, but was well compatible with the hydrogenated nitrile-butadiene elastomer.

The rearrangements of naphthylnitrenes: UV/Vis and IR spectra of azirines, cyclic ketenimines, and cyclic nitrile ylides.

PubMed

Maltsev, Alexander; Bally, Thomas; Tsao, Meng-Lin; Platz, Matthew S; Kuhn, Arvid; Vosswinkel, Michael; Wentrup, Curt

2004-01-14

Ar matrix photolysis of 1- and 2-naphthyl azides 3 and 4 at 313 nm initially affords the singlet naphthyl nitrenes, (1)()1 and (1)()2. Relaxation to the corresponding lower energy, persistent triplet nitrenes (3)()1 and (3)()2 competes with cyclization to the azirines 15 and 18, which can also be formed photochemically from the triplet nitrenes. On prolonged irradiation, the azirines can be converted to the seven-membered cyclic ketenimines 10 and 13, respectively, as described earlier by Dunkin and Thomson. However, instead of the o-quinoid ketenimines 16 and 19, which are the expected primary ring-opening products of azirines 15 and 18, respectively, we observed their novel bond-shift isomers 17 and 20, which may be formally regarded as cyclic nitrile ylides. The existence of such ylidic heterocumulenes has been predicted previously, but this work provides the first experimental observation of such species. The factors which are responsible for the special stability of the ylidic species 17 and 20 are discussed.

Room temperature decarboxylative cyanation of carboxylic acids using photoredox catalysis and cyanobenziodoxolones: a divergent mechanism compared to alkynylation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc04907a Click here for additional data file.

PubMed Central

Le Vaillant, Franck; Wodrich, Matthew D.

2017-01-01

The one-step conversion of aliphatic carboxylic acids to the corresponding nitriles has been accomplished via the merger of visible light mediated photoredox and cyanobenziodoxolones (CBX) reagents. The reaction proceeded in high yields with natural and non-natural α-amino and α-oxy acids, affording a broad scope of nitriles with excellent tolerance of the substituents in the α position. The direct cyanation of dipeptides and drug precursors was also achieved. The mechanism of the decarboxylative cyanation was investigated both computationally and experimentally and compared with the previously developed alkynylation reaction. Alkynylation was found to favor direct radical addition, whereas further oxidation by CBX to a carbocation and cyanide addition appeared more favorable for cyanation. A concerted mechanism is proposed for the reaction of radicals with EBX reagents, in contrast to the usually assumed addition elimination process. PMID:28451301

Nitrogen isotope ratio and its evolution on Titan

NASA Astrophysics Data System (ADS)

Krasnopolsky, V.

2017-09-01

14N/15N ratios in the Sun, Jupiter, comets, and the inner planets indicate that Earth, Venus, and Mars got their nitrogen as N2 gas and NH3 ice in proportion 3 : 1. An alternative explanation is that planetesimals were another reservoir of N with 14N/15N = 270. 14N/15N = 168 in N2 and 60 in HCN on Titan, and the great difference is explained by strong enrichment in 15N by a factor of 8 in predissociation of N2 at 80-100 nm (Liang et al. 2007) and no fractionation in other 12 processes that form N. The calculated 14N/15N = 57 in nitriles, in perfect agreement with the observations. Modeling of nitrogen isotope fractionation by formation of nitriles and sputtering through the history of Titan with the much greater solar EUV and wind in the earlier epochs supports ammonia similar to that in comets as a source of nitrogen on Titan.

UV–Vis Light-induced Aging of Titan’s Haze and Ice

NASA Astrophysics Data System (ADS)

Couturier-Tamburelli, Isabelle; Piétri, Nathalie; Le Letty, Vincent; Chiavassa, Thierry; Gudipati, Murthy

2018-01-01

The study of the photochemical aging of aerosols is an important tool for understanding Titan’s stratosphere/troposphere composition and evolution, particularly the haze. Laboratory simulations of the photoreactivity of the haze aerosol analogs provide insight into the photochemical evolution of Titan’s atmosphere at and below the haze layers. Here we use experimental simulations to investigate the evolution of the laboratory analogs of these organic aerosols under ultraviolet (UV)–visible (Vis) photons, which make it through the haze layers during their sedimentation process. We present experimental results for the aging of Titan’s aerosol analogs obtained from two dominant nitrogen-containing organics, HC3N and HCN, under simulated Titan atmospheric conditions (photons and temperature). We report that volatile nitriles condensed on haze particles could be incorporated through photochemistry and provide one such sink mechanism for nitrile compounds. We provide laboratory evidence that the organic aerosols could photochemically evolve during their sedimentation through Titan’s atmosphere.

Activity Enhancement Based on the Chemical Equilibrium of Multiple-Subunit Nitrile Hydratase from Bordetella petrii.

PubMed

Liu, Yi; Liu, Ping; Lin, Lu; Zhao, Yueqin; Zhong, Wenjuan; Wu, Lunjie; Zhou, Zhemin; Sun, Weifeng

2016-09-01

The maturation mechanism of nitrile hydratase (NHase) of Pseudomonas putida NRRL-18668 was discovered and named as "self-subunit swapping." Since the NHase of Bordetella petrii DSM 12804 is similar to that of P. putida, the NHase maturation of B. petrii is proposed to be the same as that of P. putida. However, there is no further information on the application of NHase according to these findings. We successfully rapidly purified NHase and its activator through affinity his tag, and found that the cell extracts of NHase possessed multiple types of protein ingredients including α, β, α2β2, and α(P14K)2 who were in a state of chemical equilibrium. Furthermore, the activity was significantly enhanced through adding extra α(P14K)2 to the cell extracts of NHase according to the chemical equilibrium. Our findings are useful for the activity enhancement of multiple-subunit enzyme and for the first time significantly increased the NHase activity according to the chemical equilibrium.

Ionic Borate-Based Covalent Organic Frameworks: Lightweight Porous Materials for Lithium-Stable Solid State Electrolytes

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

Black, Hayden T.; Harrison, Katharine Lee

2016-10-01

The synthesis and characterization of the first polyelectrolyte of intrinsic microporosity (PEIM) is described. The novel material was synthesized via reaction between the nitrile group in the polymer backbone and n-butyl lithium, effectively anchoring an imine anion to the porous framework while introducing a mobile lithium counterion. The PEIM was characterized by 13C, 1H, and 7Li NMR experiments, revealing quantitative conversion of the nitrile functionality to the anionic imine. Variable temperature 7Li NMR analysis of the dry PEIM and the electrolyteswollen PEIM revealed that lithium ion transport within the dry PEIM was largely due to interchain hopping of the Limore » + ions, and that the mobility of polymer associated Li + was reduced after swelling in electrolyte solution. Meanwhile, the swollen PEIM supported efficient transport of dissolved Li + within the expanded pores. These results are discussed in the context of developing novel solid or solid-like lithium ion electrolytes using the new PEIM material.« less

Extraordinarily high conductivity of flexible adhesive films by hybrids of silver nanoparticle-nanowires

NASA Astrophysics Data System (ADS)

Muhammed Ajmal, C.; Mol Menamparambath, Mini; Ryeol Choi, Hyouk; Baik, Seunghyun

2016-06-01

Highly conductive flexible adhesive (CFA) film was developed using micro-sized silver flakes (primary fillers), hybrids of silver nanoparticle-nanowires (secondary fillers) and nitrile butadiene rubber. The hybrids of silver nanoparticle-nanowires were synthesized by decorating silver nanowires with silver nanoparticle clusters using bifunctional cysteamine as a linker. The dispersion in ethanol was excellent for several months. Silver nanowires constructed electrical networks between the micro-scale silver flakes. The low-temperature surface sintering of silver nanoparticles enabled effective joining of silver nanowires to silver flakes. The hybrids of silver nanoparticle-nanowires provided a greater maximum conductivity (54 390 S cm-1) than pure silver nanowires, pure multiwalled carbon nanotubes, and multiwalled carbon nanotubes decorated with silver nanoparticles in nitrile butadiene rubber matrix. The resistance change was smallest upon bending when the hybrids of silver nanoparticle-nanowires were employed. The adhesion of the film on polyethylene terephthalate substrate was excellent. Light emitting diodes were successfully wired to the CFA circuit patterned by the screen printing method for application demonstration.

Occurrence of enzymes involved in biosynthesis of indole-3-acetic acid from indole-3-acetonitrile in plant-associated bacteria, Agrobacterium and Rhizobium.

PubMed Central

Kobayashi, M; Suzuki, T; Fujita, T; Masuda, M; Shimizu, S

1995-01-01

The occurrence of a hitherto unknown pathway involving the action of two enzymes, a nitrile hydratase and an amidase for the biosynthesis of indole-3-acetic acid was discovered in phytopathogenic bacteria Agrobacterium tumefaciens and in leguminous bacteria Rhizobium. The nitrile hydratase acting on indole-3-acetonitrile was purified to homogeneity through only two steps from the cell-free extract of A. tumefaciens. The molecular mass of the purified enzyme estimated by HPLC was about 102 kDa, and the enzyme consisted of four subunits identical in molecular mass. The enzyme exhibited a broad absorption spectrum in the visible range with absorption maxima at 408 nm and 705 nm, and it contained cobalt and iron. The enzyme stoichiometrically catalyzed the hydration of indole-3-acetonitrile into indole-3-acetamide with a specific activity of 13.7 mol per min per mg and a Km of 7.9 microM. Images Fig. 1 PMID:11607511

From microporous regular frameworks to mesoporous materials with ultrahigh surface area: dynamic reorganization of porous polymer networks.

PubMed

Kuhn, Pierre; Forget, Aurélien; Su, Dangsheng; Thomas, Arne; Antonietti, Markus

2008-10-08

High surface area organic materials featuring both micro- and mesopores were synthesized under ionothermal conditions via the formation of polyaryltriazine networks. While the polytrimerization of nitriles in zinc chloride at 400 degrees C produces microporous polymers, higher reaction temperatures induce the formation of additional spherical mesopores with a narrow dispersity. The nitrogen-rich carbonaceous polymer materials thus obtained present surface areas and porosities up to 3300 m(2) g(-1) and 2.4 cm(3) g(-1), respectively. The key point of this synthesis relies on the occurrence of several high temperature polymerization reactions, where irreversible carbonization reactions coupled with the reversible trimerization of nitriles allow the reorganization of the dynamic triazine network. The ZnCl2 molten salt fulfills the requirement of a high temperature solvent, but is also required as catalyst. Thus, this dynamic polymerization system provides not only highly micro- and mesoporous materials, but also allows controlling the pore structure in amorphous organic materials.

ALMA observations of Titan : Vertical and spatial distribution of nitriles

NASA Astrophysics Data System (ADS)

Moreno, R.; Lellouch, E.; Vinatier, S.; Gurwell, M.; Moullet, A.; Lara, L. M.; Hidayat, T.

2015-10-01

We report submm observations of Titan performed with the ALMA interferometer centered at the rotational frequencies of HCN(4-3) and HNC(4-3), i.e. 354 and 362 GHz. These measurements yielded disk-resolved emission spectra of Titan with an angular resolution of ~0.47''. Titan's angular surface diameter was 0.77''. Data were acquired in summer 2012 near the greatest eastern and western elongations of Titan at a spectral resolution of 122 kHz (λ/d λ = 3106). We have obtained maps of several nitriles present in Titan' stratosphere: HCN, HC3N, CH3CN, HNC, C2H5CNand other weak lines (isotopes, vibrationnally excited lines).We will present radiative transfer analysis of the spectra acquired. With the combination of all these detected rotational lines, we will constrain the atmospheric temperature, the spatial and vertical distribution of these species, as well as isotopic ratios. Moreover, Doppler lineshift measurements will enable us to constrain the zonal wind flow in the upper atmosphere.

Nafion®-catalyzed microwave-assisted Ritter reaction: An atom-economic solvent-free synthesis of amides

EPA Science Inventory

An atom-economic solvent-free synthesis of amides by the Ritter reaction of alcohols and nitriles under microwave irradiation is reported. This green protocol is catalyzed by solid supported Nafion®NR50 with improved efficiency and reduced waste production.

Nanoparticle-supported and magnetically recoverable palladium (Pd) catalyst: a selective and sustainable oxidation protocol with high turnover number

EPA Science Inventory

A magnetic nanoparticle-supported ruthenium hydroxide catalyst was readily prepared from inexpensive starting materials and shown to catalyze hydration of nitriles with excellent yield in benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity...

Titan's organic aerosols: Molecular composition and structure of laboratory analogues inferred from pyrolysis gas chromatography mass spectrometry analysis

NASA Astrophysics Data System (ADS)

Morisson, Marietta; Szopa, Cyril; Carrasco, Nathalie; Buch, Arnaud; Gautier, Thomas

2016-10-01

Analogues of Titan's aerosols are of primary interest in the understanding of Titan's atmospheric chemistry and climate, and in the development of in situ instrumentation for future space missions. Numerous studies have been carried out to characterize laboratory analogues of Titan aerosols (tholins), but their molecular composition and structure are still poorly known. If pyrolysis gas chromatography mass spectrometry (pyr-GCMS) has been used for years to give clues about their chemical composition, highly disparate results were obtained with this technique. They can be attributed to the variety of analytical conditions used for pyr-GCMS analyses, and/or to differences in the nature of the analogues analyzed, that were produced with different laboratory set-ups under various operating conditions. In order to have a better description of Titan's tholin's molecular composition by pyr-GCMS, we carried out a systematic study with two major objectives: (i) exploring the pyr-GCMS analytical parameters to find the optimal ones for the detection of a wide range of chemical products allowing a characterization of the tholins composition as comprehensive as possible, and (ii) highlighting the role of the CH4 ratio in the gaseous reactive medium on the tholin's molecular structure. We used a radio-frequency plasma discharge to synthetize tholins with different concentrations of CH4 diluted in N2. The samples were pyrolyzed at temperatures covering the 200-700°C range. The extracted gases were then analyzed by GCMS for their molecular identification. The optimal pyrolysis temperature for characterizing the molecular composition of our tholins by GCMS analysis is found to be 600°C. This temperature choice results from the best compromise between the number of compounds released, the quality of the signal and the appearance of pyrolysis artifacts. About a hundred molecules are identified as pyrolysates. A common major chromatographic pattern appears clearly for all the samples even if the number of released compounds can significantly differ. The hydrocarbon chain content increases in tholins when the CH4 ratio increases. A semi-quantitative study of the nitriles (most abundant chemical family in our chromatograms) released during the pyrolysis shows the existence of a correlation between the amount of a nitrile released and its molecular mass, similarly to the previous quantification of nitriles in the plasma gas-phase. Moreover, numerous nitriles are present both in tholins and in the gas phase, confirming their suspected role in the gas phase as precursors of the solid organic particles.

Evaluation of Biobased Hydraulic Fluids in Military Construction Equipment

DTIC Science & Technology

2007-10-31

systems. They are basically divided into two groups. One is natural rubber and the other one is a synthetic elastomer. Their formulations and physical...compatibility test. This reference elastomer was specially formulated with Nitrile or Buna N ( NBR -L) material and is widely used in the many

Thermal Extraction–Two-Dimensional Gas Chromatography–Mass Spectrometry with Heart-Cutting for Nitrogen Heterocyclics in Biomass Burning Aerosols

EPA Science Inventory

A thermal extraction-two-dimensional gas chromatography-mass spectrometry (TE-GC-MS) method (with heart-cutting) is developed for quantitatively assessing nitrogen (N-bearing organic species (e.g., pyrrole, pyridine, nitriles, and amines) in aerosols emitted from agricultural fir...

Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst.

PubMed

Venkatesan, Shanmuganathan; Kumar, Annamalai Senthil; Lee, Jyh-Fu; Chan, Ting-Shan; Zen, Jyh-Myng

2012-05-14

The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

EPA Science Inventory

One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

The Reduction of a Nitrile (CN) Group by Sodium Borohydride. The Preparation of Phosphine--Amine and Phosphine--Iimidate Complesex of Tungsten Carbonyl.

ERIC Educational Resources Information Center

Faust, Kristen E.; Storhoff, Bruce N.

1989-01-01

Describes an experiment for advanced-level undergraduate students for extending student experiences involving recording and interpreting infrared (IR) and nuclear magnetic resonance (NMR) spectra from reactions of organometallic compounds. Experimental procedures, analyses and structural assignments, and suggestions for extension and modification…

A Convenient, TiCl4/SnCl4-Mediated Synthesis of N-Phenyl or N-Aryl Benzamidines and N-Phenylpicolinamidines

PubMed Central

Patil, Umesh D.; Mahulikar, Pramod P.

2012-01-01

A new, TiCl4-or SnCl4-mediated, solvent-free method was developed for the synthesis of N-Aryl benzamidines and N-phenylpicolinamidines, in moderate-to-good yield, using suitable amines and nitriles as starting materials. PMID:24052858

Could nitrile derivatives of turnip (Brassica rapa) glucosinolates be Hepato-and/or cholangiotoxic in cattle?

USDA-ARS?s Scientific Manuscript database

Turnip (Brassica rapa ssp. rapa) and rape (Brassica napus ssp. biennis) and other brassica forage crops are generally regarded as “safe” feed for cattle during late summer and fall in New Zealand. However, when Pithomyces chartarum spore counts are high there are epidemics of sporidesmin toxicity (...

The Application of Magnesium(I) Compounds to Energy Storage Materials - Phase 2

DTIC Science & Technology

2013-06-24

currently exploring the use of 10 as a catalyst for a number of other processes, e.g. the selective hydroboration of ketone , aldehydes and nitriles...hydroboration of ketones ; (vi) a variety of related results, including the preparation of an iron(I) dimer with the shortest Fe-Fe multiple bond

Biodegradation potential of cyano-based ionic liquid anions in a culture of Cupriavidus spp. and their in vitro enzymatic hydrolysis by nitrile hydratase.

PubMed

Neumann, Jennifer; Pawlik, Magdalena; Bryniok, Dieter; Thöming, Jorg; Stolte, Stefan

2014-01-01

Biodegradation tests with bacteria from activated sludge revealed the probable persistence of cyano-based ionic liquid anions when these leave waste water treatment plants. A possible biological treatment using bacteria capable of biodegrading similar compounds, namely cyanide and cyano-complexes, was therefore examined. With these bacteria from the genera Cupriavidus, the ionic liquid anions B(CN)₄(-), C(CN)₃(-), N(CN)₂(-) combined with alkaline cations were tested in different growth media using ion chromatography for the examination of their primary biodegradability. However, no enhanced biodegradability of the tested cyano-based ionic liquids was observed. Therefore, an in vitro enzymatic hydrolysis test was additionally run showing that all tested ionic liquid (IL) anions can be hydrolysed to their corresponding amides by nitrile hydratase, but not by nitrilase under the experimental conditions. The biological stability of the cyano-based anions is an advantage in technological application, but the occurrence of enzymes that are able to hydrolyse the parent compound gives a new perspective on future cyano-based IL anion treatment.

A molecular study of gas solubility in nitrile rubber

NASA Astrophysics Data System (ADS)

Khawaja, Musab; Mostofi, Arash; Sutton, Adrian

2015-03-01

One of the most important uses of elastomers in the oil industry is for seals to encase and protect sensitive monitoring equipment from contamination by gases and liquids at the high pressures and temperatures in the well. Failure of such seals sometimes occurs on decompression when they are returned to the surface. The conditions in the well lead to gases being absorbed by Nitrile rubber (NBR) seals. NBR exhibits a strong permselectivity towards CO2 compared to other gases; something attributed experimentally to the enhanced solubility of CO2. In this study an explanation is sought at the molecular level for this phenomenon. A series of molecular mechanics calculations are performed to compute solubilities of different gases in NBR. The effect of acrylonitrile content on their solubilities is studied for the first time by simulation, and we discuss the important issue of convergence with respect to the sampling of different elastomer configurations. It is observed that the presence of cyano groups has a marked impact on the solubility of CO2 and an explanation is offered.

Advanced Booster Composite Case/Polybenzimidazole Nitrile Butadiene Rubber Insulation Development

NASA Technical Reports Server (NTRS)

Gentz, Steve; Taylor, Robert; Nettles, Mindy

2015-01-01

The NASA Engineering and Safety Center (NESC) was requested to examine processing sensitivities (e.g., cure temperature control/variance, debonds, density variations) of polybenzimidazole nitrile butadiene rubber (PBI-NBR) insulation, case fiber, and resin systems and to evaluate nondestructive evaluation (NDE) and damage tolerance methods/models required to support human-rated composite motor cases. The proposed use of composite motor cases in Blocks IA and II was expected to increase performance capability through optimizing operating pressure and increasing propellant mass fraction. This assessment was to support the evaluation of risk reduction for large booster component development/fabrication, NDE of low mass-to-strength ratio material structures, and solid booster propellant formulation as requested in the Space Launch System NASA Research Announcement for Advanced Booster Engineering Demonstration and/or Risk Reduction. Composite case materials and high-energy propellants represent an enabling capability in the Agency's ability to provide affordable, high-performing advanced booster concepts. The NESC team was requested to provide an assessment of co- and multiple-cure processing of composite case and PBI-NBR insulation materials and evaluation of high-energy propellant formulations.

2 H-1,2,3-Triazole-Based Dipeptidyl Nitriles: Potent, Selective, and Trypanocidal Rhodesain Inhibitors by Structure-Based Design.

PubMed

Giroud, Maude; Kuhn, Bernd; Saint-Auret, Sarah; Kuratli, Christoph; Martin, Rainer E; Schuler, Franz; Diederich, François; Kaiser, Marcel; Brun, Reto; Schirmeister, Tanja; Haap, Wolfgang

2018-04-26

Macrocyclic inhibitors of rhodesain (RD), a parasitic cysteine protease and drug target for the treatment of human African trypanosomiasis, have shown low metabolic stability at the macrocyclic ether bridge. A series of acyclic dipeptidyl nitriles was developed using structure-based design (PDB ID: 6EX8 ). The selectivity against the closely related cysteine protease human cathepsin L (hCatL) was substantially improved, up to 507-fold. In the S2 pocket, 3,4-dichlorophenylalanine residues provided high trypanocidal activities. In the S3 pocket, aromatic residues provided enhanced selectivity against hCatL. RD inhibition ( K i values) and in vitro cell-growth of Trypanosoma brucei rhodesiense (IC 50 values) were measured in the nanomolar range. Triazole-based ligands, obtained by a safe, gram-scale flow production of ethyl 1 H-1,2,3-triazole-4-carboxylate, showed excellent metabolic stability in human liver microsomes and in vivo half-lives of up to 1.53 h in mice. When orally administered to infected mice, parasitaemia was reduced but without complete removal of the parasites.

Slip resistant properties of footwear on ice.

PubMed

Gao, Chuansi; Abeysekera, John; Hirvonen, Mikko; Grönqvist, Raoul

2004-05-15

Current research on slipperiness of footwear has mainly focused on floors and lubricated floors. Slips and falls on icy and snowy surfaces involve not only outdoor workers, but also pedestrians and the general public; and occur in cold regions and in winter season in many parts of the world. However, in comparison with the size of the problem, research on slips and falls on icy and snowy surfaces has been scarce. The objective of this paper is to explore the slip resistant properties of footwear (soling materials, roughness and hardness) on ice. The coefficients of kinetic friction of four different soling materials (synthetic rubber, nitrile rubber, natural rubber and polyurethane) were measured on ice (-12 degrees C). The outsole roughness and hardness were also measured. Results showed that the polyurethane soling did not perform better than synthetic rubber, nitrile rubber and natural rubber on pure hard ice (-12 degrees C). Soling roughness was positively correlated with the coefficient of kinetic friction. The most slip resistant soling material (polyurethane) on floors and lubricated floors may not provide sufficient slip resistance on ice.

Key intermediates in nitrogen transformation during microwave pyrolysis of sewage sludge: a protein model compound study.

PubMed

Zhang, Jun; Tian, Yu; Cui, Yanni; Zuo, Wei; Tan, Tao

2013-03-01

The nitrogen transformations with attention to NH3 and HCN were investigated at temperatures of 300-800°C during microwave pyrolysis of a protein model compound. The evolution of nitrogenated compounds in the char, tar and gas products were conducted. The amine-N, heterocyclic-N and nitrile-N compounds were identified as three important intermediates during the pyrolysis. NH3 and HCN were formed with comparable activation energies competed to consume the same reactive substances at temperatures of 300-800°C. The deamination and dehydrogenation of amine-N compounds from protein cracking contributed to the formation of NH3 (about 8.9% of Soy-N) and HCN (6.6%) from 300 to 500°C. The cracking of nitrile-N and heterocyclic-N compounds from the dehydrogenation and polymerization of amine-N generated HCN (13.4%) and NH3 (31.3%) between 500 and 800°C. It might be able to reduce the HCN and NH3 emissions through controlling the intermediates production at temperatures of 500-800°C. Copyright © 2013 Elsevier Ltd. All rights reserved.

Prediction of distal residue participation in enzyme catalysis

PubMed Central

Brodkin, Heather R; DeLateur, Nicholas A; Somarowthu, Srinivas; Mills, Caitlyn L; Novak, Walter R; Beuning, Penny J; Ringe, Dagmar; Ondrechen, Mary Jo

2015-01-01

A scoring method for the prediction of catalytically important residues in enzyme structures is presented and used to examine the participation of distal residues in enzyme catalysis. Scores are based on the Partial Order Optimum Likelihood (POOL) machine learning method, using computed electrostatic properties, surface geometric features, and information obtained from the phylogenetic tree as input features. Predictions of distal residue participation in catalysis are compared with experimental kinetics data from the literature on variants of the featured enzymes; some additional kinetics measurements are reported for variants of Pseudomonas putida nitrile hydratase (ppNH) and for Escherichia coli alkaline phosphatase (AP). The multilayer active sites of P. putida nitrile hydratase and of human phosphoglucose isomerase are predicted by the POOL log ZP scores, as is the single-layer active site of P. putida ketosteroid isomerase. The log ZP score cutoff utilized here results in over-prediction of distal residue involvement in E. coli alkaline phosphatase. While fewer experimental data points are available for P. putida mandelate racemase and for human carbonic anhydrase II, the POOL log ZP scores properly predict the previously reported participation of distal residues. PMID:25627867

Phase Equilibria and Transport Properties in the Systems AgNO3/RCN/H2O. R = CH3, C2H5, C3H7, C4H,, C6H5, and C6H5CH2

NASA Astrophysics Data System (ADS)

Das, Surjya P.; Wittekopf, Burghard; Weil, Konrad G.

1988-11-01

Silver nitrate can form homogeneous liquid phases with some organic nitriles and water, even when there is no miscibility between the pure liquid components. We determined the shapes of the single phase regions in the ternary phase diagram for the following systems: silver nitrate /RCN /H2O with R =CH3, C3H7, C6H5, and C6H5CH2 at room temperature and for R =C6H5 also at 60 °C and O °C. Furthermore we studied kinematic viscosities, electrical conductivities, and densities of mixtures containing silver nitrate, RCN, and water with the mole ratios X /4 /1 (0.2≦ X ≦S 3.4). In these cases also R = C2H5 and C4H9 were studied. The organic nitriles show different dependences of viscosity and conductivity on the silver nitrate content from the aliphatic ones.

A novel nitrilase from Rhodobacter sphaeroides LHS-305: cloning, heterologous expression and biochemical characterization.

PubMed

Wang, Hualei; Li, Guinan; Li, Mingyang; Wei, Dongzhi; Wang, Xuedong

2014-01-01

In this study, a novel nitrilase gene from Rhodobacter sphaeroides was cloned and overexpressed in Escherichia coli. The open reading frame of the nitrilase gene includes 969 base pairs, which encodes a putative polypeptide of 322 amino acid residues. The molecular weight of the purified native nitrilase was about 560 kDa determined by size exclusion chromatography. This nitrilase showed one single band on SDS-PAGE with a molecular weight of 40 kDa. This suggested that the native nitrilase consisted of 14 subunits with identical size. The optimal pH and temperature of the purified enzyme were 7.0 and 40 °C, respectively. The kinetic parameters V max and K m toward 3-cyanopyridine were 77.5 μmol min(-1) mg(-1) and 73.1 mmol/l, respectively. The enzyme can easily convert aliphatic nitrile and aromatic nitriles to their corresponding acids. Furthermore, this enzyme demonstrated regioselectivity in hydrolysis of aliphatic dinitriles. This specific characteristic makes this nitrilase have a great potential for commercial production of various cyanocarboxylic acids by hydrolyzing readily available dinitriles.

Effect of end-group cross-linking on transport properties of sulfonated poly(phenylene sulfide nitrile)s for proton exchange membranes

NASA Astrophysics Data System (ADS)

Kang, Na Rae; Lee, So Young; Shin, Dong Won; Hwang, Doo Sung; Lee, Kang Hyuck; Cho, Doo Hee; Kim, Ji Hoon; Lee, Young Moo

2016-03-01

A series of end-group cross-linked membranes (Az-XESPSN) were prepared by click reaction to investigate the effects of cross-linking on the morphology and proton transport properties of proton exchange membranes. The morphological transformations resulting from thermal annealing and cross-linking were observed by means of atomic force microscopy (AFM) and transmission electron microscopy (TEM). Compared to the non-cross-linked ESPSN membranes, the Az-XESPSN membranes exhibited lower water uptake and improved mechanical and chemical stabilities. In addition, the Az-XESPSN membranes exhibited higher proton conductivities (0.018-0.028 S cm-1) compared to those of the ESPSN membranes (0.0044-0.0053 S cm-1) and Nafion 212 (0.0061 S cm-1), particularly in conditions of elevated temperature (120 °C) and low relative humidity (35%). Such enhancements can be attributed to a synergistic effect of well-defined hydrophilic ionic clusters and triazole groups that function as proton carriers under anhydrous conditions. Furthermore, the Az-XESPSN membranes exhibited significantly enhanced single cell performance and long-term stability compared to those of ESPSN membranes.

Photoinduced intramolecular charge transfer and photophysical characteristics of (2Z)-3-[4-(dimethylamino) phenyl]-2-(2-methylphenyl) prop-2-ene-nitrile (DPM) in different media

NASA Astrophysics Data System (ADS)

Asiri, Abdullah M.; El-Daly, Samy A.; Alamry, Khalid A.; Arshad, Muhammad Nadeem; Pannipara, Mehboobali

2015-10-01

A new fluorophore, (2Z)-3-[4-(dimethylamino) phenyl]-2-(2-methylphenyl) prop-2-ene-nitrile (DPM), was synthesized by knoevenagel condensation of 4-(dimethylamino) benzaldehyde and 2-methylbenzyl cyanide in ethanol using NaOH as base. The electronic absorption and emission characteristic of DPM was studied in different solvents. The X-ray crystallographic structure of DPM was also investigated. A crystalline solid of DPM gives a strong green emission at about 533 nm; these phenomena are important for the application of DPM dye in organic photo emitting diode. DPM exhibits a red shift in its emission spectrum as solvent polarity increases, indicating a large change in the dipole moment of dye molecule upon excitation due to intramolecular charge transfer in excited DPM*. The fluorescence quantum yield depends strongly on the properties of the solvents, which was attributed to positive and negative solvatokinetic effects. The DPM dye displays solubilization in cationic (CTAB) micelle and could be used as a probe to determine the critical micelle concentration (CMC) of CTAB.

Chemical Resistance of Disposable Nitrile Gloves Exposed to Simulated Movement

PubMed Central

Phalen, Robert N.; Wong, Weng Kee

2012-01-01

Large discrepancies between laboratory permeation testing and field exposures have been reported, with indications that hand movement could account for a portion of these differences. This study evaluated the influence of simulated movement on chemical permeation of 30 different disposable nitrile glove products. Products were investigated out-of-box and with exposure to simulated whole-glove movement. Permeation testing was conducted using ethanol as a surrogate test chemical. A previously designed pneumatic system was used to simulate hand movement. No movement and movement tests were matched-paired to control for environmental conditions, as were statistical analyses. Permeation data were collected for a 30-min exposure period or until a breakthrough time (BT) and steady-state permeation rate (SSPR) could be determined. A third parameter, area under the curve at 30 min (AUC-30), was used to estimate potential worker exposure. With movement, a significant decrease in BT (p ≤ 0.05), ranging from 6–33%, was observed for 28 products. The average decrease in BT was 18% (p ≤ 0.001). With movement, a significant increase in SSPR (p ≤ 0.05), ranging from 1–78%, was observed with 25 products. The average increase in SSPR was 18% (p ≤ 0.001). Significant increases in AUC-30 (p ≤ 0.05), ranging from 23–277%, were also observed for all products where it could be calculated. On average, there was a 58% increase (p ≤ 0.001). The overall effect of movement on permeation through disposable nitrile gloves was significant. Simulated movement significantly shortened the BT, increased the SSPR, and increased the cumulative 30-min exposure up to three times. Product variability also accounted for large differences, up to 40 times, in permeation and cumulative exposure. Glove selection must take these factors into account. It cannot be assumed that all products will perform in a similar manner. PMID:23009187

Formation of nitrile species on Ag nanostructures supported on a-Al2O3: a new corrosion route for silver exposed to the atmosphere.

PubMed

Peláez, R J; Espinós, J P; Afonso, C N

2017-04-28

The aging of supported Ag nanostructures upon storage in ambient conditions (air and room temperature) for 20 months has been studied. The samples are produced on glass substrates by pulsed laser deposition (PLD); first a 15 nm thick buffer layer of amorphous aluminum oxide (a-Al 2 O 3 ) is deposited, followed by PLD of Ag. The amount of deposited Ag ranges from that leading to a discontinuous layer up to an almost-percolated layer with a thickness of <6 nm. Some regions of the as-grown silver layers are converted, by laser induced dewetting, into round isolated nanoparticles (NPs) with diameters of up to ∼25 nm. The plasmonic, structural and chemical properties of both as-grown and laser exposed regions upon aging have been followed using extinction spectroscopy, scanning electron microscopy and x-ray photoelectron spectroscopy, respectively. The results show that the discontinuous as-grown regions are optically and chemically unstable and that the metal becomes oxidized faster, the smaller the amount of Ag. The corrosion leads to the formation of nitrile species due to the reaction between NO x species from the atmosphere adsorbed at the surface of Ag, and hydrocarbons adsorbed in defects at the surface of the a-Al 2 O 3 layer during the deposition of the Ag nanostructures by PLD that migrate to the surface of the metal with time. The nitrile formation thus results in the main oxidation mechanism and inhibits almost completely the formation of sulphate/sulphide. Finally, the optical changes upon aging offer an easy-to-use tool for following the aging process. They are dominated by an enhanced absorption in the UV side of the spectrum and a blue-shift of the surface plasmon resonance that are, respectively, related to the formation of a dielectric overlayer on the Ag nanostructure and changes in the dimensions/features of the nanostructures, both due to the oxidation process.

Whole glove permeation of cyclohexanol through disposable nitrile gloves on a dextrous robot hand and comparison with the modified closed-loop ASTM F739 method 1. No fist clenching.

PubMed

Mathews, Airek R; Que Hee, Shane S

2017-04-01

The aim was to develop a whole glove permeation method for cyclohexanol to generate permeation parameter data for a non-moving dextrous robot hand (normalized breakthrough time t b , standardized breakthrough time t s , steady state permeation rate P s , and diffusion coefficient D). Four types of disposable powderless, unsupported, and unlined nitrile gloves from the same producer were investigated: Safeskin Blue and Kimtech Science Blue, Purple, and Sterling. The whole glove method developed involved a peristaltic pump for water circulation through chemically resistant Viton tubing to continually wash the inner surface of the test glove via holes in the tubing, a dextrous robot hand operated by a microprocessor, a chemically protective nitrile glove to protect the robot hand, an incubator to maintain 35°C temperature, and a hot plate to maintain 35°C at the sampling point of the circulating water. Aliquots of 1.0 mL were sampled at regular time intervals for the first 60 min followed by removal of 0.5 mL aliquots every hour to 8 hr. Quantification was by the internal standard method after gas chromatography-selective ion electron impact mass spectrometry using a non-polar capillary column. The individual glove values of t b and t s differed for the ASTM closed loop method except for Safeskin Blue, but did not for the whole glove method. Most of the kinetic parameters agreed within an order of magnitude for the two techniques. The order of most protective to least protective glove was Blue and Safeskin, then Purple followed by Sterling for the whole gloves. The analogous order for the modified F739 ASTM closed loop method was: Safeskin, Blue, Purple, and Sterling, almost the same as for the whole glove. The Sterling glove was "not recommended" from the modified ASTM data, and was "poor" from the whole glove data.

Vibrational Stark effect spectroscopy at the interface of Ras and Rap1A bound to the Ras binding domain of RalGDS reveals an electrostatic mechanism for protein-protein interaction.

PubMed

Stafford, Amy J; Ensign, Daniel L; Webb, Lauren J

2010-11-25

Electrostatic fields at the interface of the Ras binding domain of the protein Ral guanine nucleotide dissociation stimulator (RalGDS) with the structurally analogous GTPases Ras and Rap1A were measured with vibrational Stark effect (VSE) spectroscopy. Eleven residues on the surface of RalGDS that participate in this protein-protein interaction were systematically mutated to cysteine and subsequently converted to cyanocysteine in order to introduce a nitrile VSE probe in the form of the thiocyanate (SCN) functional group. The measured SCN absorption energy on the monomeric protein was compared with solvent-accessible surface area (SASA) calculations and solutions to the Poisson-Boltzmann equation using Boltzmann-weighted structural snapshots from molecular dynamics simulations. We found a weak negative correlation between SASA and measured absorption energy, indicating that water exposure of protein surface amino acids can be estimated from experimental measurement of the magnitude of the thiocyanate absorption energy. We found no correlation between calculated field and measured absorption energy. These results highlight the complex structural and electrostatic nature of the protein-water interface. The SCN-labeled RalGDS was incubated with either wild-type Ras or wild-type Rap1A, and the formation of the docked complex was confirmed by measurement of the dissociation constant of the interaction. The change in absorption energy of the thiocyanate functional group due to complex formation was related to the change in electrostatic field experienced by the nitrile functional group when the protein-protein interface forms. At some locations, the nitrile experiences the same shift in field when bound to Ras and Rap1A, but at others, the change in field is dramatically different. These differences identify residues on the surface of RalGDS that direct the specificity of RalGDS binding to its in vivo binding partner, Rap1A, through an electrostatic mechanism.

Spectral and Vertical Distribution Properties of Titan's Particulates from Thermal-IR CIRS Data: Physical Implications

NASA Technical Reports Server (NTRS)

Anderson, Carrie M.; Samuelson, Robert; Vinatier, Sandrine

2011-01-01

Analyses of far-IR spectra between 20 and 560/cm (500 and 18 micron) recorded by the Cassini Composite Infrared Spectrometer (CIRS) yield the spectral dependence and the vertical distribution of Titan's photochemical aerosol and stratospheric ice clouds. Below the stratopause (approx. 300 km) the aerosol appears to be incompletely mixed for the following reasons: 1) the altitude dependence of the aerosol mass absorption coefficient is larger at higher altitudes than at lower altitudes, 2} the aerosol scale height varies with altitude, which implies some kind of layering effect, and 3) the aerosol abundance varies with latitude. The spectral shape of the aerosol opacity appears to be independent in altitude and latitude below the stratopause, even though inhomogeneities in the abundance appear to be prevalent throughout this altitude region. This implies that aerosol chemistry is restricted to altitude regions above the stratopause, where pressures are less than approx 0.1 mbar. The aerosol exhibits an extremely broad emisSion feature with a spectral peak at 140/cm (71 micron), which is not evident in laboratory simulated Titan aerosols (tholin) that are created at pressures greater than 0.1 mbar. A strong broad emission feature centered roughly around 160 cm-1 corresponds very closely to those found in nitrile ice spectra. This feature is pervasive throughout the region from high northern to high southern latitudes. The inference of nitrile ices is consistent with the highly restricted altitude ranges over which these features are observed, and appear to be dominated by HCN and HC3N. At low and moderate latitudes these clouds are observed to be located between 60 and 100 km, whereas at high northern latitudes during northern winter these clouds are observed at altitudes between 150 and 165 km. The ubiquitous nature of these nitrile ice clouds is inconsistent with a simple meridional circulation concept, suggesting that the true dynamical situation is more complex.

2-[(4-Benzhydrylpipérazin-1-yl)méthyl]acrylonitrile

PubMed Central

Ben Amor, Fatma; Ould M’hamed, Mohamed; Mrabet, Hédi; Driss, Ahmed; Efrit, Mohamed Lotfi

2008-01-01

In the title compound, 2-[(4-benz­hydryl­piperazin-1-yl)­methyl]­acrylo­nitrile, C21H23N3, the substituted piperazine ring adopts a chair conformation and the dihedral angle between the mean planes of the aromatic rings is 71.61 (8)°. PMID:21201087

Enhanced Stability of PtRu Supported on N-Doped Carbon for the Anode of a DMFC

DTIC Science & Technology

2012-09-18

nitrogen functionalities are most likely limited to pyrrolic , N-C=O and amine groups. In the case of PtRu/C (N- doped), the ion implantation introduces...suggesting the presence of graphitic, quaternary, pyridinic, C-N=O, pyrrolic , amine and nitrile groups.32,46 Initial DMFC performance and electrochemical

Developing kairomone-based lures and traps targeting female Spilonota ocellana (Lepidoptera: Tortricidae) in apple orchards treated with ex pheromones

USDA-ARS?s Scientific Manuscript database

Spilonota ocellana (Denis and Schiffermüller) can be a serious pest of organic apples in British Columbia. Recent discovery that S. ocellana moths are attracted by a lure combining acetic acid (AA) and benzyl nitrile (BN), a caterpillar-induced apple leaf volatile, provides an opportunity to develo...

Chemical constituents of Bauhinia aurea.

PubMed

Shang, Xiao-Ya; Li, Shuai; Wang, Su-Juan; Yang, Yong-Chun; Shi, Jian-Gong

2012-01-01

A new dihydroflavonol glycoside dimer 6,6-bisastilbin (1) and a new nitrile-containing metabolite (Z)-5α,6β-dihydroxy-4β-methoxy-2-cyclohexene-Δ(1,α)-acetonitrile (2), together with three known analogs, bauhinin, bauhinilide, and dehydrodicatechin A, have been isolated from an ethanol extract of Bauhinia aurea. Their structures were determined by spectroscopic and chemical methods.

21 CFR 573.310 - Crambe meal, heat toasted.

Code of Federal Regulations, 2012 CFR

2012-04-01

...; oil, not more than 4 percent; crude protein, not less than 24 percent; crude fiber, not more than 26 percent; glucosinolate calculated as epi-progoitrin, not more than 4 percent; goitrin, not more than 0.1 percent; nitrile calculated as 1-cyano-2-hydroxy-3-butene, not more than 1.4 percent. At least 50 percent...

21 CFR 573.310 - Crambe meal, heat toasted.

Code of Federal Regulations, 2010 CFR

2010-04-01

...; oil, not more than 4 percent; crude protein, not less than 24 percent; crude fiber, not more than 26 percent; glucosinolate calculated as epi-progoitrin, not more than 4 percent; goitrin, not more than 0.1 percent; nitrile calculated as 1-cyano-2-hydroxy-3-butene, not more than 1.4 percent. At least 50 percent...

21 CFR 573.310 - Crambe meal, heat toasted.

Code of Federal Regulations, 2013 CFR

2013-04-01

...; oil, not more than 4 percent; crude protein, not less than 24 percent; crude fiber, not more than 26 percent; glucosinolate calculated as epi-progoitrin, not more than 4 percent; goitrin, not more than 0.1 percent; nitrile calculated as 1-cyano-2-hydroxy-3-butene, not more than 1.4 percent. At least 50 percent...

21 CFR 573.310 - Crambe meal, heat toasted.

Code of Federal Regulations, 2014 CFR

2014-04-01

...; oil, not more than 4 percent; crude protein, not less than 24 percent; crude fiber, not more than 26 percent; glucosinolate calculated as epi-progoitrin, not more than 4 percent; goitrin, not more than 0.1 percent; nitrile calculated as 1-cyano-2-hydroxy-3-butene, not more than 1.4 percent. At least 50 percent...

21 CFR 573.310 - Crambe meal, heat toasted.

Code of Federal Regulations, 2011 CFR

2011-04-01

...; oil, not more than 4 percent; crude protein, not less than 24 percent; crude fiber, not more than 26 percent; glucosinolate calculated as epi-progoitrin, not more than 4 percent; goitrin, not more than 0.1 percent; nitrile calculated as 1-cyano-2-hydroxy-3-butene, not more than 1.4 percent. At least 50 percent...

Undergraduate Organic Experiment: Tetrazole Formation by Microwave Heated (3 + 2) Cycloaddition in Aqueous Solution

ERIC Educational Resources Information Center

DeFrancesco, Heather; Dudley, Joshua; Coca, Adiel

2018-01-01

An undergraduate experiment for the organic laboratory is described that utilizes microwave heating to prepare 5- substituted 1H-tetrazole derivatives through a (3 + 2) cycloaddition between aryl nitriles and sodium azide. The reaction mixture is analyzed by thin layer chromatography. The products are purified through an acid-base extraction and…

How primitive are the gases in Titan's atmosphere?

PubMed

Owen, T

1987-01-01

Titan's atmosphere contains a mixture of nitrogen, methane, argon, hydrogen, simple hydrocarbons and nitriles, carbon monoxide, and carbon dioxide. Sources of nitrogen may be as a product of the photodissociation of ammonia or trapped in the ices that formed the satellite. Reasons for the abundance of deuterium are examined and its association with nitrogen on Titan is explained.

Composite Material Hazard Assessment at Crash Sites

DTIC Science & Technology

2015-01-01

advanced composite materials. All personnel involved in rescue in close crash-site proximity are required to wear self -contained breathing apparatus...close crash-site proximity are required to wear self -contained breathing apparatus, chemical protective clothing, leather gloves, and neoprene...Take extra precaution when handling these materials. Nitrile rubber gloves can be worn underneath the leather gloves to provide chemical hazard

Sinterable Ceramic Powders from Laser-Heated Gases.

DTIC Science & Technology

1988-02-01

ether . carboxylic acid. and aldehyde clases: water is also included.Acrigto William and Goodman.’ a single crystalline sili- The single-crstalline...represent commonly available organic families, Including aliphatic and aromatic hydrocarbons, chlorides, ethers , ketones , esters, alcohols, aldehydes...Hydrocarbons Ketone Amine Chlorides Low-alcohols 8f . Ether Ester - _Aldehyde Ether Ketones High-alcohols 04 Carboxylic Ester I acid Ether o . Nitrile

Multicomponent Macrocyclization Reactions (MCMRs) Employing Highly Reactive Acyl Ketene and Nitrile Oxide Intermediates

PubMed Central

Knapp, John M.; Fettinger, James C.; Kurth, Mark J.

2011-01-01

An efficient synthesis of spiro-fused macrolactams by a multicomponent macrocyclization reaction (MCMR) is reported. The use of highly reactive, transient intermediates in this MCMR permits short reaction times, even at high dilution. The methods employed for this MCMR were first developed as a four component strategy for the synthesis of β-ketoamide isoxazolines. PMID:21827181

Wear resistance and friction reduction in acrylo nitrile butadiene rubber through hybrid combination of graphite flakes and nano tungsten disulphide

NASA Astrophysics Data System (ADS)

Agrawal, Neha; Pandey, Akanksha; Parihar, A. S.; Mishra, A. K.; Gandhi, M. N.; Bhattacharyya, A. R.; Mukhopadhyay, K.; Prasad, N. E.

2016-05-01

Friction and wear have considerable role in the life span of two interacting parts. Incorporation of nanofillers in polymers/elastomers matrix causes commendable changes in its tribologicalproperties. The main purpose of this work is to reduce the coefficient of friction and wear rate of Acrylo Nitrile Butadiene rubber (NBR). To achieve such objective traditionally well knownlubricants graphite(G), tungsten disulphide (WS2) and there hybrid combination was incorporated in NBR matrix. Effect of applied load (force) and concentration of fillers on tribological properties of NBR had been studied. The filler incorporation enhanced the hardnessby 8%, showed resistance to hydraulic oil and aging effect also got improved significantly. A particular optimized concentration of NBR with hybrid combination of 2% WS2 and 4% Graphite showed minimum coefficient of friction as well as wear rate. A hypothesis could be attributed that similar lamellar structure of WS2 and Graphite along with formation of a stable nanoscale disulfide tribofilmcould result in lowering of friction. These substantially improved properties of nanoreinforced rubber materials would definitely pave promising path for plethora of potential technological applications.

High performance light-colored nitrile-butadiene rubber nanocomposites.

PubMed

Lei, Yanda; Guo, Baochun; Chen, Feng; Zhu, Lixin; Zhou, Wenyou; Jia, Demin

2011-12-01

High mechanical performance nitrile-butadiene rubber (NBR) with light color was fabricated by the method of in situ formation of zinc disorbate (ZDS) or magnesium disorbate (MDS). The in situ formed ZDS and its polymerization via internal mixing was confirmed by X-ray diffaraction. The mechanical properties, ageing resistance, morphology and the dynamic mechanical analysis were fully studied. It was found that with increasing loading of metallic disorbate both the curing rate and the ionic crosslink density was largely increased. The modulus, tensile strength and tear strength were largely increased. With a comparison between internal mixing and opening mixing, the mechanical performance for the former one was obviously better than the latter one. The high performance was ascribed to the finely dispersion nano domains with irregular shape and obscure interfacial structures. Except for the NBR vulcanizate with a high loading of MDS, the others' ageing resistance with incorporation of these two metallic disorbate was found to be good. Dynamic mechanical analysis (DMA) showed that, with increasing loading of metallic disorbate, the highly increased storage modulus above -20 degrees C, the up-shifted glass transition temperature (Tg) and the reduced mechanical loss were ascribed to strengthened interfacial interactions.

[Identification of migrants from nitrile-butadiene rubber gloves].

PubMed

Mutsuga, Motoh; Kawamura, Yoko; Wakui, Chiseko; Maitani, Tamio

2003-04-01

Polyvinyl chloride gloves containing di(2-ethylhexyl) phthalate are restricted for food contact use. In their place, disposable gloves made from nitrile-butadiene rubber (NBR) are used in contact with foodstuffs. Some unknown substances were found to migrate into n-heptane from NBR gloves. By GC/MS, HR-MS and NMR, their chemical structures were confirmed to be 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (used as a plasticizer), 4,4'-butylidenedi(6-tert-butyl-m-cresol), a mixture of styrenated phenols consisting of 2-(alpha-methylbenzyl)phenol, 4-(alpha-methylbenzyl)phenol, 2,6-di(alpha-methylbenzyl)phenol, 2,4-di(alpha-methylbenzyl)phenol and 2,4,6-tri(alpha-methylbenzyl)phenol (used as antioxidants), and 2,4-di-tert-butylphenol, which seems to a degradation product of antioxidant. Migration levels of these compounds were 1.68 micrograms/cm2 of 2,4-di-tert-butylphenol, 2.80 micrograms/cm2 of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 46.08 micrograms/cm2 of styrenated phenols and 4.22 micrograms/cm2 of 4,4'-butylidenedi(6-tert-butyl-m-cresol) into n-heptane, respectively. The content of total styrenated phenols was 6,900 micrograms/g in NBR gloves.

Improving Thermo-Oxidative Stability of Nitrile Rubber Composites by Functional Graphene Oxide.

PubMed

Zhong, Rui; Zhang, Zhao; Zhao, Hongguo; He, Xianru; Wang, Xin; Zhang, Rui

2018-05-30

Graphene oxide (GO), modified with anti-aging agent p -phenylenediamine (PPD), was added into nitrile rubber (NBR) in order to improve the thermo-oxidative stability of NBR. The modification of GO and the transformation of functional groups were characterized by Fourier transform infrared spectroscopy (FTIR), Raman, and X-ray diffraction (XRD). Mechanical performances of NBR composites before and after the thermo-oxidative aging were recorded. The results of dynamic mechanical analysis (DMA) show an increased storage modulus (G') and a decreased value of area of tan δ peak after introducing modified GO into NBR. It indicates that filler particles show positive interaction with molecular chains. The thermo-oxidative stability of composites was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). Then, the thermo-oxidative aging kinetic parameters were obtained by the Flynn⁻Wall⁻Ozawa (FWO) equation. The results of aging tests show that the thermo-oxidative stability of rubber matrix increases obviously after introducing GO⁻PPD. In addition, mechanical properties (tensile strength and elongation at break) of both before and after aged NBR/GO⁻PPD composites were superior to that of NBR. This work provides meaningful guidance for achieving multifunction thermo-oxidative aging resistance rubber composites.

Predicting the solubility of gases in Nitrile Butadiene Rubber in extreme conditions using molecular simulation

NASA Astrophysics Data System (ADS)

Khawaja, Musab; Molinari, Nicola; Sutton, Adrian; Mostofi, Arash

In the oil and gas industry, elastomer seals play an important role in protecting sensitive monitoring equipment from contamination by gases - a problem that is exacerbated by the high pressures and temperatures found down-hole. The ability to predict and prevent such permeative failure has proved elusive to-date. Nitrile butadiene rubber (NBR) is a common choice of elastomer for seals due to its resistance to heat and fuels. In the conditions found in the well it readily absorbs small molecular weight gases. How this behaviour changes quantitatively for different gases as a function of temperature and pressure is not well-understood. In this work a series of fully atomistic simulations are performed to understand the effect of extreme conditions on gas solubility in NBR. Widom particle insertion is used to compute solubilities. The importance of sampling and allowing structural relaxation upon compression are highlighted, and qualitatively reasonable trends reproduced. Finally, while at STP it has previously been shown that the solubility of CO2 is higher than that of He in NBR, we observe that under the right circumstances it is possible to reverse this trend.

Structural and Spectroscopic Analysis of the Kinase Inhibitor Bosutinib and an Isomer of Bosutinib Binding to the Abl Tyrosine Kinase Domain

PubMed Central

Levinson, Nicholas M.; Boxer, Steven G.

2012-01-01

Chronic myeloid leukemia (CML) is caused by the kinase activity of the BCR-Abl fusion protein. The Abl inhibitors imatinib, nilotinib and dasatinib are currently used to treat CML, but resistance to these inhibitors is a significant clinical problem. The kinase inhibitor bosutinib has shown efficacy in clinical trials for imatinib-resistant CML, but its binding mode is unknown. We present the 2.4 Å structure of bosutinib bound to the kinase domain of Abl, which explains the inhibitor's activity against several imatinib-resistant mutants, and reveals that similar inhibitors that lack a nitrile moiety could be effective against the common T315I mutant. We also report that two distinct chemical compounds are currently being sold under the name “bosutinib”, and report spectroscopic and structural characterizations of both. We show that the fluorescence properties of these compounds allow inhibitor binding to be measured quantitatively, and that the infrared absorption of the nitrile group reveals a different electrostatic environment in the conserved ATP-binding sites of Abl and Src kinases. Exploiting such differences could lead to inhibitors with improved selectivity. PMID:22493660

Wear resistance and friction reduction in acrylo nitrile butadiene rubber through hybrid combination of graphite flakes and nano tungsten disulphide

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

Agrawal, Neha, E-mail: neha87bhu@gmail.com; Indian Institute of Technology Bombay, Powai, Mumbai 400076, Maharashtra; Pandey, Akanksha

Friction and wear have considerable role in the life span of two interacting parts. Incorporation of nanofillers in polymers/elastomers matrix causes commendable changes in its tribologicalproperties. The main purpose of this work is to reduce the coefficient of friction and wear rate of Acrylo Nitrile Butadiene rubber (NBR). To achieve such objective traditionally well knownlubricants graphite(G), tungsten disulphide (WS{sub 2}) and there hybrid combination was incorporated in NBR matrix. Effect of applied load (force) and concentration of fillers on tribological properties of NBR had been studied. The filler incorporation enhanced the hardnessby 8%, showed resistance to hydraulic oil and agingmore » effect also got improved significantly. A particular optimized concentration of NBR with hybrid combination of 2% WS{sub 2} and 4% Graphite showed minimum coefficient of friction as well as wear rate. A hypothesis could be attributed that similar lamellar structure of WS{sub 2} and Graphite along with formation of a stable nanoscale disulfide tribofilmcould result in lowering of friction. These substantially improved properties of nanoreinforced rubber materials would definitely pave promising path for plethora of potential technological applications.« less

Ruthenium-Catalyzed Cycloaddition of 1-Haloalkynes with Nitrile Oxides and Organic Azides; Synthesis of 4-Halo Isoxazoles and 5-Halo Triazoles

PubMed Central

Oakdale, James S.; Sit, Rakesh K.

2015-01-01

(Cyclopentadienyl)(cyclooctadiene) ruthenium(II) chloride [CpRuCl(cod)] catalyzes the reaction between nitrile oxides and electronically deficient 1-choro-, 1-bromo- and 1-iodoalkynes leading to 4-haloisoxazoles. Organic azides are also suitable 1,3-dipoles, resulting in 5-halo-1,2,3-triazoles. These air tolerant reactions can be performed at room temperature with 1.25 equiv of the respective 1,3-dipole relative to the alkyne component. Reactive 1-haloalkynes include propiolic amides, esters, ketones and phosphonates. Post-functionalization of the halogenated azole products can be accomplished using palladium-catalyzed cross-coupling reactions as well as via manipulation of reactive amide groups. The lack of catalysis observed with Cp*RuCl(cod) is attributed to steric demands of the Cp* (η5-C5Me5) ligand in comparison to the parent Cp (η5-C5H5). This hypothesis is supported by the poor reactivity of (η5-C5Me4CF3)RuCl(cod), which serves as a an isosteric mimic of Cp* and as an isoelectronic analog of Cp. PMID:25059647

Oxygen-Free Biochemistry: The Putative CHN Foundation for Exotic Life in a Hydrocarbon World?

PubMed

Lv, Kong-Peng; Norman, Lucy; Li, Yi-Liang

2017-11-01

Since Earth's biochemistry is carbon-based and water-borne, the main strategies for searching for life elsewhere are "follow the carbon" and "follow the water." Recently, however, there is a growing focus on the prospect that putative exotic life on other planets could rely on unearthly biochemistries. Here, we hypothesize a novel oxygen-free organic chemistry for supporting potential exotic biosystems, which is named CHN biochemistry. This oxygen-free CHN biochemistry starts from simple oxygen-free species (including hydrocarbons, hydrogen cyanide, and nitriles) and produces a range of functional macromolecules that may function in similar ways to terran macromolecules, such as sugars (cyanosugars), acids (cyanoacids), amino acids (amino cyanoacids), and nucleobases (cyanonucleobases). These CHN macromolecules could further interact with each other to generate higher "cyanoester" and "cyanoprotein" systems. In addition, theoretical calculations indicate that the energy changes of some reactions are consistent with their counterparts in Earth's biochemistry. The CHN biochemistry-based life would be applicable in habitats with a low bioavailability of oxygen, such as the alkane lakes of Titan and non-aquatic liquids on extrasolar bodies. Key Words: Oxygen-free biochemistry-Titan-Hydrocarbons-Hydrogen cyanide-Nitriles. Astrobiology 17, 1173-1181.

Acrylate-induced allergic contact dermatitis in a car windscreen repairer.

PubMed

Fremlin, G; Sansom, J

2014-10-01

We report a case of an allergic skin reaction to ultraviolet-cured acrylates in a windscreen repair worker. The patient presented with a 6 month history of fingertip dryness, vesicles and desquamation. He had worked as a self-employed car windscreen repairer for 19 years. Previous management with vinyl glove protection and treatment with clobetasol propionate ointment had produced little improvement. He was patch tested to the British Society for Cutaneous Allergy standard and preservatives series and to the two acrylates used in his work environment, identified using safety data sheets, methyl methacrylate 2% pet and 2-hydroxyethylmethacrylate (2-HEMA) 2% pet. A positive reaction was seen at Day 4 to 2-HEMA, but all other patch tests were negative. An occupational allergic contact dermatitis to 2-HEMA was diagnosed. The patient was given avoidance advice and advised to use nitrile gloves. Although he was unable to give up his current work, he has continued his job using nitrile gloves with marked improvement. © The Author 2014. Published by Oxford University Press on behalf of the Society of Occupational Medicine. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Prediction of distal residue participation in enzyme catalysis.

PubMed

Brodkin, Heather R; DeLateur, Nicholas A; Somarowthu, Srinivas; Mills, Caitlyn L; Novak, Walter R; Beuning, Penny J; Ringe, Dagmar; Ondrechen, Mary Jo

2015-05-01

A scoring method for the prediction of catalytically important residues in enzyme structures is presented and used to examine the participation of distal residues in enzyme catalysis. Scores are based on the Partial Order Optimum Likelihood (POOL) machine learning method, using computed electrostatic properties, surface geometric features, and information obtained from the phylogenetic tree as input features. Predictions of distal residue participation in catalysis are compared with experimental kinetics data from the literature on variants of the featured enzymes; some additional kinetics measurements are reported for variants of Pseudomonas putida nitrile hydratase (ppNH) and for Escherichia coli alkaline phosphatase (AP). The multilayer active sites of P. putida nitrile hydratase and of human phosphoglucose isomerase are predicted by the POOL log ZP scores, as is the single-layer active site of P. putida ketosteroid isomerase. The log ZP score cutoff utilized here results in over-prediction of distal residue involvement in E. coli alkaline phosphatase. While fewer experimental data points are available for P. putida mandelate racemase and for human carbonic anhydrase II, the POOL log ZP scores properly predict the previously reported participation of distal residues. 2015 The Authors Protein Science published by Wiley Periodicals, Inc. on behalf of The Protein Society.

Two new polytypes of 2,4,6-tri­bromo­benzo­nitrile

PubMed Central

Britton, Doyle; Noland, Wayland E.; Tritch, Kenneth J.

2016-01-01

Three polymorphs of 2,4,6-tri­bromo­benzo­nitrile (RCN), C7H2Br3N, two of which are novel and one of which is a redetermination of the original structure first determined by Carter & Britton [(1972). Acta Cryst. B28, 945–950] are found to be polytypic. Each has a layer structure which differs only in the stacking of the layers. Each layer is composed of mol­ecules associated through C≡N⋯Br contacts which form R 2 2(10) rings. Two such rings are associated with each N atom; one with each ortho-Br atom. No new polytypes of 1,3,5-tri­bromo-2-iso­cyano­benzene (RNC) were found but a re-determination of the original structure by Carter et al. [(1977). Cryst. Struct. Commun. 6, 543–548] is presented. RNC was found to be isostructural with one of the novel polytypes of RCN. Unit cells were determined for 23 RCN samples and 11 RNC samples. Polytypes could not be distinguished based on crystal habits. In all four structures, each mol­ecule of the asymmetric unit lies across a mirror plane. PMID:26958382

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

PubMed

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

2012-06-27

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

The physical and degradation properties of starch-graft-acrylonitrile/carboxylated nitrile butadiene rubber latex films.

PubMed

Misman, M A; Azura, A R; Hamid, Z A A

2015-09-05

Starch-graft-acrylonitrile (ANS) is compounded with carboxylated nitrile butadiene rubber (XNBR) latex. The control XNBR and the ANS/XNBR latex films were prepared through a coagulant dipping process. The films were subjected to ageing and soil burial procedures. For the biodegradation experiment, the surface of the film was assessed after the 2nd, 4th and 8th week of soil burial. The ANS, XNBR, and ANS/XNBR colloidal stability were determined with a Malvern Zetasizer. For the dipped latex films, the mechanical, morphological and thermal properties were analyzed. The addition of ANS into the XNBR latex increased the stability of the colloidal dispersions, decreased the latex film tensile strength, but increased the elongation at break due to the bipolar interaction of the ANS and XNBR particles. The ANS/XNBR latex films aged faster than the control films while the morphological analysis showed the existence of a starch crystal region and the formation of microbial colonies on the surfaces of the films. Based on the TGA-DTA curves, a higher ΔT was observed for the ANS/XNBR latex films signifying high thermal energy needed for the film to thermally degrade. Copyright © 2015 Elsevier Ltd. All rights reserved.

Composites Based on Core-Shell Structured HBCuPc@CNTs-Fe3O4 and Polyarylene Ether Nitriles with Excellent Dielectric and Mechanical Properties

NASA Astrophysics Data System (ADS)

Pu, Zejun; Zhong, Jiachun; Liu, Xiaobo

2017-10-01

Core-shell structured magnetic carbon nanotubes (CNTs-Fe3O4) coated with hyperbranched copper phthalocyanine (HBCuPc) (HBCuPc@CNTs-Fe3O4) hybrids were prepared by the solvent-thermal method. The results indicated that the HBCuPc molecules were decorated on the surface of CNTs-Fe3O4 through coordination behavior of phthalocyanines, and the CNTs-Fe3O4 core was completely coaxial wrapped by a functional intermediate HBCuPc shell. Then, polymer-based composites with a relatively high dielectric constant and low dielectric loss were fabricated by using core-shell structured HBCuPc@CNTs-Fe3O4 hybrids as fillers and polyarylene ether nitriles (PEN) as the polymer matrix. The cross-sectional scanning electron microscopy (SEM) images of composites showed that there is almost no agglomeration and internal delamination. In addition, the rheological analysis reveals that the core-shell structured HBCuPc@CNTs-Fe3O4 hybrids present better dispersion and stronger interface adhesion with the PEN matrix than CNTs-Fe3O4, thus resulting in significant improvement of the mechanical, thermal and dielectric properties of polymer-based composites.

Fluorogenic Strain-Promoted Alkyne-Diazo Cycloadditions

PubMed Central

Friscourt, Frédéric; Fahrni, Christoph J.; Boons, Geert-Jan

2016-01-01

Fluorogenic reactions in which non- or weakly-fluorescent reagents produce highly fluorescent products are attractive for detecting a broad range of compounds in the fields of bio-conjugation and material sciences. We report here that Fl-DIBO, a dibenzocyclooctyne derivative modified with a cyclopropenone moiety, can undergo fast strain-promoted cycloadditions under catalyst-free conditions with azides, nitrones, nitrile oxides as well as mono- and disubstituted diazo-derivatives. While the reaction with nitrile oxides, nitrones and disubstituted diazo compounds gave cycloadducts with low quantum yield, monosubstituted diazo reagents produced 1H-pyrazole derivatives that exhibited a ~160-fold fluorescence enhancement over Fl-DIBO combined with a greater than 10,000-fold increase in brightness. Concluding from quantum chemical calculations, fluorescence quenching of 3H-pyrazoles, which are formed by reaction with disubstituted diazo-derivatives, is likely due to the presence of energetically low-lying (n,π*) states. The fluorogenic probe Fl-DIBO was successfully employed for the labeling of diazo-tagged proteins without detectable background signal. Diazo-derivatives are emerging as attractive reporters for the labeling of biomolecules and the studies presented here demonstrate that Fl-DIBO can be employed for visualizing such biomolecules without the need for probe washout. PMID:26330090

High Dielectric Constants of Composites of Fiber-Like Copper Phthalocyanine-Coated Graphene Oxide Embedded in Poly(arylene Ether Nitriles)

NASA Astrophysics Data System (ADS)

Li, Jingwei; Pu, Zejun; Wang, Zicheng; Long, Ya; Jia, Kun; Liu, Xiaobo

2015-07-01

The surfaces of graphene oxide (GO) sheets were coated with fiber-like copper phthalocyanine (CuPc) by use of a solvothermal process. The product, GO@ CuPc, was used as a filler in high-performance poly(arylene ether nitrile) (PEN) composites. Films of the composites had high thermal stability, and glass-transition temperatures in the range 170-182°C. Thermogravimetric analysis revealed their initial decomposition temperatures were in the range 470-483°C. Scanning electron microscopy showed that dispersion of GO@ CuPc in PEN was much better than that of unmodified GO; this can be attributed to relatively strong interaction between GO@CuPc and the PEN matrix. All the composite films were highly flexible and had enhanced mechanical properties. Tensile strengths of the composites were as high as 89 MPa in the presence of 1 wt.% GO@CuPc, an increase of 20% compared with pure PEN film. Dielectric constants of the composite films were as high as 52 at 100 Hz when the GO@CuPc content was 5%. Because of these excellent mechanical and dielectric properties, PEN/GO@CuPc composites have much potential for use as film capacitors.

Isotopic Ratios in Nitriles from Submillimeter Spectroscopy Using SMA and ALMA

NASA Astrophysics Data System (ADS)

Gurwell, Mark A.; Moreno, Raphael; Vinatier, Sandrine; Lellouch, Emmanuel; Butler, Bryan J.; Moullet, Arielle; Lara, Luisa; Hidayat, Taufiq

2016-10-01

We present submillimeter spectroscopic observations of Titan obtained using the Submillimeter Array (SMA) in 2011, and the Atacama Large Millimeter/Submillimeter Array (ALMA) in 2012, some of which have previously been presented but not fully analyzed (1, 2, 3). The SMA observations were obtained at low spatial resolution, providing disk average spectra, but the ALMA observations provide low resolution mapping of Titan (~0.4"-0.6" when Titan was 0.77" surface diameter). We will present detailed radiative transfer analysis of detected spectral lines to derive isotopic ratios in two nitriles: HCN (D/H, 13C/12C, 15N/14N) and HC3N (15N/14N). The analysis makes use of nearly concurrent CIRS temperature profiles as important constraints for the vertical profiles of these species, allowing high precision measurements of the ratios. Finally, we will highlight current and future ALMA observations that will allow monitoring of non-symmetric molecular species in Titan's upper atmosphere from Earth, beyond the end of the Cassini mission.(1) Gurwell et al (2011) EPSC-DPS Joint Meeting 2011, p270. (2) Moreno et al (2014) EPSC 2014 Abstracts, Vol. 9, id. EPSC2014-438. (3) Moreno etal (2014), DPS meeting #46, id.211.19

Thermomechanical properties of zirconium tungstate/hydrogenated nitrile butadiene rubber (HNBR) composites for low-temperature applications

NASA Astrophysics Data System (ADS)

Akulichev, Anton G.; Alcock, Ben; Tiwari, Avinash; Echtermeyer, Andreas T.

2016-12-01

Rubber compounds for pressure sealing application typically have inferior dimensional stability with temperature fluctuations compared with their steel counterparts. This effect may result in seal leakage failures when subjected to decreases in temperature. Composites of hydrogenated nitrile butadiene rubber (HNBR) and zirconium tungstate as a negative thermal expansion filler were prepared in order to control the thermal expansivity of the material. The amount of zirconium tungstate (ZrW2O8) was varied in the range of 0 to about 40 vol%. The coefficient of thermal expansion (CTE), bulk modulus, uniaxial extension and compression set properties were measured. The CTE of the ZrW2O8-filled HNBR decreases with the filler content and it is reduced by a factor of 2 at the highest filler concentration used. The filler effect on CTE is found to be stronger when HNBR is below the glass transition temperature. The experimental thermal expansion data of the composites are compared with the theoretical estimates and predictions given by FEA. The effect of ZrW2O8 on the mechanical characteristics and compression set of these materials is also discussed.

Bottom-up electrochemical preparation of solid-state carbon nanodots directly from nitriles/ionic liquids using carbon-free electrodes and the applications in specific ferric ion detection and cell imaging

NASA Astrophysics Data System (ADS)

Niu, Fushuang; Xu, Yuanhong; Liu, Mengli; Sun, Jing; Guo, Pengran; Liu, Jingquan

2016-03-01

Carbon nanodots (C-dots), a new type of potential alternative to conventional semiconductor quantum dots, have attracted numerous attentions in various applications including bio-chemical sensing, cell imaging, etc., due to their chemical inertness, low toxicity and flexible functionalization. Various methods including electrochemical (EC) methods have been reported for the synthesis of C-dots. However, complex procedures and/or carbon source-containing electrodes are often required. Herein, solid-state C-dots were simply prepared by bottom-up EC carbonization of nitriles (e.g. acetonitrile) in the presence of an ionic liquid [e.g. 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6)], using carbon-free electrodes. Due to the positive charges of BMIM+ on the C-dots, the final products presented in a precipitate form on the cathode, and the unreacted nitriles and BMIMPF6 can be easily removed by simple vacuum filtration. The as-prepared solid-state C-dots can be well dispersed in an aqueous medium with excellent photoluminescence properties. The average size of the C-dots was found to be 3.02 +/- 0.12 nm as evidenced by transmission electron microscopy. Other techniques such as UV-vis spectroscopy, fluorescence spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy were applied for the characterization of the C-dots and to analyze the possible generation mechanism. These C-dots have been successfully applied in efficient cell imaging and specific ferric ion detection.Carbon nanodots (C-dots), a new type of potential alternative to conventional semiconductor quantum dots, have attracted numerous attentions in various applications including bio-chemical sensing, cell imaging, etc., due to their chemical inertness, low toxicity and flexible functionalization. Various methods including electrochemical (EC) methods have been reported for the synthesis of C-dots. However, complex procedures and/or carbon source-containing electrodes are often required. Herein, solid-state C-dots were simply prepared by bottom-up EC carbonization of nitriles (e.g. acetonitrile) in the presence of an ionic liquid [e.g. 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6)], using carbon-free electrodes. Due to the positive charges of BMIM+ on the C-dots, the final products presented in a precipitate form on the cathode, and the unreacted nitriles and BMIMPF6 can be easily removed by simple vacuum filtration. The as-prepared solid-state C-dots can be well dispersed in an aqueous medium with excellent photoluminescence properties. The average size of the C-dots was found to be 3.02 +/- 0.12 nm as evidenced by transmission electron microscopy. Other techniques such as UV-vis spectroscopy, fluorescence spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy were applied for the characterization of the C-dots and to analyze the possible generation mechanism. These C-dots have been successfully applied in efficient cell imaging and specific ferric ion detection. Electronic supplementary information (ESI) available: Fig. S1. TEM image of the products generated via an electrochemical method using pure BMIMBF4 aqueous solution as the electrolyte; Fig. S2. TEM and HRTEM (inset) images of the water-dispersed solution of C-dots generated from the EC process using electrolytes with a BMIMPF6/3-methylaminopropionitrile volume ratio of 1 : 9 Fig. S3. The effect of pH on the fluorescence intensity (I) of the C-dots; experimental details for detection of Fe3+ in tap water; Fig. S4. Calibration curve for detection of Fe3+ in tap water using the standard addition method. See DOI: 10.1039/c6nr00023a

Flooded Cell Permeation Testing of Elastomers

DTIC Science & Technology

1994-03-01

cured hydrin (EC) elastomer 3. oxide cured neoprene (CR) 4. sulphur cured styrene-butadiene rubber (SBR) 5. sulphur cured nitrile rubber ( NBR ) 6. cured...Road Adelphi, MD 20783-1197 11. SUPPLEMENTARY NOTES Presented at the meeting of the American Chemical Society, Rubber Division, Orlando, Florida, 26 Oct...6 2. Permeation rate-time curve for DMSO through natural rubber ............................... 6 3. Permeation rate-time curve for DMSO through

Landfill Liners and Covers: Properties and Application to Army Landfills.

DTIC Science & Technology

1984-06-01

polymers, TPE can be seamed by heat techniques. Materials such as thermoplastic EPDM and nitrile rubber /PVC blends are still being tested to determine their...such as polyethylene (PE), polyvinyl chloride (PVC), butyl rubber , ethylene propylene diene monomer ( EPDM ), chlorinated polyethylene (CPE), and others...chlorosulfonated polyethy- lene (CSPE), chlorinated polyethylene (CPE), butyl rubber , ethylene propylene S rubber ( EPDM ), neoprene, high-density polyethylene

XANES Analysis of Organic Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

DTIC Science & Technology

2011-01-01

indicate that they contain molecular precursors of prebiotic interest such as amino acids, nitrile-bearing compounds, and amphiphilic compounds. In...living organisms on Earth remains a mystery. Among the most studied scenarios are those encompassing an extraterres- trial origin of prebiotic ...products of these residues have been partly identified using chromatography techniques, which indicate that they contain molecular precursors of prebiotic

Relationship of Interfacial Compatibility to Durability of Adhesive - Bonded Joints

DTIC Science & Technology

1981-03-01

same as BR-238, but with the nitrile rubber removed. Because the phenolic matrix resin has different binding properties to the elastomer than do the...primer, which formed phase separated rubber particles having poor mechanical linkage with the matrix resin , resulted in significant loss in shear...having good mechanical linkage with the matrix resin , resulted in good shear strength retention andsignificantly increased toughness. An adhesive

Purifying contaminated water

DOEpatents

Daughton, Christian G.

1983-01-01

Process for removing biorefractory compounds from contaminated water (e.g., oil shale retort waste-water) by contacting same with fragmented raw oil shale. Biorefractory removal is enhanced by preactivating the oil shale with at least one member of the group of carboxylic, acids, alcohols, aldehydes, ketones, ethers, amines, amides, sulfoxides, mixed ether-esters and nitriles. Further purification is obtained by stripping, followed by biodegradation and removal of the cells.

Measurement of Henry's Law Constants Using Internal Standards: A Quantitative GC Experiment for the Instrumental Analysis or Environmental Chemistry Laboratory

ERIC Educational Resources Information Center

Ji, Chang; Boisvert, Susanne M.; Arida, Ann-Marie C.; Day, Shannon E.

2008-01-01

An internal standard method applicable to undergraduate instrumental analysis or environmental chemistry laboratory has been designed and tested to determine the Henry's law constants for a series of alkyl nitriles. In this method, a mixture of the analytes and an internal standard is prepared and used to make a standard solution (organic solvent)…

Preparation of Perfluorinated Imidoylamidoxime Polymers

NASA Technical Reports Server (NTRS)

Rosser, R. W.; Kratzer, R. H.; Paciorek, K. J. L.; Ito, T. I.

1982-01-01

Perfluorinated imidoylamidoxime polymers with excellent resistance to heat, chemicals and solvents are prepared by condensing a perfluorinated nitrile with a perfluorinated amidoxime in vacuum or inert atmosphere from 20 degrees to 70 degrees C. When both reactants are difunctional, oligomeric or polymeric products are obtained. After cyclization of imidoylamidoxime groups to 1,2,4-oxadiazole linkages, process yields highly resistant elastomers. Competing side reactions are inhibited by low processing temperature.

21 CFR 177.1480 - Nitrile rubber modified acrylonitrile-methyl acrylate copolymers.

Code of Federal Regulations, 2013 CFR

2013-04-01

...) Specifications. (i) Nitrogen content is in the range 16.5-19 percent as determined by Kjeldahl analysis. (ii... copolymers in the form of particles of a size that will pass through a U.S. standard sieve No. 6 and that will be held on a U.S. standard sieve No. 10: (i) Extracted copolymer not to exceed 2.0 parts per...

21 CFR 177.1480 - Nitrile rubber modified acrylonitrile-methyl acrylate copolymers.

Code of Federal Regulations, 2011 CFR

2011-04-01

...) Specifications. (i) Nitrogen content is in the range 16.5-19 percent as determined by Kjeldahl analysis. (ii... copolymers in the form of particles of a size that will pass through a U.S. standard sieve No. 6 and that will be held on a U.S. standard sieve No. 10: (i) Extracted copolymer not to exceed 2.0 parts per...

21 CFR 177.1480 - Nitrile rubber modified acrylonitrile-methyl acrylate copolymers.

Code of Federal Regulations, 2012 CFR

2012-04-01

...) Specifications. (i) Nitrogen content is in the range 16.5-19 percent as determined by Kjeldahl analysis. (ii... copolymers in the form of particles of a size that will pass through a U.S. standard sieve No. 6 and that will be held on a U.S. standard sieve No. 10: (i) Extracted copolymer not to exceed 2.0 parts per...

Rechargeable Lithium/Polymer Cathode Batteries

DTIC Science & Technology

1989-06-15

rechargeable lithium batteries. PPy films prepared with P-anion and/or t.substrate precoated with niLrile butadieve rubber ( NBR ) were excellent cathode...in the polymerization and with NBR (nitrile butadiene rubber )-guided- solution gives beautiful reversibility of anion grown method(4,5). Since an...Tokyo, Japan 169 density of 2.5 mA cm- 2 (3). Moreover, PPy prepa- ration through the host polymer of NBR insulat- SCorrosion Research Center, ing film

Sonar Transducer Reliability Improvement Program (STRIP)

DTIC Science & Technology

1981-01-01

Fair *[51] EPDM NORDOL 1370 - Poor *[511 NATURAL 1155- Poor *[51] NITRILE 6100 - Good *[51] VITON CTBN (BF635075) - Poor *[511 CORK- RUBBER ... aging problems have been found. A report entitled "Reliability and Service Life Concepts for Sonar Transducer Applications" has been completed. - A draft...or aging problems have been found. See Section 9. * A report entitled "Reliability and Service Life Concepts for Sonar Transducer Applications" has

Dependence of Some Mechanical Properties of Elastic Bands on the Length and Load Time

ERIC Educational Resources Information Center

Triana, C. A.; Fajardo, F.

2012-01-01

We present a study of the maximum stress supported by elastics bands of nitrile as a function of the natural length and the load time. The maximum tension of rupture and the corresponding variation in length were found by measuring the elongation of an elastic band when a mass is suspended from its free end until it reaches the breaking point. The…

Seamless Collapsible Fuel Tanks. Phase 1

DTIC Science & Technology

1982-03-01

TITLE (and Subtitle) 5. TYrE OF REPORT & PERIOD COVERED Final Report: Phase I Seamless Collapsible Fuel Tanks April 1980 - March 1982 6. PERFORMING...KEY WORDS (Continue on reverse side it neceessery nd identify by block number) tubular weaving, pillow tanks, fuel resistance , water resistance ...ends x 28 picks per inch in a plain or basket weave. The fabric is then coated both sides with an appropriate fuel- resistant compound, usually a nitrile

Laboratory Evaluation of Nitrile Fuel Tank Materials (Phase 2)

DTIC Science & Technology

2013-09-01

NOTICES Disclaimers The findings in this report are not to be construed as an official Department of the Army position unless so designated...by other authorized documents. Citation of manufacturer’s or trade names does not constitute an official endorsement or approval of the use...thereof. Destroy this report when it is no longer needed. Do not return it to the originator. Army Research Laboratory Aberdeen Proving Ground, MD

Synthesis of aminocarbonyl N-acylhydrazones by a three-component reaction of isocyanides, hydrazonoyl chlorides, and carboxylic acids.

PubMed

Giustiniano, Mariateresa; Meneghetti, Fiorella; Mercalli, Valentina; Varese, Monica; Giustiniano, Francesco; Novellino, Ettore; Tron, Gian Cesare

2014-10-17

A novel one-pot multicomponent synthesis of α-aminocarbonyl N-acylhydrazones starting from readily available hydrazonoyl chlorides, isocyanides, and carboxylic acids is reported. The strategy exploits the ability of the carboxylic acid as a third component to suppress all competing reactions between nitrile imines and isocyanides, channeling the course of the reaction toward the formation of this novel class of compounds.

Polarization and Piezoelectric Properties of a Nitrile Substituted Polyimide

NASA Technical Reports Server (NTRS)

Simpson, Joycelyn; Ounaies, Zoubeida; Fay, Catharine

1997-01-01

This research focuses on the synthesis and characterization of a piezoelectric (beta-CN)- APB/ODPA polyimide. The remanent polarization and piezoelectric d(sub 31) and g(sub 33) coefficients are reported to assess the effect of synthesis variations. Each of the materials exhibits a level of piezoelectricity which increases with temperature. The remanent polarization is retained at temperatures close to the glass transition temperature of the polyimide.

Mechanical, thermal, morphological, and rheological characteristics of high performance 3D-printing lignin-based composites for additive manufacturing applications

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

Nguyen, Ngoc A.; Bowland, Christopher C.; Naskar, Amit K.

Here, the article presents different mechanical, thermal and rheological data corresponding to the morphological formation within various renewable lignin-based composites containing acrylonitrile butadiene styrene (ABS), acrylonitrile butadiene rubber (NBR41, 41 mol% nitrile content), and carbon fibers (CFs). The data of 3D-printing properties and morphology of 3D-printed layers of selected lignin-based composites are revealed.

Purifying contaminated water. [DOE patent application

DOEpatents

Daughton, C.G.

1981-10-27

Process is presented for removing biorefactory compounds from contaminated water (e.g., oil shale retort waste-water) by contacting same with fragmented raw oil shale. Biorefractory removal is enhanced by preactivating the oil shale with at least one member of the group of carboxylic acids, alcohols, aldehydes, ketones, ethers, amines, amides, sulfoxides, mixed ether-esters and nitriles. Further purification is obtained by stripping, followed by biodegradation and removal of the cells.

Castable and High Modulus Acoustic Dampening Material

DTIC Science & Technology

2007-02-22

high impact strength and high dampening laminate structures (e.g., fiberglass parts, etc.). It appears that a carboxy-terminated butadiene nitrile ( CTBN ...Sanjana reference also states that the preferred glass transition temperature for the CTBNs is "<-200". The greater the difference from room...temperature (or the temperature of interest) that the glass transition of the CTBN is, the less acoustic or vibrational energy will be absorbed/dampened

Selected Economic Translations on Eastern Europe (164th in the Series)

DTIC Science & Technology

1960-04-15

processing—namely, the study groups for polyacryl -nitril fibers and the study groups for polyester fibers, which in serious application of the principles of ...decomposition plants, electrolysis cells for chloride of potassium , dry rotor compressors, revolving calenders for viscose dryers, automatic thrust...ojg CD ^ tZ ft,? . . -; r;-; r »OOOOW U7 Photocopies of this report may be purchased from: PHOTOIXJPLiCATION SERVICE LIBRARY OF CONGRESS

Nitrations Conference Held at Menlo Park, California on 27-29 July 1983.

DTIC Science & Technology

1983-09-01

MECHANISM OF HOMOGENEOUS GAS-PHASE DECOMPOSITION OF NITROTOLUENES" D. F. McMillen, C. W. Larson, and D. M. Golden...NITROAROMATICS. THE MECHANISM OF HOMOGENEOUS GAS-PHASE DECOMPOSITION OF NITROTOLUENES" i 6:00 Wine Tasting 7:00 Banquet, International Dining Room THURSDAY, JULY...which undergo hydrolysis or oxidations in strong acid solutions can he easily nitrated. Aryl nitriles, which could not be dinitrated without

Synthesis of diazatricyclic core of Madangamines from cis-perhydroisoquinolines.

PubMed

Quirante, Josefina; Paloma, Laura; Diaba, Faïza; Vila, Xavier; Bonjoch, Josep

2008-01-18

Synthesis of the tricyclic core of madangamine alkaloids has been achieved in a 10-step sequence starting from a 4-(aminomethyl)anisole derivative. A Birch reduction and acylation with cyanoacetic acid followed by an intramolecular Michael process renders a polyfunctionalized cis-perhydroisoquinoline. A diastereoselective allylation and reduction of amide, nitrile, and ketone groups leads to a bicyclic alcohol, which undergoes aminocyclization through the nosyl derivative to the diazatricyclic ring.

Mechanical, thermal, morphological, and rheological characteristics of high performance 3D-printing lignin-based composites for additive manufacturing applications

DOE PAGES

Nguyen, Ngoc A.; Bowland, Christopher C.; Naskar, Amit K.

2018-05-29

Here, the article presents different mechanical, thermal and rheological data corresponding to the morphological formation within various renewable lignin-based composites containing acrylonitrile butadiene styrene (ABS), acrylonitrile butadiene rubber (NBR41, 41 mol% nitrile content), and carbon fibers (CFs). The data of 3D-printing properties and morphology of 3D-printed layers of selected lignin-based composites are revealed.

Adsorption of acrylonitrile on diamond and silicon (001)-(2 x 1) surfaces: effects of dimer structure on reaction pathways and product distributions.

PubMed

Schwartz, Michael P; Barlow, Daniel E; Russell, John N; Butler, James E; D'Evelyn, Mark P; Hamers, Robert J

2005-06-15

Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) are used to compare the reaction of acrylonitrile with Si(001) and C(001) (diamond) surfaces. Our results show that reaction with Si(001) and C(001) yield very different product distributions that result from fundamental differences in the ionic character of these surfaces. While acrylonitrile reacts with the C(001) surface via a [2 + 2] cycloaddition reaction in a manner similar to nonpolar molecules such as alkenes and disilenes, reaction with the Si(001) surface occurs largely through the nitrile group. This work represents the first experimental example of how differences in dimer structure lead to very different chemistry for C(001) compared to that for Si(001). The fact that Si(001) reacts with the strongly polar nitrile group of acrylonitrile indicates that the zwitterionic character of this surface controls its reactivity. C(001) dimers, on the other hand, behave more like a true molecular double bond, albeit a highly strained one. Consequently, while alternative strategies will be necessary for chemical modification of Si(001), traditional schemes from organic chemistry for functionalization of alkenes and disilenes may be available for building molecular layers on C(001).

Swelling and tribological properties of melt-mixed fluoroelastomer/nitrile rubber blends under crude oil

NASA Astrophysics Data System (ADS)

Tagelsir, Yasin; Li, San-Xi; Lv, Xiaoren; Wang, Shijie; Wang, Song; Osman, Zeinab

2018-01-01

The melt-mixed fluoroelastomer (FKM)/ nitrile rubber (NBR) blends of (90/10, 80/20, 70/30, 60/40 and 50/50) ratios with same hardness were prepared, and their swelling and tribological properties under crude oil were investigated for the purpose of developing high performance cost-effective elastomers meeting requirement of oil extraction progressive cavity pump stator. Differential scanning calorimetry confirmed compatible blend system for all blends. Field emission scanning electron microscopy (FE-SEM) showed co-continuous morphology of 200-400 nm phase size for all blends, expect FKM/NBR (90/10) which exhibited partially continuous phase morphology of 100-250 nm phase size. The results of swelling and linear wear tests under crude oil indicated that swelling percentage, coefficient of friction and specific wear rate of FKM/NBR blends were much better than NBR, with FKM/NBR (90/10 and 80/20) showing swelling percentage and specific wear rate very close to FKM. Attenuated total reflectance-Fourier transform infrared spectroscopy disclosed that fracture of macromolecular chains was the main mechanochemical effect of unswollen and swollen worn surfaces, in addition to oxygenated degradation detected with increasing NBR ratio in the blends. The fracture of macromolecular chains resulted in slight fatigue wear mechanism, which was also confirmed by FE-SEM of the worn surfaces.

Glove material, reservoir formation, and dose affect glove permeation and subsequent skin penetration.

PubMed

Nielsen, Jesper Bo; Sørensen, Jens Ahm

2012-02-15

Protective gloves are used to reduce dermal exposure when managing chemical exposures at the work place. Different glove materials may offer different degrees of protection. The present study combined the traditional ASTM (American Society for Testing and Materials) model with the Franz diffusion cell to evaluate overall penetration through glove and skin as well as the deposition in the different reservoirs. Benzoic acid was applied on latex or nitrile gloves placed on top of human skin. The amounts of chemical were quantified in the glove material, between glove and skin, within the skin, and in the receptor chamber. Both glove materials reduce total penetration of benzoic acid, but nitrile gloves offer a significantly better protection than latex gloves. This difference was less pronounced at the higher of the two concentrations of benzoic acid applied. Thus, glove types that offer relevant protection at low concentrations does not necessarily give appropriate protection at high concentrations. Significant amounts of benzoic acid could be extracted from the glove materials after exposure. If a chemical is accumulated in the glove material, reuse of single-use gloves should be cautioned. The reuse of gloves is generally not to be recommended without effective decontamination. Copyright © 2011 Elsevier B.V. All rights reserved.

Evaluation of Biomass-Derived Distillate Fuel as Renewable Heating Oil

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

Mante, Ofei D.; Butcher, Thomas A.; Wei, George

The utilization of advanced biofuels in stationary applications, such as home heating, is considered as an early entry point for biomass-derived fuels into the distillate fuel market sector. Two renewable fuels produced by a biomass fluidized catalytic cracking (BFCC) process, followed by hydroprocessing and fractionation, were tested. The evaluation was performed on a pure (100%) distillate fraction, 50% blend of the distillate fraction with petroleum-based heating oil, and 20% blend of a heavier gas oil fraction. Combustion experiments were carried out in a transparent quartz chamber and a typical oil-fired residential boiler. The flame stability, size, and shape produced bymore » the fuels were examined. The flue gas was analyzed for O 2, CO, NO x, and smoke. The elastomer compatibility test was performed with nitrile slabs at 43 °C for 1 month. Fuel stability was examined at 80 °C for 1 week. The results from the combustion studies suggest that the distillate fuel blends could be used as alternative fuels to No. 2 heating oil, even up to 100% without any operational issues. The distillate fuels were found to be stable. and the nitrile slab volume swell (~10%) suggests that the fuel could be compatible to legacy elastomers.« less

Evaluation of Biomass-Derived Distillate Fuel as Renewable Heating Oil

DOE PAGES

Mante, Ofei D.; Butcher, Thomas A.; Wei, George; ...

2015-09-18

The utilization of advanced biofuels in stationary applications, such as home heating, is considered as an early entry point for biomass-derived fuels into the distillate fuel market sector. Two renewable fuels produced by a biomass fluidized catalytic cracking (BFCC) process, followed by hydroprocessing and fractionation, were tested. The evaluation was performed on a pure (100%) distillate fraction, 50% blend of the distillate fraction with petroleum-based heating oil, and 20% blend of a heavier gas oil fraction. Combustion experiments were carried out in a transparent quartz chamber and a typical oil-fired residential boiler. The flame stability, size, and shape produced bymore » the fuels were examined. The flue gas was analyzed for O 2, CO, NO x, and smoke. The elastomer compatibility test was performed with nitrile slabs at 43 °C for 1 month. Fuel stability was examined at 80 °C for 1 week. The results from the combustion studies suggest that the distillate fuel blends could be used as alternative fuels to No. 2 heating oil, even up to 100% without any operational issues. The distillate fuels were found to be stable. and the nitrile slab volume swell (~10%) suggests that the fuel could be compatible to legacy elastomers.« less

Standardization of skin cleansing in vivo: part I. Development of an Automated Cleansing Device (ACiD).

PubMed

Sonsmann, F K; Strunk, M; Gediga, K; John, C; Schliemann, S; Seyfarth, F; Elsner, P; Diepgen, T L; Kutz, G; John, S M

2014-05-01

To date, there are no legally binding requirements concerning product testing in cosmetics. This leads to various manufacturer-specific test methods and absent transparent information on skin cleansing products. A standardized in vivo test procedure for assessment of cleansing efficacy and corresponding barrier impairment by the cleaning process is needed, especially in the occupational context where repeated hand washing procedures may be performed at short intervals. For the standardization of the cleansing procedure, an Automated Cleansing Device (ACiD) was designed and evaluated. Different smooth washing surfaces of the equipment for ACiD (incl. goat hair, felt, felt covered with nitrile caps) were evaluated regarding their skin compatibility. ACiD allows an automated, fully standardized skin washing procedure. Felt covered with nitrile as washing surface of the rotating washing units leads to a homogenous cleansing result and does not cause detectable skin irritation, neither clinically nor as assessed by skin bioengineering methods (transepidermal water loss, chromametry). Automated Cleansing Device may be useful for standardized evaluation of the cleansing effectiveness and parallel assessment of the corresponding irritancy potential of industrial skin cleansers. This will allow objectifying efficacy and safety of industrial skin cleansers, thus enabling market transparency and facilitating rational choice of products. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Optimizing isothiocyanate formation during enzymatic glucosinolate breakdown by adjusting pH value, temperature and dilution in Brassica vegetables and Arabidopsis thaliana

NASA Astrophysics Data System (ADS)

Hanschen, Franziska S.; Klopsch, Rebecca; Oliviero, Teresa; Schreiner, Monika; Verkerk, Ruud; Dekker, Matthijs

2017-01-01

Consumption of glucosinolate-rich Brassicales vegetables is associated with a decreased risk of cancer with enzymatic hydrolysis of glucosinolates playing a key role. However, formation of health-promoting isothiocyanates is inhibited by the epithiospecifier protein in favour of nitriles and epithionitriles. Domestic processing conditions, such as changes in pH value, temperature or dilution, might also affect isothiocyanate formation. Therefore, the influences of these three factors were evaluated in accessions of Brassica rapa, Brassica oleracea, and Arabidopsis thaliana. Mathematical modelling was performed to determine optimal isothiocyanate formation conditions and to obtain knowledge on the kinetics of the reactions. At 22 °C and endogenous plant pH, nearly all investigated plants formed nitriles and epithionitriles instead of health-promoting isothiocyanates. Response surface models, however, clearly demonstrated that upon change in pH to domestic acidic (pH 4) or basic pH values (pH 8), isothiocyanate formation considerably increases. While temperature also affects this process, the pH value has the greatest impact. Further, a kinetic model showed that isothiocyanate formation strongly increases due to dilution. Finally, the results show that isothiocyanate intake can be strongly increased by optimizing the conditions of preparation of Brassicales vegetables.

Selective Transformation of Various Nitrogen-Containing Exhaust Gases toward N2 over Zeolite Catalysts.

PubMed

Zhang, Runduo; Liu, Ning; Lei, Zhigang; Chen, Biaohua

2016-03-23

In this review we focus on the catalytic removal of a series of N-containing exhaust gases with various valences, including nitriles (HCN, CH3CN, and C2H3CN), ammonia (NH3), nitrous oxide (N2O), and nitric oxides (NO(x)), which can cause some serious environmental problems, such as acid rain, haze weather, global warming, and even death. The zeolite catalysts with high internal surface areas, uniform pore systems, considerable ion-exchange capabilities, and satisfactory thermal stabilities are herein addressed for the corresponding depollution processes. The sources and toxicities of these pollutants are introduced. The important physicochemical properties of zeolite catalysts, including shape selectivity, surface area, acidity, and redox ability, are described in detail. The catalytic combustion of nitriles and ammonia, the direct catalytic decomposition of N2O, and the selective catalytic reduction and direct catalytic decomposition of NO are systematically discussed, involving the catalytic behaviors as well as mechanism studies based on spectroscopic and kinetic approaches and molecular simulations. Finally, concluding remarks and perspectives are given. In the present work, emphasis is placed on the structure-performance relationship with an aim to design an ideal zeolite-based catalyst for the effective elimination of harmful N-containing compounds.

Structure of thiocyanate hydrolase: a new nitrile hydratase family protein with a novel five-coordinate cobalt(III) center.

PubMed

Arakawa, Takatoshi; Kawano, Yoshiaki; Kataoka, Shingo; Katayama, Yoko; Kamiya, Nobuo; Yohda, Masafumi; Odaka, Masafumi

2007-03-09

Thiocyanate hydrolase (SCNase) of Thiobacillus thioparus THI115 is a cobalt(III)-containing enzyme catalyzing the degradation of thiocyanate to carbonyl sulfide and ammonia. We determined the crystal structures of the apo- and native SCNases at a resolution of 2.0 A. SCNases in both forms had a conserved hetero-dodecameric structure, (alphabetagamma)(4). Four alphabetagamma hetero-trimers were structurally equivalent. One alphabetagamma hetero-trimer was composed of the core domain and the betaN domain, which was located at the center of the molecule and linked the hetero-trimers with novel quaternary interfaces. In both the apo- and native SCNases, the core domain was structurally conserved between those of iron and cobalt-types of nitrile hydratase (NHase). Native SCNase possessed the post-translationally modified cysteine ligands, gammaCys131-SO(2)H and gammaCys133-SOH like NHases. However, the low-spin cobalt(III) was found to be in the distorted square-pyramidal geometry, which had not been reported before in any protein. The size as well as the electrostatic properties of the substrate-binding pocket was totally different from NHases with respect to the charge distribution and the substrate accessibility, which rationally explains the differences in the substrate preference between SCNase and NHase.

Fluorogenic Strain-Promoted Alkyne-Diazo Cycloadditions.

PubMed

Friscourt, Frédéric; Fahrni, Christoph J; Boons, Geert-Jan

2015-09-28

Fluorogenic reactions, in which non- or weakly fluorescent reagents produce highly fluorescent products, are attractive for detecting a broad range of compounds in the fields of bioconjugation and material sciences. Herein, we report that a dibenzocyclooctyne derivative modified with a cyclopropenone moiety (Fl-DIBO) can undergo fast strain-promoted cycloaddition reactions under catalyst-free conditions with azides, nitrones, nitrile oxides, as well as mono- and disubstituted diazo-derivatives. Although the reaction with nitrile oxides, nitrones, and disubstituted diazo compounds gave cycloadducts with low quantum yield, monosubstituted diazo reagents produced 1H-pyrazole derivatives that exhibited an approximately 160-fold fluorescence enhancement over Fl-DIBO combined with a greater than 10,000-fold increase in brightness. Concluding from quantum chemical calculations, fluorescence quenching of 3H-pyrazoles, which are formed by reaction with disubstituted diazo-derivatives, is likely due to the presence of energetically low-lying (n,π*) states. The fluorogenic probe Fl-DIBO was successfully employed for the labeling of diazo-tagged proteins without detectable background signal. Diazo-derivatives are emerging as attractive reporters for the labeling of biomolecules, and the studies presented herein demonstrate that Fl-DIBO can be employed for visualizing such biomolecules without the need for probe washout. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemistry of nitrile anions in the interstellar medium

NASA Astrophysics Data System (ADS)

Carles, S.; Le Garrec, J.-L.; Guillemin, J.-C.; Biennier, L.

2015-12-01

Despite the extreme conditions of temperature (down to 10K) and density (down to 100 molecules/cm3), the giant molecular clouds and the circumstellar envelopes present a rich and complex chemistry. To date, more than 180 molecules have been detected in the InterStellar Medium (ISM) with a large abundance of nitriles (RC≡N). In addition, several anions have been recently observed in this medium: C4H¯, C6H¯, C8H¯, CN¯, C3N¯ and C5N¯. These last species should play a key role in the molecular growth towards complexity. To explore this hypothesis, their reactivity must be studied in the laboratory. The FALP-MS and the CRESU experimental apparatuses of the Rennes University are able to measure absolute rate coefficient of various chemical reactions, including the ion - molecule reactions, in gas phase at low temperature (from 300K for the FALP-MS down to 15K for the CRESU). Therefore, these experimental tools are particularly adapted to the kinetic studies of reactions potentially involved in the Interstellar Medium. One of the difficulties encountered in experiments with anions is their generation. We describe here the formation of the CN¯ and C3N¯ anions by dissociative electron attachment on the molecular precursors BrCN and BrC3N.

Novel Elastomeric Closed Cell Foam - Nonwoven Fabric Composite Material (Phase III)

DTIC Science & Technology

2008-10-01

increasing the polymer content of the foam. From laboratory studies, processing was found to improve by using different types of NBR rubber . The AF07 B...Foam Optimization (Task 1) Prior development of fire retarded closed cell foam yielded attractive candidates for scale-up. Nitrile-butadiene rubber ... NBR ) and polyvinyl chloride (PVC) blends provided the most cost effective solutions. Two types of formulas were chosen for optimization. The first

Automotive and Construction Equipment for Arctic Use, Materials Problems

DTIC Science & Technology

1991-11-01

followed. Nitrile rubber ( NBR ) is one of the most common materials used in seal manufacture. It is a copolymer of butadiene and acrylonitrile and is... rubber and other elastomers, and many plastics. This problem is exacerbated, especially in equipment with diesel engines, because the engines run...their original condition in a short time on removal of the stress. The group includes natural rubbers as well as synthetic polymers. Many of these

Characterization of Engine Mount Elastomers

DTIC Science & Technology

2005-02-01

blend of carbon black filled nitrile rubber ( NBR ), polyvinylchloride (PVC), and diisooctyl phthalate (DIOP) that was formulated at PSL (as AMRL 2046...a suitable replacement for natural rubber and neoprene rubber in engine mounts where exposure to hydrocarbon fluids is a concern. The data for NBR ...range 3-7 MPa. The loss factors of the elastomers at 1 Hz, 20oC varied considerably, from 0.02 for natural rubber to 0.27 for ethylene acrylic

Biologically Active Zone Enhancement (BAZE) for In Situ RDX Degradation in Ground Water

DTIC Science & Technology

2010-01-01

geotechnical laboratory testing, will be performed in Level D protection with the addition of chemical resistant gloves. The level of protection for...splash hazards), • Chemical- resistant boots (PVC, Neoprene, Rubber) or work boots with covers ( steel-toed as appropriate), • Inner gloves (latex or...vinyl), • Outer, chemical- resistant gloves (nitrile, PVC, Neoprene), • Safety glasses or goggles, • Hard hat (as required by OSHA), and • Splash

A Divergent Mechanistic Course of Pd(0)-Catalyzed Aza-Claisen Rearrangement and Aza-Rautenstrauch-Type Cyclization of N-Allyl-Ynamides

PubMed Central

DeKorver, Kyle A.; Hsung, Richard P.; Lohse, Andrew G.; Zhang, Yu

2010-01-01

A fascinating mechanistic study of ynamido-palladium-π-allyl complexes is described that features isolation of a unique silyl-ketenimine via aza-Claisen rearrangement, which can be accompanied by an unusual thermal N-to-C 1,3-Ts shift in the formation of tertiary nitriles, and a novel cyclopentenimine formation via a palladium catalyzed aza-Rautenstrauch-type cyclization pathway. PMID:20337418

Nitroethylation of Vinyl Triflates and Bromides

PubMed Central

Padilla–Salinas, Rosaura; Walvoord, Ryan R.; Tcyrulnikov, Sergei

2013-01-01

A two-carbon homologation of vinyl triflates and bromides for the synthesis of homoallylic nitro products is described. This palladium-catalyzed double coupling of nitromethane exploits the anion stabilizing and leaving group properties of nitromethane, generating the homo allyl nitro products via a tandem cross-coupling/π-allylation sequence. The resultant process provides a mild and convenient entry of nitroethylated products, which are versatile precursors to β,γ-unsaturated carbonyls, homoallylic amines, and nitrile oxides. PMID:23885976

Photochemical Degradation of Composition B and Its Components

DTIC Science & Technology

2007-09-01

recorded on the toluene (5.7 mg yield ), ether I (35 mg), and aceto- nitrile (17.8 mg) fractions. Irradiation of solution explosives in soils A...the soil was Soxhlet extracted with acetonitrile for 93 hours. The acetonitrile was removed with a rotary evaporator and the residue redissolved in...ionization to yield an anion of m/z 226. The traces show differences observed in samples with different initial preparation protocols at 15 days. Distance

Catalytic hydroboration by an imido-hydrido complex of Mo(IV).

PubMed

Khalimon, Andrey Y; Farha, Philip; Kuzmina, Lyudmila G; Nikonov, Georgii I

2012-01-11

The imido-hydrido complex (ArN)Mo(H)(Cl)(PMe(3))(3) catalyses a variety of hydroboration reactions, including the first example of catalytic addition of HBCat to nitriles to form the bis(borylated) amines RCH(2)N(BCat)(2). The latter species easily undergoes chemoselective coupling with aldehydes R'C(O)H to yield imines RCH(2)N=C(H)R'. This journal is © The Royal Society of Chemistry 2012

Copper-containing zeolite catalysts

DOEpatents

Price, G.L.; Kanazirev, V.

1996-12-10

A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, is formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl{sub 2}, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

Copper-containing zeolite catalysts

DOEpatents

Price, Geoffrey L.; Kanazirev, Vladislav

1996-01-01

A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl.sub.2, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

Crystal structure of 2-diazo-imidazole-4,5-dicarbo-nitrile.

PubMed

Parrish, Damon A; Kramer, Stephanie; Windler, G Kenneth; Chavez, David E; Leonard, Philip W

2015-07-01

In the title compound, C5N6, all the atoms are approximately coplanar. In the crystal, mol-ecules are packed with short contact distances of 2.885 (2) (between the diazo N atom connected to the ring and a cyano N atom on a neighboring mol-ecule) and 3.012 (2) Å (between the terminal diazo N atom and an N atom of a neighboring imidazole ring).

Nitrenes, carbenes, diradicals, and ylides. Interconversions of reactive intermediates.

PubMed

Wentrup, Curt

2011-06-21

Rearrangements of aromatic and heteroaromatic nitrenes and carbenes can be initiated with either heat or light. The thermal reaction is typically induced by flash vacuum thermolysis, with isolation of the products at low temperatures. Photochemical experiments are conducted either under matrix isolation conditions or in solution at ambient temperature. These rearrangements are usually initiated by ring expansion of the nitrene or carbene to a seven-membered ring ketenimine, carbodiimide, or allene (that is, a cycloheptatetraene or an azacycloheptatetraene when a nitrogen is involved). Over the last few years, we have found that two types of ring opening take place as well. Type I is an ylidic ring opening that yields nitrile ylides or diazo compounds as transient intermediates. Type II ring opening produces either dienylnitrenes (for example, from 2-pyridylnitrenes) or 1,7-(1,5)-diradicals (such as those formed from 2-quinoxalinylnitrenes), depending on which of these species is better stabilized by resonance. In this Account, we describe our achievements in elucidating the nature of the ring-opened species and unraveling the connections between the various reactive intermediates. Both of these ring-opening reactions are found, at least in some cases, to dominate the subsequent chemistry. Examples include the formation of ring-opened ketenimines and carbodiimides, as well as the ring contraction reactions that form five-membered ring nitriles (such as 2- and 3-cyanopyrroles from pyridylnitrenes, N-cyanoimidazoles from 2-pyrazinyl and 4-pyrimidinylnitrenes, N-cyanopyrazoles from 2-pyrimidinylnitrenes and 3-pyridazinylnitrenes, and so forth). The mechanisms of formation of the open-chain and ring-contraction products were unknown at the onset of this study. In the course of our investigation, several reactions with three or more consecutive reactive intermediates have been unraveled, such as nitrene, seven-membered cyclic carbodiimide, and open-chain nitrile ylide. It has been possible in some cases to observe them all and determine their interrelationships by means of a combination of matrix-isolation spectroscopy, photochemistry, flash vacuum thermolysis, and computational chemistry. These studies have led to a deeper understanding of the nature of reactive intermediates and chemical reactivity. Moreover, the results indicate new directions for further exploration: ring-opening reactions of carbenes, nitrenes, and cyclic cumulenes can be expected in many other systems.

CIRS-Observed Titan’s Stratospheric Ice Clouds Studied in the Laboratory

NASA Astrophysics Data System (ADS)

Nna-Mvondo, Delphine; Anderson, Carrie; Samuelson, Robert E.

2018-06-01

Stratospheric ice clouds have been repeatedly observed in Titan’s atmosphere by the Cassini Composite InfraRed Spectrometer (CIRS) since the Cassini spacecraft entered into orbit around Saturn in 2004. Most of these stratospheric ice clouds form as a result of vapor condensation, composed of a combination of pure and mixed nitriles and hydrocarbons. So far, the crystalline cyanoacetylene (HC3N) ν6 band at 506 cm‑1 and a co-condensed nitrile ice feature at 160 cm‑1, dominated by a mixture of HCN and HC3N ices, have been identified in the CIRS limb spectra. However, the presence of other observed stratospheric ice emission features, such as the ν8 band of dicyanoacetylene (C4N2) at 478 cm‑1 and the Haystack emission feature at 220 cm‑1, are puzzling since they have no associated observed vapor emission features. As well, recently, a massive stratospheric ice cloud system, the High-Altitude South Polar (HASP) cloud, was discovered in Titan’s early southern winter stratosphere with an emission feature near 210 cm‑1. We are investigating in laboratory these perplexing stratospheric ices to better understand their formation mechanisms, identify their chemical compositions, and determine their optical properties. We perform transmission spectroscopy of thin films of pure and mixed nitrile ices, as well as ices combined with hydrocarbons, from 50 cm‑1 to 11700 cm‑1, at deposition temperature 30 K - 150 K, using the SPECTRAL high-vacuum chamber at NASA GSFC. The spectral evolution with time and temperature is studied, the ice phase formation identified, and optical constants computed. The first surprising yet significant result reveals that the libration mode of HCN is drastically altered by the surrounding molecules when mixing occurs in a co-condensed phase. For propionitrile ice, we observe peculiar temperature and time-driven ice phase transitions, revealed by significant spectral changes until a stable crystalline phase is achieved. Comparing our laboratory spectra to the CIRS data, we found that a HCN-C6H6 mixed ice is a good match for the HASP cloud emission feature. We present a summary of our laboratory results, which provide crucial inputs to deepen our understanding of Titan's stratospheric chemistry.

Permeation of Comite through protective gloves.

PubMed

Zainal, Hanaa; Que Hee, Shane S

2006-09-01

The goal of the study was to assess how protective disposable (Safeskin) and chemical protective (Sol-Vex) nitrile gloves were against Comite emulsifiable concentrate formulation containing propargite (PROP) as active pesticidal ingredient, because there were no explicit recommendations for the gloves that should be worn for hand protection. The glove material was exposed in ASTM-type I-PTC-600 permeation cells at 30.0+/-0.5 degrees C, and gas chromatography-mass spectrometry used for PROP analysis. Aqueous solutions of Comite at 40.4 mg/mL permeated both Safeskin and Sol-Vex nitrile by 8h. Safeskin showed a mean PROP mass permeated of 176+/-27 microg after 8h compared with a mean mass permeated for Sol-Vex of 3.17+/-4.08 microg. Thus, Sol-Vex was about 56 times more protective than Safeskin for an 8-h exposure. However, the kinetics of the permeation revealed that Safeskin can be worn for at least 200 min before disposal. When undiluted Comite challenged both types of nitrile, much faster permeation was observed. Safeskin gloves showed two steady state periods. The first had lag times (t(l)) values of about 1h, although normalized breakthrough times (t(b)) were < 10 min. The second steady state rate (P(s)) was on average four times the rate of the first period, and the second steady state period t(l) was about three times as long as that of the first steady state period, and about the same t(l) as for the aqueous solution. Sol-Vex gloves exposed continuously to undiluted Comite permeated above the normalized breakthrough threshold beyond 2.7h. A risk assessment revealed that the PROP skin permeation rate of 7.1 ng cm(-2)h(-1) was much slower than the first steady state Safeskin glove P(s) of 62,000 ng cm(-2)h(-1). Infrared analysis showed that the glove surfaces were not degraded by the Comite challenge. The chemically protective Sol-Vex gloves protected adequately against undiluted formulation for about 2.7h, whereas they provided protection for nearly 8h when the formulation was diluted with water to the highest concentration for field application. In contrast, the disposable Safeskin gloves did not protect at all for the undiluted formulation, but did for 200 min when the formulation was diluted with water to the highest concentration for spraying.

Thermographic Detection of Buried Debonds,

DTIC Science & Technology

1988-03-01

fabricated. Each specimen was made of 0.32 in. of 4340 steel bonded to p a 0.2 in. of silica-filled nitrile butyl rubber ( NBR ) insulation that was bonded...in. of steel and 0.25 in. of rubber insulation. Thermographic resolution from heat application was determined experimentally. In addition, a computer...video imaging for detecting adhesive bonding flaws. The flaws, buried beneath 0.3 in. of steel and 0.2 in. of rubber in these motors, have been

Industrial-hygiene walk-through survey report of Copolymer Rubber and Chemical Corporation, Baton Rouge, Louisiana. Industrywide study

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

Roberts, D.R.; Krishnan, E.R.

1986-06-01

A walk through survey was conducted at the Copolymer Rubber and Chemical Corporation, Baton Rouge, Louisiana. The facility produces 465 million pounds of styrene butadiene rubber (SBR) and 15 million pounds of nitrile butadiene rubber (NBR) annually, requiring 120 million pounds of 1,3-butadiene. Of 470 employees, 143 were directly involved in reaction, recovery, and finishing operations, and were potentially exposed to 1,3-butadiene 8 hours per day.

Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion.

PubMed

Xu, Boran; Hartigan, Elizabeth M; Feula, Giancarlo; Huang, Zheng; Lumb, Jean-Philip; Arndtsen, Bruce A

2016-12-19

We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and antidepressant properties of novel 2-substituted 4,5-dihydro-1H-imidazole derivatives.

PubMed

Wentland, M P; Bailey, D M; Alexander, E J; Castaldi, M J; Ferrari, R A; Haubrich, D R; Luttinger, D A; Perrone, M H

1987-08-01

A unique combination of alpha 2-adrenoreceptor antagonist and serotonin-selective reuptake inhibitory activities has been identified in a series of 2-substituted 4,5-dihydro-1H-imidazole derivatives. This combination of blocking activities has provided one of these derivatives, napamezole hydrochloride (2), with potential as an antidepressant. A discussion of the syntheses of these compounds includes a convenient method for the conversion of nitriles to imidazolines with ethylenediamine and trimethylaluminum.

Demonstration/Validation for Federal Specification MMM-A-121 Hazardous Air Pollutant-Free Adhesive Replacement

DTIC Science & Technology

2011-04-01

oils, and bonds leather , nitrile rubber, most plastics, and gasketing materials to a variety of substrates. This product has previously been...DIRECTOR US ARMY RESEARCH LAB IMNE ALC HRR 2800 POWDER MILL RD ADELPHI MD 20783-1197 1 DIRECTOR US ARMY RESEARCH LAB RDRL CIM L 2800... POWDER MILL RD ADELPHI MD 20783-1197 1 DIRECTOR US ARMY RESEARCH LAB RDRL CIM P 2800 POWDER MILL RD ADELPHI MD 20783-1197 1

Federal Specification MMM-A-1617B for Adhesive, Rubber-Base, General-Purpose HAP-Free Replacement

DTIC Science & Technology

2011-05-01

A-1617B Type-I adhesive (table 1) (5). This adhesive is a natural rubber and SBR combination recommended for bonding cotton duck, leather , felt...cotton duck, leather , felt, and cork to themselves, aluminum, steel, or natural rubber (5). Clifton FA-1051 low-HAP (experimental) adhesive is...oils. This adhesive bonds leather , nitrile rubber, most plastics, and gasketing materials to a variety of substrates. The carrier solvent is acetone

Design and Synthesis of Bifunctional Oxime Reactivators of OP- inhibited Cholinesterase

DTIC Science & Technology

2013-08-01

was introduce the 2- aldehyde as a nitrile via the pyridine N-oxide. Another approach (II), was to simply perform 2- hydoxymethylation of pyridines...original design plan called for introducing an aldehyde that could be coupled to various amines and diamines through reductive amination. Interestingly...chromatography DCM: MeOH (90:10) as a yellow oil. Synthesis of 37 (Oxime formation general procedure) To the ketone 36 (340 mg, 1,123 mmol) in 1

Adhesion of nitrile rubber (NBR) to polyethylene terephthalate (PET) fabric. Part 1: PET surface modification by methylenediphenyl di-isocyanate (MDI)

NASA Astrophysics Data System (ADS)

Razavizadeh, Mahmoud; Jamshidi, Masoud

2016-01-01

Fiber to rubber adhesion is an important subject in rubber composite industry. It is well known that surface physical, mechanical and chemical treatments are effective methods to improve interfacial bonding. Ultra violet (UV) light irradiation is an efficient method which is used to increase interfacial interactions. In this research UV assisted chemical modification of PET fabric was used to increase its bonding to nitrile rubber (NBR). NBR is perfect selection to produce fuel and oil resistant rubber parts but it has weak bonding to fabrics. For this purpose at first, the PET fabric was carboxylated under UV irradiation and then methylenediphenyl diisocyanate (MDI) was reacted and grafted to carboxylated PET. T-peel test was used to evaluate PET fabric to NBR bonding strength. Attenuated total reflectance-Fourier transform infrared spectroscopy (FTIR-AT) was used to assess surface modifications of the PET fabrics. The chemical composition of the PET surfaces before and after carboxylation and MDI grafting was investigated by X-ray photoelectron spectroscopy (XPS). It was found that at vulcanizing temperature of 150 °C, carboxylation in contrary to MDI grafting, improved considerably PET to NBR adhesion. Finally effect of curing temperature on PET to NBR bonding strength was determined. It was found that increasing vulcanizing temperature to 170 °C caused considerable improvement (about 134%) in bonding strength.

Isolation and identification of some unknown substances in disposable nitrile-butadiene rubber gloves used for food handling.

PubMed

Mutsuga, M; Wakui, C; Kawamura, Y; Maitani, T

2002-11-01

In Japan, disposable gloves made from nitrile-butadiene rubber (NBR) are frequently used in contact with foods. In a previous paper, we investigated substances migrating from various gloves made of polyvinyl chloride, polyethylene, natural rubber and NBR. Zinc di-n-butyldithiocarbamate (ZDBC), diethyldithiocarbamate (ZDEC) used as vulcanization accelerators, di(2-ethylhexyl)phthalate (DEHP) used as a plasticizer and many unknown compounds that migrated from NBR gloves into n-heptane were detected by GC/MS. In this paper, six unknown compounds were obtained from one kind of NBR glove by n-hexane extraction and each was isolated by silica gel chromatography. From the results of NMR and mass spectral analysis of the six unknown compounds, their structures are proposed as 1,4-dione-2,5-bis(1,1-dimethylpropyl)cyclohexadiene (1), 2-(1,1-dimethylethyl)-4-(1,1,3,3-tetra methylbutyl)phenol (2), 2,6-bis(1,1-dimethylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (3), 2,4-bis(1,1,3,3-tetramethylbutyl)phenol (4), 2-(1,1-dimethylethyl)4,6-bis(1,1,3,3-tetramethylbutyl)phenol (5) and 2,4,6-tris(1,1,3,3-tetramethylbutyl)phenol (6). Compound 1 was observed in five of the seven kinds of NBR gloves, and compounds 2-4 and 6, which are not listed in Chemical Abstract (CA), were present in four kinds of gloves.

Endocrine disruptive effects of chemicals eluted from nitrile-butadiene rubber gloves using reporter gene assay systems.

PubMed

Satoh, Kanako; Nonaka, Ryouichi; Ohyama, Ken-ichi; Nagai, Fumiko; Ogata, Akio; Iida, Mitsuru

2008-03-01

Disposable gloves made of nitrile-butadiene rubber (NBR) are used for contact with foodstuffs rather than polyvinyl chloride gloves containing di(2-ethylhexyl)phthalate (DEHP), because endocrine-disruptive effects are suspected for phthalate diesters including DEHP. However, 4,4'-butylidenebis(6-t-butyl-m-cresol) (BBBC), 2,4-di-t-butylphenol, and 2,2,4-trimetyl-1,3-pentanediol diisobutyrate can be eluted from NBR gloves, and possibly also detected in food. In this study, we examined the endocrine-disrupting effects of these chemicals via androgen receptor (AR) and estrogen receptor (ER)-mediated pathways using stably transfected reporter gene cell lines expressing AR (AR-EcoScreen system) and ER (MVLN cells), respectively. We also examined the binding activities of these chemicals to AR and ER. The IC50 value of BBBC for antagonistic androgen was in the range of 10(-6)M. The strength of inhibition was about 5 times that of a known androgen antagonist, 1,1'-(2,2-dichloroethylidene)bis[4-chlorobenzene] (p,p'-DDE), and similar to that of bisphenol A. The IC50 value of BBBC for antagonistic estrogen was in the range of 10(-6)M. These results suggest that BBBC and its structural homologue, 4,4'-thiobis(6-t-butyl-m-cresol) are androgen and estrogen antagonists. It is therefore necessary to study these chemicals in vivo, and clarify their effect on the endocrine system.

The Brassica epithionitrile 1-cyano-2,3-epithiopropane triggers cell death in human liver cancer cells in vitro.

PubMed

Hanschen, Franziska S; Herz, Corinna; Schlotz, Nina; Kupke, Franziska; Bartolomé Rodríguez, María M; Schreiner, Monika; Rohn, Sascha; Lamy, Evelyn

2015-11-01

Glucosinolates are secondary metabolites present in Brassica vegetables. Alkenyl glucosinolates are enzymatically degraded forming nitriles or isothiocyanates, but in the presence of epithiospecifier protein, epithionitriles are released. However, studies on the occurrence of epithionitriles in Brassica food and knowledge about their biological effects are scarce. Epithionitrile formation from glucosinolates of seven Brassica vegetables was analyzed using GC-MS and HPLC-DAD. Bioactivity of synthetic and plant-derived 1-cyano-2,3-epithiopropane (CETP) - the predominant epithionitrile in Brassica vegetables - in three human hepatocellular carcinoma (HCC) cell lines and primary murine hepatocytes was also evaluated. The majority of the Brassica vegetables were producers of nitriles or epithionitriles as hydrolysis products and not of isothiocyanates. For example, Brussels sprouts and savoy cabbage contained up to 0.8 μmol CETP/g vegetable. Using formazan dye assays, concentrations of 380-1500 nM CETP were observed to inhibit the mitochondrial dehydrogenase activity of human HCC cells without impairment of cell growth. At 100-fold higher CETP concentrations, cell death was observed. Presence of plant matrix increased CETP-based toxicity. These in vitro data provide no indication that epithionitriles will severely affect human health by Brassica consumption. In contrast to isothiocyanates, no evidence of selective toxicity against HCC cells was found. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Permeation of limonene through disposable nitrile gloves using a dextrous robot hand

PubMed Central

Banaee, Sean; S Que Hee, Shane

2017-01-01

Objectives: The purpose of this study was to investigate the permeation of the low-volatile solvent limonene through different disposable, unlined, unsupported, nitrile exam whole gloves (blue, purple, sterling, and lavender, from Kimberly-Clark). Methods: This study utilized a moving and static dextrous robot hand as part of a novel dynamic permeation system that allowed sampling at specific times. Quantitation of limonene in samples was based on capillary gas chromatography-mass spectrometry and the internal standard method (4-bromophenol). Results: The average post-permeation thicknesses (before reconditioning) for all gloves for both the moving and static hand were more than 10% of the pre-permeation ones (P≤0.05), although this was not so on reconditioning. The standardized breakthrough times and steady-state permeation periods were similar for the blue, purple, and sterling gloves. Both methods had similar sensitivity. The lavender glove showed a higher permeation rate (0.490±0.031 μg/cm2/min) for the moving robotic hand compared to the non-moving hand (P≤0.05), this being ascribed to a thickness threshold. Conclusions: Permeation parameters for the static and dynamic robot hand models indicate that both methods have similar sensitivity in detecting the analyte during permeation and the blue, purple, and sterling gloves behave similarly during the permeation process whether moving or non-moving. PMID:28111415

Contamination of Critical Surfaces from NVR Glove Residues Via Dry Handling and Solvent Cleaning

NASA Technical Reports Server (NTRS)

Sovinski, Marjorie F.

2004-01-01

Gloves are often used to prevent the contamination of critical surfaces during handling. The type of glove chosen for use should be the glove that produces the least amount of non-volatile residue (NVR). This paper covers the analysis of polyethylene, nitrile, latex, vinyl, and polyurethane gloves using the contact transfer and gravimetric determination methods covered in the NASA GSFC work instruction Gravimetric Determination and Contact Transfer of Non-volatile Residue (NVR) in Cleanroom Glove Samples, 541-WI-5330.1.21 and in the ASTM Standard E-1731M-95, Standard Test Method for Gravimetric Determination of Non-Volatile Residue from Cleanroom Gloves. The tests performed focus on contamination of critical surfaces at the molecular level. The study found that for the most part, all of the gloves performed equally well in the contact transfer testing. However, the polyethylene gloves performed the best in the gravimetric determination testing, and therefore should be used whenever solvent contact is a possibility. The nitrile gloves may be used as a substitute for latex gloves when latex sensitivity is an issue. The use of vinyl gloves should be avoided, especially if solvent contact is a possibility. A glove database will be established by Goddard Space Flight Center (GSFC) Code 541 to compile the results from future testing of new gloves and different glove lots.

Novel in-situ nanocomposites of phthalonitrile end-capped polyarylene ether nitrile/copper phthalocyanine

NASA Astrophysics Data System (ADS)

Tong, Lifen; Wei, Renbo; Liu, Xiaobo

2017-01-01

A novel phthalonitrile end-capped polyarylene ether nitrile (PEN-Ph)/copper phthalocyanine (CuPc) nanocomposites which possesses crosslinking reaction combined with crystallization behaviour were prepared successfully through in-situ reaction and hot-compression. In the presence of copper ion, CuPc were formed through crosslinking reaction among the phthalonitrile at the end of the PEN-Ph main chain and 1, 3, 5-Tri-(3, 4-dicyanophenoxy) benzene (TPh). Besides, the formed CuPc can play the role of nucleating agent to improve the crystallinity of the polymers. The influence of the crosslinking reaction and crystallization behaviour were investigated. The results show that the crystallization and crosslinking coexist in the system at the same time. Scanning electron microscope (SEM) images show that the crystals of the PEN-Ph grow after the hot-compressing procedure. Moreover, the glass transition temperature (Tg) increases while the crystallinity declines slightly with the low amount of copper ions. The increase of Tg is mainly caused by the crosslinking reaction, indicating that the copper can be used as a crosslinking agent in this system. Due to formation of the CuPc and the crystallization behaviour, the dielectric constant increased as expected from 3.2 to 4.9 while the dielectric loss decreased. Therefore, the PEN-Ph/CuPc in-situ nanocomposites will have a good prospect for application in electronic field.

Stimuli-responsive cement-reinforced rubber.

PubMed

Musso, Simone; Robisson, Agathe; Maheshwar, Sudeep; Ulm, Franz-Josef

2014-05-14

In this work, we report the successful development of a cement-rubber reactive composite with reversible mechanical properties. Initially, the composite behaves like rubber containing inert filler, but when exposed to water, it increases in volume and reaches a stiffness that is intermediate between that of hydrogenated nitrile butadiene rubber (HNBR) and hydrated cement, while maintaining a relatively large ductility characteristic of rubber. After drying, the modulus increases even further up to 400 MPa. Wet/drying cycles prove that the elastic modulus can reversibly change between 150 and 400 MPa. Utilizing attenuated total reflection Fourier transform infrared spectroscopy), we demonstrate that the high pH produced by the hydration of cement triggers the hydrolysis of the rubber nitrile groups into carboxylate anions. Thus, the salt bridges, generated between the carboxylate anions of the elastomer and the cations of the filler, are responsible for the reversible variations in volume and elastic modulus of the composite as a consequence of environmental moisture exposure. These results reveal that cement nanoparticles can successfully be used to accomplish a twofold task: (a) achieve an original postpolymerization modification that allows one to work with carboxylate HNBR (HXNBR) not obtained by direct copolymerization of carboxylate monomers with butadiene, and (b) synthesize a stimuli-responsive polymeric composite. This new type of material, having an ideal behavior for sealing application, could be used as an alternative to cement for oil field zonal isolation applications.

Isotopic Anomalies in Primitive Solar System Matter: Spin-State-Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

NASA Technical Reports Server (NTRS)

Wirstrom, Eva S.; Charnley, Steven B.; Cordiner, Martin A.; Milam, Stefanie N.

2012-01-01

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula, Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest N=15 enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that solar system N-15 and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Exploring Nitrilase Sequence Space for Enantioselective Catalysis†

PubMed Central

Robertson, Dan E.; Chaplin, Jennifer A.; DeSantis, Grace; Podar, Mircea; Madden, Mark; Chi, Ellen; Richardson, Toby; Milan, Aileen; Miller, Mark; Weiner, David P.; Wong, Kelvin; McQuaid, Jeff; Farwell, Bob; Preston, Lori A.; Tan, Xuqiu; Snead, Marjory A.; Keller, Martin; Mathur, Eric; Kretz, Patricia L.; Burk, Mark J.; Short, Jay M.

2004-01-01

Nitrilases are important in the biosphere as participants in synthesis and degradation pathways for naturally occurring, as well as xenobiotically derived, nitriles. Because of their inherent enantioselectivity, nitrilases are also attractive as mild, selective catalysts for setting chiral centers in fine chemical synthesis. Unfortunately, <20 nitrilases have been reported in the scientific and patent literature, and because of stability or specificity shortcomings, their utility has been largely unrealized. In this study, 137 unique nitrilases, discovered from screening of >600 biotope-specific environmental DNA (eDNA) libraries, were characterized. Using culture-independent means, phylogenetically diverse genomes were captured from entire biotopes, and their genes were expressed heterologously in a common cloning host. Nitrilase genes were targeted in a selection-based expression assay of clonal populations numbering 106 to 1010 members per eDNA library. A phylogenetic analysis of the novel sequences discovered revealed the presence of at least five major sequence clades within the nitrilase subfamily. Using three nitrile substrates targeted for their potential in chiral pharmaceutical synthesis, the enzymes were characterized for substrate specificity and stereospecificity. A number of important correlations were found between sequence clades and the selective properties of these nitrilases. These enzymes, discovered using a high-throughput, culture-independent method, provide a catalytic toolbox for enantiospecific synthesis of a variety of carboxylic acid derivatives, as well as an intriguing library for evolutionary and structural analyses. PMID:15066841

Rational Design of N- S- Fe- Doped Nanoporous Carbon Catalysts from Covalent Triazine Framework for High Efficient ORR.

PubMed

Zhu, Yuanzhi; Chen, Xifan; Liu, Jing; Zhang, Junfeng; Xu, Danyun; Peng, Wenchao; Li, Yang; Zhang, Guoliang; Zhang, Fengbao; Fan, Xiaobin

2018-05-15

Porous organic polymers (POFs) are promising precursors for developing high performance transition metal-nitrogen-carbon (M-N/C) catalysts towards ORR. But the rational design of POFs precursors remain a great challenge, because of the elusive structural association between the sacrificial POFs and the final M-N/C catalysts. Based on covalent triazine frameworks (CTFs), we developed a series of sulfur-doped Fe-N/C catalysts by selecting six different aromatic nitriles as building blocks. A new mixed solvent of molten FeCl3 and S was used for CTF polymerization, which benefit the formation of Fe-Nx site and make the subsequent pyrolysis process more convenient. Comprehensive study on these CTF-derived catalysts shows their ORR activities are not directly dependent on the theoretical N/C ratio of the building block, but closely correlated to the ratios of the nitrile group to benzene ring (Nnitrile/Nbenzene) and geometries of the building blocks. The high ratios of the Nnitrile/Nbenzene are crucial for ORR activity of the final catalysts due to the formation of more N-doped microporous and Fe-Nx sites in pyrolysis possess. The optimized catalyst shows high ORR performances in acid and superior ORR activity to the Pt/C catalysts under alkaline conditions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The organic aerosols of Titan

NASA Technical Reports Server (NTRS)

Khare, B. N.; Sagan, C.; Thompson, W. R.; Arakawa, E. T.; Suits, F.; Calcott, T. A.; Williams, M. W.; Shrader, S.; Ogino, H.; Willingham, T. O.

1986-01-01

A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan prepared by continuous dc discharge through a 0.9 N2/0.1 CH4 gas mixture at 0.2 mb is determined from X-ray to microwave frequencies. Values of n (approx. 1.65) and k (approx. 0.004 to 0.08) in the visible are consistent with deductions made by groundbased and spaceborne observations of Titan. Many infrared absorption features are present in k(lambda), including the 4.6 micrometer nitrile band. Molecular analysis of the volatile components of this tholin was performed by sequential and nonsequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycylic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition,acid hydrolysis produces a racemic mixture of biological and nonbiological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.

Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations.

PubMed

Cao, Jun

2015-06-28

In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π(*) transition induces a cleavage of the C-N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π(*) excitation of the imine chromophore results in a cleavage of the C-C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N-O bond cleavages on both S1((1)ππ(*)) and S2((1)nNπ(*)) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

Flash Vacuum Pyrolysis of Azides, Triazoles, and Tetrazoles.

PubMed

Wentrup, Curt

2017-03-08

Flash vacuum pyrolysis (FVP) of azides is an extremely valuable method of generating nitrenes and studying their thermal rearrangements. The nitrenes can in many cases be isolated in low-temperature matrices and observed spectroscopically. NH and methyl, alkyl, aralkyl, vinyl, cyano, aryl and N-heteroaryl, acyl, carbamoyl, alkoxycarbonyl, imidoyl, boryl, silyl, phosphonyl, and sulfonyl nitrenes are included. FVP of triazoloazines generates diazomethylazines and azinylcarbenes, which often rearrange to the energetically more stable arylnitrenes. N 2 elimination from monocyclic 1,2,3-triazoles can generate iminocarbenes, 1H-azirines, ketenimines, and cyclization products, and 1,2,4-triazoles are precursors of nitrile ylides. Benzotriazoles are preparatively useful precursors of cyanocyclopentadienes, carbazoles, and aza-analogues. FVP of 5-aryltetrazoles can result in double N 2 elimination with formation of arylcarbenes or of heteroarylcarbenes, which again rearrange to arylnitrenes. Many 5-substituted and 2,5-disubstituted tetrazoles are excellent precursors of nitrile imines (propargylic, allenic, or carbenic), which are isolable at low temperatures in some cases (e.g., aryl- and silylnitrile imines) or rearrange to carbodiimides. 1,5-Disubstituted tetrazoles are precursors of imidoylnitrenes, which also rearrange to carbodiimides or add intramolecularly to aryl substituents to yield indazoles and related compounds. Where relevant for the mechanistic understanding, pyrolysis under flow conditions or in solution or the solid state will be mentioned. Results of photolysis reactions and computational chemistry complementing the FVP results will also be mentioned in several places.

Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

NASA Astrophysics Data System (ADS)

Cao, Jun

2015-06-01

In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π* transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π* excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S1(1ππ*) and S2(1nNπ*) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

Poster 12: Nitrile and Hydrocarbon Spatial Abundance Variations in Titan's Atmosphere

NASA Astrophysics Data System (ADS)

Thelen, Alexander E.; Nixon, Conor A.; Molter, Edward; Serigano, Joseph; Cordiner, Martin A.; Charnley, Steven B.; Teanby, Nick; Chanover, Nancy

2016-06-01

Many minor constituents of Titan's atmosphere exhibit latitudinal variations in abundance as a result of atmospheric circulation, photochemical production and subsequent destruction throughout Titan's seasonal cycle [1,2]. Species with observed spatial abundance variations include hydrocarbons - such as CH3CCH - and nitriles - HCN, HC3N, CH3CN, and C2H5CN - as found by Cassini [3,4]. Recent calibration images of Titan taken by the Atacama Large Millimeter/Submillimeter Array (ALMA) allow for measurements of rotational transition lines of these species in spatially resolved regions of Titan's disk [5]. Abundance profiles in Titan's lower/middle atmosphere are retrieved by modeling high resolution ALMA spectra using the Non-linear Optimal Estimator for MultivariatE Spectral analySIS (NEMESIS) radiative transfer code [6]. We present continuous abundance profiles for various species in Titan's atmosphere obtained from ALMA data in 2014. These species show polar abundance enhancements which can be compared to studies using Cassini data [7]. Measurements in the mesosphere will constrain molecular photochemical and dynamical models, while temporal variations inform our knowledge of chemical lifetimes for the large inventory of organic species produced in Titan's atmosphere. The synthesis of the ALMA and Cassini datasets thus allow us to observe the important changes in production and circulation of numerous trace components of Titan's atmosphere, which are attributed to Titan's seasons.

The Pyrolytic Profile of Lyophilized and Deep-Frozen Compact Part of the Human Bone

PubMed Central

Lodowska, Jolanta; Wolny, Daniel; Kurkiewicz, Sławomir; Węglarz, Ludmiła

2012-01-01

Background. Bone grafts are used in the treatment of nonunion of fractures, bone tumors and in arthroplasty. Tissues preserved by lyophilization or deep freezing are used as implants nowadays. Lyophilized grafts are utilized in the therapy of birth defects and bone benign tumors, while deep-frozen ones are applied in orthopedics. The aim of the study was to compare the pyrolytic pattern, as an indirect means of the analysis of organic composition of deep-frozen and lyophilized compact part of the human bone. Methods. Samples of preserved bone tissue were subjected to thermolysis and tetrahydroammonium-hydroxide- (TMAH-) associated thermochemolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS). Results. Derivatives of benzene, pyridine, pyrrole, phenol, sulfur compounds, nitriles, saturated and unsaturated aliphatic hydrocarbons, and fatty acids (C12–C20) were identified in the pyrolytic pattern. The pyrolyzates were the most abundant in derivatives of pyrrole and nitriles originated from proteins. The predominant product in pyrolytic pattern of the investigated bone was pyrrolo[1,2-α]piperazine-3,6-dione derived from collagen. The content of this compound significantly differentiated the lyophilized graft from the deep-frozen one. Oleic and palmitic acid were predominant among fatty acids of the investigated samples. The deep-frozen implants were characterized by higher percentage of long-chain fatty acids than lyophilized grafts. PMID:22619606

Isotopic Anomalies in Primitive Solar System Matter: Spin-State Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

NASA Technical Reports Server (NTRS)

Wirstrom, Eva S.; Charnley, Steven B.; Cordiner, Martin A.; Milan, Stefanie N.

2012-01-01

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15, This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar core. Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotop c enrichments measured in carbonaceous meteorites, However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores, We also show that while the nitriles, HCN and HNC, contain the greatest N-15 enrichment, this is not expected to correlate with extreme D emichment. These calculations therefore support the view that Solar System N-15 and D isotopic anomalies have an interstellar heritage, We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Transition from Gaseous Compounds to Aerosols in Titan's Atmosphere

NASA Technical Reports Server (NTRS)

Lebonnois, Sebastien; Bakes, E. L. O.; McKay, Christopher P.; DeVincenzi, Donald (Technical Monitor)

2002-01-01

We investigate the chemical transition of simple molecules like C2H2 and HCN into aerosol particles in the context of Titan's atmosphere. Experiments that synthesize analogs (tholins) for these aerosols can help understand and constrain these polymerization mechanisms. Using information available from these experiments, we suggest chemical pathways that can link simple molecules to macromolecules, that will be the precursors to aerosol particles: polymers of acetylene and cyanoacetylene, polycyclic aromatics (PAHs), polymers of HCN and other nitriles, and polynes. Although our goal here is not to build a detailed kinetic model for this transition, we propose parameterizations to estimate the production rates of these macromolecules, their C/N and C/H ratios, and the loss of parent molecules (C2H2, HCN, HC3N and other nitriles, C6H6) from the gas phase to the haze. We use a 1-dimensional photochemical model of Titan's atmosphere to estimate the formation rate of precursors macromolecules. We find a production zone slightly lower than 200 km altitude with a total production rate of 4 x 10(exp -14) g/ sq cm s and a C/N approx. = 4. These results are compared with experimental data, and to microphysical models requirements. The Cassini/Huygens mission will bring a detailed picture of the haze distribution and properties, that will be a great challenge for our understanding of those chemical processes.

Ion Neutral Mass Spectrometer Measurements from Titan

NASA Technical Reports Server (NTRS)

Waite, J. H., Jr.; Niemann, H.; Yelle, R. V.; Kasprzak, W.; Cravens, T.; Luhmann, J.; McNutt, R.; Ip, W.-H.; Gell, D.; Muller-Wordag, I. C. F.

2005-01-01

Introduction: The Ion Neutral Mass Spectrometer (INMS) aboard the Cassini orbiter has obtained the first in situ composition measurements of the neutral densities of molecular nitrogen, methane, argon, and a host of stable carbon-nitrile compounds in its first flyby of Titan. The bulk composition and thermal structure of the moon s upper atmosphere do not appear to be changed since the Voyager flyby in 1979. However, the more sensitive techniques provided by modern in-situ mass spectrometry also give evidence for large-spatial-scale large-amplitude atmospheric waves in the upper atmosphere and for a plethora of stable carbon-nitrile compounds above 1174 km. Furthermore, they allow the first direct measurements of isotopes of nitrogen, carbon, and argon, which provide interesting clues about the evolution of the atmosphere. The atmosphere was first accreted as ammonia and ammonia ices from the Saturn sub-nebula. Subsequent photochemistry likely converted the atmosphere into molecular nitrogen. The early atmosphere was 1.5 to 5 times more substantial and was lost via escape over the intervening 4.5 billion years due to the reduced gravity associated with the relatively small mass of Titan. Carbon in the form of methane has continued to outgas over time from the interior with much of it being deposited in the form of complex hydrocarbons on the surface and some of it also being lost to space.

Experimental and Computational Studies of Binding of Dinitrogen, Nitriles, Azides, Diazoalkanes, Pyridine and Pyrazines to M(PR3)2(CO)3 (M=Mo, W; R=Me, iPr)

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

Hoff, C.D.; Muckerman, J.; Achord, P.

2009-08-17

The enthalpies of binding of a number of N-donor ligands to the complex Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3} in toluene have been determined by solution calorimetry and equilibrium measurements. The measured binding enthalpies span a range of {approx}10 kcal mol{sup -1}: {Delta}H{sub binding} = -8.8 {+-} 1.2 (N{sub 2}-Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}); -10.3 {+-} 0.8 (N{sub 2}); -11.2 {+-} 0.4 (AdN{sub 3} (Ad = 1-adamantyl)); -13.8 {+-} 0.5 (N{sub 2}CHSiMe{sub 3}); -14.9 {+-} 0.9 (pyrazine = pz); -14.8 {+-} 0.6 (2,6-Me{sub 2}pz); -15.5 {+-} 1.8 (Me{sub 2}NCN); -16.6 {+-} 0.4 (CH{sub 3}CN); -17.0 {+-} 0.4 (pyridine); -17.5 {+-} 0.8more » ([4-CH{sub 3}pz][PF{sub 6}] (in tetrahydrofuran)); -17.6 {+-} 0.4 (C{sub 6}H{sub 5}CN); -18.6 {+-} 1.8 (N{sub 2}CHC(=O)OEt); and -19.3 {+-} 2.5 kcal mol{sup -1} (pz)Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}). The value for the isonitrile AdNC (-29.0 {+-} 0.3) is 12.3 kcal mol{sup -1} more exothermic than that of the nitrile AdCN (-16.7 {+-} 0.6 kcal mol{sup -1}). The enthalpies of binding of a range of arene nitrile ligands were also studied, and remarkably, most nitrile complexes were clustered within a 1 kcal mol{sup -1} range despite dramatic color changes and variation of v{sub CN}. Computed structural and spectroscopic parameters for the complexes Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L are in good agreement with experimental data. Computed binding enthalpies for Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L exhibit considerable scatter and are generally smaller compared to the experimental values, but relative agreement is reasonable. Computed enthalpies of binding using a larger basis set for Mo(PMe{sub 3}){sub 2}(CO){sub 3}L show a better fit to experimental data than that for Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L using a smaller basis set. Crystal structures of Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdCN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(Me{sub 2}NCN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,6-F{sub 2}C{sub 6}H{sub 3}CN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,4,6-Me{sub 3}C{sub 6}H{sub 2}CN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,6-Me{sub 2}pz), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdCN), Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdNC), and W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdNC) are reported.« less

Nitrite fixation by humic substances: Nitrogen-15 nuclear magnetic resonance evidence for potential intermediates in chemodenitrification

USGS Publications Warehouse

Thorn, K.A.; Mikita, M.A.

2000-01-01

Studies have suggested that NO2/-, produced during nitrification and denitrification, can become incorporated into soil organic matter and, in one of the processes associated with chemodenitrification, react with organic matter to form trace N gases, including N2O. To gain an understanding of the nitrosation chemistry on a molecular level, soil and aquatic humic substances were reacted with 15N-labeled NaNO2, and analyzed by liquid phase 15N and 13C nuclear magnetic resonance (NMR). The International Humic Substances Society (IHSS) Pahokee peat and peat humic acid were also reacted with Na15NO2 and analyzed by solid-state 15N NMR. In Suwannee River, Armadale, and Laurentian fulvic acids, phenolic rings and activated methylene groups underwent nitrosation to form nitrosophenols (quinone monoximes) and ketoximes, respectively. The oximes underwent Beckmann rearrangements to 2??amides, and Beckmann fragmentations to nitriles. The nitriles in turn underwent hydrolysis to 1??amides. Peaks tentatively identified as imine, indophenol, or azoxybenzene nitrogens were clearly present in spectra of samples nitrosated at pH 6 but diminished at pH 3. The 15N NMR spectrum of the peat humic acid exhibited peaks corresponding with N-nitroso groups in addition to nitrosophenols, ketoximes, and secondary Beckmann reaction products. Formation of N-nitroso groups was more significant in the whole peat compared with the peat humic acid. Carbon-13 NMR analyses also indicated the occurrence of nitrosative demethoxylation in peat and soil humic acids. Reaction of 15N-NH3 fixated fulvic acid with unlabeled NO2/- resulted in nitrosative deamination of aminohydroquinone N, suggesting a previously unrecognized pathway for production of N2 gas in soils fertilized with NH3.Studies have suggested that NO2-, produced during nitrification and denitrification, can become incorporated into soil organic matter and, in one of the processes associated with chemodenitrification, react with organic matter to form trace N gases, including N2O. To gain an understanding of the nitrosation chemistry on a molecular level, soil and aquatic humic substances were reacted with 15N-labeled NaNO2, and analyzed by liquid phase 15N and 13C nuclear magnetic resonance (NMR). The International Humic Substances Society (IHSS) Pahokee peat and peat humic acid were also reacted with Na15NO2 and analyzed by solid-state 15N NMR. In Suwannee River, Armadale, and Laurentian fulvic acids, phenolic rings and activated methylene groups underwent nitrosation to form nitrosophenols (quinone monoximes) and ketoximes, respectively. The oximes underwent Beckmann rearrangements to 2?? amides, and Beckmann fragmentations to nitriles. The nitriles in turn underwent hydrolysis to 1?? amides. Peaks tentatively identified as imine, indophenol, or azoxybenzene nitrogens were dearly present in spectra of samples nitrosated at pH 6 but diminished at pH 3. The 15N NMR spectrum of the peat humic acid exhibited peaks corresponding with N-nitroso groups in addition to nitrosophenols, ketoximes, and secondary Beckmann reaction products. Formation of N-nitroso groups was more significant in the whole peat compared with the peat humic acid. Carbon-13 NMR analyses also indicated the occurrence of nitrosative demethoxylation in peat and soil humic acids. Reaction of 15N-NH3 fixated fulvic acids with unlabeled NO2- resulted in nitrosative deamination of aminohydroquinone N, suggesting a previously unrecognized pathway for production of N2 gas in soils fertilized with NH3.

Dielectric Properties of Piezoelectric Polyimides

NASA Technical Reports Server (NTRS)

Ounaies, Z.; Young, J. A.; Simpson, J. O.; Farmer, B. L.

1997-01-01

Molecular modeling and dielectric measurements are being used to identify mechanisms governing piezoelectric behavior in polyimides such as dipole orientation during poling, as well as degree of piezoelectricity achievable. Molecular modeling on polyimides containing pendant, polar nitrile (CN) groups has been completed to determine their remanent polarization. Experimental investigation of their dielectric properties evaluated as a function of temperature and frequency has substantiated numerical predictions. With this information in hand, we are then able to suggest changes in the molecular structures, which will then improve upon the piezoelectric response.

Field Demonstration of Biobased Fluids in Military Construction Equipment

DTIC Science & Technology

2007-07-01

155C 35.85 @155C 38.0 @180C Swelling of Synthetic Rubber , NBR , L, % FTM 3603 30.5 20.63 11.17 12.76 20.05 Evaporation Loss, %, 100 deg C, 1...basically divided into two groups. One is natural rubber and the other one is a synthetic elastomer. Their formulations and physical properties are not...reference elastomer was specially formulated with Nitrile or Buna N ( NBR -L) material and is widely used in the many hydraulic specifications including

Experimental comparison of manufacturing techniques of toughened and nanoreinforced polyamides

NASA Astrophysics Data System (ADS)

Siengchin, S.; Bergmann, C.; Dangtungee, R.

2011-11-01

Composites consisting of polyamide-6 (PA-6), nitrile rubber (NBR), and sodium fluorohectorite (FH) or alumina silicate (Sungloss; SG) were produced by different techniques with latex precompounding. Their tensile and thermomechanical properties were determined by using tensile tests and a dynamic-mechanical analysis, performed at various temperatures. The PA-6/NBR composite systems produced by the direct melt compounding outperformed those obtained by using the masterbatch technique with respect to the strength and ductility, but the latter ones had a higher storage modulus.

Effect of electron beam irradiation on the properties of crosslinked rubbers

NASA Astrophysics Data System (ADS)

Banik, Indranil; Bhowmick, Anil K.

2000-05-01

Influence of electron beam (EB) irradiation on the mechanical and dynamic mechanical properties of crosslinked fluorocarbon (FKM) rubber, natural rubber (NR), ethylene propylene diene monomer (EPDM) rubber and nitrile rubber (NBR) has been investigated. The modulus, gel fraction, glass transition temperature ( Tg) and storage modulus increased, while the elongation at the break and the loss tangent (tan δ) Tg decreased. FKM and NBR vulcanizates have been shown to have EB radiation resistance up to 1500 kGy.

Synthesis of High Molecular Weight Para-Phenylene PBI

DTIC Science & Technology

1974-11-01

acid , and the viscous material stirred at 1500 under nitrogen for 3 hours. The flask was then cooled in ice, opened, and 2 g (6.56 mole) of 2 -[p...11 1. Monomers 11 2 . Polymers 18 0 V REFERENCES 23 ILLUSTRATIONS FIGURE PAGE 1. X-RAY DIFFRACTION PATTERN OF ACID INSOLUBLE POLYMER 24 2 . X-RAY...solvents. Other acid derivatives such as esters, amides, and nitriles were also employed as monomers with the same results. NH 2 ,NH 2 - 4HCI + 1- I NH2

Permeation of Military Fuels Through Nitrile-Coated Fabrics Used for Collapsible Fuel Storage Containers

DTIC Science & Technology

2014-03-01

resistance; while decreasing the amount of acrylonitrile content improves low-temperature flexibility, but increases transport rates of military fuels through...tanks do suffer from an increase in total weight and reduced flexibility, which may influence storage, transportation , and setup of the containers...exterior surfaces. The transport of the fuel can be described by Fick’s first law (11): c J=-P x   (1) Where J is the fuel vapor flux, P is

Fourier transform infrared and Raman spectroscopic characterization of homogeneous solution concentration gradients near a container wall at different temperatures

NASA Technical Reports Server (NTRS)

Loo, B. H.; Burns, D. H.; Lee, Y. G. L.; Emerson, M. T.

1991-01-01

Fourier transform infrared (FTIR) and Raman spectroscopic techniques were used to study the solution concentration gradient in succino nitrile-rich and water-rich homogeneous solutions. The spectroscopic data shows significant concentration dependency. Although FTIR-attenuated total reflectance could not yield surface spectra since the evanescent infrared wave penetrated deep into the bulk solution, it showed that water-rich clusters were decreased at higher temperatures. This result is consistent with the calorimetric results reported earlier.

An Adhesive for Field Repair of Composites

DTIC Science & Technology

1988-06-01

epoxy. Epon 828. toughened with carboxy terminated butadiene nitrile rubber, ( CTBN ). and cured with a cycloaliphatic diamine, diamino dicycohexyl methane...adhesives were made by mixing 80 grams of EPON 828. 18 grams CTBN and between .28 and 3.4 grams of PACM-20. The mixture was heated to 160°C at which time .2...grams of PACM-20 with between 1 and 12 grams of the 828- CTBN mixture. This adduct was allowed to react overniqht at room temperature. A second set of

Demonstration/Validation of Hazardous Air Pollutant-Free Adhesive Replacement for Federal Specification MMM-A-121 on the Stryker Infantry Carrier Vehicle

DTIC Science & Technology

2013-06-01

high-performance contact adhesive (baseline) can be used to bond most rubber, cloth, metal, wood , foamed glass, paper honeycomb, decorative plastic ...and gasket adhesive (baseline) may be used to bond metal, wood , most plastics , neoprene, SBR, and butyl rubber (11). Key features are high immediate...nitrile rubber, most plastics and gasketing materials to a variety of substrates (13). This product contains 0% HAPs (14) and has been added to the

The Determination of the Smoke Hazards Resulting from the Burning of Shipboard Materials Utilized by the US Navy.

DTIC Science & Technology

1981-08-31

Interior Paairt r’ts RorzotalSapleIeun Forle Tranduer Figure I. Combustion Products Test Chamber. .. 2. *Sold hda 0 Ol~n kb 3’. 8.iIdg IN= W I Vll ue2...hydrocarbons (alkanes, alkenes, and alkynes), alcohols, aldehydes, ketones, ethers, carboxylic acids , aromatic hydrocarbons, polycyclic aromatic hydrocarbons...carboxylic acids , a few nitriles, acetaldehyde, and acetone. A few exotic fluorine containing organic compounds have unusually low refractive indices for

Potentially Prebiotic Syntheses of Condensed Phosphates

NASA Technical Reports Server (NTRS)

Keefe, Anthony D.; Miller, Stanley L.

1996-01-01

In view of the importance of a prebiotic source of high energy phosphates, we have investigated a number of potentially prebiotic processes to produce condensed phosphates from orthophosphate and cyclic trimetaphosphate from tripolyphosphate. The reagents investigated include polymerizing nitriles, acid anhydrides, lactones, hexamethylene tetramine and carbon suboxide. A number of these processes give substantial yields of pyrophosphate from orthophosphate and trimetaphosphate from tripolyphosphate. Although these reactions may have been applicable in local areas, they are not sufficiently robust to have been of importance in the prebiotic open ocean.

Nickel-Catalyzed Highly Regioselective Hydrocyanation of Terminal Alkynes with Zn(CN)2 Using Water as the Hydrogen Source.

PubMed

Zhang, Xingjie; Xie, Xin; Liu, Yuanhong

2018-06-08

The first efficient and general nickel-catalyzed hydrocyanation of terminal alkynes with Zn(CN) 2 in the presence of water has been developed. The reaction provides a regioselective protocol for the synthesis of functionalized vinyl nitriles with a range of structural diversity under mild reaction conditions while obviating use of the volatile and hazardous reagent of HCN. Deuterium-labeling experiments confirmed the role of water as the hydrogen source in this hydrocyanation reaction.

Process for preparing perfluorotriazine elastomers and precursors thereof

NASA Technical Reports Server (NTRS)

Rosser, R. W.; Chen, T. S.; Cheng, C. H. (Inventor)

1984-01-01

Perfluoroether triazine elastomers having improved properties and utility in seals, gaskets, sealing components and the like are prepared from oligomeric imidoylamidines that have, in turn, been prepared by the process of (1) reacting a perfluorodinitrile with liquid ammonia to yield a perfluorodiamidine, (2) isolating the perfluorodiamidine, (3) reacting the isolated diamidine with a perfluorodinitrile to yield a perfluoror(imidoylamidine) dinitrile, and then repeating step (1), (2), and (3) to sequentially grow an oligomer of desired molecular size. The isolated amidine and nitrile intermediates are also described.

Perfluoro (Imidoylamidine) diamidines

NASA Technical Reports Server (NTRS)

Rosser, R. W.; Chen, T. S.; Cheng, C. H. (Inventor)

1986-01-01

Perfluoroether triazine elastomers having improved properties are prepared from oligomeric imidoylamidines that were in turn, prepared by the process of: (1) reacting a perfluorodinitrile with liquid ammonia to yield a perfluorodiamidine, (2) isolating the perfluorodiamidine, (3) reacting the isolated diamidine with a perfluorodinitrile to yield a perfluoro(imidoylamidine) dinitrile, and then repeating the steps to sequentially grow an oligomer of desired molecular size. The isolated amidine and nitrile intermediates are also disclosed. The elastomers can be fashioned into seals, gaskets, and sealing components and the like.

The improvement of the mechanical properties of PMMA denture base by Al2O3 particles with nitrile rubber

NASA Astrophysics Data System (ADS)

Alhareb, Ahmed Omran; Akil, Hazizan Md; Ahmad, Zainal Arifin

2017-07-01

Poly methyl methacrylate (PMMA) is mostly used for fabrication of denture base by heat-curing technique. Therefore, the purpose of this study is to investigate the effect of Al2O3 filler as toughening particles together with nitrile butadiene rubber (NBR) particles as impact modifier were used to reinforce PMMA denture base materials on the impact strength (IS) and fracture toughness (KIC). PMMA powder was mixed with liquid methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) as crosslinking agent. The powder components are PMMA, benzoyl peroxide, NBR (5, 7.5 and 10 wt%), and Al2O3 filler (5 wt%) treated by silane. The liquid components are 90% of methyl methacrylate and 10 % ethylene glycol dimethacryate. FTIR analyses confirmed that the Al2O3 filler was successfully treated with silane as coupling agent. The morphology of fracture surfaces was characterized using field emission scanning electron microscopy (FESEM). The results shown that IS and KIC improved significantly when using treated the Al2O3 filler. IS has increased to 56% (8.26 KJ/m2) and 73% (2.77 MPa.m1/2) for KIC when treated Al2O3 filler compared to unreinforced PMMA matrix. Statistical analyses of data results were significantly improved (P<0.05) when using 7.5 wt% NBR with treated Al2O3 filler compared to other the compositions.

Molecular Simulation of Gas Solubility in Nitrile Butadiene Rubber.

PubMed

Khawaja, M; Sutton, A P; Mostofi, A A

2017-01-12

Molecular simulation is used to compute the solubility of small gases in nitrile butadiene rubber (NBR) with a Widom particle-insertion technique biased by local free volume. The convergence of the method is examined as a function of the number of snapshots upon which the insertions are performed and the number of insertions per snapshot and is compared to the convergence of the unbiased Widom insertion technique. The effect of varying the definition of local free volume is also investigated. The acrylonitrile content of the polymer is altered to examine its influence on the solubility of helium, CO 2 , and H 2 O, and the solubilities of polar gases are found to be enhanced relative to those of nonpolar gases, in qualitative agreement with experiment. To probe this phenomenon further, the solubilities are decomposed into contributions from the neighborhoods of different atoms, using a Voronoi cell construction, and a strong bias is found for CO 2 and H 2 O in particular to be situated near nitrogen sites in the elastomer. Temperature is shown to suppress the solubility of CO 2 and H 2 O but to increase that of helium. Increasing pressure is found to suppress the solubility of all gases but at different rates, according to a balance between their molecular sizes and electrostatic interactions with the polymer. These results are relevant to the use of NBR seals at elevated temperatures and pressures, such as in oil and gas wells.

Permeability of different types of medical protective gloves to acrylic monomers.

PubMed

Lönnroth, Emma-Christin; Wellendorf, Hanne; Ruyter, Eystein

2003-10-01

Dental personnel and orthopedic surgeons are at risk when manually handling products containing methyl methacrylate (MMA). Dental products may also contain cross-linking agents such as ethylene glycol dimethacrylate (EGDMA) or 1,4-butanediol dimethacrylate (1,4-BDMA). Skin contact with monomers can cause hand eczema, and the protection given by gloves manufactured from different types of material is not well known. The aim of this study was to determine the breakthrough time (BTT, min) as a measure of protection (according to the EU standard EN-374-3) for a mixture consisting of MMA, EGDMA and 1,4-BDMA. Fifteen different gloves representing natural rubber latex material, synthetic rubber material (e.g. nitrile rubbers), and synthetic polymer material were tested. The smallest monomer MMA permeated within 3 min through all glove materials. A polyethylene examination glove provided the longest protection period to EGDMA and 1, 4-BDMA (> 120 min and 25.0 min), followed by the surgical glove Tactylon (6.0 min and 8.7 min) and the nitrile glove Nitra Touch (5.0 min and 8.7 min). This study showed that the breakthrough time (based on permeation rate) cannot be regarded as a 'safe limit'. When the permeation rate is low, monomers may have permeated before BTT can be determined. Using double gloves with a synthetic rubber inner glove and a natural rubber outer glove provided longer protection when the inner glove was rinsed in water before placing the outer glove on top.

Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

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

Cao, Jun, E-mail: caojunbnu@mail.bnu.edu.cn

2015-06-28

In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π{sup *} transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π{sup *} excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed intomore » 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S{sub 1}({sup 1}ππ{sup *}) and S{sub 2}({sup 1}n{sub N}π{sup *}) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.« less

Towards more thermally stable Li-ion battery electrolytes with salts and solvents sharing nitrile functionality

NASA Astrophysics Data System (ADS)

Kerner, Manfred; Lim, Du-Hyun; Jeschke, Steffen; Rydholm, Tomas; Ahn, Jou-Hyeon; Scheers, Johan

2016-11-01

The overall safety of Li-ion batteries is compromised by the state-of-the-art electrolytes; the thermally unstable lithium salt, lithium hexafluorophosphate (LiPF6), and flammable carbonate solvent mixtures. The problem is best addressed by new electrolyte compositions with thermally robust salts in low flammability solvents. In this work we introduce electrolytes with either of two lithium nitrile salts, lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA) or lithium 4,5-dicyano-2-trifluoromethylimidazolide (LiTDI), in solvent mixtures with high flashpoint adiponitrile (ADN), as the main component. With sulfolane (SL) and ethylene carbonate (EC) as co-solvents the liquid temperature range of the electrolytes are extended to lower temperatures without lowering the flashpoint, but at the expense of high viscosities and moderate ionic conductivities. The anodic stabilities of the electrolytes are sufficient for LiFePO4 cathodes and can be charged/discharged for 20 cycles in Li/LiFePO4 cells with coulombic efficiencies exceeding 99% at best. The excellent thermal stabilities of the electrolytes with the solvent combination ADN:SL are promising for future electrochemical investigations at elevated temperatures (> 60 °C) to compensate the moderate transport properties and rate capability. The electrolytes with EC as a co-solvent, however, release CO2 by decomposition of EC in presence of a lithium salt, which potentially makes EC unsuitable for any application targeting higher operating temperatures.

Ice chemistry on outer solar system bodies: Carboxylic acids, nitriles, and urea detected in refractory residues produced from the UV photolysis of N{sub 2}:CH{sub 4}:CO-containing ices

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

Materese, Christopher K.; Cruikshank, Dale P.; Sandford, Scott A.

Radiation processing of the surface ices of outer solar system bodies may result in the production of new chemical species even at low temperatures. Many of the smaller, more volatile molecules that are likely produced by the photolysis of these ices have been well characterized by laboratory experiments. However, the more complex refractory material formed in these experiments remains largely uncharacterized. In this work, we present a series of laboratory experiments in which low-temperature (15-20 K) N{sub 2}:CH{sub 4}:CO ices in relative proportions 100:1:1 are subjected to UV irradiation, and the resulting materials are studied with a variety of analyticalmore » techniques including infrared spectroscopy, X-ray absorption near-edge structure spectroscopy, gas chromatography coupled with mass spectrometry, and high-resolution mass spectroscopy. Despite the simplicity of the reactants, these experiments result in the production of a highly complex mixture of molecules from relatively low-mass volatiles (tens of daltons) to high-mass refractory materials (hundreds of daltons). These products include various carboxylic acids, nitriles, and urea, which are also expected to be present on the surface of outer solar system bodies, including Pluto and other transneptunian objects. If these compounds occur in sufficient concentrations in the ices of outer solar system bodies, their characteristic bands may be detectable in the near-infrared spectra of these objects.« less

Abundance and Temperature Variations in Titan's Atmosphere as Revealed by ALMA

NASA Astrophysics Data System (ADS)

Thelen, A. E.; Nixon, C. A.; Chanover, N.; Molter, E.; Cordiner, M. A.; Serigano, J., IV; Irwin, P. G.; Charnley, S. B.; Teanby, N. A.

2016-12-01

Photochemistry in Titan's atmosphere produces a wealth of organic molecular species through the dissociation of it's main constituents: N2 and CH4. Chemical species including hydrocarbons (CXHY) and nitriles (CXHY[CN]Z) exhibit latitudinal variations in abundance as observed by Cassini, attributed to atmospheric circulation and Titan's seasonal cycle. Flux calibration images of Titan taken by the Atacama Large Millimeter/Submillimeter Array (ALMA) with beam sizes smaller than Titan's angular diameter ( 0.7'') allow for measurements of rotational transition lines in spatially resolved regions of Titan's disk. We present nitrile abundance profiles and temperature measurements derived from CO lines obtained by ALMA in 2014, as Titan transitioned into northern summer. Vertical profiles in Titan's lower/middle atmosphere were retrieved by modeling high resolution ALMA spectra using the Non-linear Optimal Estimator for MultivariatE Spectral analySIS (NEMESIS) radiative transfer code. We present a comparison of the abundance variations of chemical species to measurements made using Cassini data. Temperature profiles derived from CO lines are compared to Cassini Composite Infrared Spectrometer temperature fields. The techniques presented here will allow us to determine temporal changes in Titan's atmospheric chemical composition after the end of the Cassini mission by utilizing high resolution ALMA data. Comparisons of chemical species with strong abundance enhancements over the poles will inform our knowledge of chemical lifetimes in Titan's atmosphere, and allow us to observe the important changes in production and circulation of numerous organic molecules which are attributed to Titan's seasons.

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

Cantrill, E.R.; Ray, A.; Stevens, M.G.

The interfacial bond between fiber and matrix is one of the most important factors influencing fiber-reinforced composites. This is particularly apparent in cellulose wood pulp reinforced cement/quartz composites cured by autoclaving under saturated steam at 180 C. Scanning electron microscopy (SEM) studies have shown that there is little modification of the surface of the hydrated calcium silicate matrix immediately adjacent to the cellulose fiber surface, provided the cellulose fiber is relatively free from lignin, hemicelluloses, or chemicals from the pulping process. Coutts & Campbell (1979) in their investigation of water cured cement composites, applied several commercial coupling agents to cellulosemore » fibres and established that two of these agents significantly increased the strength of the interfacial bond. In this paper, the surface of cellulose fibres was modified by sodium silicate, CTBN [carboxy terminated butadiene nitrile] and ATBN [amino terminated butadiene nitrile] in order to enhance the interfacial bond, and also to increase the resistance of the cellulose to oxidation, alkaline or thermal degradation, and algal attack. Algal attack can occur as the calcium silicate matrix is neutralized by atmospheric carbonation, especially in external wall board applications of the sheet composite. In addition, suitable coatings will protect the cellulose fiber from degradation arising from the presence of elevated temperature and alkaline solutions during the autoclaving process. Cellulose reinforced composites with substandard strengths, due to inhibited autoclave reactions, cannot be reautoclaved as the resultant material is too brittle due, in part, to the degradation of the cellulose fiber.« less

Effect of magnetic and thermal properties of iron oxide nanoparticles (IONs) in nitrile butadiene rubber (NBR) latex

NASA Astrophysics Data System (ADS)

Ong, Hun Tiar; Julkapli, Nurhidayatullaili Muhd; Hamid, Sharifah Bee Abd; Boondamnoen, O.; Tai, Mun Foong

2015-12-01

Nitrile butadiene rubber (NBR) gloves are one of the most important personal protective equipments but they are possible to tear off and contaminate food or pharmaceutical and healthcare products during manufacturing and packaging process. High tendency of torn glove remaining in food or products due to white or light flesh-coloured glove is not easy to be detected by naked eyes. In this paper, iron oxide nanoparticles (IONs) selected as additive for NBR to improve its detectability by mean of magnetic properties. IONs synthesized via precipitation method and compounded with NBR latex before casting on petri dish. The properties of IONs were investigated by X-ray Diffractometry (XRD), Transmission Electron Microscope (TEM), Raman Spectroscopy and Vibrating Sample Magnetometer (VSM). Meanwhile NBR/IONs composites were studied by Thermogravimetry Analysis (TGA), Differential Scanning Calorimetry (DSC) and Vibrating Sample Magnetometer (VSM). It observed that, synthesized IONs shows of 25.28 nm crystallite with 25.86 nm semipherical (changed as) shape. Meanwhile, Magnetite and maghemite phase are found in range of 670 cm-1 and 700 cm-1 respectively, which it contributes magnetization saturation of 73.96 emu/g at 10,000 G by VSM. Thermal stability and magnetic properties were increased with incorporating IONs into NBR latex up to 20 phr. NBR/IONs 5 phr has the optimum thermal stability, lowest glass transition temperature (-14.83 °C) and acceptable range of magnetization saturation (3.83 emu/g at 10,000 G) to form NBR gloves with magnetic detectability.

Widely different luminescence lifetimes of the [Delta]RRR, [Lambda]SSS and the [Delta]RRS, [Lambda]SSR diastereomers of fac-tris[(8-quinolyl)phenylmethylsily] iridium(III): Exciplex formation with solvents by distinct [sigma]-donor and [pi]-acceptor binding mechanisms

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

Djurovich, P.I.; Cook, W.; Joshi, R.

1994-01-13

Luminescence lifetimes ([tau][sub m]) of the [sigma]-bond-to-ligand charge-transfer (SBLCT) excited states of two diastereomers of fac-tris[(8-quinolyl)phenylmethylsilyl]iridium(III) differ by about a factor of 2 and are strongly solvent dependent. The [tau][sub m] values of the more symmetric [Delta]RRR, [Lambda]SSS diastereomer (A) are generally longer than those of the less symmetric [Delta]RRS, [Lambda]SSR diastereomer (B); [tau][sub m]'s of both diastereomers are substantially shortened relative to their values in aliphatic hydrocarbons by exciplex formation with a variety of weakly coordinating solvents including aromatic hydrocarbons, olefins, ethers, ketones, alcohols, and nitriles. Quenching constants (k[sub q]) due to exciplex formation are found to be muchmore » larger for B than they are for A in the [sigma]-donor solvents (cyclic ethers, ketones, alcohols, and nitriles); however, k[sub q] values of B are slightly smaller than those of A in [pi]-acceptor solvents (aromatic hydrocarbons, olefins). The results suggest that [sigma]-donor solvents form exciplexes by binding at the metal center, whereas [pi]-acceptor solvents bind at a quinolyl radical anion ligand site. A and B may prove useful as luminescent environmental probes which can distinguish between [sigma]-donor and [pi]-acceptor binding sites. 19 refs., 1 fig., 1 tab.« less

Rechargeable lithium/polymer cathode batteries

NASA Astrophysics Data System (ADS)

Osaka, Tetsuya; Nakajima, Toshiki; Shiota, Koh; Owens, Boone B.

1989-06-01

Polypyrrole (PPy) and polyaniline (PAn) were investigated for cathode materials of rechargeable lithium batteries. PPy films prepared with PF6(-) anion and/or platinum substrate precoated with nitrile butadiene rubber (NBR) were excellent cathode materials because of rough and/or highly oriented film structure. PAn films were successfully prepared from non-aqueous propylene carbonate solution containing aniline, CF3COOH and lithium perchlorate. Its acidity strongly affects the anion doping-undoping behavior. The PAn cathode prepared in high acidic solution (e.g., 4:1 ratio of acid:aniline) gives the excellent battery performance.

Facile ionothermal synthesis of microporous and mesoporous carbons from task specific ionic liquids.

PubMed

Lee, Je Seung; Wang, Xiqing; Luo, Huimin; Baker, Gary A; Dai, Sheng

2009-04-08

An expedient, template-free, high-yield, and solventless route to nitrogen-rich micro- and mesoporous carbons is reported based on direct, atmospheric-pressure carbonization of task-specific ionic liquids bearing one or more nitrile side chains. The resulting textural properties (pore regime, surface area) are highly dependent upon the structural motifs of the ions comprising the corresponding parent ionic liquid, and uniform carbon films are routinely deposited with this novel methodology, highlighting excited new opportunities in the development of advanced functional carbon composites.

Novel spirobicyclic artemisinin analogues (artemalogues): Synthesis and antitumor activities.

PubMed

Liu, Gang; Song, Shanshan; Shu, Shiqi; Miao, Zehong; Zhang, Ao; Ding, Chunyong

2015-10-20

The sesquiterpene lactone framework of artemisinin was used as a drug repositioning prototype for the development of novel antitumor drugs. Several series of novel artemisinin analogues (artemalogues) were designed and synthesized through 1,3-dipolar cycloaddition of artemisitene with nitrile oxides or nitrones. The isoxazolidine-containing spirobicyclic artemalogue 11b turns out to be the most potent with low micromolar IC₅₀ values against all three tumor cells, which were at least 4- to 14-fold more potent than the parent artemisinin. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Exploiting the Electrophilic and Nucleophilic Dual Role of Nitrile Imines: One-Pot, Three-Component Synthesis of Furo[2,3-d]pyridazin-4(5H)-ones.

PubMed

Giustiniano, Mariateresa; Mercalli, Valentina; Amato, Jussara; Novellino, Ettore; Tron, Gian Cesare

2015-08-21

An expeditious multicomponent reaction to synthesize tetrasubstituted furo[2,3-d]pyridazin-4(5H)-ones is reported. In brief, hydrazonoyl chlorides react with isocyanoacetamides, in the presence of TEA, to give 1,3-oxazol-2-hydrazones which, without being isolated, can react with dimethylacetylene dicarboxylate to afford furo[2,3-d]pyridazin-4(5H)-ones with an unprecedented level of complexity in a triple domino Diels-Alder/retro-Diels-Alder/lactamization reaction sequence.

Multicomponent Reaction of Z-Chlorooximes, Isocyanides, and Hydroxylamines as Hypernucleophilic Traps. A One-Pot Route to Aminodioximes and Their Transformation into 5-Amino-1,2,4-oxadiazoles by Mitsunobu-Beckmann Rearrangement.

PubMed

Mercalli, Valentina; Massarotti, Alberto; Varese, Monica; Giustiniano, Mariateresa; Meneghetti, Fiorella; Novellino, Ettore; Tron, Gian Cesare

2015-10-02

Synthetically useful aminodioximes are prepared via a novel three-component reaction among Z-chlorooximes, isocyanides, and hydroxylamines by exploiting the preferential attack of isocyanides to nitrile N-oxides via a [3 + 1] cycloaddition reaction. The results of quantum mechanical studies of the reaction mechanism are also discussed. Furthermore, the one-pot conversion of aminodioximes to 1,2,3-oxadiazole-5-amines via Mitsunobu-Beckmann rearrangement is reported for the first time.

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

Lebrilla, C.B.; Schulze, C.; Schwarz, H.

The gas-phase reaction of bare Fe/sup +/ atoms with linear alkyl nitriles generates end-on complexes which, depending on geometrical constraints, specifically interact with remote C-H bonds. Based on chain length effect studies and the investigation of labeled precursors, a mechanism is suggested which accounts for the chemospecificity observed for the loss of H/sub 2/ and C/sub 2/H/sub 4/ from RCN/Fe/sup +/ complexes. This mechanism does not follow the analogous reaction of Fe/sup +/ with alkenes and alkynes but involves an initial C-H insertion of the remote CH bonds followed by a C-C insertion.

A review of syntheses of 1,5-disubstituted tetrazole derivatives.

PubMed

Sarvary, Afshin; Maleki, Ali

2015-02-01

This report provides a brief overview of the various representative literature procedures for the synthesis of 1,5-disubstituted tetrazoles (1,5-DSTs) and fused 1,5-disubstituted tetrazoles with more than 120 references. Most of the published methods for the synthesis of 1,5-DSTs include the use of nitriles, amides, thioamides, imidoyl chlorides, heterocumulenes, isocyanates, isothiocyanates, carbodiimides, ketenimines, ketones, amines, and alkenes as the starting materials. The transformation of 1- and 5-substituted tetrazoles into 1,5-DSTs is also covered in this report.

Acoustic emission analysis: A test method for metal joints bonded by adhesives

NASA Technical Reports Server (NTRS)

Brockmann, W.; Fischer, T.

1978-01-01

Acoustic emission analysis is applied to study adhesive joints which had been subjected to mechanical and climatic stresses, taking into account conditions which make results applicable to adhesive joints used in aerospace technology. Specimens consisting of the alloy AlMgSi0.5 were used together with a phenolic resin adhesive, an epoxy resin modified with a polyamide, and an epoxy resin modified with a nitrile. Results show that the acoustic emission analysis provides valuable information concerning the behavior of adhesive joints under load and climatic stresses.

Nickel-Catalyzed Phosphine Free Direct N-Alkylation of Amides with Alcohols.

PubMed

Das, Jagadish; Banerjee, Debasis

2018-03-16

Herein, we developed an operational simple, practical, and selective Ni-catalyzed synthesis of secondary amides. Application of renewable alcohols, earth-abundant and nonprecious nickel catalyst facilitates the transformations, releasing water as byproduct. The catalytic system is tolerant to a variety of functional groups including nitrile, allylic ether, and alkene and could be extended to the synthesis of bis-amide, antiemetic drug Tigan, and dopamine D2 receptor antagonist Itopride. Preliminary mechanistic studies revealed the participation of a benzylic C-H bond in the rate-determining step.

Organic solids produced by electrical discharges in reducing atmospheres: Molecular analysis

NASA Technical Reports Server (NTRS)

Khare, B. N.; Sagan, C.; Zumberge, J. E.; Sklarew, D.; Nagy, B.

1978-01-01

The complex brown polymer produced on passage of an electrical discharge through a mixture of methane, ammonia, and water, is analyzed by pyrolytic GC/MS. Pyrolyzates include a wide range of alkanes, alkenes, aromatic hydrocarbons, aliphatic and aromatic nitriles, pyrroles, and pyridine. Similar pyrolyzates are obtained from polypeptides and polynucleotides with hydrocarbon moieties. This polymer is remarkably stable up to 950 C; its degradation products are candidate constituents of planetary aerosols in the outer solar system and the grains and gas in the interstellar medium.

1-[(3,5-Dimethyl-1H-pyrazol-1-yl)carbon­yl]-5-methyl­indolizine-3-carbo­nitrile

PubMed Central

Gu, Wei-Jin; Xie, Wen-Li; Wang, Ting-Ting

2012-01-01

In the title mol­ecule, C16H14N4O, the indolizine ring system is essentially planar, with a maximum deviation of 0.013 (3) Å, and forms a dihedral angle of 7.52 (12)° with the pyrazole ring. In the crystal, weak C—H⋯O hydrogen bonds and π–π stacking inter­actions, with a centroid–centroid distance of 3.6378 (16) Å, link mol­ecules along [001]. PMID:23476226

The full-scale process and design changes for elimination of insulation edge separations and voids in tang flap area

NASA Technical Reports Server (NTRS)

Danforth, Richard A.

1991-01-01

Qualification of the full-scale process and design changes for elimination of redesigned solid rocket motor tang nitrile butadiene rubber insulation edge separations and voids was performed from 24 March to 3 December 1990. The objectives of this test were: to qualify design and process changes on flight hardware using a tie ply between the redesigned solid rocket motor steel case and the nitrile butadiene rubber insulation over the tang capture features; to qualify the use of methyl ethyl ketone in the tang flap region to reduce voids; and to determine if holes in the separator film reduce voids in the tang flap region. The tie ply is intended to aid insulation flow during the insulation cure process, and thus reduce or eliminate edge unbonds. Methyl ethyl ketone is intended to reduce voids in the tang flap area by providing better tacking characteristics. The perforated film was intended to provide possible vertical breathe paths to reduce voids in the tang area. Tang tie ply testing consisted of 270 deg of the tang circumference using a new layup method and 90 deg of the tang circumference using the current layup methods. Tie ply process success was defined as a reduction of insulation unbonds. Lack of any insulation edge unbonds on the tang area where the new process was used, and the presence of 17 unbonds with the current process, proves the test to be a success. Successful completion of this test has qualified the new processes.

Probing α-relaxation with nuclear magnetic resonance echo decay and relaxation: a study on nitrile butadiene rubber.

PubMed

Sturniolo, Simone; Pieruccini, Marco; Corti, Maurizio; Rigamonti, Attilio

2013-01-01

One dimensional (1)H NMR measurements have been performed to probe slow molecular motions in nitrile butadiene rubber (NBR) around its calorimetric glass transition temperature Tg. The purpose is to show how software aided data analysis can extract meaningful dynamical data from these measurements. Spin-lattice relaxation time, free induction decay (FID) and magic sandwich echo (MSE) measurements have been carried out at different values of the static field, as a function of temperature. It has been evidenced how the efficiency of the MSE signal in reconstructing the original FID exhibits a sudden minimum at a given temperature, with a slight dependence from the measuring frequency. Computer simulations performed with the software SPINEVOLUTION have shown that the minimum in the efficiency reconstruction of the MSE signal corresponds to the average motional frequency taking a value around the inter-proton coupling. The FID signals have been fitted with a truncated form of a newly derived exact correlation function for the transverse magnetization of a dipolar interacting spin pair, which allows one to avoid the restriction of the stationary and Gaussian approximations. A direct estimate of the conformational dynamics on approaching the Tg is obtained, and the results are in agreement with the analysis performed via the MSE reconstruction efficiency. The occurrence of a wide distribution of correlation frequencies for the chains motion, with a Vogel-Fulcher type temperature dependence, is addressed. A route for a fruitful study of the dynamics accompanying the glass transition by a variety of NMR measurements is thus proposed. Copyright © 2013 Elsevier Inc. All rights reserved.

XNBR-grafted halloysite nanotube core-shell as a potential compatibilizer for immiscible polymer systems

NASA Astrophysics Data System (ADS)

Paran, S. M. R.; Naderi, G.; Ghoreishy, M. H. R.

2016-09-01

Halloysite nanotubes (HNTs) grafted with carboxylated nitrile byutadiene rubber (XNBR) were synthesized via a sol-gel method. The HNTs as an inorganic cores were pre-treated with 3-Glycidoxypropyl trimethoxysilane, then successfully coated with the XNBR as an organic shell. The properties of XNBR-grafted HNTs were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results suggested that the XNBR grafted to the surfaces of HNTs successfully. Then the TPE nanocomposites based on polyamide-6 (PA6) and nitrile butadiene rubber (NBR) containing various XNBR-grafted and pristine HNTs were prepared via a direct melt mixing method. The morphology, mechanical, dynamic mechanical and rheological properties of the prepared TPE nanocomposites were investigated. The results show that the XNBR-grafted HNTs can effectively improve the morphology and mechanical properties of the PA6/NBR TPEs. The morphology study of the prepared nanocomposites show that the effect of XNBR-grafted HNTs on the size reduction of NBR phase is markedly more effective than the pristine HNTs and rose by 50% in the same concentrations. Mechanical measurements show that the Young's modulus of the TPE nanocomposites rose by 60% in just 7 wt% of XNBR-grafted HNT loading. The results indicate that the introduction of HNT/XNBR core-shells into the PA6/NBR TPEs can enhances the interfacial interactions and provides a more fine rubber phase morphology and controlled mechanical properties in comparison with the accordingly TPE nanocomposites containing pristine HNTs.

ALMA observations of Titan's atmospheric chemistry and seasonal variation

NASA Astrophysics Data System (ADS)

Cordiner, Martin

2017-04-01

Titan is the largest moon of Saturn, with a thick (1.45 bar) atmosphere composed primarily of molecular nitrogen and methane. Photochemistry in Titan's upper atmosphere results in the production of a wide range of organic molecules, including hydrocarbons, nitriles and aromatics, some of which could be of pre-biotic relevance. Thus, we obtain insights into the possible molecular inventories of primitive (reducing) planetary atmospheres. Titan's atmosphere also provides a unique laboratory for testing our understanding of fundamental processes involving the chemistry and spectroscopy of complex organic molecules. In this talk, results will be presented from our studies using the Atacama Large Millimeter/submillimeter Array (ALMA) during the period 2012-2015, focussing in particular on the detection and mapping of emission from various nitrile species. By combining data from multiple ALMA observations, our spectra have reached an unprecedented sensitivity level, enabling the first spectroscopic detection and mapping of C2H3CN (vinyl cyanide) on Titan. Liquid-phase simulations of Titan's seas indicate that vinyl cyanide molecules could combine to form vesicle membranes (similar to the cells of terrestrial biology), and the astrobiological implications of this discovery will be discussed. Furthermore, ALMA observations provide instantaneous snapshot mapping of Titan's entire Earth-facing hemisphere, for gases inaccessible to previous instruments. Combined with complementary data obtained from the Cassini Saturn orbiter, as well as theoretical models and laboratory studies, our observed, seasonally variable, spatially resolved abundance patterns are capable of providing new insights into photochemical production and transport in primitive planetary atmospheres in the Solar System and beyond.

Abiotic Organic Chemistry in Hydrothermal Systems.

NASA Astrophysics Data System (ADS)

Simoneit, B. R.; Rushdi, A. I.

2004-12-01

Abiotic organic chemistry in hydrothermal systems is of interest to biologists, geochemists and oceanographers. This chemistry consists of thermal alteration of organic matter and minor prebiotic synthesis of organic compounds. Thermal alteration has been extensively documented to yield petroleum and heavy bitumen products from contemporary organic detritus. Carbon dioxide, carbon monoxide, ammonia and sulfur species have been used as precursors in prebiotic synthesis experiments to organic compounds. These inorganic species are common components of hot spring gases and marine hydrothermal systems. It is of interest to further test their reactivities in reductive aqueous thermolysis. We have synthesized organic compounds (lipids) in aqueous solutions of oxalic acid, and with carbon disulfide or ammonium bicarbonate at temperatures from 175-400° C. The synthetic lipids from oxalic acid solutions consisted of n-alkanols, n-alkanoic acids, n-alkyl formates, n-alkanones, n-alkenes and n-alkanes, typically to C30 with no carbon number preferences. The products from CS2 in acidic aqueous solutions yielded cyclic thioalkanes, alkyl polysulfides, and thioesters with other numerous minor compounds. The synthesis products from oxalic acid and ammonium bicarbonate solutions were homologous series of n-alkyl amides, n-alkyl amines, n-alkanes and n-alkanoic acids, also to C30 with no carbon number predominance. Condensation (dehydration) reactions also occur under elevated temperatures in aqueous medium as tested by model reactions to form amide, ester and nitrile bonds. It is concluded that the abiotic formation of aliphatic lipids, condensation products (amides, esters, nitriles, and CS2 derivatives (alkyl polysulfides, cyclic polysulfides) is possible under hydrothermal conditions and warrants further studies.

Crystal structure of tetra-kis-[μ2-2-(di-methyl-amino)-ethano-lato-κ(3) N,O:O]di-μ3-hydroxido-di-thio-cyanato-κ(2) N-dichromium(III)dilead(II) di-thio-cyanate aceto-nitrile monosolvate.

PubMed

Rusanova, Julia A; Semenaka, Valentyna V; Omelchenko, Irina V

2016-04-01

The tetra-nuclear complex cation of the title compound, [Cr2Pb2(NCS)2(OH)2(C4H10NO)4](SCN)2·CH3CN, lies on an inversion centre. The main structural feature of the cation is a distorted seco-norcubane Pb2Cr2O6 cage with a central four-membered Cr2O2 ring. The Cr(III) ion is coordinated in a distorted octa-hedron, which involves two N atoms of one bidentate ligand and one thio-cyanate anion, two μ2-O atoms of 2-(di-methyl-amino)-ethano-late ligands and two μ3-O atoms of hydroxide ions. The coordination geometry of the Pb(II) ion is a distorted disphenoid, which involves one N atom, two μ2-O atoms and one μ3-O atom. In addition, weak Pb⋯S inter-actions involving the coordinating and non-coordinating thio-cyanate anions are observed. In the crystal, the complex cations are linked through the thio-cyanate anions via the Pb⋯S inter-actions and O-H⋯N hydrogen bonds into chains along the c axis. The chains are further linked together via S⋯S contacts. The contribution of the disordered solvent aceto-nitrile mol-ecule was removed with the SQUEEZE [Spek (2015 ▸). Acta Cryst. C71, 9-18] procedure in PLATON. The solvent is included in the reported mol-ecular formula, weight and density.

Evolution of Interstellar Ices

NASA Astrophysics Data System (ADS)

Allamandola, Louis J.; Bernstein, Max P.; Sandford, Scott A.; Walker, Robert L.

1999-10-01

Infrared observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the building blocks of comets. Ices in molecular clouds are dominated by the very simple molecules H2O, CH3OH, NH3, CO, CO2, and probably H2CO and H2. More complex species including nitriles, ketones, and esters are also present, but at lower concentrations. The evidence for these, as well as the abundant, carbon-rich, interstellar, polycyclic aromatic hydrocarbons (PAHs) is reviewed. Other possible contributors to the interstellar/pre-cometary ice composition include accretion of gas-phase molecules and in situ photochemical processing. By virtue of their low abundance, accretion of simple gas-phase species is shown to be the least important of the processes considered in determining ice composition. On the other hand, photochemical processing does play an important role in driving dust evolution and the composition of minor species. Ultraviolet photolysis of realistic laboratory analogs readily produces H2, H2CO, CO2, CO, CH4, HCO, and the moderately complex organic molecules: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN (nitriles), and hexamethylenetetramine (HMT, C6H12N4), as well as more complex species including amides, ketones, and polyoxymethylenes (POMs). Inclusion of PAHs in the ices produces many species similar to those found in meteorites including aromatic alcohols, quinones and ethers. Photon assisted PAH-ice deuterium exchange also occurs. All of these species are readily formed and are therefore likely cometary constituents.

Rhenium 2-oxoalkyl (enolate) complexes: Synthesis and carbon-carbon bond-forming reactions with nitriles

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

Stack, J.G.; Doney, J.J.; Bergman, R.G.

1990-02-01

The (2-oxoalkyl)rhenium complexes (rhenium enolates) (CO){sub 5}ReCH{sub 2}COR{sup 1} (R{sup 1} = OEt, Me, Ph, 1-3) can be prepared on a multigram scale by alkylation of (CO){sub 5}ReNa with ClCH{sub 2}COR{sup 1}. The secondary enolate (CO){sub 5}ReCH(Me)CO{sub 2}Et (4) can also be prepared in a similar fashion with use of MsOCH(Me)CO{sub 2}Et (Ms = CH{sub 3}SO{sub 2}{sup {minus}}). The mono(phosphine) enolates cis-(Ph{sub 3}P)(CO){sub 4}ReCH{sub 2}R{sup 2}(R{sup 2} = CO{sub 2}Et, CO{sub 2}Bu{sup t}, CONEt{sub 2}, COMe, COPh, CN, 8-13) are prepared in high yield via alkylation of (Ph{sub 3}P)(CO){sub 4}ReNa with ClCH{sub 2}R{sup 2}. Synthesis of the secondary enolate cis-(Ph{submore » 3}P)(CO){sub 4}ReCH(Me)CO{sub 2}Et (14) is accomplished in 75% yield by alkylation with TfOCH(Me)CO{sub 2}Et (Tf = CF{sub 3}SO{sub 2}{sup {minus}}). The chelating phosphine complex is substitutionally inert under forcing thermal and photochemical conditions. Kinetic studies of the nitrile insertion reaction revealed a weak linear dependence of the rate constant of the reaction on the concentration of added CH{sub 3}CN in benzene; we believe this to be a medium effect.« less

Acrylamide biodegradation ability and plant growth-promoting properties of Variovorax boronicumulans CGMCC 4969.

PubMed

Liu, Zhong-Hua; Cao, Yu-Min; Zhou, Qian-Wen; Guo, Kun; Ge, Feng; Hou, Jun-Yi; Hu, Si-Yi; Yuan, Sheng; Dai, Yi-Jun

2013-11-01

Species of the genus Variovorax are often isolated from nitrile or amide-containing organic compound-contaminated soil. However, there have been few biological characterizations of Variovorax and their contaminant-degrading enzymes. Previously, we reported a new soil isolate, Variovorax boronicumulans CGMCC 4969, and its nitrile hydratase that transforms the neonicotinoid insecticide thiacloprid into an amide metabolite. In this study, we showed that CGMCC 4969 is able to degrade acrylamide, a neurotoxicant and carcinogen in animals, during cell growth in a mineral salt medium as well as in its resting state. Resting cells rapidly hydrolyzed 600 mg/L acrylamide to acrylic acid with a half-life of 2.5 min. In in vitro tests, CGMCC 4969 showed plant growth-promoting properties; it produced a siderophore, ammonia, hydrogen cyanide, and the phytohormone salicylic acid. Interestingly, in soil inoculated with this strain, 200 mg/L acrylamide was completely degraded in 4 days. Gene cloning and overexpression in the Escherichia coli strain Rosetta (DE3) pLysS resulted in the production of an aliphatic amidase of 345 amino acids that hydrolyzed acrylamide into acrylic acid. The amidase contained a conserved catalytic triad, Glu59, Lys 134, and Cys166, and an "MRHGDISSS" amino acid sequence at the N-terminal region. Variovorax boronicumulans CGMCC 4969, which is able to use acrylamide for cell growth and rapidly degrade acrylamide in soil, shows promising plant growth-promoting properties. As such, it has the potential to be developed into an effective Bioaugmentation strategy to promote growth of field crops in acrylamide-contaminated soil.

Simulation of Titan's atmospheric photochemistry. Formation of non-volatile residue from polar nitrile ices

NASA Astrophysics Data System (ADS)

Couturier-Tamburelli, Isabelle; Piétri, Nathalie; Gudipati, Murthy S.

2015-06-01

We studied the photochemistry of frozen ice of a polar Titan's atmospheric molecule cyanodiacetylene (HC5N) to determine the possible contribution of this compound to the lower altitude photochemistry of haze layers found on Titan. We used infrared analysis to examine the residue produced by irradiation of solid HC5N at λ > 300 nm. The resulting polymer is orange-brown in color. Based on theoretical analysis and the general tendency of HC5N and C4N2 to undergo similar ice photochemistry at longer wavelengths accessible in Titan's lower atmosphere, we conclude that Titan's lower atmosphere is photochemically active in the regions of cloud, ice, and aerosol formation. C4N2is a symmetric molecule with no net dipole moment whereas, HC5N has a large dipole moment of ~4 D. Consequently, though both these molecules have very similar molecular weight and size, their sublimation temperatures are different, HC5N subliming around 170 K compared to 160 K for C4N2. Based on our studies we conclude that in Titan's atmosphere the cyanoacetylene class of molecules (HCN, HC3N, HC5N, etc.) would condense first followed by the dicyanoacetylenes (C2N2, C4N2, C6N2, etc.), leading to fractionation of different class of molecules. From the fluxes used in the laboratory and depletion of the original HC5N signals, we estimate Titan's haze ice photochemistry involving polar nitriles to be significant and very similar to their non-polar counterparts.

Industrywide studies report of an in-depth survey at Copolymer Rubber and Chemical Corporation, Baton Rouge, Louisiana

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

Krishnan, E.R.; Fajen, J.M.

1987-05-08

An in depth industrial hygiene survey was conducted at the Copolymer Rubber and Chemical Corporation located in Baton Rouge, Louisiana. The facility produced styrene-butadiene rubber and nitrile-butadiene rubber by continuous emulsion polymerization. The ultimate use of this product was for the manufacture of tire and rubber products. The authors recommend that leaking pumps which can present a potential for 1,3-butadiene exposure in the tank farm and recovery areas should be controlled through the use of dual mechanical seals. Employees assigned to maintenance tasks should use respirators with organic vapor cartridges.

Organic solids produced by electrical discharge in reducing atmospheres - Tholin molecular analysis

NASA Technical Reports Server (NTRS)

Khare, B. N.; Sagan, C.; Zumberge, J. E.; Sklarew, D. S.; Nagy, B.

1981-01-01

The complex dark brown solid of a class called tholins, produced on passage of an electrical discharge through a roughly equimolar mixture of methane and ammonia with 2.6% water vapor, is analyzed by vacuum pyrolysis followed by gas chromatography and mass spectrometry. Pyrolyzates include a wide range of aliphatic and aromatic nitriles, alkanes, alkenes, aromatic hydrocarbons, pyrrole, and pyridine. This tholin is remarkably stable to 950 C. It and its degradation products are candidate constituents of planetary aerosols in the outer solar system and of the grains in the interstellar medium.

Intensive Titan exploration begins.

PubMed

Mahaffy, Paul R

2005-05-13

The Cassini Orbiter spacecraft first skimmed through the tenuous upper atmosphere of Titan on 26 October 2004. This moon of Saturn is unique in our solar system, with a dense nitrogen atmosphere that is cold enough in places to rain methane, the feedstock for the atmospheric chemistry that produces hydrocarbons, nitrile compounds, and Titan's orange haze. The data returned from this flyby supply new information on the magnetic field and plasma environment around Titan, expose new facets of the dynamics and chemistry of Titan's atmosphere, and provide the first glimpses of what appears to be a complex, fluid-processed, geologically young Titan surface.

Ion neutral mass spectrometer results from the first flyby of Titan.

PubMed

Waite, J Hunter; Niemann, Hasso; Yelle, Roger V; Kasprzak, Wayne T; Cravens, Thomas E; Luhmann, Janet G; McNutt, Ralph L; Ip, Wing-Huen; Gell, David; De La Haye, Virginie; Müller-Wordag, Ingo; Magee, Brian; Borggren, Nathan; Ledvina, Steve; Fletcher, Greg; Walter, Erin; Miller, Ryan; Scherer, Stefan; Thorpe, Rob; Xu, Jing; Block, Bruce; Arnett, Ken

2005-05-13

The Cassini Ion Neutral Mass Spectrometer (INMS) has obtained the first in situ composition measurements of the neutral densities of molecular nitrogen, methane, molecular hydrogen, argon, and a host of stable carbon-nitrile compounds in Titan's upper atmosphere. INMS in situ mass spectrometry has also provided evidence for atmospheric waves in the upper atmosphere and the first direct measurements of isotopes of nitrogen, carbon, and argon, which reveal interesting clues about the evolution of the atmosphere. The bulk composition and thermal structure of the moon's upper atmosphere do not appear to have changed considerably since the Voyager 1 flyby.

Hydrolysis of Letrozole catalyzed by macrocyclic Rhodium (I) Schiff-base complexes.

PubMed

Reddy, P Muralidhar; Shanker, K; Srinivas, V; Krishna, E Ravi; Rohini, R; Srikanth, G; Hu, Anren; Ravinder, V

2015-03-15

Ten mononuclear Rhodium (I) complexes were synthesized by macrocyclic ligands having N4 and N2O2 donor sites. Square planar geometry is assigned based on the analytical and spectral properties for all complexes. Rh(I) complexes were investigated as catalysts in hydrolysis of Nitrile group containing pharmaceutical drug Letrozole. A comparative study showed that all the complexes are efficient in the catalysis. The percent yields of all the catalytic reaction products viz. drug impurities were determined by spectrophotometric procedures and characterized by spectral studies. Copyright © 2014 Elsevier B.V. All rights reserved.

Dynamical simulation of electron transfer processes in self-assembled monolayers at metal surfaces using a density matrix approach.

PubMed

Prucker, V; Bockstedte, M; Thoss, M; Coto, P B

2018-03-28

A single-particle density matrix approach is introduced to simulate the dynamics of heterogeneous electron transfer (ET) processes at interfaces. The characterization of the systems is based on a model Hamiltonian parametrized by electronic structure calculations and a partitioning method. The method is applied to investigate ET in a series of nitrile-substituted (poly)(p-phenylene)thiolate self-assembled monolayers adsorbed at the Au(111) surface. The results show a significant dependence of the ET on the orbital symmetry of the donor state and on the molecular and electronic structure of the spacer.

Design and Synthesis of Tight Pitch FLCs for Analog Voltage-Limited Electro-Optic Modulators

DTIC Science & Technology

1994-05-27

or decision, unless so designated b other documentation. 12a. DISTRIBUTION/AVAILABILITY STATEMENT 𔃼b, DISTRIBUTION CODE Approved for public release...other end, a wide variety of cores can be synthesized. This is the preferred method for making about 40% of the cores shown in Figure 1. [PGO(Ar) -- B ...methanol, and finally dehydration to the nitrile 51 using phosphorus pentoxide. 0 OHO %%’QL X1) Bu2 BOTf A). 482 ) CH3CHO 49 it N •N O =Xc DEAD, TPP C8H17 O H

2,4 Diamino benzonitrile

NASA Technical Reports Server (NTRS)

Frost, Lawrence W. (Inventor)

1980-01-01

Deep curable polymers having heterocyclic ring systems such as isoindoloquinazolinedione ring systems prepared from novel cyanoimide polymers, most desirably 2'-cyanoimide polymers. Preferably the cyanoimide polymers are prepared from a diamine having at least one nitrile group in the two position to an amine group and a dianhydride having at least two cyclic anhydride groups. Copolymers may be prepared having other linkages, notably imide linkages, in addition to isoindoloquinazolinedione ring systems and/or other similar heterocyclic ring systems. The copolymers can be prepared by use of diamines containing one or more cyanoimide groupings and/or imide groups in their structure.

Natrolite zeolite supported copper nanoparticles as an efficient heterogeneous catalyst for the 1,3-diploar cycloaddition and cyanation of aryl iodides under ligand-free conditions.

PubMed

Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Khalaj, Mehdi

2015-09-01

In this paper, we report the preparation of Natrolite zeolite supported copper nanoparticles as a heterogeneous catalyst for 1,3-diploar cycloaddition and synthesis aryl nitriles from aryl iodides under ligand-free conditions. The catalyst was characterized using XRD, SEM, TEM, EDS and TG-DTA. The experimental procedure is simple, the products are formed in high yields and the catalyst can be recycled and reused several times without any significant loss of catalytic activity. Copyright © 2015 Elsevier Inc. All rights reserved.

A benzothiazole-based fluorescent probe for hypochlorous acid detection and imaging in living cells

NASA Astrophysics Data System (ADS)

Nguyen, Khac Hong; Hao, Yuanqiang; Zeng, Ke; Fan, Shengnan; Li, Fen; Yuan, Suke; Ding, Xuejing; Xu, Maotian; Liu, You-Nian

2018-06-01

A benzothiazole-based turn-on fluorescent probe with a large Stokes shift (190 nm) has been developed for hypochlorous acid detection. The probe displays prompt fluorescence response for HClO with excellent selectivity over other reactive oxygen species as well as a low detection limit of 0.08 μM. The sensing mechanism involves the HClO-induced specific oxidation of oxime moiety of the probe to nitrile oxide, which was confirmed by HPLC-MS technique. Furthermore, imaging studies demonstrated that the probe is cell permeable and can be applied to detect HClO in living cells.

Mechanical, thermal, morphological, and rheological characteristics of high performance 3D-printing lignin-based composites for additive manufacturing applications.

PubMed

Nguyen, Ngoc A; Bowland, Christopher C; Naskar, Amit K

2018-08-01

The article presents different mechanical, thermal and rheological data corresponding to the morphological formation within various renewable lignin-based composites containing acrylonitrile butadiene styrene (ABS), acrylonitrile butadiene rubber (NBR41, 41 mol% nitrile content), and carbon fibers (CFs). The data of 3D-printing properties and morphology of 3D-printed layers of selected lignin-based composites are revealed. This data is related to our recent research article entitled "A general method to improve 3D-printability and inter-layer adhesion in lignin-based composites" (Nguyen et al., 2018 [1]).

Testing of Disposable Protective Garments Against Isocyanate Permeation From Spray Polyurethane Foam Insulation.

PubMed

Mellette, Michael P; Bello, Dhimiter; Xue, Yalong; Yost, Michael; Bello, Anila; Woskie, Susan

2018-05-12

Diisocyanates (isocyanates), including methylene diphenyl diisocyanate (MDI), are the primary reactive components of spray polyurethane foam (SPF) insulation. They are potent immune sensitizers and a leading cause of occupational asthma. Skin exposure to isocyanates may lead to both irritant and allergic contact dermatitis and possibly contribute to systemic sensitization. More than sufficient evidence exists to justify the use of protective garments to minimize skin contact with aerosolized and raw isocyanate containing materials during SPF applications. Studies evaluating the permeation of protective garments following exposure to SPF insulation do not currently exist. To conduct permeation testing under controlled conditions to assess the effectiveness of common protective gloves and coveralls during SPF applications using realistic SPF product formulations. Five common disposable garment materials [disposable latex gloves (0.07 mm thickness), nitrile gloves (0.07 mm), vinyl gloves (0.07 mm), polypropylene coveralls (0.13 mm) and Tyvek coveralls (0.13 mm)] were selected for testing. These materials were cut into small pieces and assembled into a permeation test cell system and coated with a two-part slow-rise spray polyurethane foam insulation. Glass fiber filters (GFF) pretreated with 1-(9-anthracenylmethyl)piperazine) (MAP) were used underneath the garment to collect permeating isocyanates. GFF filters were collected at predetermined test intervals between 0.75 and 20.00 min and subsequently analyzed using liquid chromatography-tandem mass spectrometry. For each garment material, we assessed (i) the cumulative concentration of total isocyanate, including phenyl isocyanate and three MDI isomers, that effectively permeated the material over the test time; (ii) estimated breakthrough detection time, average permeation rate, and standardized breakthrough time; from which (iii) recommendations were developed for the use of similar protective garments following contamination by two-component spray polyurethane foam systems and the limitations of such protective garments were identified. Each type of protective garment material demonstrated an average permeation rate well below the ASTM method F-739 standardized breakthrough rate threshold of 100.0 ng/cm2 min-1. Disposable latex gloves displayed the greatest total isocyanate permeation rate (4.11 ng/cm2 min-1), followed by the vinyl and nitrile gloves, respectively. The Tyvek coverall demonstrated a greater average rate of isocyanate permeation than the polypropylene coveralls. Typical isocyanate loading was in the range of 900 to 15,000 ng MDI/cm2. Permeation test data collected during this study indicated that each type of protective garment evaluated, provided a considerable level of protection (i.e. 10-110-fold reduction from the level of direct exposure) against the isocyanate component of the SPF insulation mixture. Nitrile gloves and polypropylene coveralls demonstrated the lowest rate of permeation and the lowest cumulative permeation of total isocyanate for each garment type.

Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects.

PubMed

Hack, John; Grills, David C; Miller, John R; Mani, Tomoyasu

2016-02-18

Ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N) infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.

Degradation of Biofumigant Isothiocyanates and Allyl Glucosinolate in Soil and Their Effects on the Microbial Community Composition

PubMed Central

Hanschen, Franziska S.; Yim, Bunlong; Winkelmann, Traud; Smalla, Kornelia; Schreiner, Monika

2015-01-01

Brassicales species rich in glucosinolates are used for biofumigation, a process based on releasing enzymatically toxic isothiocyanates into the soil. These hydrolysis products are volatile and often reactive compounds. Moreover, glucosinolates can be degraded also without the presence of the hydrolytic enzyme myrosinase which might contribute to bioactive effects. Thus, in the present study the stability of Brassicaceae plant-derived and pure glucosinolates hydrolysis products was studied using three different soils (model biofumigation). In addition, the degradation of pure 2-propenyl glucosinolate was investigated with special regard to the formation of volatile breakdown products. Finally, the influence of pure glucosinolate degradation on the bacterial community composition was evaluated using denaturing gradient gel electrophoresis of 16S rRNA gene amplified from total community DNA. The model biofumigation study revealed that the structure of the hydrolysis products had a significant impact on their stability in the soil but not the soil type. Following the degradation of pure 2-propenyl glucosinolate in the soils, the nitrile as well as the isothiocyanate can be the main degradation products, depending on the soil type. Furthermore, the degradation was shown to be both chemically as well as biologically mediated as autoclaving reduced degradation. The nitrile was the major product of the chemical degradation and its formation increased with iron content of the soil. Additionally, the bacterial community composition was significantly affected by adding pure 2-propenyl glucosinolate, the effect being more pronounced than in treatments with myrosinase added to the glucosinolate. Therefore, glucosinolates can have a greater effect on soil bacterial community composition than their hydrolysis products. PMID:26186695

Detection and mapping of organic molecules in Titan's atmosphere using ALMA

NASA Astrophysics Data System (ADS)

Cordiner, Martin

2016-06-01

Titan's atmospheric photochemistry results in the production of a wide range of organic molecules, including hydrocarbons, nitriles, aromatics and other complex species of possible pre-biotic relevance. Studies of Titan's atmospheric chemistry thus provide a unique opportunity to explore the origin and evolution of organic matter in primitive (terrestrial) planetary atmospheres. The Atacama Large Millimeter/submillimeter Array (ALMA) is a powerful new facility, well suited to the study of molecular emission from Titan's upper and middle-atmosphere. Results will be presented from our ongoing studies of Titan using ALMA data obtained during the period 2012-2014 [1,2], including detection and mapping of emission from C2H5CN, HNC, HC3N, CH3CN and CH3CCH. In addition, combining data from multiple ALMA Band 6 observations, we obtained high-resolution spectra with unprecedented sensitivity, enabling the first detection of C2H3CN (vinyl cyanide) on Titan, and derived a mean C2H3CN C2H5CN abundance ratio above 300 km of 0.3. Vinyl cyanide has recently been investigated as a possible constituent of (pre-biotic) vesicle membranes in Titan's liquid CH4 oceans [3]. Radiative transfer models and possible chemical formation pathways for the detected molecules will be discussed. ALMA observations provide instantaneous snapshot mapping of Titan's entire Earth-facing hemisphere for gases inaccessible to previous studies, and therefore provide new insights into photochemical production and transport, particularly at higher altitudes. Our maps show spatially resolved peaks in Titan's northern and southern hemispheres, consistent with the molecular distributions found in previous studies at infrared wavelengths by Voyager and Cassini, but high-altitude longitudinal asymmetries in our nitrile data indicate that the mesosphere may be more spatially variable than previously thought.

Spectroscopic detection and mapping of vinyl cyanide on Titan

NASA Astrophysics Data System (ADS)

Cordiner, Martin; Yukiko Palmer, Maureen; Lai, James; Nixon, Conor A.; Teanby, Nicholas; Charnley, Steven B.; Vuitton, Veronique; Kisiel, Zbigniew; Irwin, Patrick; Molter, Ned; Mumma, Michael J.

2017-10-01

The first spectroscopic detection of vinyl cyanide (otherwise known as acrylonitrile; C2H3CN) on Titan was obtained by Palmer et al. (2017), based on three rotational emission lines observed with ALMA at millimeter wavelengths (in receiver band 6). The astrobiological significance of this detection was highlighted due to the theorized ability of C2H3CN molecules to combine into cell membrane-like structures under the cold conditions found in Titan's hydrocarbon lakes. Here we report the detection of three additional C2H3CN transitions at higher frequencies (from ALMA band 7 flux calibration data). We present the first emission maps for this gas on Titan, and compare the molecular distribution with that of other nitriles observed with ALMA including HC3N, CH3CN, C2H5CN and HNC. The molecular abundance patterns are interpreted based on our understanding of Titan's high-altitude photochemistry and time-variable global circulation. Similar to the short-lived HC3N molecule, vinyl cyanide is found to be most abundant in the vicinity of the southern (winter) pole, whereas the longer-lived CH3CN is more concentrated in the north. The vertical abundance profile of C2H3CN (from radiative transfer modeling), as well as its latitudinal distribution, are consistent with a short photochemical lifetime for this species. Complementary results from our more recent (2017) nitrile mapping studies at higher spatial resolution will also be discussed.REFERENCES:Palmer, M. Y., Cordiner, M. A., Nixon, C. A. et al. "ALMA detection and astrobiological potential of vinyl cyanide on Titan", Sci. Adv. 2017, 3, e1700022

Novel imino thioether complexes of platinum(II): synthesis, structural investigation, and biological activity.

PubMed

Sgarbossa, Paolo; Sbovata, Silvia Mazzega; Bertani, Roberta; Mozzon, Mirto; Benetollo, Franco; Marzano, Cristina; Gandin, Valentina; Michelin, Rino A

2013-05-20

The reactions of the nitrile complexes cis- and trans-[PtCl2(NCR)2] (R = Me, Et, CH2Ph, Ph) with an excess of ethanethiol, EtSH, in the presence of a catalytic amount of n-BuLi in tetrahydrofuran (THF), afforded in good yield the bis-imino thioether derivatives cis-[PtCl2{E-N(H)═C(SEt)R}2] (R = Me (1), Et (2), CH2Ph (3), Ph (4)) and trans-[PtCl2{E-N(H)═C(SEt)R}2] (R = Me (5), Et (6), CH2Ph (7), Ph (8)). The imino thioether ligands assumed the E configuration corresponding to a cis addition of the thiol to the nitrile triple bond. The spectroscopic properties of these complexes have been reported along with the molecular structures of 1, 2, and 7 as established by X-ray crystallography which indicated that these compounds exhibit square-planar coordination geometry around the platinum center. Four N-H···Cl intermolecular contacts (N-H···Cl ca. 2.5-2.7 Å) between each chlorine atom and the N-H proton of the imino thioether ligand gave rise to "dimers" Pt2Cl4L4 (L = imino thioether) formed by two PtCl2L2 units. The cytotoxic properties of these new platinum(II) complexes were evaluated against various human cancer cell lines. Among all derivatives, trans-[PtCl2{E-N(H)═C(SEt)CH2Ph}2] showed the greatest in vitro cytotoxic activity being able to decrease cancer cell viability roughly 3-fold more effectively than cisplatin.

Differential effects of Phe19 and Phe20 on fibril formation by amyloidogenic peptide A beta 16-22 (Ac-KLVFFAE-NH2).

PubMed

Inouye, Hideyo; Gleason, Katherine A; Zhang, Dong; Decatur, Sean M; Kirschner, Daniel A

2010-08-01

The sequence KLVFFAE (A beta 16-22) in Alzheimer's beta-amyloid is thought to be a core beta-structure that could act as a template for folding other parts of the polypeptide or molecules into fibrillar assemblies rich in beta-sheet. To elucidate the mechanism of the initial folding process, we undertook combined X-ray fiber/powder diffraction and infrared (IR) spectroscopy to analyze lyophilized A beta 16-22 and solubilized/dried peptide containing nitrile probes at F19 and/or F20. Solubilized/dried wild-type (WT) A beta 16-22 and the peptide containing cyanophenylalanine at F19 (19CN) or at F20 (20CN) gave fiber patterns consistent with slab-like beta-crystallites that were cylindrically averaged around the axis parallel to the polypeptide chain direction. The WT and 19CN assemblies showed 30-A period arrays arising from the stacking of the slabs along the peptide chain direction, whereas the 20CN assemblies lacked any such stacking. The electron density projection along the peptide chain direction indicated similar side-chain dispositions for WT and 20CN, but not for 19CN. These X-ray results and modeling imply that in the assembly of WT A beta 16-22 the F19 side chain is localized within the intersheet space and is involved in hydrophobic contact with amino acids across the intersheet space, whereas the F20 side chain localized near the slab surface is less important for the intersheet interaction, but involved in slab stacking. IR observations for the same peptides in dilute solution showed a greater degree of hydrogen bonding for the nitrile groups in 20CN than in 19CN, supporting this interpretation. (c) 2010 Wiley-Liss, Inc.

Rotational Spectroscopy of 4-HYDROXY-2-BUTYNENITRILE

NASA Astrophysics Data System (ADS)

Motiyenko, R. A.; Margulès, L.; Guillemin, J.-C.

2015-06-01

Recently we studied the rotational spectrum of hydroxyacetonitrile (HOCH_2CN, HAN) in order to provide a firm basis for its possible detection in the interstellar medium Different plausible pathways of the formation of HAN in the interstellar conditions were proposed; however, up to now, the searches for this molecule were unsuccessful. To continue the study of nitriles that represent an astrophysical interest we present in this talk the analysis of the rotational spectrum of 4-hydroxy-2-butynenitrile (HOCH_2CC-CN, HBN), the next molecule in the series of hydroxymethyl nitriles. Using the Lille spectrometer the spectrum of HBN was measured in the frequency range 50 -- 500 GHz. From the spectroscopic point of view HBN molecule is rather similar to HAN, because of -OH group tunnelling in gauche conformation. As it was previously observed for HAN, due to this large amplitude motion, the splittings in the rotational spectra of HBN are easily resolved making the spectral analysis more difficult. Additional difficulties arise from the near symmetric top character of HBN (κ = -0.996), and very dense spectrum because of relatively small values of rotational constants and a number of low-lying excited vibrational states. The analysis carried out in the frame of reduced axis system approach of Pickett allows to fit within experimental accuracy all the rotational transitions in the ground vibrational state. Thus, the results of the present study provide a reliable catalog of frequency predictions for HBN. The support of the Action sur Projets de l'INSU PCMI, and ANR-13-BS05-0008-02 IMOLABS is gratefully acknowledged Margulès L., Motiyenko R.A., Guillemin J.-C. 68th ISMS, 2013, TI12. Danger G. et al. Phys. Chem. Chem. Phys. 2014, 16, 3360. Pickett H.M. J. Chem. Phys. 1972, 56, 1715.

Organic Compounds Produced by Photolysis of Realistic Interstellar and Cometary Ice Analogs Containing Methanol

NASA Astrophysics Data System (ADS)

Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Chang, Sherwood; Scharberg, Maureen A.

1995-11-01

The infrared (IR) spectra of ultraviolet (UV) and thermally processed, methanol-containing interstellar/ cometary ice analogs at temperatures from 12 to 300 K are presented. Infrared spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry indicate that CO (carbon monoxide), CO2 (carbon dioxide), CH4 (methane), HCO (the formyl radical), H2CO (formaldehyde), CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C=-N (nitriles) are formed. In addition, the organic materials remaining after photolyzed ice analogs have been warmed to room temperature contain (in rough order of decreasing abundance), (1) hexamethylenetetramine (HMT, C6H12N4), (2) ethers, alcohols, and compounds related to polyoxymethylene {POM, ( CH2O )n}, and (3) ketones {R-C(=O)-R'} and amides {H2NC(=O)-R}. Most of the carbon in these residues is thought to come from the methanol in the original ice. Deuterium and 13C isotopic labeling demonstrates that methanol is definitely the source of carbon in HMT. High concentrations of HMT in interstellar and cometary ices could have important astrophysical consequences. The ultraviolet photolysis of HMT frozen in H2O ice readily produces the "XCN" band observed in the spectra of protostellar objects and laboratory ices, as well as other nitriles. Thus, HMT may be a precursor of XCN and a source of CN in comets and the interstellar medium. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia, formaldehyde, and amino acids. Thus, HMT may be a significant source of prebiogenic compounds on asteroidal parent bodies. A potential mechanism for the radiative formation of HMT in cosmic ices is outlined.

Differential role of CYP2E1-mediated metabolism in the lethal and vestibulotoxic effects of cis-crotononitrile in the mouse

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

Boadas-Vaello, Pere; Jover, Eric; Diez-Padrisa, Nuria

2007-12-15

Several alkylnitriles are toxic to sensory systems, including the vestibular system, through yet undefined mechanisms. This study addressed the hypothesis that the vestibular toxicity of cis-crotononitrile depends on CYP2E1-mediated bioactivation. Wild-type (129S1) and CYP2E1-null female mice were exposed to cis-crotononitrile at 0, 2, 2.25 or 2.5 mmol/kg (p.o.) in either a baseline condition or following exposure to 1% acetone in drinking water to induce CYP2E1 expression. The exposed animals were assessed for vestibular toxicity using a behavioral test battery and through surface observation of the vestibular sensory epithelia by scanning electron microscopy. In parallel groups, concentrations of cis-crotononitrile and cyanidemore » were assessed in whole blood. Contrary to our hypothesis, CYP2E1-null mice were slightly more susceptible to the vestibular toxicity of cis-crotononitrile than were control 129S1 mice. Similarly, rather than enhance vestibular toxicity, acetone pretreatment actually reduced it slightly in 129S1 controls, although not in CYP2E1-null mice. In addition, significant differences in mortality were recorded, with the greatest mortality occurring in 129S1 mice after acetone pretreatment. The highest mortality recorded in the 129S1 + acetone mice was associated with the lowest blood concentrations of cis-crotononitrile and the highest concentrations of cyanide at 6 h after nitrile exposure, the time when deaths were initially recorded. We conclude that cis-crotononitrile is a CYP2E1 substrate as hypothesized, but that CYP2E1-mediated metabolism of this nitrile is not necessary for vestibular toxicity; rather, this metabolism constitutes a major pathway for cyanide release and subsequent lethality.« less

Ultraviolet irradiation effects incorporation of nitrate and nitrite nitrogen into aquatic natural organic matter

USGS Publications Warehouse

Thorn, Kevin A.; Cox, Larry G.

2012-01-01

One of the concerns regarding the safety and efficacy of ultraviolet radiation for treatment of drinking water and wastewater is the fate of nitrate, particularly its photolysis to nitrite. In this study, 15N NMR was used to establish for the first time that UV irradiation effects the incorporation of nitrate and nitrite nitrogen into aquatic natural organic matter (NOM). Irradiation of 15N-labeled nitrate in aqueous solution with an unfiltered medium pressure mercury lamp resulted in the incorporation of nitrogen into Suwannee River NOM (SRNOM) via nitrosation and other reactions over a range of pH from approximately 3.2 to 8.0, both in the presence and absence of bicarbonate, confirming photonitrosation of the NOM. The major forms of the incorporated label include nitrosophenol, oxime/nitro, pyridine, nitrile, and amide nitrogens. Natural organic matter also catalyzed the reduction of nitrate to ammonia on irradiation. The nitrosophenol and oxime/nitro nitrogens were found to be susceptible to photodegradation on further irradiation when nitrate was removed from the system. At pH 7.5, unfiltered irradiation resulted in the incorporation of 15N-labeled nitrite into SRNOM in the form of amide, nitrile, and pyridine nitrogen. In the presence of bicarbonate at pH 7.4, Pyrex filtered (cutoff below 290–300 nm) irradiation also effected incorporation of nitrite into SRNOM as amide nitrogen. We speculate that nitrosation of NOM from the UV irradiation of nitrate also leads to production of nitrogen gas and nitrous oxide, a process that may be termed photo-chemodenitrification. Irradiation of SRNOM alone resulted in transformation or loss of naturally abundant heterocyclic nitrogens.

Crystal structure of tetra­kis­[μ2-2-(di­methyl­amino)­ethano­lato-κ3 N,O:O]di-μ3-hydroxido-di­thio­cyanato-κ2 N-dichromium(III)dilead(II) di­thio­cyanate aceto­nitrile monosolvate

PubMed Central

Rusanova, Julia A.; Semenaka, Valentyna V.; Omelchenko, Irina V.

2016-01-01

The tetra­nuclear complex cation of the title compound, [Cr2Pb2(NCS)2(OH)2(C4H10NO)4](SCN)2·CH3CN, lies on an inversion centre. The main structural feature of the cation is a distorted seco-norcubane Pb2Cr2O6 cage with a central four-membered Cr2O2 ring. The CrIII ion is coordinated in a distorted octa­hedron, which involves two N atoms of one bidentate ligand and one thio­cyanate anion, two μ2-O atoms of 2-(di­methyl­amino)­ethano­late ligands and two μ3-O atoms of hydroxide ions. The coordination geometry of the PbII ion is a distorted disphenoid, which involves one N atom, two μ2-O atoms and one μ3-O atom. In addition, weak Pb⋯S inter­actions involving the coordinating and non-coordinating thio­cyanate anions are observed. In the crystal, the complex cations are linked through the thio­cyanate anions via the Pb⋯S inter­actions and O—H⋯N hydrogen bonds into chains along the c axis. The chains are further linked together via S⋯S contacts. The contribution of the disordered solvent aceto­nitrile mol­ecule was removed with the SQUEEZE [Spek (2015 ▸). Acta Cryst. C71, 9–18] procedure in PLATON. The solvent is included in the reported mol­ecular formula, weight and density. PMID:27375871

Halocarbons and other trace heteroatomic organic compounds in volcanic gases from Vulcano (Aeolian Islands, Italy)

NASA Astrophysics Data System (ADS)

Schwandner, Florian M.; Seward, Terry M.; Giże, Andrew P.; Hall, Keith; Dietrich, Volker J.

2013-01-01

Adsorbent-trapped volcanic gases, sublimates and condensates from active vents of the La Fossa crater on the island of Vulcano (Aeolian Islands, Italy) as well as ambient and industrial air were quantitatively analyzed by Short-Path Thermal Desorption-Solid Phase Microextraction-Cryotrapping-Gas Chromatography/Mass Spectrometry (SPTD-SPME-CF-GC-MS). Among the over 200 detected and quantified compounds are alkanes, alkenes, arenes, phenols, aldehydes, carboxylic acids, esters, ketones, nitriles, PAHs and their halogenated, methylated and sulfonated derivatives, as well as various heterocyclic compounds including thiophenes and furans. Most compounds are found at concentrations well above laboratory, ambient air, adsorbent and field blank levels. For some analytes (e.g., CFC-11, CH2Cl2, CH3Br), concentrations are up to several orders of magnitude greater than even mid-latitudinal industrial urban air maxima. Air or laboratory contamination is negligible or absent on the basis of noble gas measurements and their isotopic ratios. The organic compounds are interpreted as the product of abiogenic gas-phase radical reactions. On the basis of isomer abundances, n-alkane distributions and substitution patterns the compounds are thought to have formed by high-temperature (e.g., 900 °C) alkyl free radical reactions and halide electrophilic substitution on arenes, alkanes and alkenes. The apparent abiogenic organic chemistry of volcanic gases may give insights into metal transport processes during the formation and alteration of hydrothermal ore deposits, into the natural volcanic source strength of ozone-depleting atmospheric trace gases (i.e., halocarbons), into possibly sensitive trace gas redox pairs as potential early indicators of subsurface changes on volcanoes in the state of imminent unrest, and into the possible hydrothermal origin of early life on Earth, as indicated by the presence of simple amino acids, nitriles, and alkanoic acids.

ICE CHEMISTRY ON OUTER SOLAR SYSTEM BODIES: ELECTRON RADIOLYSIS OF N{sub 2}-, CH{sub 4}-, AND CO-CONTAINING ICES

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

Materese, Christopher K.; Cruikshank, Dale P.; Sandford, Scott A.

Radiation processing of the surface ices of outer Solar System bodies may be an important process for the production of complex chemical species. The refractory materials resulting from radiation processing of known ices are thought to impart to them a red or brown color, as perceived in the visible spectral region. In this work, we analyzed the refractory materials produced from the 1.2-keV electron bombardment of low-temperature N{sub 2}-, CH{sub 4}-, and CO-containing ices (100:1:1), which simulates the radiation from the secondary electrons produced by cosmic ray bombardment of the surface ices of Pluto. Despite starting with extremely simple icesmore » dominated by N{sub 2}, electron irradiation processing results in the production of refractory material with complex oxygen- and nitrogen-bearing organic molecules. These refractory materials were studied at room temperature using multiple analytical techniques including Fourier-transform infrared spectroscopy, X-ray absorption near-edge structure (XANES) spectroscopy, and gas chromatography coupled with mass spectrometry (GC-MS). Infrared spectra of the refractory material suggest the presence of alcohols, carboxylic acids, ketones, aldehydes, amines, and nitriles. XANES spectra of the material indicate the presence of carboxyl groups, amides, urea, and nitriles, and are thus consistent with the IR data. Atomic abundance ratios for the bulk composition of these residues from XANES analysis show that the organic residues are extremely N-rich, having ratios of N/C ∼ 0.9 and O/C ∼ 0.2. Finally, GC-MS data reveal that the residues contain urea as well as numerous carboxylic acids, some of which are of interest for prebiotic and biological chemistries.« less

Ice Chemistry on Outer Solar System Bodies: Electron Radiolysis of N2-, CH4-, and CO-Containing Ices

NASA Astrophysics Data System (ADS)

Materese, Christopher K.; Cruikshank, Dale P.; Sandford, Scott A.; Imanaka, Hiroshi; Nuevo, Michel

2015-10-01

Radiation processing of the surface ices of outer Solar System bodies may be an important process for the production of complex chemical species. The refractory materials resulting from radiation processing of known ices are thought to impart to them a red or brown color, as perceived in the visible spectral region. In this work, we analyzed the refractory materials produced from the 1.2-keV electron bombardment of low-temperature N2-, CH4-, and CO-containing ices (100:1:1), which simulates the radiation from the secondary electrons produced by cosmic ray bombardment of the surface ices of Pluto. Despite starting with extremely simple ices dominated by N2, electron irradiation processing results in the production of refractory material with complex oxygen- and nitrogen-bearing organic molecules. These refractory materials were studied at room temperature using multiple analytical techniques including Fourier-transform infrared spectroscopy, X-ray absorption near-edge structure (XANES) spectroscopy, and gas chromatography coupled with mass spectrometry (GC-MS). Infrared spectra of the refractory material suggest the presence of alcohols, carboxylic acids, ketones, aldehydes, amines, and nitriles. XANES spectra of the material indicate the presence of carboxyl groups, amides, urea, and nitriles, and are thus consistent with the IR data. Atomic abundance ratios for the bulk composition of these residues from XANES analysis show that the organic residues are extremely N-rich, having ratios of N/C ∼ 0.9 and O/C ∼ 0.2. Finally, GC-MS data reveal that the residues contain urea as well as numerous carboxylic acids, some of which are of interest for prebiotic and biological chemistries.

Development of a dry actuation conducting polymer actuator for micro-optical zoom lenses

NASA Astrophysics Data System (ADS)

Kim, Baek-Chul; Kim, Hyunseok; Nguyen, H. C.; Cho, M. S.; Lee, Y.; Nam, Jae-Do; Choi, Hyouk Ryeol; Koo, J. C.; Jeong, H.-S.

2008-03-01

The objective of the present work is to demonstrate the efficiency and feasibility of NBR (Nitrile Butadiene Rubber) based conducting polymer actuator that is fabricated into a micro zoon lens driver. Unlike the traditional conducting polymer that normally operates in a liquid, the proposed actuator successfully provides fairly effective driving performance for the zoom lens system in a dry environment. And this paper is including the experiment results for an efficiency improvement. The result suggested by an experiment was efficient in micro optical zoom lens system. In addition, the developed design method of actuator was given consideration to design the system.

Merging Photoredox with 1,2-Metallate Rearrangements: The Photochemical Alkylation of Vinyl Boronate Complexes.

PubMed

Silvi, Mattia; Sandford, Christopher; Aggarwal, Varinder K

2017-04-26

Vinyl boronates react with electron-deficient alkyl iodides in the presence of visible light to give boronic esters in which two new C-C bonds have been created. The reaction occurs by radical addition of an electron-deficient alkyl radical to the vinyl boronate followed by electron transfer with another molecule of alkyl iodide, continuing the chain, and triggering a 1,2-metalate rearrangement. In a number of cases, the use of a photoredox catalyst enhances yields significantly. The scope of the radical precursor includes α-iodo ketones, esters, nitriles, primary amides, α-fluorinated halo-acetates and perfluoroalkyl iodides.

Microtropins A-I: 6'-O-(2″S,3″R)-2″-ethyl-2″,3″-dihydroxybutyrates of aliphatic alcohol β-D-glucopyranosides from the branches of Microtropis japonica.

PubMed

Uemura, Yuka; Sugimoto, Sachiko; Matsunami, Katsuyoshi; Otsuka, Hideaki; Takeda, Yoshio; Kawahata, Masatoshi; Yamaguchi, Kentaro

2013-03-01

From the branches of Microtropis japonica (Celastraceae), nine aliphatic glucosides, named microtropins A-I, were isolated. The 6-position of glucose was esterified with (2S,3R)-2-ethyl-2,3-dihydroxybutyric acid. Microtropins A-D contained a rare natured product nitrile functional group in their aglycones. The absolute structures of the (2S,3R)-2-ethyl-2,3-dihydroxybutyric acid moiety and aglycone of microtropin A were determined by an X-ray crystallographic method. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

PubMed Central

MURAI, Shinji

2011-01-01

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

Microwaves in chemistry: Another way of heating reaction mixtures

NASA Astrophysics Data System (ADS)

Berlan, J.

1995-04-01

The question of a possible "microwave activation" of chemical reaction is discussed. In fact two cases should be distinguished: homogeneous or heterogeneous reaction mixtures. In homogeneous mixtures there are no (or very low) rate enhancements compared to a conventional heating, but some influence on chemioselectivity has been observed. These effects derive from fast and mass heating of microwaves, and probably, especially under reflux, from different boiling rates and/or overheating. With heterogeneous mixtures non conventional effects probably derive from mass heating and selective overheating. This is illustrated with several reactions: Diels-Alder, naphthalene sulphonation, preparation of cyanuric acid, hydrolysis of nitriles, transposition reaction on solid support.

Effects of neutral and anionic substituents on the carbonyl stretching bands of substituted methylbenzoates

NASA Astrophysics Data System (ADS)

Vassileva, P. J.; Binev, I. G.; Juchnovski, I. N.

Effects of neutral and anionic substitutents on frequencies (ν CO) and integrated intensities ( ACO) of the carbonyl stretching bands of substituted methylbenzoates (solvent dimethyl sulphoxide) have been studied in relation to Hammett's equation: satisfactory correlations have been found between ν CO and σ + constants, as well as by using the dual-parameter equations to Yukawa, Tsuno and Taft; ACO have been found to increase in cases of strong electron-releasing substituents. It has been found that constants of anionic substituents, determined on the basis of nitrile i.r. frequencies and intensities, reflect satisfactorily the effects of these substituents on ν CO and ACO of methylbenzoates.

Risk evaluation of possible human hazards by chemicals, particles, and infectious units

NASA Astrophysics Data System (ADS)

Weber, Lothar W.; Spleiss, Martin

1996-12-01

Formation of laser plume by laser-tissue interaction means an inhomogeneous, pluriphasic and dynamic multicomponent system of biological material and induced modifications. While IR_laser applications often simulate processes of thermal food preservation, UV-lasers favor formation of aromatic organic compounds as VOC. Along with traces of PAH, nitriles and O-/N-containing heterocyclic compounds two classes of dialkyldiketopyrroli(di)nes are special formed VOC as laser solvents. Inhalable particles or partially dried and modified biomass contain - along with infectious particles - a lot of temperature degradation products. Ames tests and Comet-assays gave hint to some mutagenic activities present in laser smoke.

Viscoelastic properties of elastomeric materials for O-ring applications

NASA Technical Reports Server (NTRS)

Bower, Mark V.

1989-01-01

Redesign of the Space Shuttle Solid Rocket Booster necessitated re-evaluation of the material used in the field joint O-ring seals. This research project was established to determine the viscoelastic characteristics of five candidate materials. The five materials are: two fluorocarbon compounds, two nitrile compounds, and a silicon compound. The materials were tested in a uniaxial compression test to determine the characteristic relaxation functions. These tests were performed at five different temperatures. A master material curve was developed for each material from the experimental data. The results of this study are compared to tensile relaxation tests. Application of these results to the design analysis is discussed in detail.

Gas-phase reactions in extraterrestrial environments: laboratory investigations by crossed molecular beams.

PubMed

Balucani, Nadia; Casavecchia, Piergiorgio

2006-12-01

We have investigated gas-phase reactions of N((2)D) with the most abundant hydrocarbons in the atmosphere of Titan by the crossed molecular beam technique. In all cases, molecular products containing a novel CN bond are formed, thus suggesting possible routes of formation of gas-phase nitriles in the atmosphere of Titan and primordial Earth. The same approach has been recently extended to the study of radical-radical reactions, such as the reaction of atomic oxygen with the CH(3) and C(3)H(5) radicals. Products other than those already considered in the modeling of planetary atmospheres and interstellar medium have been identified.

Formation of Monolayers by the Coadsorption of Thiols on Gold: Variation in the Length of the Head Group, Tail Group, and Solvent

DTIC Science & Technology

1989-05-01

The lack of a stable gold oxide1 9 obviates the need for special handling procedures and simplifies analysis by ellipsometry (the optical constants... analysis of a series of samples of varying composition. The standard error in both the O(ls) intensity and O/Au ratio was 3%. The O(ls) and Au(4f7/2...involved in the analysis of the XPS data. -0.5 120 Water 0.0 -90 COSOa 0.5 60 ,30 1.0. , 0 0.6 H Bromide 50 e Nitrile 0.7 0 Alcohol 0 Carboxylic

Exploring molecular complexity with ALMA (EMoCA): Simulations of branched carbon-chain chemistry in Sgr B2(N)

NASA Astrophysics Data System (ADS)

Garrod, R. T.; Belloche, A.; Müller, H. S. P.; Menten, K. M.

2017-05-01

Context. Using millimeter wavelength data from the Atacama Large Millimeter/submillimeter Array (ALMA), the EMoCA spectral line survey recently revealed the presence of both the straight-chain (normal) and branched (iso) forms of propyl cyanide (C3H7CN) toward the Galactic Center star-forming source Sgr B2(N2). This was the first interstellar detection of a branched aliphatic molecule. Aims: Through computational methods, we seek to explain the observed I:n ratio for propyl cyanide, and to predict the abundances of the four different forms of the homologous nitrile, butyl cyanide (C4H9CN). We also investigate whether other molecules will show a similar degree of branching, by modeling the chemistry of alkanes up to pentane (C5H12). Methods: We use the coupled three-phase chemical kinetics model, MAGICKAL, to simulate the chemistry of the hot-core source Sgr B2(N2), using an updated chemical network that includes grain-surface/ice-mantle formation routes for branched nitriles and alkanes. The network explicitly considers radical species with an unpaired electron on either the primary or secondary carbon in a chain. We also include mechanisms for the addition of the cyanide radical, CN, to hydrocarbons with multiple bonds between carbon atoms, using activation energy barriers from the literature. We use the EMoCA survey data to search for the straight-chain form of butyl cyanide toward Sgr B2(N2). Results: The observed I:n ratio for propyl cyanide is reproduced by the models, with intermediate to fast warm-up timescales providing the most accurate result. Butyl cyanide is predicted to show similar abundances to propyl cyanide, and to exhibit strong branching, with the sec form clearly dominant over all others. Normal and iso-butyl cyanide are expected to have similar abundances to each other, while the tert form is significantly less abundant. The addition of CN to acetylene and ethene is found to be important to the production of vinyl, ethyl, propyl, and butyl cyanide. The alkanes also show significant branching. We report a non-detection of n-C4H9CN toward Sgr B2(N2), with an abundance at least 1.7 times lower than that of n-C3H7CN. This value is within the range predicted by the chemical models. Conclusions: The models indicate that the degree of branching rises with increasing molecular size. The efficiency of CN addition to unsaturated hydrocarbons boosts the abundances of nitriles in the model, and enhances the ratio of straight-to-branched molecule production. Other types of molecule may be less abundant, but show an even greater degree of branching. The predicted abundance of, in particular, s-C4H9CN, which at its peak is comparable to that of propyl cyanide, makes it a good candidate for future detection toward Sgr B2(N2).

Recent advances in isoxazole chemistry

NASA Astrophysics Data System (ADS)

Galenko, A. V.; Khlebnikov, A. F.; Novikov, M. S.; Pakalnis, V. V.; Rostovskii, N. V.

2015-04-01

The preparation methods and reactions of isoxazoles are described and systematized on the basis of analysis of the literature published from 2005 to present. In the discussion of synthesis, major attention is focused on the most efficient approaches: condensation of hydroxylamine with 1,3-dielectrophiles and reactions of nitrile oxides with alkenes and alkynes. Five-membered ring opening reactions leading to acyclic functionalized or other heterocyclic compounds are considered. The transformations of isoxazole derivatives that occur without ring cleavage to form fused heterocyclic systems, as well as reactions that lead to the introduction of C-substituents into isoxazoles, are considered. Data on the biological activity of some isoxazole derivatives are reported. The bibliography includes 439 references.

A general method for copper-catalyzed arene cross-dimerization.

PubMed

Do, Hien-Quang; Daugulis, Olafs

2011-08-31

A general method for a highly regioselective copper-catalyzed cross-coupling of two aromatic compounds using iodine as an oxidant has been developed. The reactions involve an initial iodination of one arene followed by arylation of the most acidic C-H bond of the other coupling component. Cross-coupling of electron-rich arenes, electron-poor arenes, and five- and six-membered heterocycles is possible in many combinations. Typically, a 1/1.5 to 1/3 ratio of coupling components is used, in contrast to existing methodology that often employs a large excess of one of the arenes. Common functionalities such as ester, ketone, aldehyde, ether, nitrile, nitro, and amine are well-tolerated.

A General Method for Copper-Catalyzed Arene Cross-Dimerization

PubMed Central

Do, Hien-Quang; Daugulis, Olafs

2011-01-01

A general method for a highly regioselective, copper-catalyzed cross-coupling of two aromatic compounds by using iodine oxidant has been developed. The reactions involve an initial iodination of one arene followed by arylation of the most acidic C-H bond of the other coupling component. Cross-coupling of electron-rich arenes, electron-poor arenes, five- and six-membered heterocycles is possible in many combinations. Typically, 1/1.5 to 1/3 ratio of coupling components is used in contrast to existing methodology that often employs a large excess of one of the arenes. Common functionalities such as ester, ketone, aldehyde, ether, nitrile, nitro, and amine are well-tolerated. PMID:21823581

Divergent Syntheses of Isoquinolines and Indolo[1,2-a]quinazolines by Copper-Catalyzed Cascade Annulation from 2-Haloaryloxime Acetates with Active Methylene Compounds and Indoles.

PubMed

Jiang, Huanfeng; Yang, Jidan; Tang, Xiaodong; Wu, Wanqing

2016-03-04

A convenient and reliable method for the direct construction of isoquinolines is described. A series of isoquinoline derivatives were synthesized, with high chemo- and regioselectivities, via the copper-catalyzed cascade reaction of 2-haloaryloxime acetates with β-diketones, β-keto esters, and β-keto nitriles. This tandem annulation process features inexpensive catalysts, no need for additional ligands, and excellent functional group tolerance, which makes it have potential synthetic applications. Furthermore, this strategy could also be used to enter functionalized indolo[1,2-a]quinazolines by using indoles as the counterpart of the 2-haloaryloxime acetates.

Crystal structure of 3-amino-1-(4-meth-oxy-phen-yl)-1H-benzo[f]chromene-2-carbo-nitrile.

PubMed

Mohamed, Shaaban K; Horton, Peter N; Akkurt, Mehmet; Younes, Sabry H H; Albayati, Mustafa R

2015-07-01

In the title compound, C21H16N2O2, the meth-oxy-benzene ring is almost perpendicular to the mean plane of the naphthalene ring system, making a dihedral angle of 83.62 (5)°. The 4H-pyran ring fused with the naphthalene ring system is almost planar [maximum deviation = 0.033 (1) Å]. In the crystal, mol-ecules are linked into inversion dimers by pairs of N-H⋯N hydrogen bonds. N-H⋯O hydrogen bonds connect the dimers, forming a helical supra-molecular chain along the a-axis direction. The crystal packing also features C-H⋯π inter-actions.

[Studies on the oxidation reaction of octanol-2 with nitric acid by infrared spectroscopy].

PubMed

Zhang, G; Zhao, G; Wang, Y; Zhang, Q; Zhang, S; Lu, F

1998-04-01

In this paper, the reaction process of oxidation of octanol-2 with nitric acid has been studied by IR spectroscopy. It is found that the main components of non-sapoifiable matter are different in different oxidation degrees. The relation between oxidation products and the amount of nitric acid are investigated,the reaction mechanism has also been studied. Experimental results show that the oxidation process of octanol-2 is as follows: first, octanol-2 is oxidated to octanone-2, or to nitrate, nitrite and nitrile copmpounds, then these compounds are reoxidated to caproic acid in the meantime some by-products, such as valeric, enanthic acids are also found in oxidated products.

Interstellar molecules - Origin by catalytic reactions on grain surfaces. [compound distribution analysis

NASA Technical Reports Server (NTRS)

Anders, E.; Hayatsu, R.; Studier, M. H.

1974-01-01

To determine the compound distribution formed by surface catalysis, mixtures of CO, D2, and ND2 were heated with nickel-iron or montmorillonite clay catalysts for 49-214 hours at 250 to 300 C. Compounds identified include most of the known polyatomic interstellar molecules, as well as homologous series of acetylenes, dienes, alcohols, aldehydes, ketones, ethers, esters, nitriles, amines, etc., and cyclic compounds such as furans and pyrroles. These homologous series are uniquely characteristic of surface catalysis. A search for the heavier members of these series, predicted to occur at 1/10th to 1/1,000th the abundance of the lightest members, thus comprises a crucial test of this mechanism.

Benzoyl radicals from (hetero)aromatic aldehydes. Decatungstate photocatalyzed synthesis of substituted aromatic ketones.

PubMed

Ravelli, Davide; Zema, Michele; Mella, Mariella; Fagnoni, Maurizio; Albini, Angelo

2010-09-21

Benzoyl radicals are generated directly from (hetero)aromatic aldehydes upon tetrabutylammonium decatungstate ((n-Bu(4)N)(4)W(10)O(32)), TBADT) photocatalysis under mild conditions. In the presence of alpha,beta-unsaturated esters, ketones and nitriles radical conjugate addition ensues and gives the corresponding beta-functionalized aryl alkyl ketones in moderate to good yields (stereoselectively in the case of 3-methylene-2-norbornanone). Due to the mild reaction conditions the presence of various functional groups on the aromatic ring is tolerated (e.g. methyl, methoxy, chloro). The method can be applied to hetero-aromatic aldehydes whether electron-rich (e.g. thiophene-2-carbaldehyde) or electron-poor (e.g. pyridine-3-carbaldehyde).

Spectroscopic Investigation of O-,M-, and P-Cyanostyrenes

NASA Astrophysics Data System (ADS)

Korn, Joseph A.; Knezz, Stephanie N.; McMahon, Robert J.; Zwier, Timothy S.

2014-06-01

The atmosphere of Titan contains nitrogen, methane, and a rich mixture of more complex hydrocarbons and nitriles produced by photochemical processing. Data from the 2005 Cassini-Huygens mission suggests that among the more complex compounds are substituted benzenes that are themselves precursors to large polymeric tholins. Nitriles are particularly prevalent in Titan's atmosphere due to the dominance of N2 in the atmosphere. The cyanostyrenes are of particular interest, in part because they have the same molecular formula (C9H7N) as quinoline, a prototypical heteroaromatic, and therefore could engage in photochemical isomerization to form this molecule of significant pre-biotic relevance. As a first step in understanding the pathways leading to heteroaromatics, we have studied the isotope-selective spectroscopy of o-,m-, and p-cyanostyrene under jet-cooled conditions relevant to Titan's atmosphere. In this talk, the excitation and emission spectra for the three isomers will be presented. Using a combination of resonant two-photon ionization, LIF excitation, and dispersed fluorescence spectroscopies, the vibronic spectroscopy of the three isomers were recorded and compared. The meta isomer has two conformational isomers, which have been distinguished and studied using hole-burning methods. The talk will compare and contrast the UV spectral signatures of the set of structural and conformational isomers of the cyanostyrenes, using the ethynylstyrene counterparts as points of comparison. Sebree, J. A.; Kidwell, N. M.; Selby, T. M.; Amberger, B. K.; McMahon, R. J.; Zwier, T. S., Photochemistry of Benzylallene: Ring-Closing Reactions to Form Naphthalene. Journal of the American Chemical Society 2012, 134 (2), 1153-1163. Selby, T. M.; Clarkson, J. R.; Mitchell, D.; Fitzpatrick, J. A. J.; Lee, H. D.; Pratt, D. W.; Zwier, T. S., Isomer-Specific Spectroscopy and Conformational Isomerization Energetics of o-, m-, and p-Ethynylstyrenes. The Journal of Physical Chemistry A 2005, 109 (20), 4484-4496.

Corrosion-Prevention Capabilities of a Water-Borne, Silicone-Based, Primerless Coating

NASA Technical Reports Server (NTRS)

Calle, Luz Marina; MacDowell, Louis G.; Vinje, Rubie D.

2005-01-01

Comparative tests have been performed to evaluate the corrosion-prevention capabilities of an experimental paint of the type described in Water-Borne, Silicone-Based, Primerless Paints, NASA Tech Briefs, Vol. 26, No. 11 (November 2002), page 30. To recapitulate: these paints contain relatively small amounts of volatile organic solvents and were developed as substitutes for traditional anticorrosion paints that contain large amounts of such solvents. An additional desirable feature of these paints is that they can be applied without need for prior application of primers to ensure adhesion. The test specimens included panels of cold-rolled steel, stainless steel 316, and aluminum 2024-T3. Some panels of each of these alloys were left bare and some were coated with the experimental water-borne, silicone-based, primerless paint. In addition, some panels of aluminum 2024-T3 and some panels of a fourth alloy (stainless steel 304) were coated with a commercial solvent-borne paint containing aluminum and zinc flakes in a nitrile rubber matrix. In the tests, the specimens were immersed in an aerated 3.5-weight-percent aqueous solution of NaCl for 168 hours. At intervals of 24 hours, the specimens were characterized by electrochemical impedance spectroscopy (EIS) and measurements of corrosion potentials. The specimens were also observed visually. As indicated by photographs of specimens taken after the 168-hour immersion (see figure), the experimental primerless silicone paint was effective in preventing corrosion of stainless steel 316, but failed to protect aluminum 2024-T3 and cold-rolled steel. The degree of failure was greater in the case of the cold-rolled steel. On the basis of visual observations, EIS, and corrosion- potential measurements, it was concluded that the commercial aluminum and zinc-filled nitrile rubber coating affords superior corrosion protection to aluminum 2024-T3 and is somewhat less effective in protecting stainless steel 304.

Dynamics of the solute-solvent interactions of electronically excited 4-N,N-dimethylaminobenzonitrile (DMABN) and of 3,5,N,N-tetramethyl-4-aminobenzonitrile (TMABN) dissolved in viscous alcohols and in a viscous nitrile

NASA Astrophysics Data System (ADS)

Weisenborn, Petra C. M.; Huizer, A. Herbert; Varma, Cyril A. G. O.

1989-06-01

The time dependence of the fluorescence of solutions of 4-N,N-dimethylaminobenzonitrile (DMABN) and 3,5,N,N-tetramethyl-4-aminobenzonitrile (TMA BN) in neat polar solvents has been investigated, using a 25 ps UV-laser pulse for excitation and a streak camera for detection. Both the compounds DMABN and TMABN exhibit normal fluorescence F N and anomalous fluorescence F A, but all the solutions of TMABN show merely a single band in the fluorescence spectrum, which is a superposition of the bands F N and F A. In the case of DMABN the fluorescence in the region λ < 400 nm, where F N dominates, the fluorescence decays tri-exponentially due to fluorescence from three types of species, namely excited solute-solvent complexes, excited bare solutes and solute-solvent exciplexes. Within the lifetime of these emitting species there is probably no reverse reaction from exciplexes to excited solute-solvent complexes or excited bare solutes. This is in contrast with a previously presented picture, which includes such a reverse reaction. In the case of the solution of DMABN in n-butanol, the fluorescence at λ < 400 nm is bi-exponential. We show that this is due to an accidental degeneracy of two lifetimes. In contrast to a previous conclusion, we find that DMABN exists partially in the form of ground state solute-solvent complexes also in the solution in nitriles. The anomalous fluorescence develops in two phases, in the first one solute-solvent exciplexes are formed and in the second one the dielectric polarization of the solvent around the exciplex builds up. The rate constant for the formation of the anomalously fluorescing species, i.e. solute-solvent exciplexes, bears no relation with the longitudinal relaxation time, as claimed to have been shown previously.

Variability in surface infrared reflectance of thirteen nitrile rubber gloves at key wavelengths for analysis of captan.

PubMed

Phalen, R N; Que Hee, Shane S

2007-02-01

The aim of this study was to investigate the surface variability of 13 powder-free, unlined, and unsupported nitrile rubber gloves using attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectrophotometry at key wavelengths for analysis of captan contamination. The within-glove, within-lot, and between-lot variability was measured at 740, 1124, 1252, and 1735 cm(-1), the characteristic captan reflectance minima wavelengths. Three glove brands were assessed after conditioning overnight at relative humidity (RH) values ranging from 2 +/- 1 to 87 +/- 4% and temperatures ranging from -8.6 +/- 0.7 to 59.2 +/- 0.9 degrees C. For all gloves, 1735 cm(-1) provided the lowest background absorbance and greatest potential sensitivity for captan analysis on the outer glove surface: absorbances ranged from 0.0074 +/- 0.0005 (Microflex) to 0.0195 +/- 0.0024 (SafeSkin); average within-glove coefficients of variation (CV) ranged from 2.7% (Best, range 0.9-5.3%) to 10% (SafeSkin, 1.2-17%); within-glove CVs greater than 10% were for one brand (SafeSkin); within-lot CVs ranged from 2.8% (Best N-Dex) to 28% (SafeSkin Blue); and between-lot variation was statistically significant (p < or = 0.05) for all but two SafeSkin lots. The RH had variable effects dependent on wavelength, being minimal at 1735, 1252, and 1124 cm(-1) and highest at 3430 cm(-1) (O-H stretch region). There was no significant effect of temperature conditioning. Substantial within-glove, within-lot, and between-lot variability was observed. Thus, surface analysis using ATR-FT-IR must treat glove brands and lots as different. ATR-FT-IR proved to be a useful real-time analytical tool for measuring glove variability, detecting surface humidity effects, and choosing selective and sensitive wavelengths for analysis of nonvolatile surface contaminants.

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

Vogel, E.A.F.

A series of new tetranuclear molybdenum(II) nitrile cluster derivatives is reported. Improvements in the synthetic routes to these and other derivatives is also reported. The single crystal x-ray structure of Mo/sub 4/Cl/sub 12//sup 4/minus// is modeled. New tetrameric nitrile derivatives with the stoichiometry Mo/sub 4/Cl/sub 8/(RCN)/sub 4/ (R = Pr/sup n/, Pr/sup i/, Bu/sup t/, PhCH/sub 2/) have been isolated by ligand exchange from Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/ and/or direct synthesis from Mo/sub 4/Cl/sub 8/(PBu/sup n/sub 3//)/sub 4/. Mo/sub 4/Cl/sub 8/(Pr/sup n/CN)/sub 4/ was synthesized with higher yields and with simpler reaction conditions than Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/. Improved syntheticmore » routes for R/sub 4/Mo/sub 4/Cl/sub 12/ (R = Et/sub 4/N, Pr/sub 4/N) have been developed. (Et/sub 4/N)/sub 4/Mo/sub 4/Cl/sub 12/ can be directly synthesized from the phosphine tetramer, circumventing the preparation of the reactive species-Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/, which is the most difficult precursor to prepare. A change in reaction solvent, from dichloromethane or dichloroethane to chlorobenzene, in the preparation of (Pr/sub 4/N)/sub 4/Mo/sub 4/Cl/sub 12/ has permitted its isolation under less rigorous conditions and in high yield. A single crystal structure determination has been done on a sample of (Ph/sub 4/P)/sub 4/Mo/sub 4/Cl/sub 12/. Although, the quality of the data is poor, the structure of the Mo/sub 4/Cl/sub 12/ cluster core was refined. Four complex types have been found to fit the data. 22 refs., 12 figs., 7 tabs.« less

Metal-Assisted Oxo Atom Addition to an Fe(III) Thiolate.

PubMed

Villar-Acevedo, Gloria; Lugo-Mas, Priscilla; Blakely, Maike N; Rees, Julian A; Ganas, Abbie S; Hanada, Erin M; Kaminsky, Werner; Kovacs, Julie A

2017-01-11

Cysteinate oxygenation is intimately tied to the function of both cysteine dioxygenases (CDOs) and nitrile hydratases (NHases), and yet the mechanisms by which sulfurs are oxidized by these enzymes are unknown, in part because intermediates have yet to be observed. Herein, we report a five-coordinate bis-thiolate ligated Fe(III) complex, [Fe III (S 2 Me2 N 3 (Pr,Pr))] + (2), that reacts with oxo atom donors (PhIO, IBX-ester, and H 2 O 2 ) to afford a rare example of a singly oxygenated sulfenate, [Fe III (η 2 -S Me2 O)(S Me2 )N 3 (Pr,Pr)] + (5), resembling both a proposed intermediate in the CDO catalytic cycle and the essential NHase Fe-S(O) Cys114 proposed to be intimately involved in nitrile hydrolysis. Comparison of the reactivity of 2 with that of a more electron-rich, crystallographically characterized derivative, [Fe III S 2 Me2 N Me N 2 amide (Pr,Pr)] - (8), shows that oxo atom donor reactivity correlates with the metal ion's ability to bind exogenous ligands. Density functional theory calculations suggest that the mechanism of S-oxygenation does not proceed via direct attack at the thiolate sulfurs; the average spin-density on the thiolate sulfurs is approximately the same for 2 and 8, and Mulliken charges on the sulfurs of 8 are roughly twice those of 2, implying that 8 should be more susceptible to sulfur oxidation. Carboxamide-ligated 8 is shown to be unreactive towards oxo atom donors, in contrast to imine-ligated 2. Azide (N 3 - ) is shown to inhibit sulfur oxidation with 2, and a green intermediate is observed, which then slowly converts to sulfenate-ligated 5. This suggests that the mechanism of sulfur oxidation involves initial coordination of the oxo atom donor to the metal ion. Whether the green intermediate is an oxo atom donor adduct, Fe-O═I-Ph, or an Fe(V)═O remains to be determined.